CN114181246A - Preparation method of liquid bisphenol A bis (diphenyl phosphate) flame retardant - Google Patents
Preparation method of liquid bisphenol A bis (diphenyl phosphate) flame retardant Download PDFInfo
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- CN114181246A CN114181246A CN202111567570.5A CN202111567570A CN114181246A CN 114181246 A CN114181246 A CN 114181246A CN 202111567570 A CN202111567570 A CN 202111567570A CN 114181246 A CN114181246 A CN 114181246A
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- bisphenol
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- phosphorus oxychloride
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- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000003063 flame retardant Substances 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 title claims abstract description 21
- 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 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 112
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000005194 fractionation Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003849 aromatic solvent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000009835 boiling Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 239000001488 sodium phosphate Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 235000011009 potassium phosphates Nutrition 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229940117389 dichlorobenzene Drugs 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 abstract description 23
- 150000002148 esters Chemical group 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000012263 liquid product Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 8
- 235000011008 sodium phosphates Nutrition 0.000 description 8
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000539 dimer Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VOMWXAHMLLKRIQ-UHFFFAOYSA-N CC(=C)C1=CC=CC=C1OP(O)(O)=O Chemical compound CC(=C)C1=CC=CC=C1OP(O)(O)=O VOMWXAHMLLKRIQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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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
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
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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 a liquid bisphenol A bis (diphenyl phosphate) flame retardant, which comprises the following steps: (1) dissolving bisphenol A in an inert aromatic solvent, dropwise adding the solution into preheated phosphorus oxychloride to perform a bisphenol A phosphoryl chlorination reaction until no hydrogen chloride is discharged, and recovering excessive phosphorus oxychloride by fractionation; (2) dissolving phenol in an organic solvent, adding an inorganic alkali aqueous solution to form an organic/alkali/water three-phase system, then dropwise adding the reaction solution in the first step, stirring and reacting, separating out a water layer, washing an oil layer to be neutral, filtering to remove solids, drying filtrate, and distilling to recover the solvent. In the first step of reaction, the excessive phosphorus oxychloride is recovered by adopting a high-boiling-point solvent to assist fractionation, so that the residual phosphorus oxychloride is reduced, in the second step of reaction, the residual phosphorus oxychloride is removed by using an interface reaction technology of an organic/alkali/water three-phase system, the ester exchange reaction is prevented from forming triphenyl phosphate, and finally, the residual triphenyl phosphate in a liquid product is effectively reduced.
Description
Technical Field
The invention relates to a preparation method of a halogen-free flame retardant, in particular to a preparation method of a liquid bisphenol A bis (diphenyl phosphate) flame retardant without triphenyl phosphate, belonging to the field of preparation of halogen-free flame retardants.
Background
Bisphenol A bis (diphenyl phosphate) (BDP) is a highly efficient halogen-free flame retardant used as a flame retardant component in various engineering plastics, in particular PC/ABS copolymers. Pure bisphenol a bis (diphenyl phosphate) is a solid, but in practical applications, liquid flame retardants are often more convenient to use. In order to make bisphenol a bis (diphenyl phosphate) liquid at room temperature and not reduce the phosphorus content to ensure the flame retardant effect, the prior art adopts a strategy of adding a certain amount of dimer (DBDP) to bisphenol a bis (diphenyl phosphate) to form a mixture to reduce the melting point and ensure the phosphorus content. Among them, US albermel corporation in chinese patent CN1355808(US33068899) discloses a flame retardant based on bisphenol a bis (diphenyl phosphate) and its synthesis method, by controlling the reaction conditions and the charge ratio, a mixture of dimer (DBDP) and Trimer (TBDP) with a certain content is directly formed in the process of synthesizing bisphenol a bis (diphenyl phosphate) from the reaction of bisphenol a and phosphorus oxychloride (the synthesis route is shown in fig. 1), and the product is liquid at room temperature. The performance of the mixture flame retardant based on the bisphenol A bis (diphenyl phosphate) is not much different from that of the bisphenol A bis (diphenyl phosphate), but the mixture flame retardant is liquid at normal temperature and has the advantages of convenient use and simple production process. However, in the production process, the excessive phosphorus oxychloride is used as a solvent in the first step of reaction, and the excessive phenol esterification and end capping approach at high temperature is adopted in the second step, so that a certain amount of triphenyl phosphate (TPP) exists in the product and cannot be removed.
Although triphenyl phosphate is also a flame retardant, the higher the triphenyl phosphate content, the lower the quality of the bisphenol a bis (diphenyl phosphate) flame retardant product, because triphenyl phosphate has a small molecular weight and is volatile at lower temperatures, and can significantly reduce the performance of engineering resins at high temperatures. There are two possible routes to triphenyl phosphate production: 1) when the bisphenol A bis (phosphoryl chloride) intermediate is formed in the first step, the excessive phosphorus oxychloride is difficult to be completely distilled off, and the excessive phosphorus oxychloride continues to react with phenol to form triphenyl phosphate in the second step; 2) the reaction temperature is high during the second step of phenol esterification end capping, and the intermediate bisphenol A bis (phosphoryl chloride) and even the product bisphenol A bis (diphenyl phosphate) can be subjected to ester exchange with phenol to generate triphenyl phosphate.
In order to reduce the amount of triphenyl phosphate in the product, chinese patent (CN105037418B) discloses a method to obtain a bisphenol a phenyl phosphate flame retardant with low TPP content. The process mainly adopts a mode of redistilling to remove excessive phosphorus oxychloride and then adding part of bisphenol A for reaction to reduce the residual phosphorus oxychloride, and the process substantially leads the bisphenol A to be excessive under the condition of not significantly influencing the composition of the product, so that the operation process is more complicated, and new byproducts can be caused due to the excessive bisphenol A. In addition, since bisphenol A bis (diphenyl phosphate) is a highly viscous liquid, the excess phenol is difficult to distill off, and the residual phenol in trace amounts causes significant degradation of product color and properties. In order to remove acidic impurities such as phenol, washing with liquid caustic is still required. The american asahi swill company, chinese patent CN101307072A, discloses a method of removing acidic impurities in the product by adding an epoxy compound to form water-soluble impurities, but the use of the epoxy compound increases the production cost.
As is well known, bisphenol a reacts with diphenyl phosphoryl chloride under alkaline conditions to synthesize bisphenol a bis (diphenyl phosphate) without generating triphenyl phosphate, but high-purity bisphenol a bis (diphenyl phosphate) is solid and needs to be compounded with bisphenol a bis (diphenyl phosphate) dimer (DBDP) and the like to form a liquid flame retardant, and the dimer (DBDP) has high production cost and is not industrially produced at present. Similarly, the biphosphonyl chloride intermediate is obtained by reacting bisphenol A with phosphorus oxychloride, and the biphosphonyl A bis (diphenyl phosphate) flame retardant is prepared by reacting the biphosphonyl chloride intermediate with sodium phenolate under the condition of removing the phosphorus oxychloride, so that the generation of triphenyl phosphate by ester exchange can be avoided, but not only the sodium phenolate needs to be prepared in advance, but also the sodium phenolate in an organic solvent has poor solubility, and can be reacted with the biphosphonyl chloride intermediate under the assistance of a large amount of polar organic solvents, and the polar organic solvents are incompatible with the phosphorus oxychloride as the first raw material, so that the production process is complicated, and the practical application value is low.
Disclosure of Invention
The main object of the present invention is to provide a process for the preparation of liquid bisphenol a bis (diphenyl phosphate) liquid flame retardants essentially free of (or having a very low content of) triphenyl phosphate without significantly increasing the cost.
The above object of the present invention is achieved by the following technical solutions:
a method for preparing a liquid bisphenol A bis (diphenyl phosphate) flame retardant, comprising:
(1) phosphorylation of bisphenol A: dissolving bisphenol A in an inert aromatic solvent, dropwise adding the solution into preheated phosphorus oxychloride, carrying out a bisphenol A phosphoryl chlorination reaction by using anhydrous magnesium chloride as a catalyst until no hydrogen chloride is discharged, ending the reaction, recovering excessive phosphorus oxychloride through fractionation, and cooling the reaction solution for later use;
(2) esterification and end capping reaction: dissolving phenol in an organic solvent and adding an inorganic alkaline aqueous solution to form an organic/alkaline/water three-phase system; and (3) dropwise adding the reaction liquid obtained in the first step of reaction into an organic/alkali/water three-phase system, stirring and reacting, separating out a water layer, washing an oil layer to be neutral, filtering to remove solids, drying the filtrate, and distilling to recover the solvent to obtain the liquid bisphenol A bis (diphenyl phosphate) flame retardant.
As a preferred embodiment of the present invention, the boiling point of the inert aromatic hydrocarbon solvent described in the step (1) is higher than the boiling point (105 ℃) of phosphorus oxychloride by 10 ℃ or more, that is, the boiling point is not lower than 115 ℃ or more; preferably, the boiling point of the inert aromatic hydrocarbon solvent is 20-50 ℃ higher than the boiling point (105 ℃) of the phosphorus oxychloride, namely the boiling point is 125-155 ℃, and most preferably, the boiling point of the inert aromatic hydrocarbon solvent is 25-35 ℃ higher than the boiling point (105 ℃) of the phosphorus oxychloride, namely the boiling point is 125-135 ℃.
In a preferred embodiment of the present invention, the inert aromatic hydrocarbon solvent may be alkylbenzene or chlorobenzene, wherein the alkylbenzene may be toluene, ethylbenzene, xylene, diethylbenzene, etc., and the chlorobenzene may be chlorobenzene, dichlorobenzene or trichlorobenzene, preferably chlorobenzene or dichlorobenzene or a mixture thereof.
As a preferred embodiment of the present invention, the preheating in step (1) is preheating to 90 ℃, in terms of mole ratio, bisphenol a: 1, phosphorus oxychloride: 5.
as a preferred embodiment of the present invention, the organic solvent described in the step (2) is preferably an inert aromatic hydrocarbon solvent described in the step (1).
As a preferred embodiment of the present invention, the molar ratio of bisphenol a: phenol 1: (3.5-4.5): more preferably, the molar ratio of bisphenol a: phenol 1: 4.
as a preferred embodiment of the present invention, the molar ratio of phenol: inorganic alkaline aqueous solution ═ 1: (0.5-1.2), preferably, phenol: inorganic alkaline aqueous solution ═ 1: 1.
wherein the inorganic alkaline water solution can be sodium phosphate water solution, potassium phosphate water solution, sodium bicarbonate water solution, potassium bicarbonate water solution, sodium carbonate water solution, potassium carbonate water solution, sodium hydroxide water solution or potassium hydroxide water solution. Wherein, the alkalinity of the sodium hydroxide and the potassium hydroxide is too strong, so that the phosphorus oxychloride intermediate is hydrolyzed; the sodium bicarbonate and the potassium bicarbonate have insufficient alkalinity and incomplete reaction; sodium carbonate or potassium carbonate has a better reaction effect, and sodium phosphate or potassium phosphate has a best reaction effect.
The key to the realization of the invention is to screen and determine the proper organic solvent and alkali. Through a large number of experiments, the invention discovers that the best chlorobenzene is used as the organic solvent, the boiling point of the organic solvent meets the requirement of being higher than 10 ℃ of phosphorus oxychloride, the excessive phosphorus oxychloride in the first step of reaction is favorably recovered, and in the second step, the chlorobenzene well dissolves the phosphorus oxychloride intermediate, is insoluble in water, can form a clear interface with water, and can be removed by reduced pressure distillation. Although the xylene meets the boiling point requirement, emulsification occurs in the second step, the xylene is not clearly separated from alkaline water, and the reaction effect is poor; dichlorobenzene has a too high boiling point, and solvent residues in the product are difficult to remove.
The alkalinity of the sodium hydroxide and the potassium hydroxide is too strong, so that the phosphorus oxychloride intermediate is hydrolyzed; the sodium bicarbonate and the potassium bicarbonate have insufficient alkalinity and incomplete reaction; sodium carbonate and potassium carbonate react better, but sodium phosphate or potassium phosphate reacts best, the concrete reason is not clear, disodium hydrogen phosphate or sodium dihydrogen phosphate which is produced after the sodium phosphate reacts can form a certain buffer system, the acid-base property of the solution is prevented from being greatly changed, and the side reaction is reduced, and the disodium hydrogen phosphate and the sodium dihydrogen phosphate can be recovered and recycled after being neutralized by alkali. The cost, the reaction effect and the recycling are comprehensively considered, and the sodium phosphate is optimal.
And (3) dropwise adding the reaction solution obtained in the first step of reaction into an organic/alkali/water three-phase system at room temperature to perform reaction at room temperature in the step (2).
In the first step of bisphenol A phosphoryl chlorination reaction, anhydrous magnesium chloride is used as Lewis catalyst to catalyze the reaction of bisphenol A and phosphorus oxychloride to form an intermediate bisphenol A bis (phosphoryl chloride) intermediate, and due to the difficulty in controlling reaction conditions such as feeding, temperature and the like, isopropenylphenol impurities formed by bisphenol A often appear, and isopropenylphenyl phosphate which is a harmful impurity is formed. In order to reduce the allyl phenol impurity formed by decomposing bisphenol A, the invention adopts the technical scheme that bisphenol A is dissolved in an inert aromatic solvent with the boiling point higher than that of phosphorus oxychloride (105 ℃) by more than 10 ℃, such as alkylbenzene, chlorobenzene and the like, and is dripped into phosphorus oxychloride with 5 times of the molar weight of bisphenol A preheated to 90 ℃. The method of adding the materials by the solution is convenient to operate and more controllable in reaction, more importantly, the boiling point of the solvent is higher than the boiling point of phosphorus oxychloride by more than 10 ℃, and after the reaction is finished, excessive phosphorus oxychloride is recovered by fractionation, so that the residual of the phosphorus oxychloride is reduced. In particular, when a solvent having a boiling point higher than 25-35 ℃ that of phosphorus oxychloride is used, the recovery of phosphorus oxychloride is substantially complete, and only a portion of the solvent is distilled off. However, when the boiling point difference between the solvent and the phosphorus oxychloride is lower than 10 ℃, the separation effect is poor, and a large amount of solvent is needed to carry the excessive phosphorus oxychloride; when the boiling point of the solvent is higher than the boiling point of phosphorus oxychloride by 50 ℃, the residual solvent is difficult to remove, and the quality of the final product is influenced.
In the second esterification end-capping reaction, phenol with the molar quantity 4 times that of bisphenol A is dissolved in an organic solvent, and the organic solvent is preferably the same as the solvent (namely an inert aromatic solvent) in the first reaction, so that the types of the solvents are reduced, and the cost is reduced; and an aqueous solution of an inorganic base such as sodium carbonate, potassium carbonate, sodium phosphate or potassium phosphate in an equimolar amount of phenol is added to form an organic/alkali/water three-phase system. And (3) dropwise adding the intermediate solution formed in the first step reaction at room temperature, after the stirring reaction is finished, separating out a water layer, washing an oil layer to be neutral, filtering to remove solids, drying filtrate, and distilling and recovering a solvent to obtain a liquid product.
The invention adopts an organic/alkali/water three-phase system, phenol and an intermediate bisphenol A bis (phosphoryl chloride) intermediate are dissolved in an organic phase, and acid generated by the reaction is neutralized by the reaction of an interface and alkali in a water phase, so that the reaction is promoted to be completed; after the alkali concentration in water is reduced, the solid alkali is dissolved and supplemented, the strength of the alkali is kept stable, and the generated salt is dissolved in the water, so that the stirring is not influenced, and the large-scale production is convenient. The interface reaction technology is adopted, so that the sodium phenolate is prevented from being prepared in advance, the operation is simplified, and meanwhile, the acid condition is eliminated, the room-temperature reaction condition is mild, so that the ester exchange reaction of the intermediate and the product with the phenol is avoided, and the formation of triphenyl phosphate is eliminated.
The intermediate bisphenol A bis (phosphoryl chloride) formed in the first step under the acidic condition and the second step of phenol end capping reaction are respectively carried out under two different reaction conditions of acid/alkali so as to eliminate the generation of triphenyl phosphate. Wherein, in the first step, the phosphorus oxychloride is recovered by using a solvent to help fractional distillation, so that the residual phosphorus oxychloride brought into the second step is reduced; and in the second step, an interface reaction is carried out in an organic/alkali/water three-phase system to realize the esterification and end capping of phenol, so that the residual phosphorus oxychloride in the reaction in the first step is removed by forming water-soluble phosphate, the ester exchange side reaction between phenol and an intermediate or even a product is eliminated by adopting mild alkaline reaction conditions, and the formation of triphenyl phosphate is prevented. In addition, the organic/alkali/water three-phase system can also remove residual phenol and acidic impurities, so that the step of additionally removing phenol and acidic impurities is avoided, and the residual triphenyl phosphate in the product is effectively removed.
The invention adopts the high boiling point solvent to assist the fractionation to recover the excessive phosphorus oxychloride and the interface reaction technology of an organic/alkali/water three-phase system, eliminates the residual phosphorus oxychloride and prevents the ester exchange reaction of the intermediate and the product with phenol, thereby eliminating the formation of triphenyl phosphate and obtaining the high-quality liquid halogen-free flame retardant based on the bisphenol A phenyl phosphate without obviously increasing the cost, and the invention has good industrial application value.
Drawings
FIG. 1 is a schematic diagram of a synthesis method of a bisphenol A bis (diphenyl phosphate) -based flame retardant of the prior art.
FIG. 2 is a scheme showing the synthesis of a flame retardant for the production of bisphenol A bis (diphenyl phosphate) by the two-step process of the present invention.
FIG. 3 the synthesis reaction according to the present invention.
The chromatogram for the HPLC analysis of the product of FIG. 4, where retention time 6.115 is the time to peak for triphenyl phosphate and retention time 12.865 is the time to peak for the product liquid bisphenol A bis (diphenyl phosphate).
Detailed Description
The invention is further described below in conjunction with specific embodiments, the advantages and features of which will become apparent from the description. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be within the scope of the invention.
EXAMPLE 1 two-step preparation of liquid bisphenol A bis (diphenylphosphate)
First step phosphoryl chlorination of bisphenol A
1.67kg of phosphorus oxychloride and 5g of anhydrous magnesium chloride were added to a 5 l four-necked flask equipped with a mechanical stirrer, a constant pressure dropping funnel, a thermometer and a reflux condenser (the top end of which was connected to a tail gas outlet and to an absorption apparatus), and the mixture was heated to 90 ℃. During heating, 500g of bisphenol A was dissolved in 2 l of chlorobenzene and, when the temperature of phosphorus oxychloride reached 90 ℃, the chlorobenzene solution of bisphenol A was slowly added through a constant pressure dropping funnel, keeping the hydrogen chloride gas generated evenly and smoothly evolved. The bisphenol A solution is added after 2 hours, and then the temperature is raised and the reflux reaction is carried out until no hydrogen chloride gas is basically discharged. The reflux condenser pipe is changed into a distillation condenser pipe, and the phosphorus oxychloride is recovered by normal pressure fractionation. When the phosphorus oxychloride is not distilled out basically, the pressure is reduced to 3-5Kpa to distill part of chlorobenzene solvent. When the distilled chlorobenzene solvent is not fuming any more when meeting moisture, the reaction bottle is basically free of phosphorus oxychloride. The solution is directly used for the second step of phenol esterification end capping after being cooled to the room temperature.
Second step esterification end capping reaction
To a 10 liter four-necked flask equipped with mechanical stirring and an addition funnel, 825g (8.77mol) of phenol in an amount of 4 times the molar amount of bisphenol A was dissolved in 1 liter of chlorobenzene, and 1.44kg of sodium phosphate in an amount equivalent to the molar amount of phenol and 5 liters of water were added to form an organic/alkali/water three-phase system. Stirring at room temperature, slowly adding the intermediate solution formed in the first step reaction, and stirring for reaction for 6 hours. Separating out water layer, washing oil layer with sodium sulfite aqueous solution, washing with water to neutrality, filtering to remove solid, drying filtrate, and vacuum distilling to recover solvent to obtain 1.42kg of colorless or light yellow viscous liquid product.
The product was analyzed by HPLC under the following chromatographic conditions:
the instrument model is as follows: shimadzu LC-10A
Column type: ODS-80
Detection wavelength: 250nm
Column temperature: 30 deg.C
Mobile phase: methanol/water 85:15
Flow rate: 0.5ml/min
Sample preparation: 30mg of the sample to be tested is dissolved in 5ml of mobile phase, and the sample amount is 15ul.
HPLC analysis showed a normalized area ratio of triphenyl phosphate (TPP) of less than 0.5% (table 1 and fig. 4, retention time 6.115 in fig. 4 being the time to peak triphenyl phosphate, retention time 12.865 being the time to peak liquid bisphenol a bis (diphenyl phosphate) product).
TABLE 1 liquid chromatography results table
Examples 2 to 9
The procedure was as in example 1 and the results are shown in Table 2.
Feeding amount: the first step of phosphoryl chlorination, 500g of bisphenol A (BPA), 1.67kg of phosphorus oxychloride, 5g of anhydrous magnesium chloride and 2L of solvent; secondly, phenol with 3.5 to 4.5 times of BPA molar weight; 0.5-1.2 molar amount of phenol.
Sodium and potassium phosphates are possible to work as binary/ternary bases, but it is necessary that the amount of base is equimolar to the amount of phenol, otherwise the yield is significantly reduced. In the case of using phosphorus oxychloride in an excess of 5 times, there is generally about 10% of dimer in the first reaction step, and therefore even if phenol is fed in a stoichiometric ratio (phenol/bisphenol 4 (molar ratio)), the phenol is in excess, but the product yield is remarkably reduced by reducing the amount of phenol to 3.5, indicating that a certain excess of phenol is necessary.
The product was analyzed by HPLC using the same chromatographic conditions as in example 1.
TABLE 2 types, amounts and yields of raw materials of examples 2-9
。
Claims (10)
1. A preparation method of a liquid bisphenol A bis (diphenyl phosphate) flame retardant is characterized by comprising the following steps:
(1) dissolving bisphenol A in an inert aromatic solvent, then dropwise adding the bisphenol A into preheated phosphorus oxychloride, and carrying out a bisphenol A phosphoryl chlorination reaction by using anhydrous magnesium chloride as a catalyst until no hydrogen chloride is discharged, wherein the reaction is finished; recovering excessive phosphorus oxychloride by fractionation, and cooling the reaction liquid for later use;
(2) dissolving phenol in an organic solvent and adding an inorganic alkaline aqueous solution to form an organic/alkaline/water three-phase system; and (3) dropwise adding the reaction liquid obtained in the first step of reaction into an organic/alkali/water three-phase system, stirring and reacting, separating out a water layer, washing an oil layer to be neutral, filtering to remove solids, drying the filtrate, and distilling to recover the solvent to obtain the liquid bisphenol A bis (diphenyl phosphate) flame retardant.
2. The method according to claim 1, wherein the inert aromatic hydrocarbon solvent in the step (1) has a boiling point of not less than 115 ℃; preferably, the boiling point of the inert aromatic hydrocarbon solvent is 125-155 ℃, and most preferably, the boiling point of the inert aromatic hydrocarbon solvent is 125-135 ℃.
3. The process according to claim 1 or 2, wherein the inert aromatic hydrocarbon solvent is an alkylbenzene or chlorobenzene; preferably, the alkylbenzene is any one or a mixture of more than one of toluene, ethylbenzene, xylene or diethylbenzene, and the chlorobenzene is any one or a mixture of more than one of chlorobenzene, dichlorobenzene or trichlorobenzene.
4. The method according to claim 1, wherein the preheating in the step (1) is preheating to 90 ℃.
5. The process according to claim 1, wherein the molar ratio of bisphenol A: 1, phosphorus oxychloride: 5.
6. the method according to claim 1, wherein the organic solvent in the step (2) is the inert aromatic hydrocarbon solvent in the step (1).
7. The process according to claim 1, wherein the molar ratio of bisphenol A: phenol 1: (3.5-4.5): preferably, the molar ratio of bisphenol a: phenol 1: 4.
8. the method of claim 1, wherein the molar ratio of phenol: inorganic alkaline aqueous solution ═ 1: (0.5-1.2), preferably, phenol: inorganic alkaline aqueous solution ═ 1: 1.
9. the method according to claim 1, wherein the aqueous solution of an inorganic base is any one selected from the group consisting of an aqueous sodium phosphate solution, an aqueous potassium phosphate solution, an aqueous sodium bicarbonate solution, an aqueous potassium bicarbonate solution, an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution.
10. The method according to claim 1 or 9, wherein the aqueous solution of an inorganic base is an aqueous solution of sodium phosphate or potassium phosphate.
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Publication number | Priority date | Publication date | Assignee | Title |
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CN115028659A (en) * | 2022-07-14 | 2022-09-09 | 宿迁联盛科技股份有限公司 | Bisphenol A-bis (diphenyl phosphate) and preparation process thereof |
CN115558270A (en) * | 2022-09-16 | 2023-01-03 | 碳中和环保科技(广州)有限公司 | Regenerated modified plastic particle |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI262189B (en) * | 2000-06-28 | 2006-09-21 | Chung Shan Inst Of Science | Method of preparing tetraphenyl bisphenol a diphosphate |
CN103214513A (en) * | 2013-04-09 | 2013-07-24 | 天津市联瑞阻燃材料有限公司 | Preparation method of bisphenol A bis(diphenyl phosphate) |
CN106317108A (en) * | 2016-08-24 | 2017-01-11 | 浙江万盛股份有限公司 | Preparing method of bisphenol polycondensated phosphate ester with high product yield |
CN106496264A (en) * | 2016-09-27 | 2017-03-15 | 浙江万盛股份有限公司 | A kind of bisphenol-A is double(Diphenyl phosphoester)Continuous preparation method |
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) |
CN112409404A (en) * | 2020-12-07 | 2021-02-26 | 浙江万盛股份有限公司 | Continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) |
-
2021
- 2021-12-20 CN CN202111567570.5A patent/CN114181246B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI262189B (en) * | 2000-06-28 | 2006-09-21 | Chung Shan Inst Of Science | Method of preparing tetraphenyl bisphenol a diphosphate |
CN103214513A (en) * | 2013-04-09 | 2013-07-24 | 天津市联瑞阻燃材料有限公司 | Preparation method of bisphenol A bis(diphenyl phosphate) |
CN106317108A (en) * | 2016-08-24 | 2017-01-11 | 浙江万盛股份有限公司 | Preparing method of bisphenol polycondensated phosphate ester with high product yield |
CN106496264A (en) * | 2016-09-27 | 2017-03-15 | 浙江万盛股份有限公司 | A kind of bisphenol-A is double(Diphenyl phosphoester)Continuous preparation method |
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) |
CN112409404A (en) * | 2020-12-07 | 2021-02-26 | 浙江万盛股份有限公司 | Continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) |
Non-Patent Citations (1)
Title |
---|
黄东平 等: "双酚 A双 (二苯基磷酸酯 )阻燃剂的合成", 《南京大学学报(工程技术版)》, vol. 6, no. 4, pages 30 - 33 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115028659A (en) * | 2022-07-14 | 2022-09-09 | 宿迁联盛科技股份有限公司 | Bisphenol A-bis (diphenyl phosphate) and preparation process thereof |
CN115558270A (en) * | 2022-09-16 | 2023-01-03 | 碳中和环保科技(广州)有限公司 | Regenerated modified plastic particle |
CN115558270B (en) * | 2022-09-16 | 2023-07-21 | 碳中和环保科技(广州)有限公司 | Regenerated modified plastic particles |
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