CN103073597A - Synthesis and purification method for DOPO - Google Patents
Synthesis and purification method for DOPO Download PDFInfo
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- CN103073597A CN103073597A CN2013100024533A CN201310002453A CN103073597A CN 103073597 A CN103073597 A CN 103073597A CN 2013100024533 A CN2013100024533 A CN 2013100024533A CN 201310002453 A CN201310002453 A CN 201310002453A CN 103073597 A CN103073597 A CN 103073597A
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- cdop
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- pcl
- dopo
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- VBQRUYIOTHNGOP-UHFFFAOYSA-N O=P1Oc2ccccc2-c2ccccc12 Chemical compound O=P1Oc2ccccc2-c2ccccc12 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a synthesis and purification method for DOPO. The method includes the following steps: taking ZnC12 as the catalyst, and generating CDOP through a reaction of PCI3 and OPP at a certain temperature; adding CDOP into an NaOH aqueous solution for hydrolysis, filtering to remove insoluble substances, adding an acid treating agent, controlling pH at an acid treatment end point, and crystallizing to prepare HPPA; using toluene for recrystallization on a hydrolysate, and removing impurities; and performing decompression, dehydration and cyclization to prepare the target product DOPO. According to the method, a slightly boiling status is kept all the time inside the reactor, and high-temperature utilization at 210 DEG C-220 DEG C and generation of spontaneously combusted substances are avoided; hydrochloric acid generated in the CDOP synthetic process serves as the acid treating agent, therefore resources are used comprehensively, and discharge of a large amount of acid and alkali is avoided; and additionally, the alkaline hydrolysis acidification dehydration method is adopted to solve the problem of zinc ion removal from products.
Description
Technical field
The invention belongs to the organic synthesis field, be specifically related to the synthetic and method of purification of a kind of phosphonium flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).
Background technology
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a kind of important novel reaction type phosphonium flame retardant, its structural formula such as Figure1.The characteristics such as the synthetic fire retardant of DOPO and derivative thereof has efficiently, Halogen, smokeless, nontoxic, does not move, and flame retardant properties is lasting.DOPO can be used for the fire-retardant of multiple macromolecular material, such as linear polyester, Resins, epoxy, bismaleimides etc., is widely used in the fire-retardant of electronics, synthon, semiconductor sealing material etc.DOPO and derivative thereof also can be used for the chemical modification of macromolecular material owing to the specific function of itself simultaneously.In addition, DOPO also can be used as the blockade agent of sterilant, sterilant, solidifying agent, oxidation inhibitor, stablizer, light trigger, binding agent, harmful metal ion, organic light color agent, ultraviolet absorbers.
At present, both at home and abroad DOPO synthetic carried out research extensively and profoundly, mainly studying country has Japan, Germany, the U.S., and China starts late to the research and development of DOPO, but has also obtained some achievements.
In the prior art, German patent DE 19505352A1, US Patent No. 5650530 and US5481017 have reported the preparation method of DOPO in succession: with orthoxenol (OPP) and phosphorus trichloride (PCl
3) be raw material, Zinc Chloride Anhydrous (ZnCl
2) be catalyzer; through esterification, F-K reaction; obtain intermediate 6-chloro-(6 hydrogen)-hexichol [C; E] [1; 2]-and phospho hetero phenanthrene (CDOP), under high vacuum, carry out underpressure distillation, add alkaline solution or in organic solvent, add quantitative water and be hydrolyzed; the intermediate 2 ' of separating out-Hydroxybiphenyl-2-phospho acid (HPPA) cyclodehydration under the decompression heating obtains target product DOPO, and reaction formula is as follows:
The composition principle of bibliographical information DOPO is identical at present, and is just slightly different on concrete process procedure.In the existing patented technology distillation under vacuum under the high vacuum has been adopted in synthetic CDOP purification, the method needs higher vacuum, and the stopping property of equipment and the vacuum tightness of vacuum pump are required height, is difficult to suitability for industrialized production; Adopt filtration method purification CDOP, but do not pay close attention for wherein too high zine ion and chloride ion content; The CDOP generated time (10～20h) and hydrolysis time (6～10h) is long, and production efficiency is low, and the synthesis temperature of CDOP high (200～220 ℃) produces spontaneous combustible substance in the reactor in preparation process, have potential safety hazard.
Summary of the invention
The object of the invention provides a kind of 9, the 10-dihydro-9-oxy is assorted-synthesizing progress method of 10-phospho hetero phenanthrene-10-oxide compound, higher to overcome the foreign matter content that exists in the prior art, need the condition of high vacuum degree distillation, easily coking, the shortcoming of complex operation has solved zine ion removal problem in the product simultaneously.
The synthetic DOPO of present method divided for four steps carried out:
Step (1): with ZnCl
2Be catalyzer, at a certain temperature, pass through PCl
3Generate CDOP with the reaction of OPP;
Be hydrolyzed in step (2): the CDOP adding NaOH aqueous solution, remove by filter insolubles, add acidizer, control acid treatment endpoint pH, crystallization obtains HPPA;
Step (3): with toluene hydrolysate is carried out recrystallization, remove impurity;
Step (4): at a certain temperature, the decompression dehydration cyclisation obtains target product DOPO of the present invention.
Synthesis route is specially:
Step (1): among the synthetic CDOP, OPP and PCl
3Molar ratio be 1:1.3～1.5, use ZnCl
2Be catalyzer, its consumption is 1～2% molar equivalent of OPP consumption; Addition manner: add first OPP and ZnCl
2, be heated to 70 ℃, start stirring, evenly drip 1.1 molar equivalent PCl
3, PCl
3The dropwise reaction time be 3～5h, then be warming up to 180 ℃, drip 0.2～0.4 molar equivalent PCl
3, PCl
3The dropwise reaction time be 8～10h, the HCl water that generates in the reaction absorbs.
Step (2): in the hydrolysis of CDOP, the molar ratio of described NaOH and OPP is 2～3:1, and the weight percent concentration of the NaOH aqueous solution is 5～20%.The CDOP that the first step reaction is obtained is cooled to 90 ± 2 ℃, pours in the NaOH aqueous solution, and 40 ± 2 ℃ are stirred 1h, remove by filter insolubles, and the filtrate that obtains is carried out acid treatment; Used acidizer is the hydrochloric acid soln that produces during the first step is reacted, and control acid treatment endpoint pH is 1.0,40 ± 2 ℃ and stirs 3h, crystallize out, and distilled water wash three times are used in filtration, and drying obtains hydrolysate HPPA.
Step (3): with the hydrolysate that obtains toluene recrystallization, remove impurity.
Step (4): adopt 120～150 ℃, vacuum tightness 〉=30mmHg to carry out decompression dehydration Cyclization DOPO, in 0.5～2h, dewater and finish.
Innovation of the present invention is:
1. in the first step CDOP synthetic, at 70 ℃ of reaction 3～5h, esterification is carried out fully first, reacts 8～10h at 180 ℃ again, during add 0.2～0.4 molar equivalent PCl
3, make to keep slight boiling condition in the reactor always, avoided using the generation of 210～220 ℃ of high temperature and spontaneous combustible substance.
2. in the hydrolysis of CDOP, directly be hydrolyzed with alkali lye, avoid using the organic solvents such as high vacuum underpressure distillation and the flammable toluene of use; As acidizer, utilize resources synthetically has been avoided the discharging of a large amount of soda acids with the hydrochloric acid that generates in the CDOP building-up process; In addition, solved zine ion removal problem in the product with alkaline hydrolysis acidifying evaporation.
3. adopt toluene that hydrolysate is carried out recrystallization, remove impurity, avoided the higher problem of foreign matter content.
4. in the synthetic DOPO process of underpressure distillation, cyclodehydration, adopt 120～150 ℃, vacuum tightness 〉=30mmHg to carry out decompression dehydration and react, in 0.5～2h, just can finish dehydration.
Embodiment
The invention will be further described below by embodiment, but do not limit the scope of the invention.
Embodiment 1
OPP(200g, 1.175mol) and Zinc Chloride Anhydrous (1.6g, 0.0115mol) join in the four-hole bottle, under 70 ℃, drip phosphorus trichloride (113mL, 1.292mol) in the 3h; Be warming up to 180 ℃ after dripping off, insulation reaction 10h, during evenly add phosphorus trichloride (20.5mL, 0.234mol), until till not having HCl gas to emit, obtain containing the reaction solution of intermediate CDOP.Reaction solution is cooled to 90 ± 2 ℃, emits feed liquid to the solution that is comprised of sodium hydroxide (140.4g, 3.51mol) and water (560mL), is cooled to 40 ± 2 ℃, stirs 1h, filters.Filtrate is regulated pH=1.0 with the hydrochloric acid that the first step reaction produces, and 40 ± 2 ℃ are stirred 3h, and crystallization goes out solid, and suction filtration is with distilled water wash three times (200mL * 3); Solids is dissolved in toluene (400mL), and backflow 1h is cooled to room temperature, and hydrolysate HPPA is filtered to get in crystallization.The HPPA that obtains is heated to 150 ℃, and underpressure distillation 0.5h under vacuum tightness 〉=30mmHg obtains target product DOPO (231g, 92%).Purity is 99.2%(HPLC).Fusing point: 117～119 ℃; Zinc ion content: 2ppm.
Embodiment 2
OPP(200g, 1.175mol) and Zinc Chloride Anhydrous (1.6g, 0.0115mol) join in the four-hole bottle, under 70 ℃, drip phosphorus trichloride (113mL, 1.292mol) in the 3h; Be warming up to 180 ℃ after dripping off, insulation reaction 10h, during evenly add phosphorus trichloride (30.75mL, 0.352mol), until till not having HCl gas to emit, obtain containing the reaction solution of intermediate CDOP.Reaction solution is cooled to 90 ± 2 ℃, emits feed liquid to the solution that is comprised of sodium hydroxide (117.5g, 2.94mol) and water (560mL), is cooled to 40 ± 2 ℃, stirs 1h, filters.Filtrate is regulated pH=1.0 with the hydrochloric acid that the first step reaction produces, and 40 ± 2 ℃ are stirred 3h, and crystallization goes out solid, and suction filtration is with distilled water wash three times (200mL * 3); Solids is dissolved in toluene (400mL), and backflow 1h is cooled to room temperature, and hydrolysate HPPA is filtered to get in crystallization.The HPPA that obtains is heated to 150 ℃, and underpressure distillation 0.5h under vacuum tightness 〉=30mmHg obtains target product DOPO (238g, 93%).Purity is 99.4%(HPLC).Fusing point: 117～119 ℃; Zinc ion content: 3ppm.
Embodiment 3
OPP(200g, 1.175mol) and Zinc Chloride Anhydrous (3.2g, 0.023mol) join in the four-hole bottle, under 70 ℃, drip phosphorus trichloride (113mL, 1.292mol) in the 3h; Be warming up to 180 ℃ after dripping off, insulation reaction 8h, during evenly add phosphorus trichloride (41mL, 0.47mol), until till not having HCl gas to emit, obtain containing the reaction solution of intermediate CDOP.Reaction solution is cooled to 90 ± 2 ℃, emits feed liquid to the solution that is comprised of sodium hydroxide (94g, 2.35mol) and water (1700mL), is cooled to 40 ± 2 ℃, stirs 1h, filters.Filtrate is regulated pH=1.0 with the hydrochloric acid that the first step reaction produces, and 40 ± 2 ℃ are stirred 3h, and crystallization goes out solid, and suction filtration is with distilled water wash three times (200mL * 3); Solids is dissolved in toluene (800mL), and backflow 1h is cooled to room temperature, and hydrolysate HPPA is filtered to get in crystallization.The HPPA that obtains is heated to 120 ℃, and underpressure distillation 2h under vacuum tightness 〉=30mmHg obtains target product DOPO (241.5g, 95%).Purity is 99.6%(HPLC).Fusing point: 117～119 ℃; Zinc ion content: 5ppm.
Claims (5)
1. the synthesizing progress method of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, it is characterized in that: the party may further comprise the steps:
Step (1): with ZnCl
2Be catalyzer, at a certain temperature, pass through PCl
3Generate CDOP with the reaction of OPP;
Be hydrolyzed in step (2): the CDOP adding NaOH aqueous solution, remove by filter insolubles, add acidizer, control acid treatment endpoint pH, crystallization obtains HPPA;
Step (3): with toluene hydrolysate is carried out recrystallization, remove impurity;
Step (4): at a certain temperature, the decompression dehydration cyclisation obtains target product DOPO of the present invention.
2. the synthesizing progress method of a kind of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as claimed in claim 1 is characterized in that: in step (1): OPP and PCl
3Molar ratio be 1:1.3～1.5, use ZnCl
2Be catalyzer, its consumption is 1～2% molar equivalent of OPP consumption; Addition manner: add first OPP and ZnCl
2, be heated to 70 ℃, start stirring, evenly drip 1.1 molar equivalent PCl
3, PCl
3The dropwise reaction time be 3～5h, then be warming up to 180 ℃, drip 0.2～0.4 molar equivalent PCl
3, PCl
3The dropwise reaction time be 8～10h, the HCl water that generates in the reaction absorbs.
3. as claimed in claim 1 a kind of 9, the 10-dihydro-9-oxy is assorted-synthesizing progress method of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that: in step (2): the molar ratio of NaOH and OPP is 2～3:1, and the weight percent concentration of the NaOH aqueous solution is 5～20%; The CDOP that the first step reaction is obtained is cooled to 90 ± 2 ℃, pours in the NaOH aqueous solution, and 40 ± 2 ℃ are stirred 1h, remove by filter insolubles, and the filtrate that obtains is carried out acid treatment; Used acidizer is the hydrochloric acid soln that produces during the first step is reacted, and control acid treatment endpoint pH is 1.0,40 ± 2 ℃ and stirs 3h, crystallize out, and distilled water wash three times are used in filtration, and drying obtains hydrolysate HPPA.
4. the synthesizing progress method of a kind of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as claimed in claim 1 is characterized in that: in step (3): with the hydrolysate that obtains toluene recrystallization.
5. as claimed in claim 1 a kind of 9, the 10-dihydro-9-oxy is assorted-synthesizing progress method of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that: in step (4): adopt 120～150 ℃, vacuum tightness 〉=30mmHg to carry out decompression dehydration Cyclization DOPO, in 0.5～2h, dewater and finish.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556343A (en) * | 2017-10-20 | 2018-01-09 | 利尔化学股份有限公司 | DOPO and its intermediate preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146097A (en) * | 2011-03-03 | 2011-08-10 | 山东天一化学股份有限公司 | Method for preparing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide |
| CN102219806A (en) * | 2011-05-07 | 2011-10-19 | 普塞呋（清远）磷化学有限公司 | Preparation method of high purity cyclic phosphonate 9,10-dihydro-9-oxa-10-phosphaphenanathrene-10-oxide |
-
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- 2013-01-05 CN CN2013100024533A patent/CN103073597A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146097A (en) * | 2011-03-03 | 2011-08-10 | 山东天一化学股份有限公司 | Method for preparing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide |
| CN102219806A (en) * | 2011-05-07 | 2011-10-19 | 普塞呋（清远）磷化学有限公司 | Preparation method of high purity cyclic phosphonate 9,10-dihydro-9-oxa-10-phosphaphenanathrene-10-oxide |
Non-Patent Citations (1)
| Title |
|---|
| 黄杰等: "10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物的合成", 《精细化工》, vol. 22, no. 1, 30 November 2005 (2005-11-30), pages 853 - 855 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556343A (en) * | 2017-10-20 | 2018-01-09 | 利尔化学股份有限公司 | DOPO and its intermediate preparation method |
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