CN1952040A - Production method of 2-carboxyethyl phenyl phosphinic acid flame retardant - Google Patents
Production method of 2-carboxyethyl phenyl phosphinic acid flame retardant Download PDFInfo
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- CN1952040A CN1952040A CN 200510048704 CN200510048704A CN1952040A CN 1952040 A CN1952040 A CN 1952040A CN 200510048704 CN200510048704 CN 200510048704 CN 200510048704 A CN200510048704 A CN 200510048704A CN 1952040 A CN1952040 A CN 1952040A
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Abstract
The invention provides a production method of a 2-carboxyethyl phenyl phosphinic acid flame retardant, which takes phosphorus trichloride and benzene as raw materials to carry out the synthetic reaction of phenyl phosphorus dichloride under the catalytic action of aluminum trichloride. The flame retardant has the advantages of reducing the heat release rate of the material, having better flame retardance, reducing the release amount of corrosive toxic gas and smoke, overcoming the defects that a halogen flame retardant releases toxic and harmful gases and smoke during combustion, having higher stability and hydrolysis resistance, and being widely applied to copolymerization flame retardant modification of PET polyester fibers, nylon and glass fiber reinforced plastics. The invention can not only improve the yield of DCPP, acyl chloride and CEPPA, greatly reduce the production cost, but also fundamentally solve the problem of environmental pollution caused by a large amount of waste residues and waste liquids associated with the traditional process, and the whole process flow has stable operation, easy operation and control, reliable product quality and obvious economic benefit and social benefit.
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant, relate in particular to the production method of 2-carboxyethylphenylphacidinic acidinic flame-proof agent, belong to chemical technology field.
Background technology
In flame retardant products, early stage fire retardant contains halogen mostly, mainly is brominated flame retardant.Halogen flame can both play the effect that delays polymer combustion in gas phase and coagulation phase, especially chain-breaking reaction in the energy in gas phase has clear and definite fire retardation.But halogen flame at high temperature can be emitted obnoxious flavour, at hydrogenchloride that the scene of fire discharged or hydrogen bromide human body is had the mortality lethality of suffocating.Then can discharge carcinogenss such as PBDF during the Poly Brominated Diphenyl Ethers burning.Verified, the obnoxious flavour that the polymkeric substance that contains halogen flame is discharged when burning is scene of fire causing death's a one of the main reasons.
Phosphorus flame retardant is by being fixed into carbon and mass loss mechanism, and part gas phase fire retardant mechanism, increased one-tenth carbon amount, not only reduce the heat release rate of material, has flame retardant resistance preferably, and reduced the burst size of corrodibility toxic gas and flue gas, thereby can overcome some shortcomings of halogen flame.In addition, phosphorus flame retardant has higher flame retarding efficiency.For the copoly type fire-retardant polyester fibre, should make it to reach the desired phosphorus content of flame-retardant standard only is 0.5 (wt) %, and brominated amount is about 17 (wt) % (under kindred circumstances).
With regard to the monomer of phosphorous flame-retardant polyester, what early adopt mainly is phosphoric acid ester, alkyl diphosphine ester oligomer etc.Yet, in with the prepared flame retardant polyester of this based flame retardant, fire-retardant monomer combines with the p-o-c key in the polymkeric substance major key, because the thermostability and the chemical of this key are poor, can cause the intensity of polyester in the high temperature spinning to reduce, and make fiber and fabric that the hydrolysis reaction of p-o-c key take place in dyeing or washing process, thus fire retardant is come off, reduce its due flame retardant properties.
By studies show that, have-the organic phosphine fire retardant of p-c key, behind itself and polyethylene terephthalate copolymer, the obtained flame-retardant agent has higher hydrolytic resistance.Fig. 1 has listed 6 kinds of response type organic phosphine fire retardants.These 6 kinds of fire retardants are binary acid type compound, and all contain-the p-c key, belong to thermostability and chemical fire retardant preferably.Wherein be numbered 1,2,3 fire retardant and all can make target compound, still can not make target compound but be numbered 5,6 fire retardant, its difficult point is in the preparation and purifying of intermediate phosphorus hydrides.
When the fire retardant of numbering 2 and 4 is applied to polyester,, can give the higher intensity of flame retardant polyester, fusing point and chemical stability because fire-retardant unit is an aromatic ring structure.But these two kinds of fire retardants all need adopt the oxygenant oxidation just can obtain target compound, and compare with other fire retardant, and its technical process is long, cost is high.Being numbered 1,3,5,6 fire retardant all adopts the unsaturated organic acid addition and makes phosphorous diprotic acid, wherein the basic raw material of fire retardant 3 is orthoxenol, phosphorus trichloride and methylene-succinic acid, main raw material price (except that phosphorus trichloride) is very expensive, synthetic and the application of this compound has important academic values, but, can't realize industrialization production at present from economical and practical aspect.Fire retardant 5,6 is the product of vinylformic acid and phosphorus hydrides addition, is difficult to technically at present realize.Therefore, be necessary prior art is improved.
Summary of the invention
For overcoming many deficiencies that prior art exists, it is simple to the invention provides a kind of synthesis route, the product yield height, and production cost is low, the production method of 2-carboxyethylphenylphacidinic acidinic flame-proof agent.
The present invention realizes by following technical proposal: a kind of production method of 2-carboxyethylphenylphacidinic acidinic flame-proof agent is characterized in that comprising following process steps:
A, phenyl phosphorus dichloride---DCPP's is synthetic
A1, press pcl
3: Alcl
3: benzene=1.5～2.5: 0.5～1.5: 0.8～1.5 mol ratio, with pcl
3And Alcl
3Mix and stir, be warming up to backflow simultaneously;
A2, drip the benzene of aforementioned proportion, and be controlled within 4 hours and drip off, homo(io)thermism makes by product after a large amount of HCl gas recovery that the dropping process is produced simultaneously at 80 ℃---hydrochloric acid;
A3, the cooling of reacted material is cooled to 60 ℃, press extract: the weight ratio of Nacl=5～7: 1, adding granularity is that 120～200 purpose complexing agent Nacl carry out extracting the first time, temperature is controlled at 50 ℃, stirred 1 hour, left standstill 30 minutes, collect the upper strata feed liquid that extracts;
A4, press extract: quaternary amine=6～9: 1 weight ratio joins quaternary amine in the extract, and presses quaternary amine: the weight ratio of mixed solution=1: 1～3, and with pcl
3Wherein carry out the extraction second time with the mixed solution adding of sherwood oil, wherein, the ratio of mixed solution is: pcl
3: sherwood oil=5～10: 3, and be heated to 45-50 ℃, and stirred 40 minutes, left standstill 30 minutes, collect the supernatant liquid that extracts, make catalyst A lcl simultaneously
3Recycle;
A5, press extract again: the weight ratio of mixed solution=1: 1～3, add the mixed solution identical and extract for the third time with the A4 step, be heated to 45-50 ℃, left standstill 30 minutes, collect the supernatant liquid that extracts, make catalyst A lcl simultaneously
3Recycle;
A6, the extraction liquid that above steps is collected carry out air distillation, distill out pcl
3, the sherwood oil mixture, temperature rises to 90 ℃ of no pcl
3When steaming, crude benzol base phosphorus dichloride---the DCPP after the air distillation;
A7, with after the above-mentioned distillation crude benzol base phosphorus dichloride---DCPP carries out underpressure distillation, distills out pcl
3, the sherwood oil mixture, be 450mmHg in vacuum tightness, temperature rises to 100 ℃ of no pcl
3When steaming, crude benzol base phosphorus dichloride---the DCPP after the underpressure distillation;
A8, be 600-610mmHg with above-mentioned thick DCPP in vacuum tightness, liquidus temperature is increasing temperature and pressure distillation under the 110-125 ℃ of condition, promptly gets purified phenyl phosphorus dichloride---DCPP;
Synthesizing of B, acyl chlorides
B1, purified phenyl phosphorus dichloride DCPP under agitation is heated to 75-80 ℃;
B2, press DCPP: the weight ratio of vinylformic acid=1: 0.3～0.6, dropwise addition of acrylic acid in DCPP maintains the temperature at 80 ± 5 ℃, drips vinylformic acid in 3.5 hours;
B3, continue reaction 0.5 hour under 80 ℃ of temperature, isothermal reaction is 2 hours when being heated to 110-115 ℃ then, below the temperature drop to 40 ℃, promptly gets the acyl chlorides intermediate afterwards;
The generation of C, fire retardant CEPPA
C1, press acyl chlorides: pure water=20～35: 50～80 weight ratios are added drop-wise to pure water in the acyl chlorides intermediate;
C2, press acyl chlorides: hydrogen peroxide=20～30: 1 weight ratio, hydrogen peroxide is added drop-wise to the acyl chlorides intermediate, drip off in 4 hours, and make temperature of reaction constant at 80 ℃;
C3, continue to be cooled to 30 ℃ afterwards 80 ℃ of insulation reaction 2 hours, crystallization is filtered, is separated;
C4, with isolated product under 120 ℃ of conditions dry 4 hours, promptly get the finished product CEPPA.
Benzene in the described A1 step is the commercially available liquid benzene of benzol content at 85-99%.
Pcl in the described A1 step
3For containing pcl
3Amount is in 95～99.99% commercially available prod.
Alcl in the described A1 step
3Adopt the product of GB3959-83 regulation.
Nacl in the described A3 step adopts the product of GB345-77 regulation.
The present invention is a raw material with phosphorus trichloride and benzene, carries out phenyl phosphorus dichloride---the building-up reactions of DCPP under the katalysis of aluminum trichloride (anhydrous), and its reaction principle is as follows:
(1) phosphorus trichloride and benzene carry out following reaction in the presence of aluminum trichloride (anhydrous):
In the building-up reactions later stage, the sodium-chlor that adds ultrafine powder is as complexing agent, a large amount of residue valence links is arranged on its wedge angle and arris, can with aluminum chloride generation complex reaction, generating more stable complex compound sediment gets off, thereby the DCPP that generates is parsed, through separation and purification, as preparation 2-carboxyethyl phenyl Hypophosporous Acid, 50---the raw material of CEPPA.
In the complexing agent of aluminum chloride and sodium-chlor generation, add quaternary amine, make it to become ionic liquid, thereby make catalyst A lcl
3Recycle.Reduce raw materials consumption, optimized production technique, realized the green production of CEPPA.
(2) as follows by the reaction formula of DCPP generation CEPPA:
In said process, vinylformic acid is as electrophilic reagent, and the P atom in the attack phenyl phosphorus dichloride with DCPP electrophilic addition reaction takes place, and generates the acyl chlorides intermediate.Because two kinds of reactant chemical property are active, need not to use catalyzer, reaction quantitatively finish and by product few.The acyl chlorides intermediate is added pure water be hydrolyzed, add the hydrogen peroxide decolouring, recrystallization obtains the finished product 2-carboxyethyl phenyl phosphinic acid---CEPPA.
The present invention compared with prior art has following advantage and effect: the 2-carboxyethylphenylphacidinic acidinic flame-proof agent of producing with method provided by the invention, compare with halogen-containing flame retardant, increased neat coal amout, not only reduce the heat release rate of material, has flame retardant resistance preferably, and reduced the burst size of corrodibility toxic gas and cigarette, having overcome halogen flame discharges poisonous when burning, the shortcoming that obnoxious flavour and flue gas are big, also has higher thermostability simultaneously, oxidative stability and hydrolytic resistance, join in the polyethylene terephthalate (PET), polyester flame-retardant section fusing point height, good spinnability, with its flame-resistant terylene intensity height of making, anti-dyeing, wash durability is good, can be widely used in the PET trevira, nylon, the copolymerization of glass reinforced plastic is flame-retardant modified.Method provided by the invention has following characteristics:
1, studies, developed CEPPA (2-carboxyethyl phenyl phosphinic acid) whole production technology, technology, proportioning raw materials, controlling index.
2, use novel complexing agent, make the complex reaction gentleness, raw materials cost is low, is easy to promote the separation of DCPP, and it is simple that technology is reclaimed in complexing.
3, through laboratory and production test, obtained the optimum conditions of synthetic DCPP, comprise reaction times, reaction ratio, temperature of reaction etc.Make the DCPP yield improve, and significantly reduced production cost.
4, studied CEPPA synthesis condition, character and with the relation of flame retardant polyester performance, set up and the perfect quality index system and the method for inspection of CEPPA.
5, the three wastes that discharged at the CEPPA production process, initiated a cover complex compound waste residue processing scheme, and set up the technical process that adapts with production unit, can realize the recycling fully of discharge, reduce production cost of products significantly, realized green, safe Chemical Manufacture.
In general, the present invention has thoroughly eliminated the unsafe factor that original technology exists, both can improve the yield of DCPP, acyl chlorides, CEPPA, reduce production costs significantly, can fundamentally solve a large amount of waste residues of traditional technology association, waste liquid pollution on the environment again, whole process flow is stable, easy to operate, easy to control, and reliable product quality has remarkable economic efficiency and social benefit.
Description of drawings
Fig. 1 has listed 6 kinds of response type organic phosphine fire retardants;
Fig. 2 has listed the technical indicator of product of the present invention;
Fig. 3 is the present invention's process flow sheet.
Embodiment
Below in conjunction with embodiment the present invention is described further.
1, phenyl phosphorus dichloride---DCPP's is synthetic
(a) press pcl
3: Alcl
3: the mol ratio of benzene=1.5: 0.5: 0.8, earlier with pcl
3Drop in the reactor, drop into Alcl again
3, start stirrer, be warming up to backflow simultaneously;
(b) drip the benzene of aforementioned proportion, and be controlled within 4 hours and drip off, homo(io)thermism makes by product at 80 ℃ after a large amount of HCl gas waters that the dropping process is produced absorb simultaneously---hydrochloric acid;
(c) reacted material cooling is cooled to 60 ℃, squeeze into extraction kettle, press extract: Nacl=5: 1 weight ratio, adding granularity is that 120 purpose complexing agent Nacl carry out the extraction first time, temperature is controlled at 50 ℃, stirs after 1 hour, leaves standstill 30 minutes, the upper strata feed liquid that collection extracts, and this feed liquid squeezed in the storage tank with pump;
(d) press extract: the weight ratio of quaternary amine=6: 1, quaternary amine is added extraction kettle, press quaternary amine again: the weight ratio of mixed solution=1: 1, with pcl
3Add with the mixed solution of sherwood oil and to carry out in the still extracting second time, the ratio of mixed solution is: pcl
3: sherwood oil=5: 3, and be heated to 45 ℃, stirred 40 minutes, left standstill 30 minutes, collect the supernatant liquid that extracts, and it is squeezed in the storage tank with pump, make catalyst A lcl simultaneously
3Recycle;
(e) press extract again: the weight ratio of mixed solution=1: 1, in still, add the mixed solution identical and extract for the third time with above-mentioned steps, be heated to 45 ℃, left standstill 30 minutes, the supernatant liquid that collection extracts, and it is squeezed in the storage tank with pump, make catalyst A lcl simultaneously
3Recycle;
(f) use pump catalyst A lcl
3Squeeze into to store in the storage tank and recycle;
(g) extraction liquid of collecting in the storage tank is squeezed into pump carried out air distillation in the still kettle, distill out pcl
3, the sherwood oil mixture, temperature rises to 90 ℃ of no pcl
3When steaming, crude benzol base phosphorus dichloride---the DCPP after the air distillation;
(h) with the crude benzol base phosphorus dichloride after the above-mentioned distillation---DCPP squeezes into pump and carries out underpressure distillation in the underpressure distillation still, distills out pcl
3, the sherwood oil mixture, be 450mmHg in vacuum tightness, temperature rises to 100 ℃ of no pcl
3When steaming, crude benzol base phosphorus dichloride---the DCPP after the underpressure distillation;
(i) be 600mmHg with the thick DCPP gas clean-up after the above-mentioned underpressure distillation, liquidus temperature is increasing temperature and pressure distillation under 110 ℃ of conditions, promptly gets purified phenyl phosphorus dichloride---DCPP;
2, the intermediate acyl chlorides is synthetic
(a) with purified phenyl phosphorus dichloride---DCPP adds in the reactor, under agitation with steam heating to 75 ℃;
(b) press DCPP: the weight ratio of vinylformic acid=1: 0.3, dropwise addition of acrylic acid in DCPP maintains the temperature at 80 ± 5 ℃, drips vinylformic acid in 3.5 hours;
(c) behind reinforced the finishing, continue reaction 0.5 hour under 80 ℃ of temperature, isothermal reaction is 2 hours during then with steam heating to 110 ℃, below the temperature drop to 40 ℃, promptly gets the acyl chlorides intermediate afterwards;
3, the generation of fire retardant CEPPA
(a) press acyl chlorides: pure water=20: 50 weight ratios is added drop-wise to pure water in the acyl chlorides intermediate;
(b) press acyl chlorides: hydrogen peroxide=20: 1 weight ratios, hydrogen peroxide is added drop-wise to the acyl chlorides intermediate, drip off in 4 hours, and make temperature of reaction constant at 80 ℃;
(c) dropwise after, continued insulation reaction 2 hours, be cooled to 30 ℃ afterwards, crystallization is filtered, is separated;
(d) with isolated product under 120 ℃ of conditions dry 4 hours, promptly get the finished product CEPPA.
1, phenyl phosphorus dichloride---DCPP's is synthetic
(a) press pcl
3: Alcl
3: the mol ratio of benzene=2.5: 1.5: 1.5, earlier with pcl
3Drop in the reactor, drop into Alcl again
3, start stirrer, be warming up to backflow simultaneously;
(b) drip the benzene of aforementioned proportion, and be controlled within 4 hours and drip off, homo(io)thermism makes by product at 80 ℃ after a large amount of HCl gas waters that the dropping process is produced absorb simultaneously---hydrochloric acid;
(c) reacted material cooling is cooled to 60 ℃, squeeze into extraction kettle, press extract: Nacl=7: 1 weight ratio, adding granularity is that 200 purpose complexing agent Nacl carry out the extraction first time, temperature is controlled at 50 ℃, stirs after 1 hour, leaves standstill 30 minutes, the upper strata feed liquid that collection extracts, and this feed liquid squeezed in the storage tank with pump;
(d) press extract: the weight ratio of quaternary amine=9: 1, quaternary amine is added extraction kettle, press quaternary amine again: the weight ratio of mixed solution=1: 3, with pcl
3Add with the mixed solution of sherwood oil and to carry out in the still extracting second time, the ratio of mixed solution is: pcl
3: sherwood oil=10: 3, and be heated to 50 ℃, stirred 40 minutes, left standstill 30 minutes, collect the supernatant liquid that extracts, and it is squeezed in the storage tank with pump, make catalyst A lcl simultaneously
3Recycle;
(e) press extract again: the weight ratio of mixed solution=1: 3, in still, add the mixed solution identical and extract for the third time with above-mentioned steps, be heated to 50 ℃, left standstill 30 minutes, the supernatant liquid that collection extracts, and it is squeezed in the storage tank with pump, make catalyst A lcl simultaneously
3Recycle;
(f) use pump catalyst A lcl
3Squeeze into to store in the storage tank and recycle;
(g) extraction liquid of collecting in the storage tank is squeezed into pump carried out air distillation in the still kettle, distill out pcl
3, the sherwood oil mixture, temperature rises to 90 ℃ of no pcl
3When steaming, crude benzol base phosphorus dichloride---the DCPP after the air distillation;
(h) with the crude benzol base phosphorus dichloride after the above-mentioned distillation---DCPP squeezes into pump and carries out underpressure distillation in the underpressure distillation still, distills out pcl
3, the sherwood oil mixture, be 450mmHg in vacuum tightness, temperature rises to 100 ℃ of no pcl
3When steaming, crude benzol base phosphorus dichloride---the DCPP after the underpressure distillation;
(i) be 610mmHg with the thick DCPP gas clean-up after the above-mentioned underpressure distillation, liquidus temperature is increasing temperature and pressure distillation under 125 ℃ of conditions, promptly gets purified phenyl phosphorus dichloride---DCPP;
2, the intermediate acyl chlorides is synthetic
(a) with purified phenyl phosphorus dichloride---DCPP adds in the reactor, under agitation with steam heating to 80 ℃;
(b) press DCPP: the weight ratio of vinylformic acid=1: 0.6, dropwise addition of acrylic acid in DCPP maintains the temperature at 80 ± 5 ℃, drips vinylformic acid in 3.5 hours;
(c) behind reinforced the finishing, continue reaction 0.5 hour under 80 ℃ of temperature, isothermal reaction is 2 hours during then with steam heating to 115 ℃, below the temperature drop to 40 ℃, promptly gets the acyl chlorides intermediate afterwards;
3, the generation of fire retardant CEPPA
(a) press acyl chlorides: pure water=35: 80 weight ratios is added drop-wise to pure water in the acyl chlorides intermediate;
(b) press acyl chlorides: hydrogen peroxide=30: 1 weight ratios, hydrogen peroxide is added drop-wise to the acyl chlorides intermediate, drip off in 4 hours, and make temperature of reaction constant at 80 ℃;
(c) dropwise after, continued insulation reaction 2 hours, be cooled to 30 ℃ afterwards, crystallization is filtered, is separated;
(d) with isolated product under 120 ℃ of conditions dry 4 hours, promptly get the finished product CEPPA.
Claims (3)
1, a kind of production method of 2-carboxyethylphenylphacidinic acidinic flame-proof agent is characterized in that comprising following process steps:
A, phenyl phosphorus dichloride---DCPP's is synthetic
A1, press pcl
3: Alcl
3: benzene=1.5～2.5: 0.5～1.5: 0.8～1.5 mol ratio, with pcl
3And Alcl
3Mix and stir, be warming up to backflow simultaneously;
A2, drip the benzene of aforementioned proportion, and be controlled within 4 hours and drip off, homo(io)thermism makes by product after a large amount of HCl gas recovery that the dropping process is produced simultaneously at 80 ℃---hydrochloric acid;
A3, the cooling of reacted material is cooled to 60 ℃, press extract: the weight ratio of Nacl=5～7: 1, adding granularity is that 120～200 purpose complexing agent Nacl carry out extracting the first time, temperature is controlled at 50 ℃, stirred 1 hour, left standstill 30 minutes, collect the upper strata feed liquid that extracts;
A4, press extract: quaternary amine=6～9: 1 weight ratio joins quaternary amine in the extract, and presses quaternary amine: the weight ratio of mixed solution=1: 1～3, and with pcl
3Wherein carry out the extraction second time with the mixed solution adding of sherwood oil, wherein, the ratio of mixed solution is: pcl
3: sherwood oil=5～10: 3, and be heated to 45-50 ℃, and stirred 40 minutes, left standstill 30 minutes, collect the supernatant liquid that extracts, make catalyst A lcl simultaneously
3Recycle;
A5, press extract again: the weight ratio of mixed solution=1: 1～3, add the mixed solution identical and extract for the third time with the A4 step, be heated to 45-50 ℃, left standstill 30 minutes, collect the supernatant liquid that extracts, make catalyst A lcl simultaneously
3Recycle;
A6, the extraction liquid that above steps is collected carry out air distillation, distill out pcl
3, the sherwood oil mixture, temperature rises to 90 ℃ of no pcl
3When steaming, crude benzol base phosphorus dichloride---the DCPP after the air distillation;
A7, with after the above-mentioned distillation crude benzol base phosphorus dichloride---DCPP carries out underpressure distillation, distills out pcl
3, the sherwood oil mixture, be 450mmHg in vacuum tightness, temperature rises to 100 ℃ of no pcl
3When steaming, crude benzol base phosphorus dichloride---the DCPP after the underpressure distillation;
A8, be 600-610mmHg with above-mentioned thick DCPP in vacuum tightness, liquidus temperature is increasing temperature and pressure distillation under the 110-125 ℃ of condition, promptly gets purified phenyl phosphorus dichloride---DCPP;
Synthesizing of B, acyl chlorides
B1, purified phenyl phosphorus dichloride DCPP under agitation is heated to 75-80 ℃;
B2, press DCPP: the weight ratio of vinylformic acid=1: 0.3～0.6, dropwise addition of acrylic acid in DCPP maintains the temperature at 80 ± 5 ℃, drips vinylformic acid in 3.5 hours;
B3, continue reaction 0.5 hour under 80 ℃ of temperature, isothermal reaction is 2 hours when being heated to 110-115 ℃ then, below the temperature drop to 40 ℃, promptly gets the acyl chlorides intermediate afterwards;
The generation of C, fire retardant CEPPA
C1, press acyl chlorides: pure water=20～35: 50～80 weight ratios are added drop-wise to pure water in the acyl chlorides intermediate;
C2, press acyl chlorides: hydrogen peroxide=20～30: 1 weight ratio, hydrogen peroxide is added drop-wise to the acyl chlorides intermediate, drip off in 4 hours, and make temperature of reaction constant at 80 ℃;
C3, continue to be cooled to 30 ℃ afterwards 80 ℃ of insulation reaction 2 hours, crystallization is filtered, is separated;
C4, with isolated product under 120 ℃ of conditions dry 4 hours, promptly get the finished product CEPPA.
2, method according to claim 1 is characterized in that the benzene in the described A1 step is the liquid benzene of benzol content at 85-99%.
3, method according to claim 1 is characterized in that the pcl in the described A1 step
3For containing pcl
3Amount is at 95～99.99% product.
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| CN102286021A (en) * | 2011-06-16 | 2011-12-21 | 襄阳市布拉德化工科技有限公司 | Method for producing 2-carboxyethyl(phenyl)phosphinicacid |
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| CN101792463B (en) * | 2010-03-02 | 2012-07-11 | 苏州科技学院 | Nitrogen-containing aryl hypophosphite metal salt and preparation method thereof |
| CN102286021A (en) * | 2011-06-16 | 2011-12-21 | 襄阳市布拉德化工科技有限公司 | Method for producing 2-carboxyethyl(phenyl)phosphinicacid |
| CN102276767A (en) * | 2011-06-24 | 2011-12-14 | 苏州科技学院 | Method for preparing macromolecular halogen-free flame retardant by utilizing waste polystyrene |
| CN102276767B (en) * | 2011-06-24 | 2013-04-10 | 苏州科技学院 | Method for preparing macromolecular halogen-free flame retardant by utilizing waste polystyrene |
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