CN105294766A - Reactive phosphorus-containing halogen-free intumescent flame retardant and synthetic method thereof - Google Patents

Reactive phosphorus-containing halogen-free intumescent flame retardant and synthetic method thereof Download PDF

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CN105294766A
CN105294766A CN201510821553.8A CN201510821553A CN105294766A CN 105294766 A CN105294766 A CN 105294766A CN 201510821553 A CN201510821553 A CN 201510821553A CN 105294766 A CN105294766 A CN 105294766A
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bis
containing halogen
fire retardant
dioxy
synthetic method
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柴春鹏
罗运军
吴刚
林嘉伦
葛震
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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Abstract

The invention relates to a reactive phosphorus-containing halogen-free intumescent flame retardant and a synthetic method thereof, belonging to the field of organic fire retardants. The reactive phosphorus-containing halogen-free intumescent flame retardant has a structural formula as described in the specification. The synthetic method comprises the following steps: preparing an intermediate 2,4,8,10-tetraoxa-3,9-diphosphaspirocyclo-3,9-dioxy-3,9-diphenyl (BPPB) from primary raw materials consisting of pentaerythritol and dichlorophenylphosphine oxide; then preparing a phosphorus-containing compound containing two nitro groups, i.e., 2,4,8,10-tetraoxa-3,9-diphosphaspirocyclo-3,9-dioxy-3,9-di(3-nitrophenyl) (BPPN), by using fuming nitric acid reduction method; and reducing BPPN into the final product 2,4,8,10-tetraoxa-3,9-diphosphaspirocyclo-3,9-dioxy-3,9-di(3-aminophenyl) (BPPA) by using a reduction method. The method is simple to operate and has a good industrial application value. The prepared intumescent flame retardant has excellent flame retardation performance and good heat stability.

Description

A kind of response type phosphor-containing halogen-free expanding fire retardant and synthetic method thereof
Technical field
The present invention relates to a kind of response type phosphor-containing halogen-free expanding fire retardant and synthetic method thereof, belong to organic fire-retardant field.
Background technology
Reaction-type flame-retarding macromolecular material refers to and is incorporated in the molecular structure of macromolecular material using fire retardant as reactant, makes it namely to have flame retardant resistance when outer interpolation fire retardant, and can reach certain fire-retardant rank.Reaction-type flame-retarding macromolecular material is modification macromolecular material being carried out to molecule aspect, fundamentally overcome relevant interface problem, and direct ignition-proof element or structure being incorporated in the molecule of macromolecular material makes properties-correcting agent consumption greatly reduce, the negative impact of material property is also significantly reduced, do not have that fire retardant is volatile, stripping, move and ooze out problem, and when ignition-proof element content is identical, the flame retarding efficiency of reaction-type flame-retarding macromolecular material is higher also more lasting.The reactive expanding fire retardant of existing announcement, as the preparation method of the reactive expanding fire retardant that patent CN104497050A announces, this fire retardant is by tetramethylolmethane, phosphorus oxychloride and diaminostilbene, 3,5-pyrrolotriazine derivatives is prepared by elimination reaction, this fire retardant is used for preparing extinguishing waterborn polyurethane, excellent flame retardancy in aqueous polyurethane, and four kinds of examples all reach V-0 level.But due to a large amount of gas sent when this fire retardant burns, be unfavorable for forming fine and close carbon-coating, therefore have adverse influence to fire-retardant.The preparation method of a kind of reactive Nitrogen-and Phosphorus-containing fire retardant that patent CN104151356A announces, this fire retardant has better flame retardant properties, and practicality is very high.But because its molecule self does not contain into carbon component, therefore it can not reach requirement for the flame retardant properties in aqueous polyurethane.Therefore, the organophosphorus halogen-free expansion type flame-proof small molecules of design containing reactive group, make it to be entered by fire retardant material molecule by chemical reaction, and play intrinsically flame retarded effect, this application for halogen-free expansion type flame-proof macromolecular material is significant.
Summary of the invention
The invention provides a kind of response type phosphor-containing halogen-free expanding fire retardant and synthetic method thereof, this material not only has excellent flame retardant properties, and has response type functional group, can be used in urethane, " inherent flame retardant " modification of epoxy resin etc.; The method products obtained therefrom purity is high, and productive rate is high.
A kind of response type phosphor-containing halogen-free expanding fire retardant, called after: 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl); English abbreviation is: BPPA; Molecular formula is C 17h 20n 2o 6p 2, structural formula is:
A synthetic method for response type phosphor-containing halogen-free expanding fire retardant, concrete steps are: with tetramethylolmethane and diphenylphosphoryl dichloro for primary raw materials prepares intermediate product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-hexichol (BPPB); Then P contained compound 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-nitrophenyl) (BPPN) of method preparation containing two nitros of nitrosonitric acid reduction is adopted; Finally by method of reducing, BPPN is reduced into final product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl) (BPPA).The present invention is simple to operate, has good industrial application value.The compound excellent flame retardancy invented, Heat stability is good.
The method of the described BPPB of preparation is: under the protection of rare gas element, by tetramethylolmethane, acid binding agent and organic solvent Homogeneous phase mixing under ice bath; The ratio of the amount of substance of tetramethylolmethane and acid binding agent is at 1:4, and organic solvent is enough to tetramethylolmethane is dissolved; Then diphenylphosphoryl dichloro is dripped; Diphenylphosphoryl dichloro add-on is 2-3 times of added tetramethylolmethane molar weight; After dropwising, be warming up to more than the reflux temperature of organic solvent, until tetramethylolmethane reacts completely; Be cooled to room temperature, leave standstill, suction filtration, is washed till neutrality with a large amount of deionized water, vacuum-drying, obtains product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-hexichol (BPPB).
The method of the described BPPN of preparation is: dissolved in concentrated sulfuric acid by BPPB; Then in solution, nitrosonitric acid is dripped; Nitrosonitric acid add-on is 2 times of added BPPB molar weight; Dropwise, until after BPPB reacts completely, obtain mixed solution A; Then mixed solution A impouring is equipped with in the container of a large amount of trash ice, suction filtration, is adjusted to after pH is neutrality with cold weak caustic solution, repeatedly washes, gained faint yellow solid.Vacuum-drying no longer changes to quality, obtains product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-nitrophenyl) (BPPN).
When dripping nitrosonitric acid, temperature in system be kept to be no more than 10 DEG C;
The method of the described BPPA of preparation is: ethanol and metal-powder are mixed, and then adds a small amount of concentrated hydrochloric acid, obtains mixing solutions B; Concentrated hydrochloric acid adds several; Weak acid saturated aqueous solution is added in mixing solutions B; The mole number of added weak acid is identical with metal-powder; BPPN is added after mixing; BPPN add-on is 2.5-5 with the ratio of the molar weight of metal-powder; Until after BPPN reacts completely, with pad diatomite elimination metal mud.Revolve and steam removing second alcohol and water, in remaining solid, add saturated weak caustic solution, make mixed solution ph in neutral; Abundant stirring after washing, filter, gained solid ethyl alcohol recrystallization, drying obtains final product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl) (BPPA).
Described organic solvent comprises methylene dichloride, trichloromethane;
Described acid binding agent comprises triethylamine, pyridine and DMA;
Described metal-powder comprises: iron powder, zinc powder;
Described weakly acidic aqueous solution comprises: aqueous ammonium chloride solution, ammonium acetate aqueous solution;
Described weak caustic solution comprises sodium hydrogen carbonate solution, sodium carbonate solution.
The synthetic route of the present invention's reactive halogen-free expandable phosphonium flame retardant BPPA is as follows:
Beneficial effect:
1, this fire retardant can be used for the inherent flame retardant modification of the macromolecular material such as urethane, epoxy resin, and it not only has efficient flame retardant properties, and has good consistency with macromolecule matrix material.
2, the method adopts chemical process to be attached in same organic molecule to prepare a kind of response type phosphor-containing halogen-free expanding fire retardant by meeting fire-retardant " three sources ", and not only have the feature that productive rate is high, and the product purity of preparation is high, application prospect potentiality are large.
Embodiment:
Embodiment 1
A kind of response type phosphor-containing halogen-free expanding fire retardant, called after: 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl); English abbreviation is: BPPA; Molecular formula is C 17h 20n 2o 6p 2, structural formula is:
A kind of response type phosphor-containing halogen-free expanding fire retardant, concrete steps are as follows:
The synthesis of step one: BPPB.
Under protection of inert gas; by the PER of 34g (0.25mol) under ice bath; the methylene dichloride (molecular sieve drying 48h) of 300mL; 79.1g (1mol) pyridine mixes; vigorous stirring 30min; then in system, drip methylene dichloride (50mL) solution of the diphenylphosphoryl dichloro of 97.5g (0.5mol), dropwise in 2h.Continue reaction 0.5h under ice bath, be warming up to 50 DEG C of back flow reaction 8h afterwards.Be cooled to intensification, leave standstill 1 day, suction filtration, by massive laundering 5-6 time, vacuum-drying (90 DEG C) 24h, obtains product, productive rate 87%.M.p:263-267℃(DSC)。Infrared spectra (KBr compressing tablet) (cm -1): 2906-2971cm -1(-CH 2-), 1015cm -1(P-O-Ph), 1432cm -1(P-Ph), 1157cm -1(-P=O). 1HNMR(400MHz，DMSO-d 6)δ(ppm):7.83-7.78(m，4H)，7.72(t，J＝12Hz，2H)，7.63-7.60(m，4H)，4.64-4.54(m，4H)，4.39-4.29(m，4H)。 31PNMR(DMSO-d 6,ppm):21.04。Ultimate analysis: C, 53.67; H, 4.78; O, 25.23; P, 16.32.
The synthesis of step 2: BPPN.
By the BPPB of 70g (0.184mol), under cryosel bath, be dissolved in the vitriol oil of 170g, then drip the nitrosonitric acid of 24.61g (0.37mol), maintain rate of addition and make system temperature lower than 5 DEG C, dropwise in 2h.After dropwising, holding temperature must not, more than 10 DEG C, continue to stir 4h.By in the trash ice of reaction mixture impouring 2L after reaction stops, suction filtration, the acid solution that washing removing is a large amount of, then with cold rare NaHCO 3the acid solution remained in solution and in solid makes pH aobvious neutral.Use a large amount of washed several times with water afterwards, gained yellow solid is dried to quality not in change in vacuum drying oven, and productive rate is 90%.M.p:244-246℃(DSC)。Infrared spectra (KBr compressing tablet) (cm -1): 2906-2971cm -1(-CH 2-), 1015cm -1(P-O-Ph), 1432cm -1(P-Ph), 1157cm -1(-P=O), 1543cm -1, 1356cm -1(-NO 2). 1HNMR(400MHz，DMSO)δ(ppm):8.54(d，J＝8H)，8.45(d，J＝12Hz，2H)，8.27-8.22(m，2H)，7.95-7.90(m，2H)，4.71(t，J＝20Hz，2H)，4.56(t，J＝20Hz，2H)，4.48(t，J＝20Hz，2H)，4.34(t，J＝20Hz，2H)。 31PNMR(DMSO-d 6,ppm):31.21。Ultimate analysis: C, 43.44; H, 3.44; N, 5.95; O, 34.01; P, 13.16.
The synthesis of step 3: BPPA.
The ethanol of 240mL and 0.75mol iron powder, add 0.075mol concentrated hydrochloric acid under mechanical stirring, reaction suspension activates 2h at 70 DEG C.Then add the aqueous ammonium chloride solution of 25% of 120mL in system, slowly add the BPPN of 40g after fully stirring, react and complete in 2h.After reaction terminates, be cooled to 40 DEG C, suction filtered through kieselguhr.Revolve and steam except desolventizing, in remaining solid, add the saturated NaHCO of 150mL 3solution, stirs, and filter, filter cake washes 2 times, gained crude product ethyl alcohol recrystallization, and vacuum-drying no longer changes to quality, and productive rate is 80%.M.p:263-267℃(DSC)。Infrared spectra (KBr compressing tablet) (cm -1): 2906-2971cm -1(-CH 2-), 1015cm -1(P-O-Ph), 1432cm -1(P-Ph), 1157cm -1(-P=O), 3424-3237cm -1(-NH 2). 1HNMR(400MHz,DMSO)δ(ppm):7.20(d，J＝4.4Hz,2H)，6.96(d,J＝15Hz,2H)，6.91-6.75(m,4H)，5.52(s,2H)，4.6-4.4(m,4H)，4.39-4.19(m,4H)。 31PNMR(DMSO-d 6,ppm):33.01。Ultimate analysis: C, 49.75; H, 4.92; N, 6.81; O, 23.41; P, 15.11.
Fire retardant of the present invention prepares fire retarding epoxide resin as the flame retardant curing agent of epoxy resin, and its oxygen index reaches V-0 level, without molten drop up to 32%, UL-94; Use it for and prepare in flame retardant polyurethane, oxygen index reaches 34%, UL-94 and reaches V-0 level.
Embodiment 2
A kind of response type phosphor-containing halogen-free expanding fire retardant, called after: 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl); English abbreviation is: BPPA; Molecular formula is C 17h 20n 2o 6p 2, structural formula is:
A kind of response type phosphor-containing halogen-free expanding fire retardant, concrete steps are as follows:
Step one: the synthesis of BPPB base.
Under protection of inert gas; by the PER of 68g (0.5mol) under ice bath; the trichloromethane (molecular sieve drying 48h) of 600mL; 202.4g (2mol) triethylamine fully mixes; vigorous stirring 30min; then in system, drip trichloromethane (100mL) solution of the diphenylphosphoryl dichloro of 195.0g (1mol), dropwise in 2h.Continue reaction 0.5h under ice bath, be warming up to 60 DEG C of back flow reaction 5h afterwards.Be cooled to room temperature, leave standstill 1 day, suction filtration, with massive laundering several, vacuum-drying (90 DEG C) 24h, obtains product, productive rate 85%.
The synthesis of step 2: BPPN.
Under cryosel bath, the BPPB of 140g (0.368mol) is dissolved in the vitriol oil of 340g, stirs and solid is dissolved completely.Then drip the nitrosonitric acid of 49.22g (0.78mol), maintain rate of addition and make system temperature lower than 5 DEG C, dropwise in 2h.After dropwising, maintenance temperature of reaction is ice bath, and temperature must not, more than 10 DEG C, continue to stir 4h.By in the trash ice of reaction mixture impouring 3L after reaction stops, suction filtration, washes the acid solution that twice removing is a large amount of, then with cold KHCO 3acid solution residual in solution and in solid, after pH shows neutrality, then uses a large amount of washings twice, and gained yellow solid is dried to quality not in change in vacuum drying oven, and productive rate is 89%.
The synthesis of step 3: BPPA.
The ethanol of 480mL and 1.5mol zinc powder are fully mixed, add 0.15mol concentrated hydrochloric acid under mechanical stirring, reaction suspension activates 2h at 70 DEG C.Then add the aqueous ammonium chloride solution of 25% of 240mL in system, slowly add the BPPN of 80g after fully stirring, react and complete in 2h.After reaction terminates, be cooled to 40 DEG C, suction filtered through kieselguhr.Filtrate concentrates, the saturated KHCO of 300mL in gained residue 3the aqueous solution, stirs, and filter, filter cake washes 2 times, gained crude product ethyl alcohol recrystallization, and vacuum-drying no longer changes to quality, and productive rate is 82%.
Embodiment 3
A kind of response type phosphor-containing halogen-free expanding fire retardant, called after: 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl); English abbreviation is: BPPA; Molecular formula is C 17h 20n 2o 6p 2, structural formula is:
A kind of response type phosphor-containing halogen-free expanding fire retardant, concrete steps are as follows:
The synthesis of step one: BPPB.
N 2under protection; in the there-necked flask of 250mL, the PER of 17g (0.125mol) is added under ice bath; the trichloromethane (molecular sieve drying 48h) of 150mL; 60.6g (0.5mol) N; accelerine; vigorous stirring 30min, then drips trichloromethane (25mL) solution of the diphenylphosphoryl dichloro of 48.8g (0.25mol), dropwises in 2h in system.Continue reaction 0.5h under ice bath, be warming up to 50 DEG C of back flow reaction 6h afterwards.Be cooled to intensification, leave standstill 1 day, suction filtration, by massive laundering 5-6 time, vacuum-drying (90 DEG C) 24h, obtains product, productive rate 89%.
The synthesis of step 2: BPPN.
Add the BPPB of 17.5g (0.046mol) in 250mL there-necked flask, under cryosel bath, add in the vitriol oil of 42.5g, stir and solid is dissolved completely.Then drip the nitrosonitric acid of 5.7g (0.092mol), maintain rate of addition and make system temperature lower than 5 DEG C, dropwise in 1h.After dropwising, maintenance temperature of reaction is ice bath, and temperature must not, more than 10 DEG C, continue to stir 4h.By in the trash ice of reaction mixture impouring 1L after reaction stops, suction filtration, washes the acid solution that twice removing is a large amount of, then with cold NaHCO 3acid solution (speed can not be too fast) residual in solution and in solid, after pH shows neutrality, then uses a large amount of washings twice, and gained yellow solid is dried to quality not in change in vacuum drying oven, and productive rate is 92%.
The synthesis of step 3: BPPA.
There-necked flask, add ethanol and the 0.375mol zinc powder of 120mL, add 0.0375mol concentrated hydrochloric acid under mechanical stirring, reaction suspension activates 2h at 70 DEG C.Then add the aqueous ammonium chloride solution of 25% of 60mL in system, slowly add the BPPN of 20g after fully stirring, react and complete in 2h.After reaction terminates, be cooled to 40 DEG C, suction filtered through kieselguhr.Filtrate concentrates, the saturated NaHCO of 150mL in gained residue 3solution, stirs, and filter, filter cake washes 2 times, gained crude product ethyl alcohol recrystallization, and vacuum-drying no longer changes to quality, and productive rate is 83%.
Embodiment 4
A kind of response type phosphor-containing halogen-free expanding fire retardant, called after: 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl); English abbreviation is: BPPA; Molecular formula is C 17h 20n 2o 6p 2, structural formula is:
A kind of response type phosphor-containing halogen-free expanding fire retardant, concrete steps are as follows:
The synthesis of step one: BPPB.
N 2under protection; in the there-necked flask of 2L, the PER of 136g (1mol) is added under ice bath; the methylene dichloride (molecular sieve drying 48h) of 800mL; 320g (4mol) pyridine; vigorous stirring 30min; then in system, drip methylene dichloride (200mL) solution of the diphenylphosphoryl dichloro of 390g (2mol), dropwise in 3h.Continue reaction 0.5h under ice bath, be warming up to 50 DEG C of back flow reaction 6h afterwards.Be cooled to intensification, leave standstill 1 day, suction filtration, by massive laundering 5-6 time, vacuum-drying (90 DEG C) 24h, obtains product, productive rate 75%.
The synthesis of step 2: BPPN.
Add the BPPB of 105g (0.276mol) in 500mL there-necked flask, under cryosel bath, add in the vitriol oil of 250g, stir and solid is dissolved completely.Then drip the nitrosonitric acid of 36.9g (0.55mol), maintain rate of addition and make system temperature lower than 5 DEG C, dropwise in 2h.After dropwising, maintenance temperature of reaction is ice bath, and temperature must not, more than 10 DEG C, continue to stir 4h.By in the trash ice of reaction mixture impouring 2L after reaction stops, suction filtration, washes the acid solution that twice removing is a large amount of, then with cold NaHCO 3acid solution (speed can not be too fast) residual in solution and in solid, after pH shows neutrality, then uses a large amount of washings twice, and gained yellow solid is dried to quality not in change in vacuum drying oven, and productive rate is 85%.
The synthesis of step 3: BPPA.
There-necked flask, add ethanol and the 1mol iron powder of 320mL, add 0.1mol concentrated hydrochloric acid under mechanical stirring, reaction system activates 2h at 70 DEG C.Then add the aqueous ammonium chloride solution of 25% of 160mL in system, slowly add the BPPN of 53g after fully stirring, react and complete in 2h.After reaction terminates, be cooled to 40 DEG C, suction filtered through kieselguhr.Revolve and steam except desolventizing, in remaining solid, add the saturated NaHCO of 200mL 3solution, stirs, and filter, filter cake washes 2 times, gained crude product ethyl alcohol recrystallization, and vacuum-drying no longer changes to quality, and productive rate is 80.5%.
Embodiment 5
A kind of response type phosphor-containing halogen-free expanding fire retardant, called after: 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl); English abbreviation is: BPPA; Molecular formula is C 17h 20n 2o 6p 2, structural formula is:
A kind of response type phosphor-containing halogen-free expanding fire retardant, concrete steps are as follows:
The synthesis of step one: BPPB.
N 2under protection; in the there-necked flask of 2L, the PER of 85g (0.63mol) is added under ice bath; the trichloromethane (molecular sieve drying 48h) of 400mL; 303g (2.5mol) N; accelerine; vigorous stirring 30min, then drips trichloromethane (200mL) solution of the diphenylphosphoryl dichloro of 243.8g (1.25mol), dropwises in 2h in system.Continue reaction 0.5h under ice bath, be warming up to 50 DEG C of back flow reaction 8h afterwards.Be cooled to intensification, leave standstill 1 day, suction filtration, by massive laundering 5-6 time, vacuum-drying (90 DEG C) 24h, obtains product, productive rate 88%.
The synthesis of step 2: BPPN.
Add the BPPB of 112g (0.29mol) in 500mL there-necked flask, under cryosel bath, add in the vitriol oil of 270g, stir and solid is dissolved completely.Then drip the nitrosonitric acid of 39.4g (0.59mol), maintain rate of addition and make system temperature lower than 5 DEG C, dropwise in 2h.After dropwising, maintenance temperature of reaction is ice bath, and temperature must not, more than 10 DEG C, continue to stir 4h.By in the trash ice of reaction mixture impouring 2L after reaction stops, suction filtration, washes the acid solution that twice removing is a large amount of, then with cold KHCO 3acid solution (speed can not be too fast) residual in solution and in solid, after pH shows neutrality, then uses a large amount of washings twice, and gained yellow solid is dried to quality not in change in vacuum drying oven, and productive rate is 91%.
The synthesis of step 3: BPPA.
There-necked flask, add ethanol and the 0.25mol iron powder of 40mL, add 0.025mol concentrated hydrochloric acid under mechanical stirring, reaction suspension activates 2h at 70 DEG C.Then add the aqueous ammonium chloride solution of 25% of 60mL in system, slowly add the BPPN of 10g after fully stirring, react and complete in 2h.After reaction terminates, be cooled to 40 DEG C, suction filtered through kieselguhr.Filtrate concentrates, the saturated NaHCO of 40mL in gained residue 3, stir, filter, filter cake washes 2 times, gained crude product ethyl alcohol recrystallization, and vacuum-drying no longer changes to quality, and productive rate is 85%.

Claims (10)

1. a response type phosphor-containing halogen-free expanding fire retardant, called after: 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl); English abbreviation is: BPPA; It is characterized in that: molecular formula is C 17h 20n 2o 6p 2, structural formula is:
2. a synthetic method for response type phosphor-containing halogen-free expanding fire retardant, is characterized in that: concrete steps are: with tetramethylolmethane and diphenylphosphoryl dichloro for primary raw materials prepares intermediate product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-hexichol (BPPB); Then P contained compound 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-nitrophenyl) (BPPN) of method preparation containing two nitros of nitrosonitric acid reduction is adopted; Finally by method of reducing, BPPN is reduced into final product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl) (BPPA).
3. the synthetic method of a kind of response type phosphor-containing halogen-free expanding fire retardant as claimed in claim 2, is characterized in that: the method for the described BPPB of preparation is: under the protection of rare gas element, by tetramethylolmethane, acid binding agent and organic solvent Homogeneous phase mixing under ice bath; The ratio of the amount of substance of tetramethylolmethane and acid binding agent is at 1:4, and organic solvent is enough to tetramethylolmethane is dissolved; Then diphenylphosphoryl dichloro is dripped; Diphenylphosphoryl dichloro add-on is 2-3 times of added tetramethylolmethane molar weight; After dropwising, be warming up to more than the reflux temperature of organic solvent, until tetramethylolmethane reacts completely; Be cooled to room temperature, leave standstill, suction filtration, is washed till neutrality with a large amount of deionized water, vacuum-drying, obtains product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-hexichol (BPPB).
4. the synthetic method of a kind of response type phosphor-containing halogen-free expanding fire retardant as claimed in claim 2, is characterized in that: the method for the described BPPN of preparation is: dissolved in concentrated sulfuric acid by BPPB; Then in solution, nitrosonitric acid is dripped; Nitrosonitric acid add-on is 2 times of added BPPB molar weight; Dropwise, until after BPPB reacts completely, obtain mixed solution A; Then mixed solution A impouring is equipped with in the container of a large amount of trash ice, suction filtration, is adjusted to after pH is neutrality with cold weak caustic solution, repeatedly washes, gained faint yellow solid; Vacuum-drying no longer changes to quality, obtains product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-nitrophenyl) (BPPN).
5. the synthetic method of a kind of response type phosphor-containing halogen-free expanding fire retardant as claimed in claim 2, is characterized in that: the method for the described BPPA of preparation is: ethanol and metal-powder are mixed, and then adds a small amount of concentrated hydrochloric acid, obtains mixing solutions B; Concentrated hydrochloric acid adds several; Weak acid saturated aqueous solution is added in mixing solutions B; The mole number of added weak acid is identical with metal-powder; BPPN is added after mixing; BPPN add-on is 2.5-5 with the ratio of the molar weight of metal-powder; Until after BPPN reacts completely, with pad diatomite elimination metal mud; Revolve and steam removing second alcohol and water, in remaining solid, add saturated weak caustic solution, make mixed solution ph in neutral; Abundant stirring after washing, filter, gained solid ethyl alcohol recrystallization, drying obtains final product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl) (BPPA).
6. the synthetic method of a kind of response type phosphor-containing halogen-free expanding fire retardant as described in claim 2 or 4, is characterized in that: when dripping nitrosonitric acid, temperature in system be kept to be no more than 10 DEG C.
7. the synthetic method of a kind of response type phosphor-containing halogen-free expanding fire retardant as claimed in claim 3, is characterized in that: described organic solvent comprises methylene dichloride, trichloromethane; Described acid binding agent comprises triethylamine, pyridine and DMA.
8. the synthetic method of a kind of response type phosphor-containing halogen-free expanding fire retardant as claimed in claim 5, is characterized in that: described metal-powder comprises: iron powder, zinc powder.
9. the synthetic method of a kind of response type phosphor-containing halogen-free expanding fire retardant as claimed in claim 5, is characterized in that: described weak acid saturated aqueous solution comprises: aqueous ammonium chloride solution, ammonium acetate aqueous solution.
10. the synthetic method of a kind of response type phosphor-containing halogen-free expanding fire retardant as claimed in claim 5, is characterized in that: described weak caustic solution comprises sodium hydrogen carbonate solution, sodium carbonate solution.
CN201510821553.8A 2015-11-24 2015-11-24 Reactive phosphorus-containing halogen-free intumescent flame retardant and synthetic method thereof Pending CN105294766A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19856396A1 (en) * 1998-12-07 2000-06-08 Siemens Ag New phosphorus-containing amines, useful as epoxy resin curing agents, are prepared by reaction of phenylphosphoric acid dichloride with an aliphatic hydroxy-hydrocarbon, nitration and reduction
CN101463046A (en) * 2008-11-20 2009-06-24 西华大学 Caged bicyclic phosphate flame retardant, and preparation and use thereof
CN104151356A (en) * 2014-07-17 2014-11-19 江汉大学 Nitrogen-phosphorus containing flame retardant bis(4-aminophenoxy) phenyl phosphine oxide and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19856396A1 (en) * 1998-12-07 2000-06-08 Siemens Ag New phosphorus-containing amines, useful as epoxy resin curing agents, are prepared by reaction of phenylphosphoric acid dichloride with an aliphatic hydroxy-hydrocarbon, nitration and reduction
CN101463046A (en) * 2008-11-20 2009-06-24 西华大学 Caged bicyclic phosphate flame retardant, and preparation and use thereof
CN104151356A (en) * 2014-07-17 2014-11-19 江汉大学 Nitrogen-phosphorus containing flame retardant bis(4-aminophenoxy) phenyl phosphine oxide and preparation method thereof

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