CN106397778B - A method of improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization - Google Patents
A method of improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of methods for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization, belong to the preparation technical field of aggretion type fire retardant.By phosphorus oxychloride, pentaerythrite and catalyst AlCl under room temperature3Uniformly mixing, obtains two phosphoryl chloride phosphorus oxychloride of crude intermediate pentaerythrite diphosphate ester (SPDPC)；The SPDPC for the high-purity that step 1 obtains, 4,4- diaminodiphenylsulfone and acid binding agent are added in organic solvent, after being uniformly mixed, temperature reaction in two stages obtains high aggretion type phosphorus nitrogen expanding fire retardant.In synthesis technology of the invention, reactant is used as reaction dissolvent simultaneously, reduces the usage amount of solvent, enormously simplifies postprocessing working procedures, while the operation of anti-precipitating and recrystallization has been carried out to product, and obtained product purity is high.
Description
Technical field
The present invention relates to a kind of methods for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization, belong to aggretion type resistance
Fire the preparation technical field of agent.
Background technique
Since the 1980s, with the demand to high molecular material security application, fire retardant has become macromolecule material
Expect flame-retardant modified one of important auxiliary agent.In existing fire retardant, although traditional halogenated flame retardant flame retarding efficiency it is high, to matrix
The proper property of material influences small, but it can generate volume of smoke, corrosive gas and some in thermal decomposition and combustion process
Noxious material brings human health and seriously affects, while also will cause certain environmental pollution.Therefore, halogenated flame retardant
It is development trend from now on by the Green Flammability agent substitution of Halogen.
Poly- phosphoramide types fire retardant containing P-N junction structure integrates acid source, carbon source, gas source, has excellent thermostabilization
Property, carbon-forming performance, it is preferable with matrix compatibility, be the efficient flame-retarding agent of a kind of environmental protection, development prospect is good.But at this stage,
Such compound or expensive, or manufacture and processing technology it is complicated, application is quite limited.The research of this based flame retardant
Also relatively fewer, application range needs further to be expanded.
Chinese patent one kind is phosphorous, nitrogen response type ethoxyline resin antiflaming curing agent and preparation method thereof (CN104817685A)
Report phosphorous, nitrogen expansion type flame retardant of one kind and preparation method thereof.Prepared compound thermal stability with higher,
Dilatancy and charring rate can be used as flame-retardant additive and are used in multiple polymers, to improve the flame retardant property of polymer.But it is closed
At the compound degree of polymerization it is low, expected using effect cannot be reached, in addition, yield is very low.It has used in the synthesis process big
Organic solvent is measured, the product purity made is low, excessively complicated to the purification process of synthetic product.The trichlorine oxygen used due to it
Phosphorus amount is too big, can heavy corrosion synthesis device, or even be detrimental to health and pollute environment.In addition, above-mentioned patent does not have pairing
Structural characterization is carried out at product, is short of convincingness.Therefore, need to propose a kind of improved synthesis technology to solve the above problems.
Summary of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, provide a kind of raising aggretion type phosphorus nitrogen expansion resistance
Fire the method for agent yield and the degree of polymerization.This method is safe and reliable, intermediate purity is high obtained, the aggretion type phosphorus nitrogen expansion of synthesis
Fire retardant yield is high, the degree of polymerization is high.
The purpose of the present invention is what is be achieved through the following technical solutions.
A method of improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization, the specific steps are as follows:
Step 1: under an inert atmosphere, by phosphorus oxychloride (POCl under room temperature3), pentaerythrite (PER) and catalyst AlCl3
Uniformly mixing, is heated up to 40~80 DEG C；Until the reaction is complete, i.e., occur without hydrogen chloride gas；It is more by vacuum distillation recycling again
Remaining phosphorus oxychloride (POCl3), obtain two phosphoryl chloride phosphorus oxychloride of crude intermediate pentaerythrite diphosphate ester (SPDPC)；By SPDPC through filtering
Wash, recrystallize, being dried to obtain the SPDPC of high-purity；Phosphorus oxychloride (the POCl3) with the molar ratio of pentaerythrite (PER)
For (3~6): 1；The AlCl3Molar ratio with pentaerythrite (PER) is (0.03~0.07): 1.
Step 2: under an inert atmosphere, the SPDPC for the high-purity that step 1 is obtained, 4,4- diaminodiphenylsulfone (DDS)
It is added in organic solvent with acid binding agent, after being uniformly mixed, temperature reaction in two stages；First from room temperature to 40~
50 DEG C of 1~4h of reaction, are then warming up to 60~80 DEG C until the reaction is complete again, i.e., occur without hydrogen chloride gas；It is steamed by decompression
Extra organic solvent is removed in distillation, obtains poly- (4,4'- diaminodiphenylsulfone loop coil pentaerythrite bisphosphonates) (PCS) intumescent
Fire retardant crude product；Crude product obtains high aggretion type phosphorus nitrogen expanding fire retardant after multiple filtering and washing, anti-precipitation purification and drying；
The molar ratio of the 4,4' diaminodiphenyl sulfone (DDS) and pentaerythrite (PER) is (0.5~1.5): 1；The acid binding agent and
The molar ratio of 4,4' diaminodiphenyl sulfone (DDS) is (1~2.5): 1.
The high aggretion type phosphorus nitrogen expanding fire retardant structural formula is as follows:
Wherein n is the integer between 100~1200.
The synthetic route for the fire retardant that synthesis technology of the invention is related to is as follows:
Phosphorus oxychloride (POCl in the step 13) with the molar ratio of pentaerythrite (PER) it is (3.5~4.5): 1；
Catalyst AlCl in the step 13Molar ratio with pentaerythrite (PER) is (0.05~0.06): 1；
The solvent for being used to wash two phosphoryl chloride phosphorus oxychloride of intermediate pentaerythrite diphosphate ester (SPDPC) in the step 1 is dichloro
One of methane, chloroform, carbon tetrachloride, ether, acetone, methanol, ethyl alcohol, water, petroleum ether, n-hexane or a variety of mixing
Object, preferably methylene chloride；
The molar ratio of the 4,4' diaminodiphenyl sulfone (DDS) and pentaerythrite (PER) that are added in the step 2 be (1~
1.2): 1；
The acid binding agent being added in the step 2 is triethylamine, pyridine, piperidines, N, N- diisopropylethylamine, 4- diformazan ammonia
Yl pyridines, anhydrous aluminum chloride, anhydrous magnesium chloride, potassium phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate,
One of saleratus or a variety of mixtures, preferably triethylamine；
The molar ratio of acid binding agent and 4,4' diaminodiphenyl sulfone (DDS) in the step 2 is (1.5~2): 1；
Organic solvent in the step 2 is preferably 1-Methyl-2-Pyrrolidone, N,N-dimethylformamide, N, N- bis-
Methylacetamide, dimethyl sulfoxide, tetrahydrofuran, butanone, ethyl acetate, chloroform, dioxane, acetonitrile, benzene, toluene, diformazan
One of benzene or a variety of mixtures.
The mass ratio of organic solvent and two phosphoryl chloride phosphorus oxychloride of intermediate pentaerythrite diphosphate ester (SPDPC) in the step 2
For (7~25): 1, preferably (11~17): 1；
The solvent for being used to wash fire retardant crude product in the step 2 is chloroform, carbon tetrachloride, ether, acetone, methanol, second
One of alcohol, petroleum ether, n-hexane or a variety of mixtures；
The solvent for being used to anti-precipitation purification fire retardant crude product in the step 2 is dimethyl sulfoxide, chloroform, acetonitrile, third
One of ketone, methylene chloride, acetone or a variety of mixtures, preferably chloroform；
Drying process in the method for the present invention is 40~70 DEG C and is dried under vacuum to constant weight, preferably 50~60 DEG C vacuum drying
To constant weight；
Drying process in the method for the present invention is 70~160 DEG C dry to constant weight, preferably 110~140 DEG C dryings to perseverance
Weight；
Beneficial effect
1, in synthesis technology of the invention, hence it is evident that improve the degree of polymerization of aggretion type fire retardant, while acid binding agent makes
With greatly improving the yield of poly- (4,4' diaminodiphenyl sulfone loop coil pentaerythrite bisphosphonates) (PCS) expansion type flame retardant；
2, in synthesis technology of the invention, reactant phosphorus oxychloride is used as reaction dissolvent simultaneously, does not use additional
Organic solvent avoids generating the by-product much generated by solvent and reactant reaction, while having carried out anti-precipitating to product
With the operation of recrystallization, obtained intermediate purity is high, yield is also high, also simplifies postprocessing working procedures；
3, in synthesis technology of the invention, recycling and reusing has been carried out to extra reaction dissolvent phosphorus oxychloride, has been avoided
Because generating waste liquid polluting caused by human health and environment, meet the theory of Green Sustainable；
4, in synthesis technology of the invention, reaction temperature is low, the reaction time is shorter, low for equipment requirements, therefore advantageous
In regulation reaction condition, in addition, used materials safety is easy to get, it is cheap, it is conducive to industrialized production；
5, the aggretion type phosphorus nitrogen expansion type combustion inhibitor and curing agent 4,4 '-diaminodiphenylsulfone that technique synthesizes through the invention
(DDS) fire retarding epoxide resin prepared not only has good flame retardant property, water resistance, while also having excellent mechanical property
Energy.
Detailed description of the invention
Fig. 1 is the infrared spectrum (FTIR) of the aggretion type phosphorus nitrogen expansion type combustion inhibitor of embodiment preparation；
Fig. 2 be embodiment preparation aggretion type phosphorus nitrogen expansion type combustion inhibitor nucleus magnetic hydrogen spectrum figure (1HNMR)；
Fig. 3 be embodiment preparation aggretion type phosphorus nitrogen expansion type combustion inhibitor nuclear-magnetism phosphorus spectrogram (31PNMR)；
Fig. 4 is the aggretion type phosphorus nitrogen expansion type combustion inhibitor and curing agent 4,4 '-diamino two of technique synthesis through the invention
The thermal performance test result figure of the fire retarding epoxide resin of benzene sulfone (DDS) preparation.
Specific embodiment
Below with reference to embodiment, the content of the present invention will be further explained.
Embodiment 1
Step 1: under the protection of nitrogen, 6.8g (0.05mol) just ground pentaerythrite being added into 500ml container
(PER), the phosphorus oxychloride (POCl that 23.1g (0.15mol) has just distilled3) and 0.72g alchlor (AlCl3).Above-mentioned reaction is held
Device is connected with thermometer, mechanical agitator, reflux condensing tube and device for absorbing tail gas.It first mixes at room temperature, wherein stirring
The revolving speed of paddle is that 230r/min after mixing to system is to slowly warm up to 80 DEG C until the reaction is complete, i.e., without hydrogen chloride gas
Occur.Extra phosphorus oxychloride solvent is distilled to recover by Rotary Evaporators after reaction, obtained residue dichloromethane
Alkane washing, filtering after being repeated several times, recrystallize, the product after recrystallization is in convection oven in 120 DEG C of dryings in glacial acetic acid
To constant weight, white two phosphoryl chloride phosphorus oxychloride of intermediate pentaerythrite diphosphate ester (SPDPC) 13.5g, yield 91% are obtained；Purity is
98.5%；
Step 2: under the protection of nitrogen, 5.0g (0.02mol) just ground 4,4- diamino being added into 500ml container
Base diphenyl sulphone (DPS) (DDS), 5.9g (0.02mol) intermediate SPDPC, 4.04g triethylamine and 40ml acetonitrile.By above-mentioned reaction vessel with
Thermometer, mechanical agitator, reflux condensing tube and device for absorbing tail gas connect.First under agitation, it first mixes at room temperature
It closes, wherein the revolving speed of agitating paddle is that 240r/min after mixing to system is first warming up to 60 DEG C of reaction 1h, then heats to
80 DEG C until the reaction is complete, i.e., occurs without hydrogen chloride gas.It is evaporated under reduced pressure after reaction by Rotary Evaporators and removes solvent,
Obtained residue is washed, filtered several times with dehydrated alcohol, carries out anti-precipitation purification with dimethyl sulfoxide and methylene chloride, it will
Product after purification is dry to constant weight in 60 DEG C in vacuum drying oven.Pale powder 8.23g is obtained, i.e. aggretion type phosphorus nitrogen expands
Type fire retardant, yield 87.1%, the degree of polymerization are 1092 (being calculated by gel osmoticing chromatogram analysis).
The aggretion type phosphorus nitrogen expansion type combustion inhibitor of above-mentioned preparation is subjected to infrared test, test equipment is that TENSOR 27 is red
External spectrum instrument, German Bruker company.With KBr tabletting, test scope is 400~4000cm for infrared spectrum analysis-1.What is obtained is red
Outer spectrogram such as Fig. 1.
In infrared spectrogram shown in FIG. 1,3446,1633cm–1Place is-NH2Framework characteristic peak, in 2910cm-1And
1510cm–1Place is respectively alkyl-CH2Stretching vibration and-CH stretching vibration characteristic peak, 1516cm-1Place is the spy of C=C
Levy absorption peak；1240cm-1Place is the stretching vibration peak of P=O, 1022cm-1Place is the stretching vibration peak of P-O-C, 1078cm-1Place
It is the stretching vibration peak of P-N, 1600cm-1And 1630cm–1Place is the framework characteristic peak of phenyl ring, 1120cm–1Place is stretching for S=O
Contracting vibration peak,
The aggretion type phosphorus nitrogen expansion type combustion inhibitor of above-mentioned preparation is subjected to nuclear-magnetism1HNMR、31PNMR analysis, test equipment are
FT-80A Nuclear Magnetic Resonance, Varian company, the U.S..Test condition are as follows: TMS is internal standard, d6- DMSO is solvent, 400MHz.It surveys
Test result is as shown in Figure 2 and Figure 3.
Hydrogen in the corresponding-P-NH- of 7.95ppm it can be seen from Fig. 2 nuclear magnetic resonance spectroscopy, 6.81~7.68ppm are phenyl ring
The characteristic peak of upper proton, 4.25ppm correspond to the-CH in spirane structure2Proton in-O-, unimodal at 2.492ppm are solvent
d6-DMSO。
The absorption peak that chemical shift is -6.23ppm it can be seen from Fig. 3 nuclear magnetic resonance phosphorus spectrum is the P elements of PCS sealing end
Absorption peak, chemical shift is the absorption peak that the absorption peak of -4.81ppm is phosphorus in poly- phosphamide main chain.The above spectrum analysis is equal
Demonstrate the smooth synthesis of PCS.
Embodiment 2:
Step 1: under the protection of nitrogen, be added into 500ml container 6.8g (0.05mol) just ground PER,
The POCl that 30.6g (0.20mol) has just distilled3And 0.74g AlCl3, by above-mentioned reaction vessel and thermometer, mechanical agitator, return
Stream condenser pipe and device for absorbing tail gas connect.It first mixes at room temperature, wherein the revolving speed of agitating paddle is 230r/min, to system
After mixing, 75 DEG C are slowly increased to until the reaction is complete, i.e., is occurred without hydrogen chloride gas.Pass through rotary evaporation after reaction
Instrument is distilled to recover extra POCl3Solvent, obtained residue are washed with methylene chloride, filtering, after being repeated several times, in glacial acetic acid
Middle recrystallization, product after recrystallization is dry to constant weight in 120 DEG C in convection oven, obtains white intermediate SPDPC 13.7g,
Yield is 92.3%, purity 98.6%；
Step 2: under the protection of nitrogen, be added into 500ml container 5.7g (0.023mol) just ground DDS,
5.64g (0.019mol) intermediate SPDPC, 4.10g triethylamine and 45ml toluene.By above-mentioned reaction vessel and thermometer, machinery
Blender, reflux condensing tube and device for absorbing tail gas connect.Under agitation, it first mixes at room temperature, wherein agitating paddle
Revolving speed be that 240r/min after mixing to system is first warming up to 60 DEG C of reaction 1h, then heat to 80 DEG C up to having reacted
Entirely, i.e., occur without hydrogen chloride gas.Solvent is distilled off by Rotary Evaporators after reaction, the residue nothing that will be obtained
Water-ethanol washing, filtered several times, carry out anti-precipitation purification with dimethyl sulfoxide and acetone, by the product after purification in vacuum drying oven
In it is dry to constant weight in 60 DEG C.Obtain pale powder 8.52g, i.e. aggretion type phosphorus nitrogen expansion type combustion inhibitor, yield 88.3%,
The degree of polymerization is 997 (being calculated by gel osmoticing chromatogram analysis).
Embodiment 3:
Step 1: under the protection of nitrogen, be added into 500ml container 6.8g (0.05mol) just ground PER,
The POCl that 30.6g (0.20mol) has just distilled3And 0.74g AlCl3.By above-mentioned reaction vessel and thermometer, mechanical agitator, return
Stream condenser pipe and device for absorbing tail gas connect.It first mixes at room temperature, wherein the revolving speed of agitating paddle is 230r/min, to system
After mixing, 60 DEG C are slowly increased to until the reaction is complete, i.e., is occurred without hydrogen chloride gas.Pass through rotary evaporation after reaction
Instrument is distilled to recover extra POCl3Solvent, obtained residue are washed with methylene chloride, filtering, after being repeated several times, in glacial acetic acid
Middle recrystallization, product after recrystallization is dry to constant weight in 120 DEG C in convection oven, obtains white intermediate SPDPC 13.6g,
Yield is 91.6%, purity 98.3%；
Step 2: under the protection of nitrogen, be added into 500ml container 5.0g (0.02mol) just ground DDS,
6.53g (0.022mol) intermediate SPDPC, 3.06g pyridine and 40ml dimethyl sulfoxide.By above-mentioned reaction vessel and thermometer,
Mechanical agitator, reflux condensing tube and device for absorbing tail gas connect.Under agitation, it first mixes at room temperature, wherein stirring
The revolving speed for mixing paddle is that 240r/min after mixing to system is first warming up to 55 DEG C of reaction 1h, then heats to 80 DEG C until anti-
Should occur completely without hydrogen chloride gas.Solvent is distilled off by Rotary Evaporators after reaction, the residue that will be obtained
It is washed with dehydrated alcohol, filtered several times, anti-precipitation purification is carried out with dimethyl sulfoxide and acetonitrile, by the product after purification in vacuum
It is dry to constant weight in 60 DEG C in baking oven.Pale powder 8.83g is obtained, i.e. aggretion type phosphorus nitrogen expansion type combustion inhibitor, yield is
87.9%, the degree of polymerization is 1121 (being calculated by gel osmoticing chromatogram analysis).
Embodiment 4:
Step 1: under the protection of nitrogen, be added into 500ml container 6.8g (0.05mol) just ground PER,
The POCl that 30.6g (0.12mol) has just distilled3And 0.71g AlCl3.By above-mentioned reaction vessel and thermometer, mechanical agitator, return
Stream condenser pipe and device for absorbing tail gas connect.It first mixes at room temperature, wherein the revolving speed of agitating paddle is 230r/min, to system
After mixing, 70 DEG C are slowly increased to until the reaction is complete, i.e., is occurred without hydrogen chloride gas.Pass through rotary evaporation after reaction
Instrument is distilled to recover extra POCl3Solvent, obtained residue are washed with methylene chloride, filtering, after being repeated several times, in glacial acetic acid
Middle recrystallization, product after recrystallization is dry to constant weight in 110 DEG C in convection oven, obtains white intermediate SPDPC 12.8g,
Yield is 86.1%, purity 98.6%；
Step 2: under the protection of nitrogen, be added into 500ml container 5.0g (0.02mol) just ground DDS,
6.53g (0.025mol) intermediate SPDPC, 3.09g pyridine and 40ml tetrahydrofuran.By above-mentioned reaction vessel and thermometer, machine
Tool blender, reflux condensing tube and device for absorbing tail gas connect.Under agitation, it first mixes at room temperature, wherein stirring
The revolving speed of paddle is that 240r/min after mixing to system is first warming up to 45 DEG C of reaction 1h, then heats to 65 DEG C until reaction
Completely, i.e., occur without hydrogen chloride gas.Solvent is distilled off by Rotary Evaporators after reaction, obtained residue is used
Dehydrated alcohol washing, filtered several times, carry out anti-precipitation purification with dimethyl sulfoxide and chloroform, by the product after purification true
It is dry to constant weight in 60 DEG C in empty baking oven.Pale powder 8.71g is obtained, i.e. aggretion type phosphorus nitrogen expansion type combustion inhibitor, yield is
86.7%, the degree of polymerization is 1048 (being calculated by gel osmoticing chromatogram analysis).
Embodiment 5:
Step 1: under the protection of nitrogen, be added into 500ml container 6.8g (0.05mol) just ground PER,
The POCl that 23.1g (0.15mol) has just distilled3And 0.72g AlCl3.By above-mentioned reaction vessel and thermometer, mechanical agitator, return
Stream condenser pipe and device for absorbing tail gas connect.It first mixes at room temperature, wherein the revolving speed of agitating paddle is 230r/min, to system
After mixing, 50 DEG C are slowly increased to until the reaction is complete, i.e., is occurred without hydrogen chloride gas.Pass through rotary evaporation after reaction
Instrument is distilled to recover extra POCl3Solvent, obtained residue are washed with methylene chloride, filtering, after being repeated several times, in glacial acetic acid
Middle recrystallization, product after recrystallization is dry to constant weight in 120 DEG C in convection oven, obtains white intermediate SPDPC 13.9g,
Yield is 93.6%, purity 97.9%；
Step 2: under the protection of nitrogen, be added into 500ml container 5.0g (0.02mol) just ground DDS,
6.53g (0.025mol) intermediate SPDPC, 4.32g N, N- diisopropylethylamine and 50ml dioxane.Above-mentioned reaction is held
Device is connected with thermometer, mechanical agitator, reflux condensing tube and device for absorbing tail gas.Under agitation, first at room temperature
Mixing, wherein the revolving speed of agitating paddle is that 240r/min after mixing to system is first warming up to 60 DEG C of reaction 1h, then heats up
Until the reaction is complete to 90 DEG C, i.e., occur without hydrogen chloride gas.Solvent is distilled off by Rotary Evaporators after reaction, it will
Obtained residue washs with dehydrated alcohol, filtered several times, anti-precipitation purification is carried out with dimethyl sulfoxide and acetonitrile, after purification
Product it is dry to constant weight in 65 DEG C in vacuum drying oven.Pale powder 9.02g is obtained, i.e. aggretion type phosphorus nitrogen expansion type is fire-retardant
Agent, yield 89.7%, the degree of polymerization are 1102 (being calculated by gel osmoticing chromatogram analysis).
Embodiment 6:
Step 1: under the protection of nitrogen, be added into 500ml container 6.8g (0.05mol) just ground PER,
The POCl that 23.1g (0.20mol) has just distilled3And 0.75g AlCl3.By above-mentioned reaction vessel and thermometer, mechanical agitator, return
Stream condenser pipe and device for absorbing tail gas connect.It first mixes at room temperature, wherein the revolving speed of agitating paddle is 230r/min, to system
After mixing, 60 DEG C are slowly increased to until the reaction is complete, i.e., is occurred without hydrogen chloride gas.Pass through rotary evaporation after reaction
Instrument is distilled to recover extra POCl3Solvent, obtained residue are washed with methylene chloride, filtering, after being repeated several times, in glacial acetic acid
Middle recrystallization, product after recrystallization is dry to constant weight in 120 DEG C in convection oven, obtains white intermediate SPDPC 13.7g,
Yield is 92.7%, purity 98.9%；
Step 2: under the protection of nitrogen, be added into 500ml container 5.2g (0.021mol) just ground DDS,
6.53g (0.025mol) intermediate SPDPC, 3.91g N, N- diisopropylethylamine and 50ml N,N-dimethylformamide.It will be upper
Reaction vessel is stated to connect with thermometer, mechanical agitator, reflux condensing tube and device for absorbing tail gas.Under agitation, first
It mixes at room temperature, wherein the revolving speed of agitating paddle is that 240r/min after mixing to system is first warming up to 65 DEG C of reaction 1h,
It then heats to 80 DEG C until the reaction is complete, i.e., occurs without hydrogen chloride gas.It is removed after reaction by Rotary Evaporators distillation
Solvent is removed, obtained residue is washed with dehydrated alcohol, filtered several times, anti-precipitating is carried out with dimethyl sulfoxide and acetone and mentions
It is pure, the product after purification is dry to constant weight in 70 DEG C in vacuum drying oven.Obtain pale powder 9.08g, i.e. aggretion type phosphorus
Nitrogen expansion type combustion inhibitor, yield 89.0%, the degree of polymerization are 1073 (being calculated by gel osmoticing chromatogram analysis).
Claims (10)
1. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization, it is characterised in that: specific step is as follows:
Step 1: under an inert atmosphere, by phosphorus oxychloride, pentaerythrite and catalyst AlCl under room temperature3Uniformly mixing, is heated up to
40~80 DEG C；Until the reaction is complete, i.e., occur without hydrogen chloride gas；Extra phosphorus oxychloride is recycled by vacuum distillation again, is obtained
To two phosphoryl chloride phosphorus oxychloride of crude intermediate pentaerythrite diphosphate ester；By SPDPC crude product through filtering and washing, recrystallization and drying, height is obtained
Purity；The phosphorus oxychloride and the molar ratio of pentaerythrite are 3:1~6:1；The AlCl3Molar ratio with pentaerythrite is
0.03:1~0.07:1；
Step 2: under an inert atmosphere, SPDPC, 4,4'- diaminodiphenylsulfone and the acid binding agent of the high-purity that step 1 is obtained
It is added in organic solvent, after being uniformly mixed, temperature reaction in two stages；It is reacted first from room temperature to 40~50 DEG C
Then 1~4h is warming up to 60~80 DEG C until the reaction is complete again, i.e., occur without hydrogen chloride gas；It is removed by vacuum distillation more
Remaining organic solvent obtains poly- (4,4'- diaminodiphenylsulfone loop coil pentaerythrite bisphosphonates) expansion type flame retardant crude product；Slightly
Product obtain high aggretion type phosphorus nitrogen expanding fire retardant after multiple filtering and washing, anti-precipitation purification and drying；The 4,4'- diamino
The molar ratio of base diphenyl sulphone (DPS) and pentaerythrite is 0.5:1~1.5:1；Mole of the acid binding agent and 4,4' diaminodiphenyl sulfone
Than for 1:1~2.5:1.
2. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as described in claim 1, feature
Be: the high aggretion type phosphorus nitrogen expanding fire retardant structural formula is as follows:
Wherein n is the integer between 100~1200.
3. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as described in claim 1, feature
Be: the molar ratio of phosphorus oxychloride and pentaerythrite in the step 1 is 3.5:1~4.5:1；Urging in the step 1
Agent AlCl3Molar ratio with pentaerythrite is 0.05:1~0.06:1；The 4,4'- diamino hexichol being added in the step 2
The molar ratio of sulfone and pentaerythrite is 1:1~1.2:1；Acid binding agent and 4,4' diaminodiphenyl sulfone in the step 2 rub
You are than being 1.5:1~2:1.
4. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as described in claim 1, feature
Be: in the step 1 be used to wash two phosphoryl chloride phosphorus oxychloride of intermediate pentaerythrite diphosphate ester solvent be methylene chloride, chloroform,
One of carbon tetrachloride, ether, acetone, methanol, ethyl alcohol, water, petroleum ether, n-hexane or a variety of mixtures.
5. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as claimed in claim 1 or 3, special
Sign is: the acid binding agent being added in the step 2 is triethylamine, pyridine, piperidines, N, N- diisopropylethylamine, 4- dimethylamino
Pyridine, anhydrous aluminum chloride, anhydrous magnesium chloride, potassium phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, carbon
One of potassium hydrogen phthalate or a variety of mixtures.
6. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as claimed in claim 1 or 3, special
Sign is: the organic solvent in the step 2 is 1-Methyl-2-Pyrrolidone, N,N-dimethylformamide, N, N- dimethyl
Acetamide, dimethyl sulfoxide, tetrahydrofuran, butanone, ethyl acetate, chloroform, dioxane, acetonitrile, in benzene,toluene,xylene
One or more mixtures.
7. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as claimed in claim 6, feature
Be: the mass ratio of two phosphoryl chloride phosphorus oxychloride of organic solvent and intermediate pentaerythrite diphosphate ester in the step 2 is 7:1~25:
1。
8. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as claimed in claim 6, feature
Be: the mass ratio of two phosphoryl chloride phosphorus oxychloride of organic solvent and intermediate pentaerythrite diphosphate ester in the step 2 be 11:1~
17:1.
9. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as claimed in claim 4, feature
Be: the solvent is methylene chloride.
10. a kind of method for improving aggretion type phosphorus nitrogen expanding fire retardant yield and the degree of polymerization as claimed in claim 5, feature
Be: the acid binding agent is triethylamine.
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| CN107457865B (en) * | 2017-09-19 | 2019-03-15 | 阜南县金威工艺品有限公司 | A kind of flame-proof treatment method of willow-plaited process product |
| CN109306188B (en) * | 2018-08-23 | 2021-09-03 | 李龙德 | Protective material for lithium battery pack of new energy automobile and preparation method of protective material |
| CN109096493A (en) * | 2018-08-24 | 2018-12-28 | 北京理工大学 | A kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof |
| CN109096492A (en) * | 2018-08-24 | 2018-12-28 | 北京理工大学 | A kind of aggretion type expanding fire retardant and preparation method |
| CN112409601B (en) * | 2020-11-25 | 2022-03-11 | 清远市普塞呋磷化学有限公司 | Low-halogen high-polymerization-degree phosphate flame retardant and preparation method thereof |
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