CN107459673A - A kind of synthetic method of the fire-retardant carbon forming agent of ethylenediamine phosphorus borate - Google Patents
A kind of synthetic method of the fire-retardant carbon forming agent of ethylenediamine phosphorus borate Download PDFInfo
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- CN107459673A CN107459673A CN201710579268.9A CN201710579268A CN107459673A CN 107459673 A CN107459673 A CN 107459673A CN 201710579268 A CN201710579268 A CN 201710579268A CN 107459673 A CN107459673 A CN 107459673A
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- forming agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
A kind of synthetic method of ethylenediamine phosphorus borate, is related to a kind of fire retardant and preparation method thereof, and this method is Ethylene diamine phosphate and boric acid Hybrid Heating solid phase reaction, you can obtains fire retardant.Obtained fire retardant is phosphorous, three kinds of boron, nitrogen ignition-proof elements, and good into carbon, flame retardant effect is notable, and the boron element contained may also function as suppression cigarette effect, can be used for the carbon forming agent of TPO flame-retardant formulations, can also be used alone as fire retardant to use.Preparation method is simple, and three wastes produce, environmental protection.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of application of fire-retardant carbon forming agent of ethylenediamine phosphorus borate and synthesis side
Method.
Background technology
Expansion type flame retardant is generally made up of inorganic acid source, carbon source (also known as carbon forming agent) and source of the gas (also known as foaming agent).
In commercially available prod, lack the single substance for being provided simultaneously with three of the above function, therefore the addition of fire retardant can only be increased, so as to
Ensure that between each component more preferable mixing can be reached, to reach flame-retardancy requirements.Otherwise for different high polymer materials,
It is also required to adjust the composition and ratio of acid source, carbon source and source of the gas, so as to meet the different flame-retardancy requirements of unlike material.In view of height
The heat resistance of molecule and fire retardant in itself, in process, fire retardant each group is reached by prolonged melting mixing
Point be sufficiently mixed is irrealizable under normal circumstances.The commercially available product that can maintain high-temperature stability the long period is not
It is very common, for example, the bipentaerythrite of Cyanuramide Quadrafos (MPP) and high decomposition temperature can provide preferably it is fire-retardant
Ensure, but need to add higher addition.
In recent years, the phosphate of some organic amines, such as piperazine phosphate, piperazine pyrophosphate, Ethylene diamine phosphate
(EDAP) it is interested to researchers, it is based primarily upon the easy and cost cheap of manufacturing process.Such as Chinese mugwort Dicon A/S of Japan
(Adeka) piperazine pyrophosphate of exploitation, can be used cooperatively with melamine pyrophosphate, in polyolefin flame-retardant, it is only necessary to
25-30% addition can reaches V-0 standards, while the shortcomings that overcome APP system poor water resistance.But with regard to mesh
For preceding manufacturing process, the synthesis of piperazine pyrophosphate is complicated, low yield.South Korea struggles against this Co., Ltd. in Chinese patent
A series of salt of phosphoric acid are disclosed in 201180067852.7 to reduce cost and simplify manufacturing process, such as utilize piperazine, Mg2+
Piperazine phosphate magnesium double salt can be obtained with high yield under certain condition with phosphate anion.Ethylene diamine phosphate (EDAP) is cheap
The fire retardant being easy to get, expansion character are excellent.But due to poor heat resistance and poor water resistance the two shortcomings, EDAP is limited in polyene
Application in hydrocarbon.US0109514 reports has obtained second two using sodium pyrophosphate solution and ethylenediamine salt progress metathesis reaction
Amine pyrophosphate.US2002038855, CN 1599772 reports the imines such as ethylenediamine, diethylenetriamine and paraformaldehyde, gathered
The compound that phosphoric acid obtains in water has good heat resistance, is heated 10 minutes under 250 degree and does not have obvious Mass lost,
But water miscible problem is still than more prominent.It is similar to metal ion piperazine phosphate double salt thinking,《Plastic additive》
2013pp26, CN201310588575.5 then report the ethylenediamine trbasic zinc phosphate double salt fire retardant for polyolefin flame-retardant.
Phosphorus borate is that the field, Zhao Aiming et al. for enjoying researcher to pay close attention in flame retardant area in recent years reports phosphorus
The synthesis of sour melamine borate salt fire retardant.CN 102482452A disclose borophosphate, boric acid phosphate and metal boron phosphorus
Hydrochlorate is used as the method for flame retardant of plastic additive.Bastian Ewald et al. systematic review boron phosphoric acid in journal of writings
The structural chemistry of salt, metal boron phosphate, but the research of the compound of fire retardant is suitable as in hundreds of borophosphate still
Without system report.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate and its application.This
The fire-retardant carbon forming agent of ethylenediamine phosphorus borate prepared by method solves traditional carbon forming agent by introducing borate bridging phosphate radical
EDAP is not water-fast, the shortcomings that non-refractory, overcomes fire retardant and easily migrates in the polymer, easily separated out in process
Feature, there is excellent durability.Preparation method is simple, and condition is easily realized, three wastes, environmental protection.
The present invention is achieved by the following technical solutions：
A kind of fire-retardant carbon forming agent of ethylenediamine phosphorus borate, it is characterised in that the chemical formula of the fire-retardant carbon forming agent is：
[NH3CH2CH2NH3]2[B2P4O15], NH in formula3CH2CH2NH3For the ion of ethylenediamine protonation；As before narrated, phosphorus
Borate is more acid groups of a major class, and the Nomenclature Composition and Structure of Complexes is all sufficiently complex.B2P4O15 4-And one kind therein, the actually acid
Root is a polymeric anion.
A kind of synthetic method of the fire-retardant carbon forming agent of ethylenediamine phosphorus borate, this method comprise the following steps：By ethylenediamine phosphorus
After hydrochlorate EDAP, boric acid are well mixed with silicone oil, the solid phase reaction 1-6 hours at 150-270 DEG C, discharging i.e. obtain this it is fire-retardant into
Carbon agent；
Described Ethylene diamine phosphate EDAP, commercially available EDAP can be both used, can also be led in water or organic solvent
It is prepared by peroxophosphoric acid, ethylenediamine neutralization reaction.
A kind of synthetic method of described fire-retardant carbon forming agent of ethylenediamine phosphorus borate, Ethylene diamine phosphate EDAP and boric acid
Mol ratio is 1:0.8-1:1.3；The quality of silicone oil and Ethylene diamine phosphate is 0.2-5%.Wherein solid phase reactor can be henry
She Er blenders, rake type dryer, double cone dryer, hot air drier, vacuum drying chamber, kneader, screw extruder, banburying
Machine；The solid phase reaction 1-6 hours at 100-250 DEG C, discharging obtain the fire-retardant carbon forming agent.
Preferably, the mol ratio of Ethylene diamine phosphate EDAP and boric acid is that mol ratio is 1:0.93-1:1.1；
Preferably, the mass ratio of silicone oil and Ethylene diamine phosphate is 0.5-2.5%；
Preferably, solid phase reaction device is in rake type dryer, kneader and banbury；The wherein temperature of solid phase reaction,
Preferably, it is 180-220 DEG C.
The present invention has advantages below：
(1) raw material is easy to get.The raw material that the invention uses are commercially available prod, wide material sources.
(2) simple production process, environmental protection.Target product is can obtain by simply mixing and then heating；Production process
In only a small amount of moisture content produce.
(3) thermal stability of product is good, carbon yield is high.5% decomposition temperature of sample is 332 DEG C, and maximum decomposes speed
Carbon yield when temperature at rate is 410 DEG C, 800 DEG C is 53%.High decomposition temperature can be used in most high score
In subtree fat.
Brief description of the drawings
Influence of the reaction temperature to product thing phase in Fig. 1 embodiments 1.
The thermostabilization curve of the product of Fig. 2 embodiments 5.
Embodiment
With reference to embodiment, the present invention is described in detail：
Embodiment 1
Commercially available EDAP (Ethylene diamine phosphate) 1.28Kg is taken, is placed on 310g boric acid in 5L kneaders, stirring at normal temperature is mixed
After closing 30min, add 15g methyl phenyl silicone oils and continue to stir 30min, be warming up to 190 DEG C of reaction 3hr, discharging, obtain fire retardant
Product.
In order to further study the influence of reaction temperature, at a temperature of have studied differential responses respectively, the generation situation of product,
The thing phase of product has been tracked using x-ray powder diffraction technique.It was found that when reaction temperature is more than more than 190 DEG C, target is obtained
Product (accompanying drawing 1).210 DEG C of reaction products are taken to carry out THERMAL STABILITY discovery, 5% decomposition temperature is 332 DEG C of maximum decomposition speed
Carbon yield when temperature at rate is 410 DEG C, 800 DEG C is 53%.
Embodiment 2
Commercially available EDAP 1.28Kg are taken, are placed on 310g boric acid in 5L kneaders, after stirring at normal temperature mixing 30min, are added
15g methyl phenyl silicone oils continue to stir 30min, are passed through nitrogen, are warming up to 190 DEG C of reaction 3hr, discharging, obtain flame retardant products.
Embodiment 3
EDAP is prepared as steps described below：In the reactor with mechanical agitator, cooling device and condensation reflux unit
Middle addition 10L acetic acid, then slowly imports the phosphoric acid of 2.6Kg 85%, and stirring at normal temperature is cooled to 0 DEG C after 1 hour.Take 600g second two
Amine, it is dissolved in 2.5L methanol.Ethylenediamine methanol solution is slowly added dropwise in the acetum of phosphoric acid, it is a large amount of heavy to be instantly obtained
Form sediment.Reaction temperature is kept to be no more than 10 DEG C.After dripping off ethylenediamine methanol solution, continue stirring reaction 3 hours, filtering, use methanol
Washing precipitation.80 DEG C of dryings 12 hours.EDAP product yields 92%.
Homemade EDAP 1.22Kg are taken, are placed on 330g boric acid in rake type dryer, after stirring at normal temperature mixing 30min,
Add 20g methyl phenyl silicone oils to continue to stir 30min, be warming up to 180 DEG C of reaction 2hr, discharging, obtain flame retardant products.
Embodiment 4
EDAP 1.30Kg, 300g boric acid, 20g methyl phenyl silicone oils are taken, is sufficiently mixed in high mixer uniformly, Ran Houfang
Put in hot air drier, after stirring at normal temperature mixing 30min, be warming up to 230 DEG C of reaction 4hr, discharging, obtain flame retardant products.
Embodiment 5
System (method is with embodiment 2) EDAP 1.25Kg are derived from, are placed on 310g boric acid in banbury, stirring at normal temperature is mixed
After closing 30min, add 40g methyl phenyl silicone oils and continue to stir 30min, be warming up to 210 DEG C of reaction 3hr, discharging, obtain fire retardant
Product.
Flammability test：By taking PP systems as an example, according to general processing method, formula 1-4 model is tested respectively
Fire resistance, it is as a result as shown in the table：
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited
In specific details and shown here as the example with description.
Claims (7)
1. a kind of ethylenediamine phosphorus borate compound, it is characterised in that the compound is used for fire-retardant carbon forming agent, the fire-retardant carbon forming agent
Chemical formula be：[NH3CH2CH2NH3]2[B2P4O15], NH in formula3CH2CH2NH3For the ion of ethylenediamine protonation.
2. the synthetic method of a kind of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 1, it is characterised in that should
Method comprises the following steps：
(1) Ethylene diamine phosphate EDAP, boric acid and silicone oil are well mixed；
(2) it is heated to 150-270 DEG C, keeping temperature, solid phase reaction 1-6 hours；
(3) discharging obtains the fire-retardant carbon forming agent.
A kind of 3. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 2, it is characterised in that second
The mol ratio of two amine phosphate EDAP and boric acid is 1:0.8-1:1.3.
A kind of 4. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 2, it is characterised in that Gu
Phase reaction device is Henschel blender, rake type dryer, double cone dryer, hot air drier, vacuum drying chamber, kneader, spiral shell
One of bar extruder, banbury.
A kind of 5. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 2, it is characterised in that Gu
The temperature of phase reaction is 150-270 DEG C.
A kind of 6. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 2, it is characterised in that institute
The silicone oil used is methyl phenyl silicone oil, and the mass ratio of silicone oil and Ethylene diamine phosphate is 0.2-5%.
A kind of 7. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 3-6, it is characterised in that
The mol ratio of Ethylene diamine phosphate EDAP and boric acid is 1:0.93-1:1.1；Solid phase reaction device is rake type dryer, kneader
And screw extruder；The temperature of solid phase reaction is 180-220 DEG C；The mass ratio of silicone oil and Ethylene diamine phosphate is 0.5-2.5%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710579268.9A CN107459673A (en) | 2017-07-17 | 2017-07-17 | A kind of synthetic method of the fire-retardant carbon forming agent of ethylenediamine phosphorus borate |
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| CN201710579268.9A CN107459673A (en) | 2017-07-17 | 2017-07-17 | A kind of synthetic method of the fire-retardant carbon forming agent of ethylenediamine phosphorus borate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285626A (en) * | 2018-02-07 | 2018-07-17 | 缪琼 | A kind of polylactic acid fire proofing preparation method and application |
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| CN101693836A (en) * | 2009-10-21 | 2010-04-14 | 苏州科技学院 | Expanding type fire retardant containing boron |
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| CN102482452A (en) * | 2009-07-02 | 2012-05-30 | 巴斯夫欧洲公司 | Borophosphate, borate phosphate, and metal borophosphate as novel flame proofing additives for plastics |
| CN103265752A (en) * | 2013-06-04 | 2013-08-28 | 广东聚石化学股份有限公司 | Halogen-free flame retardant thermoplastic polyolefin cable material |
| CN104710622A (en) * | 2010-12-02 | 2015-06-17 | 陶氏环球技术有限责任公司 | Intumescent halogen-free Si-P-N-based polymer fire retardants |
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2017
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| CN102482452A (en) * | 2009-07-02 | 2012-05-30 | 巴斯夫欧洲公司 | Borophosphate, borate phosphate, and metal borophosphate as novel flame proofing additives for plastics |
| CN101693836A (en) * | 2009-10-21 | 2010-04-14 | 苏州科技学院 | Expanding type fire retardant containing boron |
| CN101781571A (en) * | 2009-12-18 | 2010-07-21 | 苏州科技学院 | Complex intumescent flame retardant |
| CN104710622A (en) * | 2010-12-02 | 2015-06-17 | 陶氏环球技术有限责任公司 | Intumescent halogen-free Si-P-N-based polymer fire retardants |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285626A (en) * | 2018-02-07 | 2018-07-17 | 缪琼 | A kind of polylactic acid fire proofing preparation method and application |
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