CN101289465B - Method for preparing bis(pentaerythritol phosphate) melamine ammonium phosphate - Google Patents
Method for preparing bis(pentaerythritol phosphate) melamine ammonium phosphate Download PDFInfo
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- CN101289465B CN101289465B CN2007101044098A CN200710104409A CN101289465B CN 101289465 B CN101289465 B CN 101289465B CN 2007101044098 A CN2007101044098 A CN 2007101044098A CN 200710104409 A CN200710104409 A CN 200710104409A CN 101289465 B CN101289465 B CN 101289465B
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- phosphoric acid
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- pentaerythritol ester
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Abstract
一种制备双(磷酸季戊四醇酯)磷酸三聚氰铵盐的方法，首先在挤压机中混合季戊四醇与五氧化二磷进行酯化反应生成双(磷酸季戊四醇酯)磷酸；接着，于溶剂存在的条件下混合双(磷酸季戊四醇酯)磷酸与三聚氰胺或其衍生物进行铵盐化反应，最后去除水分获得双(磷酸季戊四醇酯)磷酸三聚氰铵盐。该方法使用五氧化二磷作为原料，不会产生氯化氢废气，亦不需回收三氯磷酸，且该方法可在不需要使用有机溶剂的条件下进行酯化反应，能够缩短酯化反应所需时间，避免在密闭反应体系中产生高压而发生爆炸的危险。A method for preparing bis(pentaerythritol phosphate) melamine phosphate salt comprises the following steps: firstly, pentaerythritol and phosphorus pentoxide are mixed in an extruder to carry out an esterification reaction to generate bis(pentaerythritol phosphate) phosphoric acid; then, bis(pentaerythritol phosphate) phosphoric acid is mixed with melamine or its derivative in the presence of a solvent to carry out an ammonium salt reaction; and finally, water is removed to obtain bis(pentaerythritol phosphate) melamine phosphate salt. The method uses phosphorus pentoxide as a raw material, does not generate hydrogen chloride waste gas, does not need to recover trichlorophosphoric acid, and can carry out an esterification reaction without using an organic solvent, can shorten the time required for the esterification reaction, and avoids the risk of explosion caused by high pressure in a closed reaction system.
Description
Technical field
The present invention relates to the method for two (phosphoric acid pentaerythritol ester) the tricresyl phosphate paracyanogen ammonium salts of a kind of preparation, particularly relevant for a kind of method of utilizing tetramethylolmethane and Vanadium Pentoxide in FLAKES to carry out two (phosphoric acid pentaerythritol ester) the tricresyl phosphate paracyanogen ammonium salts of esterification preparation.
Background technology
Two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salt has ring texture, show that in thermogravimetric analysis and differential thermal analysis excellent thermostability is fixed, being used for polyolefine, polyurethane, polyphenylene oxide (PPO), polymethacrylate (PMMA), polyester, reaching the effect that polybutylene terephthalate (PBT) all has the difficult combustion of lifting characteristic, is a kind of expanded polystyrene veneer phosphate ester melamine salt based flame retardant.
The U.S. the 4th, 154, No. 930 patent discloses a kind of phosphoric acid amido as the polymkeric substance incombustible agent-s-triazine salt (amino-s-triazine salt of phosphoric acid).The U.S. the 4th, 478, No. 998 patents then disclose the synthetic method of two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts, and this method utilizes trimeric cyanamide to obtain the melamine ammonium salt with the chloride thing reaction of two (phosphoric acid pentaerythritol ester) phosphoric acid.The method that this part patent is disclosed is to use phosphoryl chloride (POC13) as reactant feed, can generate hydrogen chloride emission in the reaction process, in and can produce a large amount of waste water in the process of hydrogen chloride emission.On the other hand, because the resin viscosity in this reaction is big, must use the excessive phosphorus chloride of high molar ratio to react.Therefore, reclaim another shortcoming that the phosphoryl chloride waste liquid also becomes this method.
The U.S. the 6th, 737, No. 526 patent discloses another kind of method of synthesizing two (phosphoric acid pentaerythritol ester) the tricresyl phosphate paracyanogen ammonium salts of preparation with the mechanochemistry of ball mill grinding with Vanadium Pentoxide in FLAKES replacement phosphoryl chloride and tetramethylolmethane.Yet Vanadium Pentoxide in FLAKES has hyperergy, reacts easily with hydrate generation phosphoric acid, or with other reactant and generates metaphosphoric acid or react the generation phosphoric acid ester with ether compound, makes choosing of reaction solvent be subjected to considerable restriction.On the other hand, this preparation process be in enclosed system with an organic solvent as medium, and can produce water in the reaction process, cause enclosed system pressure to raise, be easy to generate the doubt on the safety.Moreover the tetramethylolmethane viscosity of molten state is high, is difficult for stirring, thereby needs the long reaction times.
Therefore, still need simply a kind of and the method for two (phosphoric acid pentaerythritol ester) the tricresyl phosphate paracyanogen ammonium salts of preparation safely.
Summary of the invention
Main purpose of the present invention is to provide a kind of preparation method that can not produce two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts of hydrogen chloride emission.
Another object of the present invention is to provide a kind of preparation method that can shorten two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts of reaction time of esterification.
Another purpose of the present invention is to provide a kind of preparation method that can improve two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts of reaction system security.
For reaching above-mentioned and other purpose, the invention provides the method for two (phosphoric acid pentaerythritol ester) the tricresyl phosphate paracyanogen ammonium salts of a kind of preparation, this method comprises esterification, is to mix tetramethylolmethane and two (phosphoric acid pentaerythritol ester) phosphoric acid of Vanadium Pentoxide in FLAKES reaction generation in extrusion machine; And the ammonium salt reaction, be under the condition that solvent exists, to mix two (phosphoric acid pentaerythritol ester) phosphoric acid and the trimeric cyanamide or derivatives thereof that esterification generated to react, obtain two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts behind the removal moisture.Method of the present invention is to use Vanadium Pentoxide in FLAKES as raw material, can not produce hydrogen chloride emission, also need not reclaim trichlorine phosphoric acid, and this method can be carried out esterification under the condition that does not need with an organic solvent, can shorten the esterification required time, avoid in the confined reaction system producing high pressure and the danger of blasting.
Embodiment
The method that the present invention prepares two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts comprises the esterification of step (a), this reaction is to carry out esterification with tetramethylolmethane and Vanadium Pentoxide in FLAKES as reactant, generates two (phosphoric acid pentaerythritol ester) phosphoric acid (b-PEPAP); And the ammonium salt reaction of step (b), this reaction is prepared two (phosphoric acid pentaerythritol ester) phosphoric acid of the esterification of mixing step in solvent (a) and trimeric cyanamide or derivatives thereof, remove moisture at last and obtain two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts (b-PEPAP MEL), reaction is shown in following formula I:
In the method for the present invention, the esterification of step (a) is to carry out in extrusion machine.The kind of extrusion machine can be divided into single-screw extrusion machine and twin-screw extruder according to profile, and its primary structure comprises propulsion source, charging, extruding, heating muff, discharging, and control etc. partly.Extrusion machine mainly utilizes external force that material is flowed in special container and reaches functions such as in various degree mixing, rubbing, shearing, heating.In a specific examples, the esterification of this step (a) is to carry out in twin-screw extruder, and carries out the esterification yield detection in the discharge port of extrusion machine.
This step (a) is to carry out esterification with tetramethylolmethane and Vanadium Pentoxide in FLAKES as reactant to generate two (phosphoric acid pentaerythritol ester) phosphoric acid, and this esterification is shown in following formula (II):
3/4P
4O
10+2C
5H
12O
4→C
10H
17P
3O
12+7/2H
2O (II)。
This tetramethylolmethane and Vanadium Pentoxide in FLAKES reactant feed are to be fed to this twin-screw extruder with predetermined proportion and speed.In the esterification of step (a), the raw materials components mole ratio of reactant is for the esterification yield that generates two (phosphoric acid pentaerythritol ester) phosphoric acid and do not make significant difference.Yet the charge ratio regular meeting of this tetramethylolmethane and Vanadium Pentoxide in FLAKES influences the ratio of melamine phosphate, and changes the characteristic of final product, and the tetramethylolmethane ratio can cause carbon source to make flame retardant resistance descend very little and problem such as product thermostability variation not at that time.Therefore in the esterification of step (a), this tetramethylolmethane and Vanadium Pentoxide in FLAKES are fed to this twin-screw extruder with the ratio of mol ratio 1:0.5 to 3 and carry out esterification; Preferred this tetramethylolmethane and Vanadium Pentoxide in FLAKES are fed to this twin-screw extruder with the ratio of mol ratio 1:0.75 to 1.33 and carry out esterification; More preferably this tetramethylolmethane and Vanadium Pentoxide in FLAKES are fed to this twin-screw extruder with the ratio of mol ratio 1:1 and carry out esterification.Input speed is then looked screw speed and is changed, and input speed can cause raw material to block at opening for feed too soon, then causes raw material can't fill up the material pipe too slowly easily, causes the raw material mixing residence time uneven and in the material pipe oversize.Therefore input speed is generally in 20 to 50 kilograms/hour the scope.
In the esterification of this step (a), by adjusting each operational condition, for example sleeve temperature and screw speed can obtain preferable esterification yield; Wherein, temperature is the important factor that influences esterification yield.The sleeve temperature that increases extrusion machine helps to improve esterification yield, yet, when surpassing 200 ℃, temperature can cause esterification products to deceive carbonization.In the inventive method, in order to the extrusion machine sleeve temperature of the esterification of carrying out the inventive method step (a) preferably in 30 to 200 ℃ scope, more preferably in 50 to 140 ℃ scope.Moreover the screw speed of extrusion machine also can influence the esterification yield of esterification.The slow speed of revolution helps to increase the residence time of reactant feed in screw rod, yet low screw speed also can cause shearing force (shear stree) to reduce, and is unfavorable for promoting esterification yield.On the other hand, if screw speed is too high, the residence time deficiency of reactant feed in screw rod also can cause esterification yield to promote.In the inventive method, in order to the extruder screw rotating speed of the esterification of carrying out the inventive method step (a) preferably 10 to 300min
-1Scope in, more preferably 50 to 200min
-1Scope in.Generally speaking, reactant feed in screw rod the residence time preferably at 0.5 minute to 4.5 minutes, more preferably at 1 minute to 4 minutes, particularly preferably in 1.5 minutes to 3.5 minutes.
The ammonium salt reaction of the inventive method step (b) is prepared two (phosphoric acid pentaerythritol ester) phosphoric acid of the esterification of mixing step (a) under the condition that solvent exists and trimeric cyanamide or derivatives thereof, for example benzoguanamine.In the ammonium salt reaction of this step (b), the addition of this trimeric cyanamide or derivatives thereof benzoguanamine is preferably two times of the employed tetramethylolmethane mole number of step (a).This step (b) can make water as solvent, will two (phosphoric acid pentaerythritol ester) phosphoric acid, trimeric cyanamide or benzoguanamine, and solvent place reactor, under agitation condition, be warming up to 30 to 90 ℃ and carry out the ammonium salt reaction, preferably under 70 to 90 ℃ condition, react.Then, removal moisture is filtered in cooling, can obtain two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts after the oven dry.
Below further specify characteristics of the present invention and effect by particular specific embodiment, but non-ly be used to limit category of the present invention.
Embodiment 1
Vanadium Pentoxide in FLAKES (P
2O
5) be fed to twin-screw extruder with tetramethylolmethane (PE) with the mol ratio of 1:1, and in 100min
-1Screw speed and 30 to 200 ℃ sleeve temperature range in carry out esterification, obtain two (phosphoric acid pentaerythritol ester) phosphoric acid ester.Discharge port sampling in extrusion machine utilizes
31The P-NMR collection of illustrative plates calculates esterification yield, and the result is embedded in table 1.
Get two (phosphoric acid pentaerythritol ester) phosphoric acid ester of 122.4 grams, the trimeric cyanamide of 111 grams and the pure water of 500 grams and place 1000 milliliters flask.Stirring is warming up to 90 ℃ and reacts, and lasts 30 minutes.Then, be cooled to 25 ℃, filter and remove redundant moisture, oven dry obtains two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts.
Embodiment 2-3
Repeat the step of embodiment 1, according to the screw speed of the listed adjustment of table 1 in order to the twin-screw extruder that carries out esterification.Discharge port sampling in extrusion machine utilizes
31The P-NMR collection of illustrative plates calculates esterification yield, and the result is embedded in table 1.
Embodiment 4
Repeat the step of embodiment 1, according to the sleeve temperature of the listed adjustment of table 1 in order to the twin-screw extruder that carries out esterification.Discharge port sampling in extrusion machine utilizes
31The P-NMR collection of illustrative plates calculates esterification yield, and the result is embedded in table 1.
Embodiment 5-6
Repeat the step of embodiment 1, according to the charge ratio of listed adjustment Vanadium Pentoxide in FLAKES of table 1 and tetramethylolmethane.Discharge port sampling in extrusion machine utilizes the 31P-NMR collection of illustrative plates to calculate esterification yield, and the result is embedded in table 1.
Comparative example 1
Repeat the step of embodiment 1, according to the sleeve temperature of the listed adjustment of table 1 in order to the twin-screw extruder that carries out esterification.Discharge port sampling in extrusion machine utilizes
31The P-NMR collection of illustrative plates calculates esterification yield, and the result is embedded in table 1.
Comparative example 2-3
Repeat the step of embodiment 1, according to the screw speed of the listed adjustment of table 1 in order to the twin-screw extruder that carries out esterification.Discharge port sampling in extrusion machine utilizes the 31P-NMR collection of illustrative plates to calculate esterification yield, and the result is embedded in table 1.
Table 1
Show according to table 1 result, the sleeve temperature of extrusion machine in 30 to 200 ℃ scope, and screw speed between 10 to 300min
-1Scope help to promote esterification yield.The raw materials components mole ratio of reactant Vanadium Pentoxide in FLAKES and tetramethylolmethane does not then make significant difference for the esterification yield that generates two (phosphoric acid pentaerythritol ester) phosphoric acid.
Claims (6)
1. a method for preparing two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts is characterized in that comprising the following steps:
(a) esterification is to mix tetramethylolmethane and two (phosphoric acid pentaerythritol ester) phosphoric acid of Vanadium Pentoxide in FLAKES reaction generation in extrusion machine,
Wherein, the mol ratio of this tetramethylolmethane and Vanadium Pentoxide in FLAKES be 1: 0.5 to 3 scope, the temperature of this extrusion machine in 30 ℃ to 200 ℃ scope, and, the screw speed of this extrusion machine 10 to 300min
-1Scope in; And
(b) ammonium salt reaction is to mix two (phosphoric acid pentaerythritol ester) phosphoric acid and the trimeric cyanamide or derivatives thereof that esterification generated to react under the condition that solvent exists, and obtains two (phosphoric acid pentaerythritol ester) tricresyl phosphate paracyanogen ammonium salts behind the removal moisture,
Wherein, this melamine derivative is a benzoguanamine, and the solvent of this step (b) is a water.
2. method according to claim 1 is characterized in that, the mol ratio of this tetramethylolmethane and Vanadium Pentoxide in FLAKES preferably at 1: 0.75 to 1.33 scope.
3. method according to claim 1 is characterized in that this extrusion machine is a twin-screw extruder.
4. method according to claim 1 is characterized in that, the temperature of this extrusion machine is preferably in 50 ℃ to 140 ℃ scope.
5. method according to claim 1 is characterized in that, the screw speed of this extrusion machine preferably 50 to 200min
-1Scope in.
6. method according to claim 1 is characterized in that, the mol ratio of this tetramethylolmethane and trimeric cyanamide or derivatives thereof is 1: 2.
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|---|---|---|---|---|
| US4478998A (en) * | 1983-05-23 | 1984-10-23 | Borg-Warner Chemicals, Inc. | Process for preparing amine salts of phosphoric acids |
| CN1446844A (en) * | 2003-04-01 | 2003-10-08 | 华东理工大学 | Expansion type fire retardant material |
| US6737526B1 (en) * | 2002-10-23 | 2004-05-18 | Chung-Shan Institute Of Science & Technology | Method for preparing melamine salt of bis-(pentaerythritol phosphate) phosphoric acid |
| CN1508173A (en) * | 2002-12-18 | 2004-06-30 | �������⻯ѧƷ�ع�����˾ | Method for preparing five retardant agent based on cyanurotriamide and polymer composition |
| CN1624074A (en) * | 2004-10-27 | 2005-06-08 | 华东理工大学 | Polypentaerythritol-type phosphate ester melamine salt intumescent flame-retardant material and preparation method thereof |
| CN1721423A (en) * | 2004-07-16 | 2006-01-18 | 中国石油天然气集团公司 | Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) |
| TW200714591A (en) * | 2005-10-12 | 2007-04-16 | Chung Shan Inst Of Science | The preparation of melamine salts of pentaerythritol-based poly phosphate |
-
2007
- 2007-04-19 CN CN2007101044098A patent/CN101289465B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4478998A (en) * | 1983-05-23 | 1984-10-23 | Borg-Warner Chemicals, Inc. | Process for preparing amine salts of phosphoric acids |
| US6737526B1 (en) * | 2002-10-23 | 2004-05-18 | Chung-Shan Institute Of Science & Technology | Method for preparing melamine salt of bis-(pentaerythritol phosphate) phosphoric acid |
| CN1508173A (en) * | 2002-12-18 | 2004-06-30 | �������⻯ѧƷ�ع�����˾ | Method for preparing five retardant agent based on cyanurotriamide and polymer composition |
| CN1446844A (en) * | 2003-04-01 | 2003-10-08 | 华东理工大学 | Expansion type fire retardant material |
| CN1721423A (en) * | 2004-07-16 | 2006-01-18 | 中国石油天然气集团公司 | Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) |
| CN1624074A (en) * | 2004-10-27 | 2005-06-08 | 华东理工大学 | Polypentaerythritol-type phosphate ester melamine salt intumescent flame-retardant material and preparation method thereof |
| TW200714591A (en) * | 2005-10-12 | 2007-04-16 | Chung Shan Inst Of Science | The preparation of melamine salts of pentaerythritol-based poly phosphate |
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