CN102443176A - Method for preparing oligomeric phosphate - Google Patents
Method for preparing oligomeric phosphate Download PDFInfo
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- CN102443176A CN102443176A CN2011103018747A CN201110301874A CN102443176A CN 102443176 A CN102443176 A CN 102443176A CN 2011103018747 A CN2011103018747 A CN 2011103018747A CN 201110301874 A CN201110301874 A CN 201110301874A CN 102443176 A CN102443176 A CN 102443176A
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Abstract
The present invention discloses a method for preparing oligomeric phosphate. According to the method, triethyl phosphate and tris(2-chloroethyl) phosphate are adopted as raw materials; a catalysts is added; a synthesis reaction is performed for 2-15 hours at a temperature of 120-210 DEG C. Compared to the traditional method, the method of the present invention has characteristics of scientific method, simple operation, high security, and low cost; the resulting by-products from the reaction can be utilized on the industry again, no pollutant is generated by the whole method, such that the method is environmentally friendly and economical.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of method for preparing low polyphosphate.
Background technology
As additive flame retardant, phosplate all is a liquid generally, and is low because of its molecular weight, vapour pressure is high, decomposition temperature is low, poor heat stability.The addition type halogen-free flame retardants dimethyl methyl phosphonate (DMMP) that for example uses in the urethane foam, diethyl ethylphosphate (DEEP); Though flame retardant effect is preferably arranged in polyurethane foam; But molecular weight is less, volatile; In foam, can move after the time length, cause the flame retardant properties of porous plastics to descend.
Along with going deep into of fire retardant research; The phosphoric acid ester fire retardant from the phosplate class to double focusing or the transition of polyphosphate based flame retardant; Especially the polymerization degree is that 2～6 SULPHOSUCCINIC ACID ESTER is claimed low polyphosphate again; Have the appropriate molecular amount, have simultaneously that steam forces down, transport property is little concurrently, an advantage such as good endurance, toxicity are low, colourless, Halogen.Adopt the oligomeric phosphoric acid of novel method preparation to belong to additive flame retardant, have certain polymerization degree, molecular weight is higher, not halogen-containing, phosphorus content is high, good flame retardation effect is a kind of good fire retardant of urethane foam, is particularly useful for soft bubble.
The low polyphosphate fire retardant Fyrol PNX that U.S. rising sun Rui Da company produces is owing to its high efficiency, and the characteristics of Halogen are highly suitable for MVSS-302 and California, USA 117 standard foam.The favourable condition that it is used for the battle wagon sponge is its HMW, makes foam article hang down smell, low volatilization and ground fog property, but there is potential safety hazard in this product on production technique.U.S. Pat 4382042 discloses the preparation method of this kind low polyphosphate; Adopt trialkyl phosphates or three alkylhalide group SULPHOSUCCINIC ACID ESTERs or trialkyl phosphite or three alkylhalide group phosphorous acid esters, Vanadium Pentoxide in FLAKES and oxyethane to react, with oxyethane gained is contained P-O-P bond structure polymer (poly phosphate or gather phosphorous acid ester) bullion then and carry out aftertreatment as raw material.The time of reaction is long, needs at least more than the 20h, and energy consumption is high; Vanadium Pentoxide in FLAKES is easy to the moisture absorption, corrodibility is big, inconvenient operation; Employing oxyethane is raw material, and production security is poor.
Summary of the invention,
Goal of the invention: the objective of the invention is to deficiency, a kind of method for preparing low SULPHOSUCCINIC ACID ESTER is provided to prior art.
Technical scheme: in order to reach the foregoing invention purpose, the present invention specifically implements like this: a kind of method for preparing low polyphosphate may further comprise the steps:
(1) make raw material with triethyl phosphate and tricresyl phosphate (2-chloroethyl) ester, its mol ratio is 1～10: 1, adds the catalyzer of raw material total mass 0.2～5%, at 120～210 ℃ of following Synthetic 2～15h, obtains bullion, wherein n=1～20;
(2) adopt epoxy compounds that bullion is deacidified down at 40～120 ℃, the epoxy compounds add-on is 0.5%～10% of a bullion quality.
Wherein, said catalyzer can be KOH, NaOH, C2H5ONa, K
2CO
3, Na
2CO
3, terepthaloyl moietie sodium, sodium tetraphenylborate, antimony glycol, stannous octoate, Dibutyltin oxide.
Wherein, said epoxy compounds is oxyethane or propylene oxide.
Beneficial effect: the present invention compares with traditional method, and methodological science is simple to operate, and is safe, and cost is low; The sub product that reacts gained simultaneously can utilize in industry once more, and a whole set of method contamination-free generates, i.e. environmental protection is economical again.
Embodiment
Embodiment 1
In the four-hole 2000ml round-bottomed flask that whisking appliance, TM, constant pressure funnel, reflux condensate device (being connected to cold-trap) are housed; The triethyl phosphate that adds 546g; 7.32g sodium tetraphenylborate under constant agitation speed, is warming up to 150 ℃ with mixture; Drip 285.5g tricresyl phosphate (2-chloroethyl) ester, make maintain simultaneously at 140～145 ℃.After dropwising, be warming up to about 150 ℃, continue reaction 3h, filtration under diminished pressure gets by-product 190g in bullion 535g and the cold-trap.The gained bullion is warming up to 80～120 ℃, and decompression removes excessive triethyl phosphate, respectively time product (viscosity 573mpa.s mainly consists of the polymerization degree and be 2～4 oligomeric phosphoric acid ester mixture) 430g and triethyl phosphate 105g.430g product is warming up to 80 ℃, drips the 20g propylene oxide, insulation 2h promptly gets product.
Embodiment 2:
In three mouthfuls of 2000ml round-bottomed flasks that whisking appliance, TM, reflux condensate device (being connected to cold-trap) are housed; The triethyl phosphate that adds 546g; 7.32g sodium tetraphenylborate and 285.5g tricresyl phosphate (2-chloroethyl) ester is warming up to 140～145 ℃ of reaction 3h, after be warming up to 165 degree insulation 2h again.Filtration under diminished pressure gets by-product 185g in bullion (color jaundice) 541g and the cold-trap.The gained bullion is warming up to 80～120 ℃, and decompression removes excessive triethyl phosphate, respectively time product (viscosity 550mpa.s mainly consists of the polymerization degree and be 2～4 oligomeric phosphoric acid ester mixture) 428g and triethyl phosphate 108g.428g product is warming up to 70 ℃, drips the 20g propylene oxide, insulation 1h promptly gets product.
Case study on implementation 3:
In three mouthfuls of 2000ml round-bottomed flasks that whisking appliance, TM, reflux condensate device (being connected to cold-trap) are housed; The triethyl phosphate that adds 546g; 7.32g antimony glycol and 285.5g tricresyl phosphate (2-chloroethyl) ester, be warming up to 180 ℃ the reaction 3h, after be warming up to again 195 ℃ the insulation 2h.Filtration under diminished pressure gets by-product 184g in bullion 544g and the cold-trap.The gained bullion is warming up to 80～120 ℃, and decompression removes excessive triethyl phosphate, respectively time product (viscosity 538mpa.s mainly consists of the polymerization degree and be 2～4 oligomeric phosphoric acid ester mixture) 426g and triethyl phosphate 115g.426g product is warming up to 60 ℃, drips the 20g propylene oxide, insulation 2h promptly gets product.
Case study on implementation 4:
In three mouthfuls of 2000ml round-bottomed flasks that whisking appliance, TM, reflux condensate device (being connected to cold-trap) are housed; The triethyl phosphate that adds 728g; 7.32g antimony glycol and 285.5g tricresyl phosphate (2-chloroethyl) ester is warming up to 150～155 ℃ of reaction 3h, after be warming up to 160 degree insulation 2h again.Filtration under diminished pressure gets by-product 186g in bullion 722g and the cold-trap.The gained bullion is warming up to 80～120 ℃, and decompression removes excessive triethyl phosphate, respectively time product (viscosity 480mpa.s mainly consists of the polymerization degree and be 2～3 oligomeric phosphoric acid ester mixture) 435g and triethyl phosphate 286g.435g product is warming up to 80 ℃, drips the 21g propylene oxide, insulation 3h promptly gets product.
Claims (3)
1. a method for preparing low polyphosphate is characterized in that, may further comprise the steps:
(1) make raw material with triethyl phosphate and tricresyl phosphate (2-chloroethyl) ester, its mol ratio is 1～10: 1, adds the catalyzer of raw material total mass 0.2～5%, at 120～210 ℃ of following Synthetic 2～15h, obtains bullion, wherein n=1～20;
(2) adopt epoxy compounds that bullion is deacidified down at 40～120 ℃, the epoxy compounds add-on is 0.5%～10% of a bullion quality.
2. the method for preparing low polyphosphate according to claim 1 is characterized in that, said catalyzer can be KOH, NaOH, C
2H
5ONa, K
2CO
3, Na
2CO
3, terepthaloyl moietie sodium, sodium tetraphenylborate, antimony glycol, stannous octoate, Dibutyltin oxide.
3. the method for preparing low polyphosphate according to claim 1 is characterized in that, said epoxy compounds is oxyethane or propylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103018747A CN102443176A (en) | 2011-09-30 | 2011-09-30 | Method for preparing oligomeric phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103018747A CN102443176A (en) | 2011-09-30 | 2011-09-30 | Method for preparing oligomeric phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102443176A true CN102443176A (en) | 2012-05-09 |
Family
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|---|---|---|---|
| CN2011103018747A Pending CN102443176A (en) | 2011-09-30 | 2011-09-30 | Method for preparing oligomeric phosphate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665383A (en) * | 2013-11-07 | 2014-03-26 | 江苏雅克科技股份有限公司 | Oligomeric phosphate compound and preparation method |
| CN104926864A (en) * | 2015-06-03 | 2015-09-23 | 邹平县星宇塑料助剂有限公司 | Preparation method of oligomeric phosphite ester |
| CN107903440A (en) * | 2017-11-29 | 2018-04-13 | 云南云天化以化磷业研究技术有限公司 | A kind of Halogen alkyl phosphoric acid ester oligomer organic fire-retardant and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293896A (en) * | 2007-04-29 | 2008-10-29 | 江苏雅克化工有限公司 | Preparation of low polyphosphate |
-
2011
- 2011-09-30 CN CN2011103018747A patent/CN102443176A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293896A (en) * | 2007-04-29 | 2008-10-29 | 江苏雅克化工有限公司 | Preparation of low polyphosphate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665383A (en) * | 2013-11-07 | 2014-03-26 | 江苏雅克科技股份有限公司 | Oligomeric phosphate compound and preparation method |
| CN104926864A (en) * | 2015-06-03 | 2015-09-23 | 邹平县星宇塑料助剂有限公司 | Preparation method of oligomeric phosphite ester |
| CN107903440A (en) * | 2017-11-29 | 2018-04-13 | 云南云天化以化磷业研究技术有限公司 | A kind of Halogen alkyl phosphoric acid ester oligomer organic fire-retardant and preparation method thereof |
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Application publication date: 20120509 |