CN102702262B - A kind of preparation method of melamine polyols phosphoric acid ester - Google Patents
A kind of preparation method of melamine polyols phosphoric acid ester Download PDFInfo
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- CN102702262B CN102702262B CN201210154014.XA CN201210154014A CN102702262B CN 102702262 B CN102702262 B CN 102702262B CN 201210154014 A CN201210154014 A CN 201210154014A CN 102702262 B CN102702262 B CN 102702262B
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Abstract
The invention discloses a kind of preparation method of melamine polyols phosphoric acid ester, first melamine polyols and dimethylamine mixing are mixed according to mol ratio 2.5 ~ 4:1, stir 10 ~ 50 minutes under normal temperature condition; Add phosphoric acid ester and catalyzer in the mixture obtained to step one again, and be uniformly mixed, then temperature is elevated to 80 ~ 120 DEG C, reacts, 1.5 ~ 2.5 hours reaction times; Then, remove residual monomer, obtain melamine polyols phosphoric acid ester finished product.The melamine polyols phosphoric acid ester obtained by preparation method of melamine polyols phosphoric acid ester of the present invention is adopted to be a kind of PAPE of nitrogen phosphorus system of response type, there is viscosity low, the advantage of good stability, and production equipment is easy, building-up process is simple to operate, favorable reproducibility.
Description
Technical field
The present invention relates to technical field of polymer chemistry, particularly relate to a kind of preparation method of melamine polyols phosphoric acid ester.
Technical background
The difficult problem that current, energy-conservation, reduction of discharging has become in many technical fields and emphasis.In country's " 12 planning ", also formulated corresponding energy-conservation, emission reduction targets for multiple technical field, for enterprise, especially some traditional production enterprises, its task that is energy-conservation, that reduce discharging is very heavy.
At present, macromolecular compound is widely used in the every field of producing, live.Wherein, urethane possesses the plurality of advantages comprising fire prevention, hypotoxicity and high-performance, other widespread use and the industry such as building, decoration due to it.But, urethane disclosed in prior art is still difficult to meet the growing requirement of building trade, not only good heat insulating is required for the urethane organic insulation material adopted in building trade, also will have higher requirement in fire prevention, toxicity etc.
In addition, polyurethane production method disclosed in prior art also cannot meet the product requirement day by day promoted, cannot efficiently, quick, the many colory polyurethane products of preparation of guaranteeing both quality and quantity.
In view of this, a kind of preparation method of novel melamine polyols phosphoric acid ester is provided, overcomes the technical problem existed in above-mentioned prior art, to enhance productivity and product performance are those skilled in the art's technical problems urgently to be resolved hurrily.
Summary of the invention
For the deficiencies in the prior art, technical problem solved by the invention is the preparation method providing a kind of melamine polyols phosphoric acid ester, the melamine polyols phosphoric acid ester obtained by the method is a kind of PAPE of nitrogen phosphorus system of response type, there is viscosity low, the advantage of good stability, and production equipment is easy, building-up process is simple to operate, favorable reproducibility.
For this reason, the preparation method of a kind of melamine polyols phosphoric acid ester provided by the invention, is characterized in that, comprise the steps:
Step one, first by melamine polyols and dimethylamine mixing mix according to mol ratio 6 ~ 12:1, under normal temperature condition stirring 10 ~ 50 minutes;
Add phosphoric acid ester and catalyzer in step 2, the mixture that obtains to step one, and be uniformly mixed, then temperature is elevated to 80 ~ 120 DEG C, reacts, 1.5 ~ 2.5 hours reaction times; The mixture of melamine polyols and dimethylamine and the mass ratio of described phosphoric acid ester are 70:25 ~ 35; Described catalyzer is thanomin manganate, and the consumption adding catalyzer is 1% ~ 2% of described phosphoric acid ester quality;
Step 3, question response system temperature drop to less than 50 DEG C, vacuumize under the condition of-0.02 ~-0.1MPa, continue to vacuumize, remove residual monomer under being then warming up to the condition of 90-130 DEG C, obtain melamine polyols phosphoric acid ester finished product.
Preferably, in step one, melamine polyols and dimethylamine mixing mix according to mol ratio 10:1.
Preferably, in step 2, the mixture of melamine polyols and dimethylamine and the mass ratio of described phosphoric acid ester are 70:30, and the consumption adding catalyzer is 1% of described phosphoric acid ester quality.
Preferably, in step 3, the mol ratio 1.8:100 of the residual monomer removed and melamine polyols phosphoric acid ester.
Preferably, in step 3, when vacuumizing, pressure is-0.1MPa, and the time vacuumized is 2 ~ 3 hours.
Compared to prior art, the preparation method of melamine polyols phosphoric acid ester provided by the invention at least comprises following beneficial effect:
Adopt melamine polyols phosphoric acid ester prepared by the preparation method of melamine polyols phosphoric acid ester of the present invention, nitrogenous, phosphorus amount is high, viscosity is low, good stability, the polyurethane foam adopting this structurally-modified rear polyvalent alcohol that is nitrogenous, phosphorus system to obtain has the low and excellent flame retardant properties of smoke density.
In addition, preparation method's step of melamine polyols phosphoric acid ester of the present invention is simple, efficiently can prepare melamine polyols phosphate ester product of good performance rapidly.Meanwhile, the inventive method production unit used is simple, and the construction cost of production line is low, and easy to operate, product favorable reproducibility.
embodiment:
To illustrate in greater detail the present invention below by by following examples, and be with it may be noted that, following examples are only illustrative, and the present invention is not by the restriction of these embodiments.
Embodiment one: the preparation one of melamine polyols phosphoric acid ester
Prepare melamine polyols phosphoric acid ester in accordance with the following steps:
Step one, in four-hole boiling flask, add melamine polyols 840 grams (molecular-weight average is 500) and dimethylamine 18.8 grams (dimethylamine is 40% aqueous solution), connect thermometer and agitator, at normal temperatures continuously stirring 20 minutes.
Step 2, then add phosphoric acid ester 360 grams, thanomin manganate catalyzer 3.6 grams, under whipped state, be warmed up to 80-100 DEG C, react 2 hours.
Step 3, reaction system is cooled to 50 DEG C after, connect condenser and vacuumize 2 hour for-0.1MPa, temperature under being 100 DEG C of-130 DEG C of conditions at pressure, remove residual monomer, melamine polyols phosphate ester product.Wherein, the mol ratio 1.8:100 of the residual monomer removed and melamine polyols phosphoric acid ester.
The product obtained is the liquid of light-coloured transparent, and, between 140-300, hydroxyl value is between 100-200 to adopt NDJ-1 type rotary viscosimeter instrument to record its viscosity (25 DEG C).
Embodiment two: the preparation two of melamine polyols phosphoric acid ester
Prepare melamine polyols phosphoric acid ester in accordance with the following steps:
Step one, in four-hole boiling flask, add melamine polyols 840 grams (molecular-weight average is 800) and dimethylamine (dimethylamine is 40% aqueous solution) 18.8 grams, connect thermometer and agitator, at normal temperatures continuously stirring 50 minutes.
Step 2, then add phosphoric acid ester 320 grams, thanomin manganate catalyzer 5 grams, under whipped state, be warmed up to 100-120 DEG C, react 2.5 hours.
Step 3, reaction system is cooled to 50 DEG C after, connect condenser and vacuumize 3 hour for-0.1MPa, temperature under being 110 DEG C of-130 DEG C of conditions at pressure, remove residual monomer, melamine polyols phosphate ester product.Wherein, the mol ratio 2.1:100 of the residual monomer removed and melamine polyols phosphoric acid ester.
The product obtained is the liquid of light-coloured transparent, and, between 200-300, hydroxyl value is between 100-200 to adopt NDJ-1 type rotary viscosimeter instrument to record its viscosity (25 DEG C).
Embodiment three: the preparation three of melamine polyols phosphoric acid ester
Prepare melamine polyols phosphoric acid ester in accordance with the following steps:
Step one, in four-hole boiling flask, add melamine polyols 840 grams (molecular-weight average is 600) and dimethylamine (dimethylamine is 40% aqueous solution) 18.8 grams, connect thermometer and agitator, at normal temperatures continuously stirring 25 minutes.
Step 2, then add phosphoric acid ester 400 grams, thanomin manganate catalyzer 4 grams, under whipped state, be warmed up to 90-110 DEG C, react 2.5 hours.
Step 3, reaction system is cooled to 50 DEG C after, connect condenser and vacuumize 2.5 hour for-0.05MPa, temperature under being 100 DEG C of-120 DEG C of conditions at pressure, remove residual monomer, melamine polyols phosphate ester product.Wherein, the mol ratio 1.9:100 of the residual monomer removed and melamine polyols phosphoric acid ester.
The product obtained is the liquid of light-coloured transparent, and, between 150-250, hydroxyl value is between 100-200 to adopt NDJ-1 type rotary viscosimeter instrument to record its viscosity (25 DEG C).
The content having above-described embodiment to disclose can be found out, adopt melamine polyols phosphoric acid ester prepared by the preparation method of melamine polyols phosphoric acid ester of the present invention, nitrogenous, phosphorus amount is high, viscosity is low, good stability, the polyurethane foam adopting this structurally-modified rear polyvalent alcohol that is nitrogenous, phosphorus system to obtain has the low and excellent flame retardant properties of smoke density.
In addition, preparation method's step of melamine polyols phosphoric acid ester of the present invention is simple, efficiently can prepare melamine polyols phosphate ester product of good performance rapidly.Meanwhile, the inventive method production unit used is simple, and the construction cost of production line is low, and easy to operate, product favorable reproducibility.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (3)
1. a preparation method for melamine polyols phosphoric acid ester, is characterized in that, comprises the steps:
Step one, first by melamine polyols and dimethylamine mixing according to mol ratio 10:1 mixing, under normal temperature condition stir 10 ~ 50 minutes;
Add phosphoric acid ester and catalyzer in step 2, the mixture that obtains to step one, and be uniformly mixed, then temperature is elevated to 80 ~ 120 DEG C, reacts, 1.5 ~ 2.5 hours reaction times; The mixture of melamine polyols and dimethylamine and the mass ratio of described phosphoric acid ester are 70:30; Described catalyzer is thanomin manganate, and the consumption adding catalyzer is 1% of described phosphoric acid ester quality;
Step 3, question response system temperature drop to less than 50 DEG C, vacuumize under the condition of-0.02 ~-0.1MPa, continue to vacuumize, remove residual monomer under being then warming up to the condition of 90-130 DEG C, obtain melamine polyols phosphoric acid ester finished product.
2. the preparation method of melamine polyols phosphoric acid ester according to claim 1, is characterized in that, in step 3, and the mol ratio 1.8:100 of the residual monomer removed and melamine polyols phosphoric acid ester.
3. the preparation method of melamine polyols phosphoric acid ester according to claim 1, is characterized in that, in step 3, when vacuumizing, pressure is-0.1MPa, and the time vacuumized is 2 ~ 3 hours.
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| CN107880314B (en) * | 2016-09-30 | 2022-01-25 | 科思创德国股份有限公司 | Composite flame retardant and polyurethane material containing same |
| CN107141443A (en) * | 2017-04-19 | 2017-09-08 | 广州朗腾聚氨酯有限公司 | A kind of flame retarding polyether composition and its preparation method and application |
| CN107964025B (en) * | 2017-10-18 | 2020-05-29 | 四川大学 | Monohydric alcohol or polyhydric alcohol containing nitrogen and phosphorus and preparation method thereof |
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| EP1856023A4 (en) * | 2005-03-03 | 2010-08-04 | South Dakota Soybean Processor | Novel polyols derived from a vegetable oil using an oxidation process |
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| CN102225952A (en) * | 2011-04-05 | 2011-10-26 | 刘方旭 | Tris-(N,N-dihydroxyethylamino)-s-triazine phosphate ester fire retardant and preparation method thereof |
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| CN102304223B (en) * | 2011-07-14 | 2013-03-27 | 广州朗腾聚氨酯有限公司 | Plant oil polyether glycol and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3440201A (en) * | 1965-08-26 | 1969-04-22 | Sherwin Williams Co | Melamine - formaldehyde phosphate ether polyol resins useful for coating compositions,process for their preparation and coating compositions containing such resins |
| US4195139A (en) * | 1977-06-08 | 1980-03-25 | Imperial Chemical Industries Limited | Fire retardant composition comprising a melamine-aldehyde-phosphate condensate |
| EP0045835B1 (en) * | 1980-06-02 | 1990-03-14 | Ludwig Dr. Eigenmann | Self-extinguishing polymeric compositions |
| US6277482B1 (en) * | 1998-10-01 | 2001-08-21 | Fred J. Amundson | Fire retarding adhesives |
| CN101263172A (en) * | 2005-09-07 | 2008-09-10 | 阿克佐诺贝尔国际涂料股份有限公司 | Melamine polyols and coatings thereof |
| CN102286027A (en) * | 2011-06-28 | 2011-12-21 | 华中科技大学 | Method for preparing phosphorus-nitrogen-carbon expansion-type fire retardant |
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