CN103382393A - Liquid reactive flame retardant agent containing nitrogen and phosphorus and preparation method thereof - Google Patents
Liquid reactive flame retardant agent containing nitrogen and phosphorus and preparation method thereof Download PDFInfo
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- CN103382393A CN103382393A CN2013102475439A CN201310247543A CN103382393A CN 103382393 A CN103382393 A CN 103382393A CN 2013102475439 A CN2013102475439 A CN 2013102475439A CN 201310247543 A CN201310247543 A CN 201310247543A CN 103382393 A CN103382393 A CN 103382393A
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Abstract
The invention relates to a liquid reactive flame retardant agent containing nitrogen and phosphorus and a preparation method thereof. The synthesis procedures include: a first step, synthesis of a reaction intermediate containing a pentabasic ring; and a second step, synthesis of the liquid reactive flame retardant agent. The main raw materials are rich in sources and low in price; the preparation process is relatively simple, and the process parameters are relatively easy to control; and the obtained product has high purity, is the flame retardant agent having a high flame retardant effect, is especially suitable for use in thermal insulation and flame retardance of polyurethane organic polymer materials, and has wide application and high cost performance.
Description
Technical field
The present invention relates to that a class is nitrogenous, phosphorus liquid reaction type fire retardant and preparation method thereof, belong to the synthetic field of lagging material flame retardant.
Background technology
Fire retardant is a kind of special auxiliary chemicals be used to improving the inflammable material combustionproperty, and purposes is extremely extensive in national life, and in all kinds of finishing materials, the figure of fire retardant is seen everywhere.Because chloride, as to contain brominated flame retardant flame retardant effect is excellent, this based flame retardant is used very extensive in field of polymer technology, but people found gradually afterwards, and this based flame retardant can volatilize the larger gaseous product of toxicity when decomposes, can cause larger injury to people's health; In addition, environmental problem becomes increasingly conspicuous at present, and the environmental problem that this type of fire retardant that contains haloid element causes when producing is also endured to the fullest extent and denounced.Therefore be conceived to development of new nitrogenous, phosphorus type flame retardant is imperative, nitrogen element and phosphoric are mutually collaborative in fire-retardant process, can play better flame retardant effect; And this based flame retardant environmental pollution degree when synthetic is less, is easy to be accepted by users.
Summary of the invention
Problem to be solved by this invention has been to provide fire-retardant nitrogenous, phosphorus liquid reaction type fire retardant of a type high temp and preparation method thereof, and this fire retardant had both had the function of heat-insulating and fire-proof, has again inexpensively, is easy to prepare and advantage that environmental is less.
One class is nitrogenous, phosphoric liquid reaction type fire retardant, and the chemical structural formula of this type of flame retardant molecule is:
R wherein
1, R
2Can be hydrogen or methyl.
The invention provides the preparation method of above-mentioned nitrogenous, phosphorus liquid reaction type fire retardant:
Reaction process is carried out in two steps, the first step produces reaction intermediate nitrogenous, the oxygen five-membered ring, nitrogenous, the phosphorus liquid reaction type flame retardant molecule of second step generation.
In the first step reaction, add 2,2 of 2mol '-dihydroxyl diethylamine in conversion unit, after its melting, adding 63.2g purity is 95% paraformaldehyde at 60 ℃, and keeping temperature of reaction is 30 ℃-85 ℃, reacts 1-30 hours.
After the first step reacts completely, carry out the gradient underpressure distillation, keep pressure in 15.5kPa-50kPa scope, maintain the temperature between 50 ℃-95 ℃, time 2-8 hour, complete to dehydration.
In the first step reaction, add 2,2 of 2mol '-dihydroxyl diethylamine in conversion unit, after its melting, add the acetone of 2mol, mix and blend at 60 ℃, then add the 2mol Anhydrous potassium carbonate, keeping temperature of reaction is 30 ℃-85 ℃, 1-30 hours reaction times.
After the first step reacts completely, carry out the gradient underpressure distillation, keep pressure in 15.5kPa-50kPa scope, maintain the temperature between 50 ℃-95 ℃, time 2-8 hour, complete to taking off acetone, remove by filter the potash water compound.
In the second step reaction, in the reaction intermediate of nitrogenous, the oxygen five-membered ring that the dimethylphosphite of the solid acid catalyst macroporous type strong acid cation resin of 0.8g-1.6g and 2mol is joined that the first step reaction produces, under 30 ℃-90 ℃, reacted 1-6 hours.
At last, nitrogenous, the phosphorus reaction type fire retardant that obtain are down to room temperature, the catalyzer in filtration and recovery system obtains faint yellow liquid reactive flame retardant, and catalyzer takes second place rear standby with dilute hydrochloric acid washing 1-2.
Description of drawings
Fig. 1 is the chemical structural formula of three kinds of reaction intermediates.
Fig. 2 is the chemical structural formula (R wherein of flame retardant products of the present invention
1, R
2Can be hydrogen or methyl).
Fig. 3 is the chemical structural formula of reaction intermediate in the embodiment of the present invention 1.
Fig. 4 is the chemical structural formula of flame retardant products in the embodiment of the present invention 1.
Fig. 5 is the chemical structural formula of reaction intermediate in the embodiment of the present invention 2.
Fig. 6 is the chemical structural formula of flame retardant products in the embodiment of the present invention 2.
Fig. 7 is the chemical structural formula of reaction intermediate in the embodiment of the present invention 3.
Fig. 8 is the chemical structural formula of flame retardant products in the embodiment of the present invention 3.
Embodiment
Embodiment 1:
1. add 2,2 of 2mol (approximately 210.3g) '-dihydroxyl diethylamine in conversion unit, after its melting, the concentration that adds 63.2g is 95% paraformaldehyde at 60 ℃, and keeping temperature of reaction is 40 ℃, reacts 1.5 hours.
2. the liquid substance that above-mentioned reaction is generated is transferred in vacuum distillation equipment, temperature maintains 80 ℃, pressure is under the condition of 17.5kPa, the moisture that generates in evaporation reaction, gradient underpressure distillation 2 hours, complete to dehydration, obtain containing pentacyclic intermediate product N-(2 '-hydroxyethyl)-1,3-nitrogen tetrahydrofuran 214.7g, productive rate is 91.7%, the chemical structural formula of intermediate product such as Figure of description 3.
3. the pentacyclic intermediate product that contains that generates in step (2) is cooled to 40 ℃, then add the solid acid catalyst macroporous type strong acid cation resin of 0.8g and the dimethylphosphite of 2mol (approximately 220.0g), mix, 50 ℃ of lower insulation reaction three hours.
4. above-mentioned fluent meterial is down to room temperature, the catalyzer in filtration and recovery system obtains faint yellow liquid reactive flame retardant.Recyclable recycling, the chemical structural formula of flame retardant products such as Figure of description 4 after catalyzer washs 1-2 time with dilute hydrochloric acid.
5. gas chromatographic analysis is known: fire retardant product N, and N-two (2-hydroxyethyl) aminomethy-lenephosphonic acids dimethyl ester purity is 90.66%, presses dimethylphosphite and calculates, the productive rate of product fire retardant is: 84.34%.
6. Infrared spectroscopy is known: 3433cm
_ 1The place is-the stretching vibration absorption peak of OH, and 1455cm
_ 1And 1392cm
_ 1The bimodal of place is〉N-CH
2-symmetric deformation absorption peak, 1227cm
_ 1The place is on bound phosphate groups-the stretching vibration absorption peak of P=O key, and 1165cm
_ 1The place is the stretching vibration absorption peak of tertiary amine-C-N-key, 1046cm
_ 1The place is-CH
2In OH-and the stretching vibration absorption peak of C-O-key, 963cm
_ 1The place is-P-O-C
2H
5In-the symmetrical stretching vibration absorption peak of P-O-.
Embodiment 2:
1. add 2,2 of 2mol (approximately 210.3g) '-dihydroxyl diethylamine in conversion unit, at 60 ℃ after its melting, the acetone that adds 4mol (approximately 232.4g), then mix and blend adds approximately 276.0g of 2mol() Anhydrous potassium carbonate, under room temperature, reaction is 24 hours.
2. the liquid substance that above-mentioned reaction is generated is transferred in vacuum distillation equipment, temperature remains on 70 ℃, pressure under the condition of 20kPa, the moisture that generates in the evaporation reaction process and unreacted acetone, underpressure distillation 4 hours, to dewatering and to take off acetone complete, remove by filter the potash water compound, obtain containing pentacyclic intermediate product 2,2-dimethyl-N-(2 '-hydroxyethyl)-1,3-nitrogen tetrahydrofuran 213.3g, productive rate 73.2%, the chemical structural formula of intermediate product such as Figure of description 5.
3. the pentacyclic intermediate product that contains that generates in step (2) is cooled to 40 ℃, then adds approximately 220.0g of the solid acid catalyst macroporous type strong acid cation resin of 1.6g and 2mol() dimethylphosphite, reaction is 4 hours under 70 ℃.
4. above-mentioned fluent meterial is down to room temperature, the catalyzer in filtration and recovery system obtains faint yellow liquid reactive flame retardant N, the amino sec.-propyl dimethyl phosphonate of N-two (2-hydroxyethyl).Recyclable recycling, the chemical structural formula of flame retardant products such as Figure of description 6 after catalyzer washs 1-2 time with dilute hydrochloric acid.
5. gas chromatographic analysis is known: fire retardant product N, and the amino sec.-propyl dimethyl phosphonate purity of N-two (2-hydroxyethyl) is 79.3%, presses dimethylphosphite and calculates, the productive rate of product fire retardant is: 75.6%.
6. Infrared spectroscopy is known: 3392cm
_ 1The place is-the stretching vibration absorption peak of OH, and 1455cm
_ 1The place is〉N-CH
2-symmetric deformation absorption peak, 1392cm
_ 1And 1365cm
_ 1The place is〉(CH
3)
2Hydrocarbon symmetric deformation absorption peak, 1200cm
_ 1The place is on bound phosphate groups-the stretching vibration absorption peak of P=O key, and 1052cm
_ 1The place is the stretching vibration absorption peak of tertiary amine-C-N-key, 949cm
_ 1The place is-P-O-C
2H
5In-the symmetrical stretching vibration absorption peak of P-O-.
Embodiment 3:
1. the diisopropanolamine (DIPA) that adds 2mol (approximately 266.4g) in conversion unit, after the diisopropanolamine (DIPA) melting, adding concentration is approximately 63.2g of 95% 2mol(at 60 ℃) paraformaldehyde, keeping temperature of reaction is 60 ℃, reacts 4 hours.
2. the liquid substance that above-mentioned reaction is generated is transferred in vacuum distillation equipment, temperature maintains 70 ℃, adopt the method for gradient decompression, system pressure is reduced to 17kPa from 50kPa, the moisture that generates in the evaporation reaction process, underpressure distillation 6 hours, to dehydration fully, obtain containing pentacyclic intermediate product 5-methyl-N-(2 '-hydroxyl sec.-propyl)-1,3-nitrogen tetrahydrofuran 247.4g, productive rate 85.3%, chemical structural formula such as Figure of description 7.
3. the pentacyclic intermediate product that contains that generates in step (2) is cooled to 40 ℃, then adds approximately 220.0g of the solid acid catalyst macroporous type strong acid cation resin of 0.8g and 2mol() dimethylphosphite, reaction is 2 hours under 50 ℃.
4. above-mentioned fluent meterial is down to room temperature, the catalyzer in filtration and recovery system obtains faint yellow liquid reactive flame retardant N, N-two (2-hydroxyl sec.-propyl) aminomethy-lenephosphonic acids dimethyl ester.Recyclable recycling after catalyzer washs 1-2 time with dilute hydrochloric acid.The chemical structural formula of flame retardant products such as Figure of description 8.
5. gas chromatographic analysis is known: fire retardant product N, and N-two (2-hydroxyl sec.-propyl) aminomethy-lenephosphonic acids dimethyl ester purity is 89.6%, presses dimethylphosphite and calculates, the productive rate of product fire retardant is: 81.2%.
6. Infrared spectroscopy is known: 1456cm
_ 1And 1415cm
_ 1The bimodal of place is〉N-CH
2-symmetric deformation absorption peak, 1218cm
_ 1The place is on phosphoric acid molecules-the stretching vibration absorption peak of P=O key, and 1158cm
_ 1The place is the stretching vibration absorption peak of tertiary amine-C-N-key, 1052cm
_ 1The place is-CH
2In OH-and the stretching vibration absorption peak of C-O-, 966cm
_ 1The place is-P-O-C
2H
5In-the symmetrical stretching vibration absorption peak of P-O-.
It should be noted that at last: the preferred embodiment that these are only patent of the present invention; be not limited to patent of the present invention; although with reference to embodiment, patent of the present invention is had been described in detail; for a person skilled in the art; it still can be modified to the technical scheme that aforementioned each embodiment puts down in writing; perhaps part technical characterictic wherein is equal to replacement; but all within the spirit and principle of patent of the present invention; any modification of doing, be equal to replacement, improvement etc., within all should being included in the protection domain of patent of the present invention.
Claims (8)
1. nitrogenous, the phosphorus liquid reaction type fire retardant of a class, the chemical structural formula of this type of flame retardant molecule is:
R wherein
1, R
2Hydrogen or methyl.
2. the preparation method of fire retardant according to claim 1, it is characterized in that: reaction process is carried out in two steps, and the first step produces the reaction intermediate of nitrogenous oxygen five-membered ring, and second step produces nitrogenous, phosphorus liquid reaction type flame retardant molecule.
3. the preparation method of fire retardant according to claim 2, it is characterized in that: in the first step reaction, add 2 of 2mol in conversion unit, 2 '-the dihydroxyl diethylamine, at 60 ℃ after its melting, adding 2mol purity is 95% paraformaldehyde, and keeping temperature of reaction is 30 ℃-85 ℃, and the reaction times is 1-30 hours.
4. the preparation method of fire retardant according to claim 3, is characterized in that: after the first step reacts completely, carry out the gradient underpressure distillation, keep pressure in 15.5kPa-50kPa scope, temperature remains between 50 ℃-95 ℃, and is time 2-8 hour, complete to dehydration.
5. the preparation method of fire retardant according to claim 2, it is characterized in that: in the first step reaction, add 2 of 2mol in conversion unit, 2 '-the dihydroxyl diethylamine, after its melting, add the acetone of 2mol at 60 ℃, mix and blend, then add the 2mol Anhydrous potassium carbonate, keeping temperature of reaction is 30 ℃-85 ℃, 1-30 hours reaction times.
6. the preparation method of fire retardant according to claim 5, it is characterized in that: after the first step reacts completely, carry out the gradient underpressure distillation, keep pressure in 15.5kPa-50kPa scope, temperature maintains between 50 ℃-95 ℃, time 2-8 hour, complete to taking off acetone, remove by filter the potash water compound.
7. the preparation method of fire retardant according to claim 2, it is characterized in that: second step reaction joins 0.8g-1.6g solid acid catalyst macroporous type strong acid cation resin and 2mol dimethylphosphite in the intermediate of the nitrogenous oxygen five-membered ring that the first step reaction produces, under 30 ℃-90 ℃, reacted 1-6 hours.
8. the preparation method of fire retardant according to claim 7, it is characterized in that: nitrogenous, the phosphorus fire retardant product that will obtain are down to room temperature, filter and recovery system in catalyzer, obtain faint yellow liquid reactive flame retardant.Catalyzer takes second place rear standby with dilute hydrochloric acid washing 1-2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237412A (en) * | 2015-09-14 | 2016-01-13 | 南京红宝丽醇胺化学有限公司 | N-methyl diisopropanolamine preparation method |
| CN112442077A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with reactive groups and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237412A (en) * | 2015-09-14 | 2016-01-13 | 南京红宝丽醇胺化学有限公司 | N-methyl diisopropanolamine preparation method |
| CN105237412B (en) * | 2015-09-14 | 2017-10-31 | 南京红宝丽醇胺化学有限公司 | A kind of preparation method of N methyl diisopropanolamine (DIPA) |
| CN112442077A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with reactive groups and preparation method and application thereof |
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Application publication date: 20131106 |