CN1891706A - Method for synthesizing phosphatic, nitrogenous expansion fire retardant - Google Patents
Method for synthesizing phosphatic, nitrogenous expansion fire retardant Download PDFInfo
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- CN1891706A CN1891706A CN 200610050687 CN200610050687A CN1891706A CN 1891706 A CN1891706 A CN 1891706A CN 200610050687 CN200610050687 CN 200610050687 CN 200610050687 A CN200610050687 A CN 200610050687A CN 1891706 A CN1891706 A CN 1891706A
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- octane
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Abstract
The invention discloses an intumescent flame retardant which contains phosphorus, nitrogen and its synthetic methods. The method for preparing flame retardant shows as follow: taking water as the solvent, bis(2,6,7-three oxygen- 1-phosphat-bicyclo [2,2,2] octane - 1-oxygen methyl) chlorine-phosphate and 4. 4 '- diamino-DMP react under the condition of catalytic, bis(2,6, 7-three oxygen- 1-phosphat-bicyclo [2,2,2] octane - 1-oxygen methyl) phosphate and 4. 4 '- diamino-DMP are purified out, the weight ratio of water and 4. 4 '- diamino-DMP is 5~20:1, the molar ratio of bis(2,6,7-three oxygen- 1-phosphat-bicyclo [2,2,2] octane - 1-oxygen methyl) chlorine-phosphate and 4. 4 '- diamino-DMP is 1: 1-2, the reaction time is 0.1~24 hours.
Description
Technical field
The invention belongs to the technical field of phosphorous expansion type flame retardant and preparation method thereof.Specifically, the present invention relates to a kind of synthetic method of phosphorous, nitrogen expansion type combustion inhibitor.
Background technology
The compound that the single component expansion type flame retardant will contain functional groups such as acid source, carbon source and source of the gas is attached on the macromole in the mode of chemosynthesis, when fire-retardant, only need add this single material of planting, have more excellent thermostability and matrix consistency with respect to the mixed type expanding fire retardant.
Americana was once reported and had been synthesized 2,4,8,10-four oxygen-3,9-hosphospiro [5,5] undecane-3,9-dioxy-3,9-two melamine salts (b-MAP) and two (2,6,7-three oxygen-1-phosphorus-dicyclo [2,2,2] octane-4-oxygen methyl) phosphoric acid ester melamine salt (Melabis) all has good flame retardancy with respect to mixed expanded type fire retardant, but only is applicable to that polyolefins is particularly polyacrylic fire-retardant.
Summary of the invention
The purpose of this invention is to provide a kind of phosphorous, nitrogen expansion type combustion inhibitor and synthetic method thereof.
Molecular structure phosphorous, nitrogen expansion type combustion inhibitor is:
Phosphorous, the synthetic method of nitrogen expansion type combustion inhibitor: with water is solvent, two (2,6,7-three Oxy-1s-phospha dicyclo [2,2,2] octane-1-oxygen methyl) chlorine phosphoric acid ester and 4,4 '-diaminodiphenyl-methane reacts under catalyst action, that purification obtains is two (2,6,7-three oxygen-1-phosphorus-dicyclo [2,2,2] phosphoric acid ester 4 octane-1-oxygen methyl), 4 '-diaminodiphenyl-methane salt, water and 4, the mass ratio of 4 '-diaminodiphenyl-methane is 5～20: 1, two (2,6,7-three Oxy-1s-phospha dicyclo [2,2,2] chlorine phosphoric acid ester and 4 octane-1-oxygen methyl), the mol ratio of 4 '-diaminodiphenyl-methane is 1: 1～2, the reaction times is 0.1～24 hour.
The solvent that adopts during described the purification is water, ethanol or acetone.Catalyzer is pyridine, triethylamine or propylamine.
The present invention has the following advantages:
1. the present invention is that phosphorus-nitrogen is expanding fire retardant, and is not halogen-containing, nontoxic, helps environmental protection, has a good application prospect, and increased new variety for containing phosphorus type flame retardant;
2. phosphorus of the present invention-nitrogen flame retardant carbon-collecting source, acid source, source of the gas are in one, and thermostability is higher, and is better with the matrix consistency, become charcoal higher, therefore join in polyester and other engineering plastics, can be issued to good flame-retardant effect in the few situation of addition;
3. preparation method of the present invention is simple, is easy to control.
Embodiment
A kind of phosphorous, nitrogen expansion type combustion inhibitor of preparation provided by the invention and synthetic method thereof realize in the following way: by two (2,6,7-three Oxy-1s-phospha dicyclo [2,2,2] octane-1-oxygen methyl) chlorine phosphoric acid ester and 4, the condensation reaction under the situation that with water is solvent of 4 '-diaminodiphenyl-methane finally generates target product two (2,6,7-three oxygen-1-phosphorus-dicyclo [2,2,2] phosphoric acid ester 4 octane-1-oxygen methyl), 4 '-diaminodiphenyl-methane salt.
Be under the situation of solvent with water, two (2,6,7-three Oxy-1s-phospha dicyclo [2,2,2] chlorine phosphoric acid ester and 4 octane-1-oxygen methyl), the final target product two (2 that generates of 4 '-diaminodiphenyl-methane reaction, 6,7-three oxygen-1-phosphorus-dicyclo [2,2,2] octane-1-oxygen methyl) phosphoric acid ester 4,4 '-diaminodiphenyl-methane salt, water and 4, the mass ratio of 4 '-diaminodiphenyl-methane are 5～20: 1, two (2,6,7-three Oxy-1s-phospha dicyclo [2,2,2] octane-1-oxygen methyl) chlorine phosphoric acid ester and 4, the mol ratio of 4 '-diaminodiphenyl-methane is 1: 1～2, and the reaction times is 0.1～24 hour.
In order to accelerate response speed, generate two (2,6,7-three oxygen-1-phosphorus-dicyclo [2,2, the 2] octane-1-oxygen methyl) phosphoric acid ester 4 of ultimate aim product, the catalyzer that 4 '-diaminodiphenyl-methane salt is adopted is any in pyridine, triethylamine, the propylamine.
The molecular structural formula of two (2,6,7-three Oxy-1s-phospha dicyclo [2,2,2] octane-1-oxygen methyl) chlorine phosphoric acid ester is:
4, the molecular structural formula of 4 '-diaminodiphenyl-methane structure is:
Providing example below further specifies the present invention; be necessary to point out it is that following example can not be interpreted as limiting the scope of the invention at this; if the person skilled in the art in this field to improvement and adjustment that the present invention makes some non-intrinsically safes, still belongs to protection scope of the present invention according to the foregoing invention content.
Embodiment 1:
In the reactor of the 250mL that import and export of nitrogen and whipping appts are housed, with 1.98g 4,4 '-diaminodiphenyl-methane, the 5mL pyridine is added in the 80ml deionized water as catalyzer, is heated to boiling, treats that DDM is all after the dissolving, add 4.4g two (2 rapidly, 6,7-three Oxy-1s-phospha dicyclo [2,2,2] chlorine phosphoric acid ester octane-1-oxygen methyl), under slowly stirring, react 10min, in sand core funnel, filter while hot, get clarifying filtrate and in ice-water bath, cool off.With behind the sedimentation and filtration with pressed powder with deionized water wash twice, use twice of washing with acetone again.In vacuum drying oven, under 80 ℃, dry 12 hours, obtain yellow powder powder solid.Yield 80%.
Embodiment 2:
In the reactor of the 250mL that import and export of nitrogen and whipping appts are housed, with 3.96g 4,4 '-diaminodiphenyl-methane, the 5mL triethylamine is that catalyzer is added in the 80ml deionized water, is heated to boiling, treats that DDM is all after the dissolving, add 9.6g two (2 rapidly, 6,7-three Oxy-1s-phospha dicyclo [2,2,2] chlorine phosphoric acid ester octane-1-oxygen methyl), under slowly stirring, react 30min, in sand core funnel, filter while hot, get clarifying filtrate and in ice-water bath, cool off.With behind the sedimentation and filtration with pressed powder with deionized water wash twice, use twice of washing with acetone again.In vacuum drying oven, under 80 ℃, dry 12 hours, obtain yellow powder powder solid.Yield 75%.
Embodiment 3:
In the reactor of the 250mL that import and export of nitrogen and whipping appts are housed, with 1.98g 4,4 '-diaminodiphenyl-methane, the 5mL pyridine is added in the 20mL deionized water as catalyzer, is heated to boiling, treats that DDM is all after the dissolving, add 4.4g two (2 rapidly, 6,7-three Oxy-1s-phospha dicyclo [2,2,2] chlorine phosphoric acid ester octane-1-oxygen methyl), under slowly stirring, react 24h, in sand core funnel, filter while hot, get clarifying filtrate and in ice-water bath, cool off.With behind the sedimentation and filtration with pressed powder with deionized water wash twice, use twice of washing with acetone again.In vacuum drying oven, under 80 ℃, dry 12 hours, obtain yellow powder powder solid.Yield 85%.
Embodiment 4:
In the reactor of the 250rnL that import and export of nitrogen and whipping appts are housed, with 1.98g 4,4 '-diaminodiphenyl-methane, the 5mL pyridine is added in the 50ml deionized water as catalyzer, is heated to boiling, treats that DDM is all after the dissolving, add 4.4g two (2 rapidly, 6,7-three Oxy-1s-phospha dicyclo [2,2,2] chlorine phosphoric acid ester octane-1-oxygen methyl), under slowly stirring, react 2h, in sand core funnel, filter while hot, get clarifying filtrate and in ice-water bath, cool off.With behind the sedimentation and filtration with pressed powder with deionized water wash twice, use twice of washing with alcohol again.In vacuum drying oven, under 80 ℃, dry 12 hours, obtain yellow powder powder solid.Yield 85%.
Embodiment 5:
In the reactor of the 250mL that import and export of nitrogen and whipping appts are housed, with 7.92g 4,4 '-diaminodiphenyl-methane, the 5mL propylamine is added in the 80ml deionized water as catalyzer, is heated to boiling, treats that DDM is all after the dissolving, add 16.6g two (2 rapidly, 6,7-three Oxy-1s-phospha dicyclo [2,2,2] chlorine phosphoric acid ester octane-1-oxygen methyl), under slowly stirring, react 1h, in sand core funnel, filter while hot, get clarifying filtrate and in ice-water bath, cool off.With behind the sedimentation and filtration with pressed powder with deionized water wash twice, use twice of washing with acetone again.In vacuum drying oven, under 80 ℃, dry 12 hours, obtain yellow powder powder solid.Yield 79%.
Claims (4)
1. phosphorous a, nitrogen expansion type combustion inhibitor is characterized in that, its molecular structure is:
One kind as claimed in claim 1 phosphorous, the synthetic method of nitrogen expansion type combustion inhibitor, it is characterized in that, be solvent with water, two (2,6,7-three Oxy-1s-phospha dicyclo [2,2,2] octane-1-oxygen methyl) chlorine phosphoric acid ester and 4,4 '-diaminodiphenyl-methane reacts under catalyst action, that purification obtains is two (2,6,7-three oxygen-1-phosphorus-dicyclo [2,2,2] phosphoric acid ester 4 octane-1-oxygen methyl), 4 '-diaminodiphenyl-methane salt, water and 4, the mass ratio of 4 '-diaminodiphenyl-methane is 5～20: 1, two (2,6,7-three Oxy-1s-phospha dicyclo [2,2,2] chlorine phosphoric acid ester and 4 octane-1-oxygen methyl), the mol ratio of 4 '-diaminodiphenyl-methane is 1: 1～2, the reaction times is 0.1～24 hour.
3. the synthetic method of a kind of phosphorous, nitrogen expansion type combustion inhibitor according to claim 2 is characterized in that, the solvent that adopts during described the purification is water, ethanol or acetone.
4. the synthetic method of a kind of phosphorous, nitrogen expansion type combustion inhibitor according to claim 2 is characterized in that described catalyzer is pyridine, triethylamine or propylamine.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610050687 CN1891706A (en) | 2006-05-11 | 2006-05-11 | Method for synthesizing phosphatic, nitrogenous expansion fire retardant |
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| CN 200610050687 CN1891706A (en) | 2006-05-11 | 2006-05-11 | Method for synthesizing phosphatic, nitrogenous expansion fire retardant |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153586A (en) * | 2011-01-25 | 2011-08-17 | 浙江大学宁波理工学院 | Compounds containing phosphorus, nitrogen and transition metal elements, and preparation method thereof |
| CN101328269B (en) * | 2008-07-20 | 2011-08-24 | 大连理工大学 | Preparation of polyphosphate flame retardant having dicyclic phosphoric acid ester structure |
| CN102219957A (en) * | 2011-05-13 | 2011-10-19 | 上海化工研究院 | Functional masterbatch of halogen-free intumescent flame retardant, and preparation method thereof |
| CN101654535B (en) * | 2009-09-10 | 2012-07-18 | 惠东美化塑胶实业有限公司 | Halogen-free flame-retardant long glass fiber reinforcement recycled polypropylene material and preparation method thereof |
| CN105838389A (en) * | 2016-04-13 | 2016-08-10 | 浙江大学宁波理工学院 | High-efficiency polyphosphate ester fire retardant and preparation method thereof |
| CN107418166A (en) * | 2017-08-22 | 2017-12-01 | 安徽悦尔伟塑料机械有限公司 | Halogen-free fire-resistant engineering plastics and preparation method thereof |
| CN107474500A (en) * | 2017-08-22 | 2017-12-15 | 安徽悦尔伟塑料机械有限公司 | High impact properties halogen-free flameproof manipulator and preparation method thereof |
| CN107556709A (en) * | 2017-08-22 | 2018-01-09 | 安徽悦尔伟塑料机械有限公司 | Fire-retardant mechanical arm of high-strength halogen-free and preparation method thereof |
| CN109354710A (en) * | 2018-10-19 | 2019-02-19 | 上海微巨实业有限公司 | A kind of phosphorous and nitrogen macromolecule expansion type flame retardant and its synthetic method |
-
2006
- 2006-05-11 CN CN 200610050687 patent/CN1891706A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328269B (en) * | 2008-07-20 | 2011-08-24 | 大连理工大学 | Preparation of polyphosphate flame retardant having dicyclic phosphoric acid ester structure |
| CN101654535B (en) * | 2009-09-10 | 2012-07-18 | 惠东美化塑胶实业有限公司 | Halogen-free flame-retardant long glass fiber reinforcement recycled polypropylene material and preparation method thereof |
| CN102153586A (en) * | 2011-01-25 | 2011-08-17 | 浙江大学宁波理工学院 | Compounds containing phosphorus, nitrogen and transition metal elements, and preparation method thereof |
| CN102153586B (en) * | 2011-01-25 | 2013-11-06 | 浙江大学宁波理工学院 | Compounds containing phosphorus, nitrogen and transition metal elements, and preparation method thereof |
| CN102219957A (en) * | 2011-05-13 | 2011-10-19 | 上海化工研究院 | Functional masterbatch of halogen-free intumescent flame retardant, and preparation method thereof |
| CN102219957B (en) * | 2011-05-13 | 2013-07-24 | 上海化工研究院 | Functional masterbatch of halogen-free intumescent flame retardant, and preparation method thereof |
| CN105838389A (en) * | 2016-04-13 | 2016-08-10 | 浙江大学宁波理工学院 | High-efficiency polyphosphate ester fire retardant and preparation method thereof |
| CN107418166A (en) * | 2017-08-22 | 2017-12-01 | 安徽悦尔伟塑料机械有限公司 | Halogen-free fire-resistant engineering plastics and preparation method thereof |
| CN107474500A (en) * | 2017-08-22 | 2017-12-15 | 安徽悦尔伟塑料机械有限公司 | High impact properties halogen-free flameproof manipulator and preparation method thereof |
| CN107556709A (en) * | 2017-08-22 | 2018-01-09 | 安徽悦尔伟塑料机械有限公司 | Fire-retardant mechanical arm of high-strength halogen-free and preparation method thereof |
| CN109354710A (en) * | 2018-10-19 | 2019-02-19 | 上海微巨实业有限公司 | A kind of phosphorous and nitrogen macromolecule expansion type flame retardant and its synthetic method |
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