CN102964632A - Dendritic phosphorus nitrogen flame retardant, and preparation method and application thereof - Google Patents
Dendritic phosphorus nitrogen flame retardant, and preparation method and application thereof Download PDFInfo
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- CN102964632A CN102964632A CN201210429345XA CN201210429345A CN102964632A CN 102964632 A CN102964632 A CN 102964632A CN 201210429345X A CN201210429345X A CN 201210429345XA CN 201210429345 A CN201210429345 A CN 201210429345A CN 102964632 A CN102964632 A CN 102964632A
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- flame retardant
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Abstract
The invention discloses a dendritic phosphorus nitrogen flame retardant, and a preparation method and application thereof. The dendritic nitrogen phosphorus flame retardant is prepared by reaction of zero generation, first generation and second generation polyamide-amine with diphenyl chlorophosphate. The dendritic phosphorus nitrogen flame retardant provided by the invention employs a physical mixing method to conduct flame retardant modification on a polymer material; synergist flame retardant effect of phosphorus and nitrogen in the flame retardant improves flame retardant effect of the polymer, reduces the usage amount of flame retardant in the polymer material, and reduces preparation cost of the flame retardant material. The dendritic phosphorus nitrogen flame retardant has good compatibility with a polymer matrix; and the special dendritic structure can be used as a reinforced phase for the polymer matrix, so as to improve the mechanical properties of the polymer material.
Description
Technical field
The present invention relates to fire retardant and preparation method thereof, be specifically related to a kind of dendroid phosphorus-nitrogen containing flame retardant and its preparation method and application, especially its application in the preparation flame retarded polymeric material.
Background technology
Along with the appearance that the mankind improve and limit, ban use of halogen flame regulation (WEEE, RoHS in 2006 in 2005, the instructions such as EuP in 2007) environmental protection and healthy requirement, halogenated flame retardant is faced with great challenge.Phosphorus-nitrogen containing flame retardant is as a kind of halogen-free expansion fire retardant, along with rising, flame-retarded technology is widely used in flame-retardant modified polymkeric substance, when the superpolymer that contains this class phosphorus-nitrogen containing flame retardant is heated, the surface can generate the uniform carbonaceous foam layer of one deck, play heat insulation, oxygen barrier, press down the effect of cigarette, and prevent the molten drop phenomenon, have good flame retardant properties.Expansion type flame retardant is generally take phosphorus nitrogen as main expandable flame retardant functional element, two kinds of mixed type and one-pack types are arranged usually, the mixed type expanding fire retardant is the fire retardant that charcoal source, acid source, source of the gas compound are mixed into by a certain percentage, the single component expansion type flame retardant is to collect acid source, charcoal source, source of the gas in same intramolecular fire retardant, compare with the polycomponent expansion type flame retardant, the single component expansion type flame retardant has better thermostability and resistance to water soak, and better matrix phase capacitive and anti-surface transport and flame retarding efficiency be advantages of higher more.The dendroid phosphorus-nitrogen containing flame retardant provides a kind of new approach for the problem that solves above-mentioned flame-retardant modified macromolecular material existence.
Summary of the invention
The primary technical problem that the present invention will solve is to provide a kind of dendroid phosphorus-nitrogen containing flame retardant with flame retardant resistance.
Invent described dendroid phosphorus-nitrogen containing flame retardant, its structure is suc as formula shown in (Ia-c):
Second technical problem that the present invention will solve is to provide a kind of preparation method of above-mentioned dendroid phosphorus-nitrogen containing flame retardant.
The preparation method of described dendroid phosphorus-nitrogen containing flame retardant, method is as follows:
Zero generation, a generation and two PAMAMs shown in the formula (IIa-c) and diphenyl phosphate chloride reaction obtain the compound shown in the formula (Ia-c).
The below is elaborated to aforesaid method.
The described reaction of the inventive method specifically can be carried out according to following: zero generation, a generation and two PAMAMs and diphenyl phosphate chloride reaction, under the condition of solvent and acid binding agent existence, in 0～80 ℃ of reaction 2～10 hours, separate to get the dendroid phosphorus-nitrogen containing flame retardant.
Described solvent is selected from one of the following: halogenated alkane, amides, ether compound, nitrile compounds; Preferred one of the following: 1,2-ethylene dichloride, trichloromethane, tetracol phenixin, DMF, N,N-dimethylacetamide, ether, propyl ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile, butyronitrile; More preferably one of following: trichloromethane, DMF, acetonitrile.
One of described acid binding agent is preferred following: triethylamine, pyridine, sodium bicarbonate, yellow soda ash, sodium hydroxide.
The molar ratio that feeds intake of described polyamide-amide and diphenyl phosphate chloride is recommended as 1.0: 4.0～and 22.0, preferred 1.0: 4.0～19.2.The molar ratio that feeds intake of described acid binding agent and diphenyl phosphate chloride is 1.0～3.5: 1.0, preferred 1.5～2.0: 1.0.The volumetric usage of described solvent is recommended as 5～10ml/g in the quality of diphenyl phosphate chloride.
The temperature of reaction of the described reaction of method is preferably 30～60 ℃, and the reaction times is preferably 4～8 hours.
Method can adopt the conventional separation method such as distillation to separate and obtain formula (I) compound after reaction finishes.
Compared with prior art, beneficial effect of the present invention is embodied in following several respects:
Dendroid phosphorus-nitrogen containing flame retardant of the present invention is not halogen-containing, good flame retardation effect, applied widely, meet environmental requirement; Dendroid phosphorus-nitrogen containing flame retardant of the present invention adopts non-halogen system, thereby has reduced " secondary harm " in the material combustion process; Dendroid phosphorus-nitrogen containing flame retardant of the present invention utilizes phosphorus, the effect of nitrogen element cooperative flame retardant, improves the flame retardant effect to macromolecular material, reduces fire retardant in the usage quantity of macromolecular material, reduces the cost of fire retardant material.Dendroid phosphorus-nitrogen containing flame retardant of the present invention and polymeric matrix have good consistency, and the wild phase that can be used as polymeric matrix of its special dendritic structure improves the mechanical property of macromolecular material.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
Synthesizing of embodiment 1: four (two phenoxy group phosphoryls)-zero PAMAM
Mechanical stirring is being housed; thermometer; in the dry 250mL four-hole bottle of reflux condensing tube and dropping funnel; the diphenyl phosphate chloride and the 50mL trichloromethane that add 26.8g (0.10mol); rear slow dropping 12.9g (0.025mol) zero PAMAM stirs; 20.0g (0.20mol) mixed solution of triethylamine and 84mL trichloromethane; being warmed up to 30 ℃ after adding stirred 8 hours; revolve the steaming trichloromethane after the filtration and get crude product; and use distilled water wash; get faint yellow solid four (two phenoxy group phosphoryls)-zero PAMAM after the oven dry; yield is 63.4%, and purity is 94.6%.FT-IR(KBr，cm
-1)：3223，1676，1548，1259，1126，1074，1006，942。
1H?NMR(CDCl
3)δ(ppm)：8.22-7.84(m，4H)，7.35-7.06(m，40H)，3.86-3.72(m，4H)，3.36-3.08(m，24H)，2.68-2.47(m，8H)。
Embodiment 2
The synthetic operation of four (two phenoxy group phosphoryls)-zero PAMAM is with embodiment 1.In the reaction of diphenyl phosphate chloride and zero PAMAM, diphenyl phosphate chloride is 4.8: 1.0 with the molar ratio that feeds intake of zero PAMAM, the molar ratio that feeds intake of acid binding agent pyridine and diphenyl phosphate chloride is 1.0: 1.5, solvent is selected acetonitrile, 50 ℃ of temperature of reaction, reaction times is 5 hours, and yield is 73.4%.
Embodiment 3
The synthetic operation of four (two phenoxy group phosphoryls)-zero PAMAM is with embodiment 1.In the reaction of diphenyl phosphate chloride and zero PAMAM, diphenyl phosphate chloride is 5.6: 1.0 with the molar ratio that feeds intake of zero PAMAM, the molar ratio that feeds intake of acid binding agent sodium bicarbonate and diphenyl phosphate chloride is 3.5: 1.0, solvent is selected ether, 15 ℃ of temperature of reaction, reaction times is 10 hours, and yield is 41.4%.
Embodiment 4
The same EXAMPLE l of synthetic operation of four (two phenoxy group phosphoryls)-zero PAMAM.In the reaction of diphenyl phosphate chloride and zero PAMAM, diphenyl phosphate chloride is 6.4: 1.0 with the molar ratio that feeds intake of zero PAMAM, the molar ratio that feeds intake of acid binding agent sodium hydroxide and diphenyl phosphate chloride is 1.5: 1.0, solvent is selected butyl ether, 0 ℃ of temperature of reaction, reaction times is 8 hours, and yield is 25.6%.
Synthesizing of 5: eight (two phenoxy group phosphoryls)-one PAMAMs of embodiment
Mechanical stirring is being housed; thermometer; in the dry 250mL four-hole bottle of reflux condensing tube and dropping funnel; the diphenyl phosphate chloride and the 50mL acetonitrile that add 26.8g (0.10mol); rear slow dropping 17.86g (0.0125mol) PAMAM stirs; 23.7g (0.30mol) mixed solution of pyridine and 120mL acetonitrile; being warmed up to 45 ℃ after adding stirred 6 hours; revolve the steaming acetonitrile after the filtration and get crude product; and use distilled water wash; get light yellow solid eight (two phenoxy group phosphoryls)-one PAMAM after the oven dry; yield is 58.5%, and purity is 93.9%.FT-IR(KBr，cm
-1)：3274，1649，1553，1255，1120，1071，1007，933。
1H?NMR(CDCl
3)δ(ppm)：8.06-7.76(m，12H)，7.30-7.11(m，80H)，5.23-5.11(m，8H)，3.28-3.10(m，32H)，2.51-2.18(m，68H)。
Embodiment 6
The synthetic operation of eight (two phenoxy group phosphoryls)-one PAMAM is with embodiment 5.In the reaction of diphenyl phosphate chloride and a PAMAM, the molar ratio that feeds intake of diphenyl phosphate chloride and a PAMAM is 8.8: 1.0, the molar ratio that feeds intake of acid binding agent yellow soda ash and diphenyl phosphate chloride is 1.0: 1.0, solvent selects 1, the 2-ethylene dichloride, 30 ℃ of temperature of reaction, the reaction times is 8 hours, yield is 44.4%.
Embodiment 7
The synthetic operation of eight (two phenoxy group phosphoryls)-one PAMAM is with embodiment 5.In the reaction of diphenyl phosphate chloride and a PAMAM, the molar ratio that feeds intake of diphenyl phosphate chloride and a PAMAM is 10.0: 1.0, the molar ratio that feeds intake of acid binding agent sodium bicarbonate and diphenyl phosphate chloride is 2.5: 1.0, solvent is selected tetrahydrofuran (THF), 15 ℃ of temperature of reaction, reaction times is 7 hours, and yield is 31.7%.
Embodiment 8
The synthetic operation of eight (two phenoxy group phosphoryls)-one PAMAM is with embodiment 5.In the reaction of diphenyl phosphate chloride and a PAMAM, the molar ratio that feeds intake of diphenyl phosphate chloride and a PAMAM is 12.0: 1.0, the molar ratio that feeds intake of acid binding agent triethylamine and diphenyl phosphate chloride is 2.5: 1.0, solvent is selected N, the N-N,N-DIMETHYLACETAMIDE, 60 ℃ of temperature of reaction, the reaction times is 5 hours, yield is 64.9%.
Synthesizing of 9: ten six (two phenoxy group phosphoryls)-two PAMAMs of embodiment
Mechanical stirring is being housed; thermometer; in the dry 500mL four-hole bottle of reflux condensing tube and dropping funnel; the diphenyl phosphate chloride and the 50mLN that add 26.8g (0.10mol); the N-N,N-DIMETHYLACETAMIDE; rear slow dropping 22.5g (0.00625mol) two PAMAMs stir; 15.0g (0.15mol) triethylamine and 218mLN; the mixed solution of N-N,N-DIMETHYLACETAMIDE; being warmed up to 60 ℃ after adding stirred 6 hours; revolve after the filtration and steam N; the N-N,N-DIMETHYLACETAMIDE gets crude product; and use distilled water wash; get light yellow solid 16 (two phenoxy group phosphoryls)-two PAMAMs after the oven dry, yield is 53.2%, and purity is 92.7%.FT-IR(KBr，cm
-1)：3286，1663，1552，1249，1128，1059，1006，941。
1H?NMR(CDCl
3)δ(ppm)：8.13-7.81(m，28H)，7.34-7.09(m，160H)，5.11-4.82(m，24H)，3.75-3.06(m，112H)，2.77-2.38(m，148H)。
Embodiment 10
The synthetic operation of 16 (two phenoxy group phosphoryls)-two PAMAMs is with embodiment 9.In the reaction of diphenyl phosphate chloride and two PAMAMs, the molar ratio that feeds intake of diphenyl phosphate chloride and two PAMAMs is 19.2: 1.0, the molar ratio that feeds intake of acid binding agent pyridine and diphenyl phosphate chloride is 2.0: 1.0, solvent is selected N, the N-N,N-DIMETHYLACETAMIDE, 70 ℃ of temperature of reaction, the reaction times is 5 hours, yield is 49.4%.
Embodiment 11
The synthetic operation of 16 (two phenoxy group phosphoryls)-two PAMAMs is with embodiment 9.In the reaction of diphenyl phosphate chloride and two PAMAMs, the molar ratio that feeds intake of diphenyl phosphate chloride and two PAMAMs is 22.0: 1.0, the molar ratio that feeds intake of acid binding agent sodium bicarbonate and diphenyl phosphate chloride is 2.6: 1.0, solvent is selected propionitrile, 45 ℃ of temperature of reaction, reaction times is 9 hours, and yield is 31.3%.
Embodiment 12
The synthetic operation of 16 (two phenoxy group phosphoryls)-two PAMAMs is with embodiment 9.In the reaction of diphenyl phosphate chloride and two PAMAMs, the molar ratio that feeds intake of diphenyl phosphate chloride and two PAMAMs is 20.0: 1.0, the molar ratio that feeds intake of acid binding agent pyridine and diphenyl phosphate chloride is 2.8: 1.0, solvent is selected trichloromethane, 55 ℃ of temperature of reaction, reaction times is 7 hours, and yield is 43.9%.
Embodiment 13
The synthetic operation of 16 (two phenoxy group phosphoryls)-two PAMAMs is with embodiment 9.In the reaction of diphenyl phosphate chloride and two PAMAMs, the molar ratio that feeds intake of diphenyl phosphate chloride and two PAMAMs is 18.2: 1.0, the molar ratio that feeds intake of acid binding agent sodium hydroxide and diphenyl phosphate chloride is 1.5: 1.0, solvent selects 1, the 2-ethylene dichloride, 45 ℃ of temperature of reaction, the reaction times is 5 hours, yield is 35.4%.
Embodiment 14: the application of dendroid phosphorus-nitrogen containing flame retardant
The synthetic operation of eight (two phenoxy group phosphoryls)-one PAMAM is with embodiment 5.5.0g eight (two phenoxy group phosphoryls)-one PAMAM is dissolved in 20mLN; the N-N,N-DIMETHYLACETAMIDE; add 71.25g polyester polyol (molecular weight is 2000) and 19.83g4; 4 '-diphenylmethanediisocyanate; be warming up to 70 ℃, and under nitrogen protection, reacted 3 hours, add again 3.92g chainextender 1; 4-butyleneglycol and a small amount of catalyzer continue reaction 5 hours.Slough organic solvent 110 ℃ of decompressions, can get dendroid phosphorus-nitrogen containing flame retardant modified polyurethane matrix material, it is as follows that the taper calorimeter is measured the result of the fire-retardant performance of this matrix material.
Annotate---flame-retardant modified urethane: the massfraction that the dendroid phosphorus-nitrogen containing flame retardant accounts for urethane is 5%.
Claims (6)
1. dendroid phosphorus-nitrogen containing flame retardant, its structure is suc as formula shown in (Ia-c):
2. the preparation method of dendroid phosphorus-nitrogen containing flame retardant as claimed in claim 1, method is as follows: zero generation, a generation and two PAMAMs shown in the formula (IIa-c) react with diphenyl phosphate chloride, obtain the compound shown in the formula (Ia-c).
3. the preparation method of dendroid phosphorus-nitrogen containing flame retardant as claimed in claim 2, it is characterized in that described reaction is specific as follows: zero generation, a generation and two PAMAMs and diphenyl phosphate chloride reaction, under the condition of solvent and acid binding agent existence, in 0～80 ℃ of reaction 2～10 hours, separate to get the dendroid phosphorus-nitrogen containing flame retardant.
4. the preparation method of dendroid phosphorus-nitrogen containing flame retardant as claimed in claim 2 or claim 3 is characterized in that the molar ratio that feeds intake of described polyamide-amide and diphenyl phosphate chloride is 1.0: 4.0～22.0, preferred 1.0: 4.0～19.2.
5. the preparation method of dendroid phosphorus-nitrogen containing flame retardant as claimed in claim 3 is characterized in that described solvent is selected from one of the following: halogenated alkane, amides, ether compound, nitrile compounds.Preferred one of the following: 1,2-ethylene dichloride, trichloromethane, tetracol phenixin, DMF, N,N-dimethylacetamide, ether, propyl ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile, butyronitrile; More preferably one of following: trichloromethane, DMF, acetonitrile.
6. the preparation method of dendroid phosphorus-nitrogen containing flame retardant as claimed in claim 3, it is one of following to it is characterized in that described acid binding agent is selected from: triethylamine, pyridine, sodium bicarbonate, yellow soda ash, sodium hydroxide, the molar ratio that feeds intake of described acid binding agent and diphenyl phosphate chloride is 1.0～3.5: 1.0.
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Cited By (7)
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| CN105017526A (en) * | 2015-08-19 | 2015-11-04 | 常熟理工学院 | Compatibilizer for toughening and reinforcing nylon 6 and preparation method and application thereof |
| CN105418971A (en) * | 2016-01-25 | 2016-03-23 | 黄国波 | Preparing method of phosphorus nitrogen high load graphene flame retardant |
| CN105504352A (en) * | 2016-01-25 | 2016-04-20 | 黄国波 | Phosphorus-nitrogen dendrimer functionalized graphene fire retardant and application thereof |
| CN106589401A (en) * | 2017-01-04 | 2017-04-26 | 安庆师范大学 | Preparation method of P-containing silica gel-supported PAMAM type dendritic polymer |
| CN107325290A (en) * | 2017-07-13 | 2017-11-07 | 东华大学 | A kind of hyperbranched polymer flame retardant and its preparation method and application |
| CN113402707A (en) * | 2021-07-05 | 2021-09-17 | 威海晨源分子新材料有限公司 | Dendritic nitrogen-phosphorus flame retardant, preparation method and application thereof, and flame retardant |
| CN114044907A (en) * | 2021-12-15 | 2022-02-15 | 兴宇汽车零部件股份有限公司 | Intumescent flame retardant functionalized POSS flame retardant and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017526A (en) * | 2015-08-19 | 2015-11-04 | 常熟理工学院 | Compatibilizer for toughening and reinforcing nylon 6 and preparation method and application thereof |
| CN105418971A (en) * | 2016-01-25 | 2016-03-23 | 黄国波 | Preparing method of phosphorus nitrogen high load graphene flame retardant |
| CN105504352A (en) * | 2016-01-25 | 2016-04-20 | 黄国波 | Phosphorus-nitrogen dendrimer functionalized graphene fire retardant and application thereof |
| CN106589401A (en) * | 2017-01-04 | 2017-04-26 | 安庆师范大学 | Preparation method of P-containing silica gel-supported PAMAM type dendritic polymer |
| CN106589401B (en) * | 2017-01-04 | 2020-07-14 | 安庆师范大学 | Preparation method of P-containing silica gel loaded PAMAM type dendritic macromolecule |
| CN107325290A (en) * | 2017-07-13 | 2017-11-07 | 东华大学 | A kind of hyperbranched polymer flame retardant and its preparation method and application |
| CN113402707A (en) * | 2021-07-05 | 2021-09-17 | 威海晨源分子新材料有限公司 | Dendritic nitrogen-phosphorus flame retardant, preparation method and application thereof, and flame retardant |
| CN114044907A (en) * | 2021-12-15 | 2022-02-15 | 兴宇汽车零部件股份有限公司 | Intumescent flame retardant functionalized POSS flame retardant and preparation method thereof |
| CN114044907B (en) * | 2021-12-15 | 2022-11-11 | 兴宇汽车零部件股份有限公司 | Intumescent flame retardant functionalized POSS flame retardant and preparation method thereof |
| WO2023109737A1 (en) * | 2021-12-15 | 2023-06-22 | 兴宇汽车零部件股份有限公司 | Intumescent, flame-retardant and functionalized poss flame retardant and preparation method therefor |
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Application publication date: 20130313 |