CN105542159B - A kind of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant and its synthetic method - Google Patents
A kind of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant and its synthetic method Download PDFInfo
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- CN105542159B CN105542159B CN201610089996.7A CN201610089996A CN105542159B CN 105542159 B CN105542159 B CN 105542159B CN 201610089996 A CN201610089996 A CN 201610089996A CN 105542159 B CN105542159 B CN 105542159B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/0206—Polyalkylene(poly)amines
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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Abstract
A kind of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant and its synthetic method, are related to a kind of phosphorous nitrogen combustion inhibitor.Preparation method：Under nitrogen protection, paraformaldehyde, solvent and polyethyleneimine are sequentially added into the container equipped with stirring magneton and condensation reflux unit, after to be dissolved; DOPO, after reaction, concentrated by rotary evaporation is added; reprecipitation, filtering, up to branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant after drying.It will be halogen-free and the polyethyleneimine of phosphorus-nitrogen containing and DOPO are introduced into molecule, which contains multiple active amine sites, can be used as basis material toughener, and the rigid phenyl ring of upper two of phosphorous DOPO can increase basis material intensity.Not only can reinforcing material flame retardant property, but also do not influence its mechanical performance.It can be used for the flame-retardant modified of polyester, epoxy resin, PBT etc..More more nitrogen cooperative flame retardants of phosphorus, flame retarding efficiency is high, few for basis material additive amount, and preparation method is easy, and raw material is cheap, and yield is higher.
Description
Technical field
The present invention relates to a kind of phosphorous nitrogen combustion inhibitor, it is specifically related to can be used for the fire-retardant of polymer material, improves material
A kind of fire-retardant and fire protecting performance branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant and its synthetic method.
Background technology
Since the combustibility of many polymer will pacify life using fire once occurs after these polymer materials
It threatens entirely, therefore flame retardance of polymer arouses the concern of relevant departments.When improving flame retardance of polymer performance and inhibiting its burning
Discharging toxic smog gas becomes the necessary of polymer development.Flame retardance of polymer divides addition type and response type.Addition type is easy to run off,
Additive amount is big, it is also possible to influence the mechanical performance of matrix.Reactive-type flame retardant can be formed uniform with the certain functional group reactions of matrix
Material that can be compatible with basis material, form intrinsically flame retarded high molecular material.
It is intrinsic fire-retardant in order to achieve the purpose that, amido or polyalcohol can be introduced, halogen system and phosphorus system are divided into.But halogen system is fire-retardant
Toxic gas is will produce, therefore environmental pollution or injury human body can be caused.Phosphorus-containing polyol or phosphorous amine compounds are to compare
Ideal fire retardant.Chinese patent CN105218859A has synthesized a kind of response type Organophosphonate fire retardant, and this compound contains
There is hydroxyl reactive group, there is better stability, Inherent Flame Retardant Polymers material can be prepared as reactive flame retardant, as
Additive flame retardant uses, and can also be plasticized.Chinese patent CN105061511A has synthesized bridged rings phosphonitrile reactive flame retardant,
The fire retardant has high rigidity, large space steric hindrance, more active sites, has fabulous thermal stability, can be used as reactive flame retardant
For in epoxy resin.Chinese patent CN105061510A is prepared for a kind of reactive type water-solubility fire retardant, which has
The structure of Amino End Group and carboxyl, suitable for obtaining intrinsically flame retarded polyamide.
Therefore, the fire retardant of the halogen-free environmental protection of inherent flame retardant with more reactivity points is researched and developed with important meaning
Justice.
Invention content
The present invention is intended to provide contain multiple reactivity sites and nitrogen content height simultaneously, and the phosphorous fire-retardant bases of DOPO
Group can be used in a kind of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant and its synthetic method of epoxy resin, polyester, PBT etc..
The chemical structural formula of the branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant (PEI-DOPO) is as follows：
Wherein, n is the degree of polymerization, n=1~20.
The preparation method of the branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant (PEI-DOPO) is as follows：
Under nitrogen protection, paraformaldehyde, molten is sequentially added into the container equipped with stirring magneton and condensation reflux unit
After to be dissolved, DOPO is added in agent and polyethyleneimine, after reaction, concentrated by rotary evaporation, and reprecipitation, filtering, up to branched chain type after drying
Macromolecular phosphorus-nitrogen containing reactive-type flame retardant.
The paraformaldehyde, the amido of polyethyleneimine, DOPO molar ratio can be 1: 1: (0.8~4.2)；The poly- second
The molecular weight of alkene imines can be 600~10000；The solvent can be n,N-Dimethylformamide, and the dosage of solvent is in mass ratio
Can be 2~20 times of each solid material gross mass；The temperature of the reaction can be 50~80 DEG C, and the time of reaction can be 4~8h；
The condition of the drying can be dry in vacuum drying chamber；The solvent of the precipitation can be ethyl acetate, and the precipitation can be anti-
It precipitates 2~4 times again.
Compared with prior art, the invention has the characteristics that：
1) it will be halogen-free and the polyethyleneimine of phosphorus-nitrogen containing and DOPO are introduced into molecule, obtain a kind of new branched type
Macromolecular structure fire retardant.
2) fire retardant (PEI-DOPO) contains multiple active amine sites, can be used as basis material toughener, Er Qiehan
The rigid phenyl ring of upper two of phosphorus DOPO can increase basis material intensity.Not only can reinforcing material flame retardant property, but also do not influence its mechanicalness
Energy.It can be used for the flame-retardant modified of polyester, epoxy resin, PBT etc..
3) upper more more nitrogen cooperative flame retardants of phosphorus of the fire retardant (PEI-DOPO), flame retarding efficiency is high, is added for basis material
Amount is few, and the fire retardant preparation method is easy, and raw material is cheap, and yield is higher, can carry out commercial industries.
Description of the drawings
Fig. 1 is 1 fire retardant PEI-DOPO's of embodiment1HNMR nuclear magnetic spectrograms.
Fig. 2 is 1 polyethyleneimine PEI's of embodiment1HNMR nuclear magnetic spectrograms.
Fig. 3 is the infrared spectrum of embodiment 1 polyethyleneimine PEI and fire retardant PEI-DOPO.
Specific implementation mode
Below by drawings and examples, the invention will be further described.
Embodiment 1：
Under nitrogen protection, 0.3g is sequentially added into the 50ml three-necked flasks equipped with stirring magneton and condensation reflux unit
Paraformaldehyde, 5ml N,N-dimethylformamides (DMF) and 1g polyethyleneimines (molecular weight 600) are dissolved in the molten of 1ml DMF
Liquid after to be dissolved, is added 2.16g DOPO, is then gradually warming up to 70 DEG C, reacts 4h, and concentrated by rotary evaporation is precipitated with ethyl acetate
Twice, it is required fire retardant (PEI-DOPO) that filtration drying, which obtains yellow solid powder,.
By Fig. 1's1HNMR nuclear magnetic spectrograms are visible, and in 6.477~8.317ppm Fig. 2 polyethyleneimines PEI occur no
Ph-H proton peaks, and the P-H proton peaks of the DOPO at pertinent literature report 8.885ppm then disappear, and illustrate fire retardant PEI-
The successful synthesis of DOPO.
It is compared by the infared spectrum of Fig. 2 polyethyleneimines PEI and fire retardant PEI-DOPO, it is seen that polyethyleneimine exists
3279cm-1The peaks N-H at place disappear, and in 1265cm-1And 1002cm-1Nearby occur the peaks P=O of DOPO and the peaks P-O respectively,
Also illustrate the successful synthesis of fire retardant PEI-DOPO.
Embodiment 2：
Under nitrogen protection, it is sequentially added into the 150ml three-necked flasks equipped with stirring magneton and condensation reflux unit
1.2g paraformaldehydes, 50ml N,N-dimethylformamides (DMF) and 6g polyethyleneimines (molecular weight 1800) are dissolved in 5ml
The solution of DMF after to be dissolved, is added 8.64g DOPO, is then gradually warming up to 60 DEG C, reacts 5h, concentrated by rotary evaporation, with acetic acid second
Ester precipitates three times, and it is PEI-DOPO that filtration drying, which obtains yellow solid powder,.
Embodiment 3：
Under nitrogen protection, 0.6g is sequentially added into the 50ml three-necked flasks equipped with stirring magneton and condensation reflux unit
Paraformaldehyde, 8ml N,N-dimethylformamides (DMF) and 25g polyethyleneimines (molecular weight 10000) are dissolved in 2ml DMF's
Solution after to be dissolved, is added 4.32g DOPO, is then gradually warming up to 55 DEG C, reacts 6h, and concentrated by rotary evaporation is heavy with ethyl acetate
It forms sediment three times, it is PEI-DOPO that filtration drying, which obtains yellow solid powder,.
Embodiment 4：
Under nitrogen protection, it is sequentially added into the 250ml three-necked flasks equipped with stirring magneton and condensation reflux unit
1.5g paraformaldehydes, 75ml N,N-dimethylformamides (DMF) and 7.5g polyethyleneimines (molecular weight 600) are dissolved in 25ml
The solution of DMF after to be dissolved, is added 10.8g DOPO, is then gradually warming up to 80 DEG C, reacts 6h, concentrated by rotary evaporation, with acetic acid second
Ester precipitates twice, and it is PEI-DOPO that filtration drying, which obtains yellow solid powder,.
The present invention is mainly with -9 oxa- -10- phospho hetero phenanthrene -10- oxides of polyethyleneimine (PEI) and 9,10- dihydros
(DOPO) it is raw material, synthesizes phosphorus-nitrogen containing reactive-type flame retardant.It mainly will first be dissolved in the paraformaldehyde and polyethyleneimine of solvent
(PEI) container for being connected with nitrogen and equipping condensation reflux unit and stirrer is added, is then added DOPO, temperature reaction, use is molten
Agent washing of precipitate, filtering vacuum drying, it is the fire retardant (PEI-DOPO) to finally obtain yellow solid powder.The present invention closes
At Large molecule active fire retardant, have preparation method it is simple, mild condition, raw material is cheap, and flame retardant property is good, and with matrix phase
Capacitive is good, it may also be used for toughening, the fire retardant are halogen-free, and are environment-friendlyflame-retardant flame-retardant materials.
Claims (9)
1. a kind of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant, it is characterised in that its chemical structural formula is as follows：
Wherein, n is the degree of polymerization, n=1~20.
2. a kind of preparation method of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant as described in claim 1, it is characterised in that its
It is as follows：
Under nitrogen protection, to equipped with stirring magneton and condensation reflux unit container in sequentially add paraformaldehyde, solvent and
After to be dissolved, DOPO is added in polyethyleneimine, and after reaction, concentrated by rotary evaporation, reprecipitation, filtering, branched chain type divides greatly to obtain the final product after drying
Sub- phosphorus-nitrogen containing reactive-type flame retardant；
The paraformaldehyde, the amido of polyethyleneimine, DOPO molar ratio be 1: 1: (0.8~4.2).
3. a kind of preparation method of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 2, it is characterised in that institute
The molecular weight for stating polyethyleneimine is 600~10000.
4. a kind of preparation method of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 2, it is characterised in that institute
It is N,N-dimethylformamide to state solvent.
5. a kind of preparation method of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 2, it is characterised in that institute
The dosage for stating solvent is 2~20 times of each solid material gross mass in mass ratio.
6. a kind of preparation method of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 2, it is characterised in that institute
The temperature for stating reaction is 50~80 DEG C, and the time of reaction is 4~8h.
7. a kind of preparation method of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 2, it is characterised in that institute
It is dry in vacuum drying chamber to state dry condition.
8. a kind of preparation method of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 2, it is characterised in that institute
The solvent for stating precipitation is ethyl acetate.
9. a kind of preparation method of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 2, it is characterised in that institute
Stating precipitation is repeated precipitation 2~4 times.
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| CN107474247B (en) * | 2017-07-28 | 2020-03-24 | 江南大学 | Preparation method of phosphorus-nitrogen synergistic water-soluble polymer flame retardant |
| CN107501492B (en) * | 2017-08-10 | 2019-06-07 | 长春工业大学 | Schiff bases formula phosphorus nitrogen expansion type combustion inhibitor and its preparation method and application |
| CN110527100A (en) * | 2019-09-12 | 2019-12-03 | 贵州省材料产业技术研究院 | Poly- phosphamide fire retardant and its preparation method and application |
| CN114957655B (en) * | 2022-05-18 | 2023-11-28 | 东莞市迪彩塑胶五金有限公司 | Phosphorus-nitrogen high-molecular flame retardant and preparation method thereof |
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| CN104017210B (en) * | 2014-06-06 | 2016-04-27 | 浙江大学宁波理工学院 | A kind of long chain type metal-complexing expansion type flame retardant and preparation method thereof |
| CN104262398B (en) * | 2014-09-23 | 2016-07-06 | 厦门大学 | A kind of phosphorus-nitrogen containing flame retardant containing activity double key and preparation method thereof and application |
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