CN110330662A - A kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound and preparation method thereof - Google Patents
A kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound and preparation method thereof Download PDFInfo
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- CN110330662A CN110330662A CN201910587875.9A CN201910587875A CN110330662A CN 110330662 A CN110330662 A CN 110330662A CN 201910587875 A CN201910587875 A CN 201910587875A CN 110330662 A CN110330662 A CN 110330662A
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Abstract
The present invention relates to a kind of polyethyleneimines and polyphosphoric acid polyelectrolyte complex compound and preparation method thereof, belong to synthetic material technical field.A ammonium polyphosphate and 40~200 parts of solvents are added in reaction vessel, the temperature for controlling reactor is 50~100 DEG C, insulated and stirred 10min (minute)~5h (hour)；1~4 part of polyethyleneimine and 20~40 parts of solvents are added to glass container, stir 10min~1h.Polyethylenimine solution is added dropwise after ammonium polyphosphate solution is transparent, time for adding is 10min~1h.It is cooled to room temperature after reaction 10min~3h, reaction resulting material is separated using filtering or being centrifuged, products therefrom distilled water, ethyl alcohol repeatedly wash, and then dry, are ground up, sieved, and obtain polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound.Reaction condition of the invention is mildly stablized, reproducible, and yield is high, is suitble to expanding production；And the polyion complex compound can be improved many performances such as the fire-retardant of polymer, high temperature resistant.
Description
Technical field
The present invention relates to a kind of polyethyleneimines and polyphosphoric acid polyelectrolyte complex compound and preparation method thereof, belong to synthesis material
Expect technical field.
Background technique
Ammonium polyphosphate (ammonium polyphosphate, APP) is also known as polyphosphoric acids, and general formula of molecular structure is
(NH4)n+2PnO3n+1, when n is sufficiently large, (NH can be written as4PO3)n, the relative molecular mass of structural unit is 97.01, theoretical phosphorus
Content is 31.92%, and theoretical nitrogen content is 14.44%.Ammonium polyphosphate has crystal type and amorphous two kinds of solid forms, crystal type
Ammonium polyphosphate is white powder, more stable at normal temperature, odorlessness.The crystal type ammonium polyphosphate being currently known shares six kinds of crystal forms
(I, II, III, IV, V and VI type), wherein common ammonium polyphosphate is I type and II type.The I type ammonium polyphosphate degree of polymerization is smaller,
Decomposition temperature is lower, water-soluble larger.The II type ammonium polyphosphate degree of polymerization is bigger, and initial decomposition temperature is up to 300 DEG C or so, often
Temperature is insoluble in water and organic solvent, and water solubility is in 0.5g/100mL or less at room temperature.Ammonium polyphosphate is a kind of important Phos
Flame retardant, at the same be also expanding fire retardant in important component, have phosphorus content height, Halogen, low cigarette, low toxicity, without corruption
The advantages that corrosion, flame retarding efficiency is high, can be used in multiple polymers.
Polyethyleneimine (Poly (ethylenimine), PEI) molecular formula is (C2H5N)n.Also known as polyethylene imine is
A kind of water soluble polymer.Colourless or faint yellow glutinous thick liquid, has hygroscopicity, is dissolved in water, ethyl alcohol, does not dissolve in benzene.
Polyethyleneimine exists in water with polymerizing cationically, can neutralize and adsorb all anionic species, moreover it is possible to chelaization heavy metal
Ion.Using the cationic of its height, paper-making water treatment, electroplate liquid, dispersing agent field can be applied to.
Ammonium polyphosphate can be dissolved in water under high temperature as a kind of special anionic polyelectrolyte on a small quantity.Polyethyleneimine is
Cationic polyelectrolyte.Ammonium polyphosphate ionizes out NH in water4 +, be left main chain on O-, charge with cationic polyelectrolyte
It associates, forms polyelectrolyte complex compound.In addition, someone is with APP, bPEI (polyethyleneimine of branching), BPE (biomass
Polyphosphate electrolyte)；The organic inorganic hybridization object fire retardant that the method preparation number of plies using LBL self-assembly is 1~6, patent
Number (CN201610480113.5).Cai Xin is in its Master's thesis (NCC/APP/SiO2The LBL self-assembly of colloid and in WPC
Fire-retardant application [D]) in use layer-by-layer, using nanocrystalline cellulose ammonium polyphosphate modifying as anionic polyelectrolyte
Matter, with cationic polyethyleneimine modified Nano SiO2As cationic polyelectrolyte, it is poly- that NCC/APP anion is constructed layer by layer
Electrolyte and PEI/SiO2The fire-retardant colloidal dispersion of cationic polyelectrolyte.Ammonium polyphosphate and polyethyleneimine are mostly used as solution
With on LBL self-assembly is fire-retardant, seldom both reports directly synthesize a kind of effective solid flame retardant.
Summary of the invention
The purpose of the present invention is preparing the polyethyleneimine of solid and polyphosphoric acid polyelectrolyte complex compound, can be added to various
In polymer.
Polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound of the invention, since ammonium polyphosphate is a kind of special poly- yin
With cationic polyelectrolyte polyethyleneimine complex reaction can occur for ionic electrolytes under certain conditions, generate purpose and produce
Object.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound of the invention, is by ammonium polyphosphate and polyethyleneimine
Reaction is prepared, mass percent are as follows: ammonium polyphosphate 30%~70%, polyethyleneimine 70%~30%.
The preparation method of a kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound of the invention, specific preparation method
It is as follows:
1) ammonium polyphosphate and solvent are added in reaction vessel, agitating and heating is reacted, and the temperature of reactor is controlled
It is 50~100 DEG C, insulated and stirred 10min~5h obtains transparent reaction liquid；
2) polyethyleneimine and solvent are added to glass container, stir 10min~1h, obtains uniformly mixed solution；
3) it will 2) obtain in 1) clear solution that solution is added drop-wise to dropwise, time for adding is 10min~1h, is stirred, control
Reaction temperature is 50~100 DEG C, insulation reaction 10min~3h；
4) using the solvent removal for filtering or being centrifuged by step 3) after reaction, products therefrom distilled water, ethyl alcohol are more
Then secondary washing is dried, is ground up, sieved, polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound are obtained.
Above-mentioned steps 1) used in ammonium polyphosphate can be the ammonium polyphosphate of I type and II type, ammonium polyphosphate and solvent
Mass ratio is 1 gram: 40~200mL；
Above-mentioned steps 2) used in be polyethyleneimine.The mass ratio of polyethyleneimine and solvent is 1 gram: 5~40mL；
Above-mentioned steps 1) used in solvent be C1~C3 alcohol, formaldehyde, acetic acid, one of deionized water or its mixing
Object；
Above-mentioned steps 2) used in solvent be C1~C3 alcohol, formaldehyde, acetic acid, one of deionized water or its mixing
Object；
The bright spot that the present invention has is: passing through the polyelectrolyte of two kinds of oppositely chargeds of ammonium polyphosphate and polyethyleneimine
Complexing has synthesized a kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound, opens polyelectrolyte as fire retardant
New method plays guiding function for the use of numerous polyelectrolyte.The infrared spectrum of products therefrom is as shown in Figure 1.This method work
Skill is simple, and the used time is shorter, and raw material is easy to get, and cost is relatively low.Product is prepared compared with ammonium polyphosphate, in polymer material is fire-retardant
The flame retardant property and mechanical property of polymer can be significantly improved.
Detailed description of the invention
Fig. 1 is polyethyleneimine and poly- phosphorus prepared by ammonium polyphosphate, the infrared spectrum of polyethyleneimine and embodiment 1
The infrared spectrum of sour polyelectrolyte complex compound.
Specific embodiment
Below by embodiment, the present invention will be further described, but embodiment is not intended to limit protection scope of the present invention.
Embodiment 1
The distilled water of the ammonium polyphosphate of a quality and 80 parts of quality is added in reaction vessel, stirs evenly and is warming up to
90 DEG C, insulated and stirred obtains transparent reaction liquid after 1 hour；The distilled water of the polyethyleneimine of 2 parts of quality and 20 parts of quality is added
Enter to glass container, obtains uniformly mixed solution after stirring 15 minutes；Polyethyleneimine is added dropwise in ammonium polyphosphate solution
Amine aqueous solution, time for adding are 30 minutes, are cooled to room temperature after continuing insulation reaction 2 hours；Reaction solution is divided using filtering
From, it is repeatedly washed with distilled water, then dries, is ground up, sieved, acquisition polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound.
From the infrared spectrum of ammonium polyphosphate and polyethyleneimine polyion complex compound it is found that the 1417cm of ammonium polyphosphate-1Place
Peak be NH4 +Typical vibration absorption peak, and disappear in ammonium polyphosphate and polyethyleneimine polyion complex compound, illustrate product
In and do not contain NH4 +.Furthermore there are 1243cm with polyethyleneimine polyion complex compound for ammonium polyphosphate-1Locate the vibration of P=O key
Absorption peak, 1068cm-1Locate the vibration absorption peak and 868cm of P-O key-1The vibration absorption peak for locating P-O-P key, illustrates P=O, P-
O-P structure is present in product.The emerging 963cm in ammonium polyphosphate and polyethyleneimine polyion complex compound-1The peak at place
For P-O-C key, illustrate that ammonium polyphosphate sloughs NH4 +, polyethyleneimine sloughs-NH2.This infrared spectrum demonstrates both poly- electrolysis
Complex reaction occurs for matter.
Embodiment 2
The distilled water of the ammonium polyphosphate of a quality and 40 parts of quality is added in reaction vessel, stirs evenly and is warming up to
100 DEG C, insulated and stirred obtains transparent reaction liquid after 1.5 hours；By the distilled water of the polyethyleneimine of 1 part of quality and 40 parts of quality
It is added to glass container, stirring obtained uniformly mixed solution after 15 minutes；Polyethylene is added dropwise in ammonium polyphosphate solution
Imide liquor, time for adding are 10 minutes, are cooled to room temperature after continuing insulation reaction 1 hour；Reaction solution is carried out using filtering
Separation, is repeatedly washed with distilled water, ethyl alcohol, then dries, is ground up, sieved, and obtains polyethyleneimine and polyphosphoric acid polyelectrolyte
Complex compound.
Embodiment 3
The distilled water of the ammonium polyphosphate of a quality and 200 parts of quality is added in reaction vessel, heating is stirred evenly
To 100 DEG C, insulated and stirred obtains transparent reaction liquid after 2 hours；By the distilled water of the polyethyleneimine of 4 parts of quality and 20 parts of quality
It is added to glass container, stirring obtains uniformly mixed solution after ten minutes；Polyethylene is added dropwise in ammonium polyphosphate solution
Imide liquor, time for adding are 1 hour, are cooled to room temperature after continuing insulation reaction 3 hours；Reaction solution is divided using filtering
From, it is repeatedly washed with distilled water, then dries, is ground up, sieved, acquisition polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound.
Embodiment 4
The distilled water of the ammonium polyphosphate of a quality and 40 parts of quality is added in reaction vessel, stirs evenly and is warming up to
50 DEG C, insulated and stirred obtains transparent reaction liquid after ten minutes；The distilled water of the polyethyleneimine of 4 parts of quality and 20 parts of quality is added
Enter to glass container, stirs and obtain uniformly mixed solution after ten minutes；Polyethyleneimine is added dropwise in ammonium polyphosphate solution
Amine aqueous solution, time for adding are 1 hour, are cooled to room temperature after continuing insulation reaction 3 hours；Reaction solution is divided using filtering
From, it is repeatedly washed with distilled water, then dries, is ground up, sieved, acquisition polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound.
Embodiment 5
The distilled water of the ammonium polyphosphate of a quality and 200 parts of quality is added in reaction vessel, heating is stirred evenly
To 50 DEG C, insulated and stirred obtains transparent reaction liquid after 2 hours；By the distilled water of the polyethyleneimine of 4 parts of quality and 40 parts of quality
It is added to glass container, stirring obtains uniformly mixed solution after ten minutes；Polyethylene is added dropwise in ammonium polyphosphate solution
Imide liquor, time for adding are 1 hour, continue insulation reaction and are cooled to room temperature after ten minutes；Reaction solution is carried out using filtering
Separation, is repeatedly washed with distilled water, then dries, is ground up, sieved, and obtains polyethyleneimine and polyphosphoric acid polyelectrolyte complex
Object.
Embodiment 6
The distilled water of the ammonium polyphosphate of a quality and 200 parts of quality is added in reaction vessel, heating is stirred evenly
To 50 DEG C, insulated and stirred obtains transparent reaction liquid after 5 hours；By the distilled water of the polyethyleneimine of 4 parts of quality and 20 parts of quality
It is added to glass container, stirring obtained uniformly mixed solution after 1 hour；Polyethyleneimine is added dropwise in ammonium polyphosphate solution
Amine aqueous solution, time for adding are 1 hour, are cooled to room temperature after continuing insulation reaction 3 hours；Reaction solution is divided using filtering
From, it is repeatedly washed with distilled water, then dries, is ground up, sieved, acquisition polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound.
Claims (4)
1. a kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound, it is characterised in that: by ammonium polyphosphate and polyethyleneimine
Reaction is prepared, mass percent are as follows:
Ammonium polyphosphate 30%-70%
Polyethyleneimine 70%-30%.
2. the preparation method of a kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound, it is characterised in that specific preparation step is such as
Under:
1) ammonium polyphosphate and solvent are added in reaction vessel, agitating and heating is reacted, and the temperature for controlling reactor is 50
~100 DEG C, insulated and stirred 10min~5h obtains transparent reaction liquid；
2) polyethyleneimine and solvent are added to glass container, stir 10min~1h, obtains uniformly mixed solution；
3) it will 2) obtain in 1) clear solution that solution is added drop-wise to dropwise, time for adding is 10min~1h, stirring, control reaction
Temperature is 50~100 DEG C, insulation reaction 10min~3h；
4) using the solvent removal for filtering or being centrifuged by step 3) after reaction, products therefrom distilled water, ethyl alcohol are repeatedly washed
It washs, then dries, is ground up, sieved, obtain polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound.
Above-mentioned steps 1) used in ammonium polyphosphate can be the ammonium polyphosphate of I type and II type, the quality of ammonium polyphosphate and solvent
Than for 1 gram: 40~200mL (milliliter)；
Above-mentioned steps 2) used in be polyethyleneimine.The mass ratio of polyethyleneimine and solvent is 1 gram: 5~40mL；
Above-mentioned steps 1) used in solvent be C1~C3 alcohol, formaldehyde, acetic acid, or mixtures thereof one of deionized water；
Above-mentioned steps 2) used in solvent be C1~C3 alcohol, formaldehyde, acetic acid, or mixtures thereof one of deionized water.
3. the preparation method of a kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound according to claim 2, special
Sign is: reaction vessel has condensation reflux unit, temperature regulating device, agitating device.
4. the preparation method of a kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound according to claim 2, special
Sign is: the sequence of step 1) and step 2) is exchanged, remaining step is constant；Or the dropwise addition sequence in step 3) is changed to 1) react
Drop is added in 2) reaction solution, remaining step is constant.
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| CN109056411A (en) * | 2018-07-18 | 2018-12-21 | 内江师范学院 | A kind of paper fire retardant of core-shell structure and its preparation method and application |
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2019
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| WO2015069689A1 (en) * | 2013-11-05 | 2015-05-14 | The Texas A&M University System | Aqueous polyelectrolyte complex as one pot nanocoating solution to impart antiflammable behavior to various substrates |
| CN103966893A (en) * | 2014-05-07 | 2014-08-06 | 浙江理工大学 | Method for preparing phosphorus-nitrogen-containing polyelectrolyte complex flame-retardant cellulosic fiber product |
| CN107057199A (en) * | 2017-05-09 | 2017-08-18 | 浙江省仙居县博达异型橡塑有限公司 | A kind of low-smoke non-halogen flame-retardant sealing strip and preparation method thereof |
| CN109056411A (en) * | 2018-07-18 | 2018-12-21 | 内江师范学院 | A kind of paper fire retardant of core-shell structure and its preparation method and application |
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Application publication date: 20191015 |