CN107312178A - A kind of preparation method and applications of hydroxyl phosphonitrilic polymer - Google Patents

A kind of preparation method and applications of hydroxyl phosphonitrilic polymer Download PDF

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Publication number
CN107312178A
CN107312178A CN201710497653.9A CN201710497653A CN107312178A CN 107312178 A CN107312178 A CN 107312178A CN 201710497653 A CN201710497653 A CN 201710497653A CN 107312178 A CN107312178 A CN 107312178A
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hydroxyl
ammonia
phosphonitrilic
phosphonitrilic polymer
polymer
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梁栋
肖敏
沈浩
莫善军
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Sun Yat Sen University
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Sun Yat Sen University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025Polyphosphazenes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

The invention discloses a kind of preparation method and applications of hydroxyl phosphonitrilic polymer, this method is after hexachlorocyclotriph,sphazene addition xylene solvent is fully dissolved, in less than 5 DEG C, whisk and be at the uniform velocity passed through dry ammonia reaction, after 2 4h of reaction, stopping is filled with ammonia, the ammonia for making reactor be in air-tight state, bottle continues to react with hexachlorocyclotriph,sphazene, in placement 8 12 hours under normal temperature, then obtained mixture suction filtration removal solvent will be reacted, filter cake obtains white powdery solids after drying.By white solid in being taken out after high-temperature polycondensation 30min, it is put into air and is cooled to room temperature.Polycondensation product is distributed to after being washed repeatedly in deionized water, in being dried under vacuum to constant weight at 90 DEG C, that is, obtains water insoluble hydroxyl phosphonitrilic polymer.Material of the present invention prepares fairly simple, environmental protection, reliable and stable, material and is easy to get, implements easily, and prepared material has good adsorption effect to the dyestuff in waste water, heavy metal ion.

Description

A kind of preparation method and applications of hydroxyl phosphonitrilic polymer
Technical field
The present invention relates to the technical field of wastewater treatment sorbing material, a kind of preparation of hydroxyl phosphonitrilic polymer is referred in particular to Method and its application.
Background technology
Current water pollution is a global problem, and particularly some developing countries for being directed to developing the economy come Say, heavy contaminating enterprises concentrate, and the sewage disposal technology and the idea of backwardness that fall behind force them to be polluted in unconscious Environment;But in face of the reality of scarcity of fresh water resources, increasing people takes up to try every possible means to look for solution, but due to The discharge capacity of industrial wastewater is huge, and intractability is big, handles not thorough, ultimately results in many pollutants and more or less enters nature In water body.The characteristics of dyeing waste water is that concentration is high, water is big, ingredient is complicated, colourity is big, and various chemical industry are contained among waste water Dyestuff.Typically, since chemical dye belongs to the organic compound of difficult degradation, thus chemical dye in water body chemically Matter is typically more stable, so can be stranded in water body environment, and is difficult in the short time by Institute of Micro-biology's drop in environment Solution.Heavy metal can not be degraded, but it can be enriched with animals and plants, and the mankind are the tops of biological chain, so as the mankind eat After the animals and plants of these heavy metal pollutions, its harmful heavy metal element is enriched with human body, most harmful to human at last it is strong Health.According to the standard of China's sewage discharge, total cadmium, total lead belong to the first pollutant, and highest permission concentration of emission is respectively 0.1mg/L and 1.0mg/L;Total copper belongs to the second pollutant, it is allowed to one-level level discharge standard concentration be respectively 0.5mg/L. Therefore, before discharge heavy metal wastewater thereby, it is necessary to strictly remove this metal ion (or being reduced under permission concentration of emission), It so just can guarantee that the health of water environment.In numerous pollution treatment methods, absorption method is because having low cost, efficiency high and appearance The advantages of easily operating continuously, it is considered to be comparatively ideal advanced treating dyestuff and Treatment On The Wasterwater of Containing Heavy Metalions.Adsorption material The main organic and/or inorganic materials of matrix, organic polymer and the class of biomaterial three of material, these sorbing materials typically contain hydroxyl, carboxylic The functional groups such as base, Ryukyu's base, phosphate radical, amido, but the research of the sorbing material containing phosphonyl group is relatively fewer, but its energy Chelating ligands key is formed with cation (dye of positive ion, metal ion), so that with certain adsorption capacity.Existing absorption Material has that adsorbance is small, the problem of each side such as separation is difficult, to recycle and reuse rate low, therefore design and exploitation are a kind of Adsorbance is big, and removal efficiency is high, and the rate of adsorption is fast, high-performance adsorbent material that is efficiently easily reclaiming, can repeatedly regenerate is inevitable Pursuit.The present invention for important source material, is developed a kind of new hydroxyl phosphonitrilic polymer and used with hexachlorocyclotriph,sphazene (HCCP) Make sorbing material, and the dyestuff and heavy metal ion being applied in processing waste water.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of system of hydroxyl phosphonitrilic polymer with shortcoming Preparation Method and its application, material of the present invention prepare fairly simple, environmental protection, reliable and stable, material and are easy to get, implement easily, institute The material of preparation has good adsorption effect to the dyestuff in waste water, heavy metal ion, to different types of dyestuff, heavy metal The adsorption capacity of ion is different, shows good adsorptive selectivity.
To achieve the above object, technical scheme provided by the present invention is as follows:
A kind of preparation method of hydroxyl phosphonitrilic polymer, comprises the following steps:
1) ammonia replaces
Hexachlorocyclotriph,sphazene by purification is added in the incomplete closed reactor for fill xylene solvent fully After dissolving, 25~100g/L is configured to, is whisked in less than 5 DEG C and is at the uniform velocity continually fed into dry ammonia, course of reaction can engender White precipitate material, after reaction 2-4h, stopping is filled with ammonia, reactor is in air-tight state, and ammonia in bottle after Continuous to be reacted with hexachlorocyclotriph,sphazene, the suction filtration after being placed 8-12 hours under normal temperature, filter cake dries naturally, obtains white powder and consolidates Body;
2) high-temperature polycondensation and hydroxylating
White powdery solids obtained above are put into drying baker, in taken out after 120~150 DEG C of polycondensation 30min into Row is cooled down, crushed, and painting is then washed with deionized water, and removes accessory substance, while chlorine is optionally substituted by a hydroxyl group, by repeatedly washing after 90 Constant weight is dried under vacuum at DEG C, you can obtain water insoluble hydroxyl phosphonitrilic polymer, the hydroxyl phosphonitrilic polymer, which has, to be inhaled Attached function, containing the active group of cation, including amino, imino group, hydroxyl can be chelated.
Obtained hydroxyl phosphonitrilic polymer is irregular graininess, and the powder of required size can be obtained after screening by grinding End, to improve adsorption capacity.
In step 1) in, the flow velocity of the ammonia is 10~20ml/min.
Above-mentioned hydroxyl phosphonitrilic polymer can be used for removing Wastewater Dyes, heavy metal ion;Wherein, the dyestuff is crystallization The combination of one or both of purple, methylene blue, the soluble-salt of the heavy metal ion is copper chloride, copper nitrate, copper sulphate, chlorination One or more in cadmium, cadmium nitrate, plumbi nitras, lead chloride.
In use, by hydroxyl phosphonitrilic polymer be added in the aqueous solution containing dyestuff or heavy metal ion solubility In the aqueous solution of salt, being stirred at room temperature after 0.5~2 hour just can complete absorption;Wherein, in solution the concentration of dyestuff for 40 ~1000mg/L, and the concentration of heavy metal ion is 20~120mg/L;The dosage of hydroxyl phosphonitrilic polymer is 0.1 in solution ~0.4g/L.
Above-mentioned hydroxyl phosphonitrilic polymer can be used as the filler of adsorption tower.
The present invention compared with prior art, has the following advantages that and beneficial effect:
1st, the present invention uses hexachlorocyclotriph,sphazene to have obvious superiority for raw material.Hexachlorocyclotriph,sphazene contains stable knot The very active easily generation substitution reaction of chlorine on the hexatomic ring of structure, abundant electron rich element (N, P), its molecule forms crosslinking The advantages of macromolecular substances.
2nd, the molecular structure feature of hydroxyl phosphonitrilic polymer material prepared by the present invention:Containing it is a large amount of can chelate heavy metal from The active group of son, including amino, imino group, hydroxyl.
3rd, the present invention is using part chlorine on ammonia substitution hexachlorocyclotriph,sphazene, so that laid a good foundation for polymerisation, because For under the high temperature conditions, condensation reaction can occur for the chlorine on amino and another molecule on a molecule, multiple molecules that Condensation around here just forms a water-soluble difficult high molecular polymer.
4th, present invention process process is simple, environment-friendly, instrument and equipment is cheap, with preferable feasibility.
5th, prepared by the present invention hydroxyl phosphonitrilic polymer (being porous carbon materials) has to the heavy metal ion in waste water Good adsorption effect, the adsorption capacity to different types of heavy metal ion is different, shows good adsorptive selectivity;Inhale It is attached test result indicates that, crystal violet, methylene blue, lead ion, cadmium ion, cupric ion adsorption are respectively reached 1795.49mg/g, 667.32mg/g, 424.45mg/g, 132.23mg/g and 109.97mg/g.
Brief description of the drawings
Fig. 1 is the stereoscan photograph (SEM) of hydroxyl phosphonitrilic polymer in embodiment 1.
Fig. 2 is the infrared spectrogram (FTIR) of hydroxyl phosphonitrilic polymer in embodiment 1.
Fig. 3 is the zero potential analysis (Zate) of hydroxyl phosphonitrilic polymer in embodiment 1.
Embodiment
With reference to multiple specific embodiments, the invention will be further described.
Embodiment 1
The preparation process for the hydroxyl phosphonitrilic polymer that the present embodiment is provided is as follows:
10.0g hexachlorocyclotriph,sphazenes (HCCP) by purification are added in 250mL boiling flasks, 150mL bis- is added Toluene solvant is fully dissolved after HCCP, obtains 66.67g/L HCCP solution, flask is placed in frozen water, and control temperature is at 5 DEG C Hereinafter, whisk down and be at the uniform velocity passed through after ammonia (ammonia flow velocity is 10~20ml/min) reaction, reaction 2-4h, stopping is filled with ammonia, Closed reactor, is placed 8-12 hours.Then filter, filter cake obtains white powdery solids after drying.By obtained white powder Shape solid is placed in drying box, in being taken out after 120~150 DEG C of polycondensation 30min, is cooled to room temperature.Obtained polycondensation product is used Washcoated 3 times of substantial amounts of deionized water, is dried under vacuum to constant weight, you can obtain 6.81g water insoluble hydroxyl at 90 DEG C Polyphosphazene polymer (HPP), it is then standby after milled 300 mesh sieve.Wherein, the ESEM of obtained hydroxyl phosphonitrilic polymer Photo, infrared spectrogram, zero potential analysis are referred to shown in Fig. 1,2,3.
Hydroxyl phosphonitrilic polymer obtained above, which contains, can largely chelate the active group of cation, including amino, imido Base, hydroxyl, available for Wastewater Dyes, heavy metal ion is removed, also can be used as the filler of adsorption tower;Wherein dyestuff is crystallization The combination of one or both of purple, methylene blue, the soluble-salt of heavy metal ion is copper chloride, copper nitrate, copper sulphate, caddy, One or more in cadmium nitrate, plumbi nitras, lead chloride.When in use, hydroxyl phosphonitrilic polymer is added to containing dyestuff In the aqueous solution or heavy metal ion soluble-salt the aqueous solution in, be stirred at room temperature after 0.5~2 hour just can complete inhale It is attached;Wherein, the concentration of dyestuff is for 40~1000mg/L in solution, and the concentration of heavy metal ion is 20~120mg/L;Solution The dosage of middle hydroxyl phosphonitrilic polymer is 0.1~0.4g/L.
The adsorption experiment of heavy metal ion:The soluble-salt of heavy metal ion is dissolved in distilled water respectively, is configured to not With the heavy metal ion solution of gradient concentration, Cu2+,Cd2+20~80mg/L of initial concentration (mg/L) scope.Pb2+It is initial dense Spend (mg/L):20~120mg/L.The heavy metal ion solution for taking 50mL to be matched somebody with somebody respectively is put into 75mL centrifuge tube, is weighed 10mg hydroxyl phosphonitrilic polymers are added in above-mentioned heavy metal ion solution and adsorbed at 30 DEG C, are slowly stirred 2h.Using Flame type atomic absorption spectrophotometer determines the initial concentration and residual concentration of heavy metal ion, and then it is poly- to calculate hydroxyl phosphonitrile The adsorption capacity of compound heavy metal ion.Concrete outcome see the table below 1.
The hydroxyl phosphonitrilic polymer of table 1 is to Pb2+、Cd2+And Cu2+Adsorbance under conditions of different initial concentrations
Embodiment 2
The preparation process for the hydroxyl phosphonitrilic polymer that the present embodiment is provided is as follows:
7.5g hexachlorocyclotriph,sphazenes (HCCP) by purification are added in 250mL boiling flasks, 150mL diformazans are added Benzene solvent is fully dissolved after HCCP, obtains 50g/L HCCP solution, flask is placed in frozen water, controls temperature below 5 DEG C, Whisk down and be at the uniform velocity passed through ammonia reaction, after reaction 2-4h, stopping is filled with ammonia, and closed reactor is placed 8-12 hours.Then cross Filter, filter cake obtains white powdery solids after drying.Obtained white powdery solids are placed in drying box, in 120~150 DEG C Taken out after polycondensation 30min, be cooled to room temperature.By obtained polycondensation product washcoated 3 times with substantial amounts of deionized water, at 90 DEG C It is dried under vacuum to constant weight, you can obtain the water insoluble hydroxyl polyphosphazene polymers (HPP) of 5.7g, then milled 300 mesh sieve It is standby afterwards.
The adsorption experiment of dyestuff:Dyestuff is dissolved in distilled water respectively, the aqueous solution of different gradient concentrations is configured to, crystallized Purple initial concentration (mg/L) 50~1000mg/L of scope, the initial concentration (mg/L) of methylene blue:40~300mg/L.Respectively The dye solution for taking 50mL to be matched somebody with somebody is put into 75mL centrifuge tube, is weighed 10mg hydroxyl phosphonitrilic polymers and is added to above-mentioned dye Adsorbed in the material aqueous solution at 30 DEG C, be slowly stirred 2h.The initial concentration of dyestuff is determined and residual using ultraviolet specrophotometer Remaining concentration, and then calculate adsorption capacity of the hydroxyl phosphonitrilic polymer to dyestuff in water.Concrete outcome see the table below 2.
Adsorbance of the hydroxyl phosphonitrilic polymer of table 2 to crystal violet and methylene blue under conditions of different initial concentrations
Remarks:Adsorption capacity QeCalculation formula it is as follows:
QeThe adsorption capacity (mg/g) of one-adsorbent
C0One-dyestuff or the initial concentration of heavy metal ion (mg/L)
CeOne-dyestuff or heavy metal ion reach the concentration (mg/L) during adsorption equilibrium
The volume (L) of mono--solution of V
The quality (g) of mono--adsorbents of W
Clearance R calculation formula is as follows:
Examples of implementation described above are only the preferred embodiments of the invention, and the implementation model of the present invention is not limited with this Enclose, therefore the change that all shape, principles according to the present invention are made, it all should cover within the scope of the present invention.

Claims (5)

1. a kind of preparation method of hydroxyl phosphonitrilic polymer, it is characterised in that comprise the following steps:
1) ammonia replaces
Hexachlorocyclotriph,sphazene by purification is added in the incomplete closed reactor for fill xylene solvent and fully dissolved Afterwards, 25~100g/L is configured to, is whisked in less than 5 DEG C and is at the uniform velocity continually fed into dry ammonia, course of reaction can engender white Deposit, after reaction 2-4h, stopping is filled with ammonia, reactor is in air-tight state, and ammonia in bottle continue with Hexachlorocyclotriph,sphazene reacts, and the suction filtration after being placed 8-12 hours under normal temperature, filter cake dries naturally, obtains white powdery solids;
2) high-temperature polycondensation and hydroxylating
White powdery solids obtained above are put into drying baker, it is cold in taking out progress after 120~150 DEG C of polycondensation 30min But, crush, painting is then washed with deionized water, remove accessory substance, while chlorine is optionally substituted by a hydroxyl group, by repeatedly washing after at 90 DEG C It is dried under vacuum to constant weight, you can obtain water insoluble hydroxyl phosphonitrilic polymer, the hydroxyl phosphonitrilic polymer has absorption work( Can, containing the active group of cation, including amino, imino group, hydroxyl can be chelated.
2. a kind of preparation method of hydroxyl phosphonitrilic polymer according to claim 1, it is characterised in that:Obtained hydroxyl phosphorus Nitrile polymer is irregular graininess, the powder of required size can be obtained after screening by grinding, to improve adsorption capacity.
3. a kind of preparation method of hydroxyl phosphonitrilic polymer according to claim 1, it is characterised in that:In step 1) in, The flow velocity of the ammonia is 10~20ml/min.
4. the application of hydroxyl phosphonitrilic polymer described in a kind of claim 1, it is characterised in that:For removing Wastewater Dyes, again Metal ion;Wherein, the dyestuff is the combination of one or both of crystal violet, methylene blue, the solubility of the heavy metal ion Salt is the one or more in copper chloride, copper nitrate, copper sulphate, caddy, cadmium nitrate, plumbi nitras, lead chloride.
In use, by hydroxyl phosphonitrilic polymer be added in the aqueous solution containing dyestuff or heavy metal ion soluble-salt In the aqueous solution, being stirred at room temperature after 0.5~2 hour just can complete absorption;Wherein, in solution dyestuff concentration for 40~ 1000mg/L, and the concentration of heavy metal ion is 20~120mg/L;In solution the dosage of hydroxyl phosphonitrilic polymer be 0.1~ 0.4g/L。
5. the application of hydroxyl phosphonitrilic polymer described in a kind of claim 1, it is characterised in that:It is used as the filler of adsorption tower.
CN201710497653.9A 2017-06-27 2017-06-27 A kind of preparation method and applications of hydroxyl phosphonitrilic polymer Pending CN107312178A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109806851A (en) * 2019-03-25 2019-05-28 东华大学 A kind of cyclodextrin porous material and preparation method thereof
CN111548476A (en) * 2020-06-12 2020-08-18 广东裕泰实业有限公司 Flame-retardant environment-friendly polyurethane material and preparation method thereof
CN113831527A (en) * 2021-11-05 2021-12-24 万华化学集团股份有限公司 Preparation method of methallyl alcohol polyoxyethylene ether

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109806851A (en) * 2019-03-25 2019-05-28 东华大学 A kind of cyclodextrin porous material and preparation method thereof
CN109806851B (en) * 2019-03-25 2022-08-09 东华大学 Cyclodextrin porous material and preparation method thereof
CN111548476A (en) * 2020-06-12 2020-08-18 广东裕泰实业有限公司 Flame-retardant environment-friendly polyurethane material and preparation method thereof
CN111548476B (en) * 2020-06-12 2021-03-30 广东裕泰实业有限公司 Flame-retardant environment-friendly polyurethane material and preparation method thereof
CN113831527A (en) * 2021-11-05 2021-12-24 万华化学集团股份有限公司 Preparation method of methallyl alcohol polyoxyethylene ether

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