Star-shaped hyperbranched polymer with triethanolamine core, carboxylate lateral group and dithiocarboxylate end group, and preparing method as well as application thereof

Patent metadata

Field	Value
Publication number	US-9283416-B2
Application number	US-201514681051-A
Country	US
Kind code	B2
Filing date	Apr 7, 2015
Priority date	Apr 8, 2014
Publication date	Mar 15, 2016
Grant date	Mar 15, 2016

Abstract

A star-shaped hyperbranched polymer with a triethanolamine core, a carboxylate lateral group and a dithiocarboxylate end group has a formula of N[CH 2 CH 2 OCOCH 2 CH 2 (COOM)N(CSSM)CH 2 CH 2 N(CSSM) 2 ] 3 , wherein M is Na + , NH 4 + or K + . The star-shaped hyperbranched polymer has an effectively stabilization effect on heavy metals in MSWI fly ash. A method thereof for stabilizing is simple, low in dosage, cheap and without secondary pollution. Therefore, heavy metals leaching concentration in fly ash stabilized production is lower than a limit of Chinese national standard. Furthermore, acid and alkali resistance thereof is sufficient, which decreases a long-term pollution risk in natural environment.

First claim

What is claimed is:

1. A star-shaped hyperbranched polymer with a triethanolamine core, a carboxylate lateral group and a dithiocarboxylate end group, wherein a formula thereof is: N[CH 2 CH 2 OCOCH 2 CH 2 (COOM)N(CSSM)CH 2 CH 2 N(CSSM) 2 ] 3 , wherein M is Na + , NH 4 + or K + ; a structural formula thereof is:

2. A method for preparing the star-shaped hyperbranched polymer as recited in claim 1 , wherein raw material of the star-shaped hyperbranched polymer comprises triethanolamine, maleic anhydride, ethylenediamine, carbon disulfide and alkali; the method comprises steps of:
(1) adding the maleic anhydride (MA for short) into a four-necked flask with a stirrer, a reflux condenser and a thermometer, then adding N,N-dimethylformamide (DMF for short) and stirring until the maleic anhydride dissolves; dropping a DMF solution of the triethanolamine (TEA for short) under nitrogen gas and a room temperature, and controlling a dropping speed for keeping a temperature lower than 25° C.; then stirring for 30 min, increasing the temperature to 80-90° C. and reacting for 5-10 h, for obtaining a star-shaped hyperbranched polymer of Triethanolamine/3Maleic anhydride (TEA/MA-3COOH for short); then cooling to 5-10° C., slowly dropping a MOH solution (\wherein M is Na + , NH 4 + or K + ), and white solid is generated; suck-filtering and then washing twice with ethanol; drying under vacuum for obtaining a star-shaped hyperbranched polymer with a triethanolamine core and a maleate end group (TEA/MA-3COOM for short); wherein a reaction formula thereof is:

(2) adding the ethylenediamine (EDA for short) into a round flask with a stirrer, a reflux condenser and a thermometer, slowly dropping the MOH solution (wherein M is Na + , NH 4 + or K + ); controlling a dropping speed for keeping a temperature lower than 10° C.; then slowly dropping a water solution of the TEA/MA-3COOM, and controlling a dropping speed for keeping a temperature lower than 10° C.; then reacting for 20-24 h under nitrogen gas and a temperature of 80-90° C.; then vacuum suck-filtering at 80° C. for obtaining a star-shaped hyperbranched polymer of Triethanolamine/Maleic anhydride/Ethylenediamine (TME-3COOM for short); wherein a reaction formula thereof is:

and
(3) adding the TME-3COOM into a round flask with a stirrer, a reflux condenser and a thermometer, slowly dropping 20-50% alkali liquid, and controlling a dropping speed for keeping a reaction mixture temperature at 5-10° C.; dropping an alcoholic solution of carbon disulfide, and controlling a dropping speed for keeping a reaction mixture temperature at 5-10° C.; then reacting for 2-5 h at 5-10° C.; increasing a temperature to 25° C. and reacting for 3-5 h; storing the reacted mixture for a night, in such a manner that white deposit is separated out; filtering and washing with a small amount of alcohol, then filtering again for obtaining a target product: the star-shaped hyperbranched polymer with the triethanolamine core, the carboxylate lateral group and the dithiocarboxylate end group (TME-3COOM-9CSSM for short); wherein a reaction formula thereof is:

3. The method, as recited in claim 2 , wherein a mole ratio of the TEA, the MA, and the alkali is 1:(3.0-3.1):(3.0-3.1); a mole ration of the TEA/MA-3COOM, the EDA, and the alkali is 1:(4.0-6.0):(4.0-6.0); a mole ratio of the TME-3COOM, the carbon disulfide, and the alkali is 1:(11.25-13.50):(11.25-13.50).

4. The method, as recited in claim 2 , wherein the alcohol is methanol, ethanol, propanol or butanol; the alkali liquid is a water solution of ammonia, sodium hydroxide or potassium hydroxide.

5. A method for stabilizing incinerated fly ash of waste, comprising applying the star-shaped hyperbranched polymer as recited in claim 1 .

6. The method, as recited in claim 5 , specifically comprising steps of:
preparing a water solution of TME-3COOM-9CSSM as a stabilizer, then dissolving the stabilizer in water and adding to the incinerated fly ash, wherein a dosage thereof is 0.5-5% of a fly ash weight; keeping stirring for 15-30 min, then drying with natural ventilation for obtaining a stabilized product of the incinerated fly ash.

Assignees

• Univ Tongji

Inventors

• Zhang Bingru
• Li Fengting
• Tian Zhipeng

Classifications

• C07C333/20

  having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms · CPC title

• A62D2101/08

  Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration · CPC title

• C07C213/06

  from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups · CPC title

• A62D3/33 Primary

  by chemical fixing the harmful substance, e.g. by chelation or complexation · CPC title

• C07C213/08

  by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups · CPC title