CN101717472A - Graft copolymer of amino-containing starch and methyl acrylate - Google Patents
Graft copolymer of amino-containing starch and methyl acrylate Download PDFInfo
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- CN101717472A CN101717472A CN200910213623A CN200910213623A CN101717472A CN 101717472 A CN101717472 A CN 101717472A CN 200910213623 A CN200910213623 A CN 200910213623A CN 200910213623 A CN200910213623 A CN 200910213623A CN 101717472 A CN101717472 A CN 101717472A
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- starch
- graft copolymer
- copolymer
- acrylic acid
- methyl acrylate
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Abstract
The invention provides a graft copolymer of amino-containing starch and methyl acrylate. The graft copolymer has starch as a main chain and polymethyl acrylate as a branched chain, and is characterized in that part of formyl radicals on the polymethyl acrylate branched chain are aminated by hydrazine hydrate into -CONHNH2; the grafting rate is 20 to 99 percent; and the nitrogen content is 1 to 20 percent. The copolymer can be used as a metal chelating agent to treat electroplating wastewater. When the copolymer is dissolved in the electroplating wastewater, functional groups in molecules are rapidly chelated with metal ions to form insoluble products, and the own network structure of the copolymer can allow precipitate to rapidly flocculate and sink at the same time so as to achieve the aim of removing the metal ions in the wastewater, wherein the removal rate of heavy metal ions is as high as over 99 percent.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to graft copolymer.
Background technology
Along with the electronic industry fast development; the pollution becoming serious of heavy metal wastewater thereby and waste; seriously polluting existent environment of people; affect people's quality of life; also seriously restricting simultaneously the electronic industry development; thereby how to solve the plating pollution problem, and administer electroplating wastewater, become the task of top priority of field of environment protection.At present existing several different methods is used to remove heavy metal ion, as: ion exchange method, reverse osmosis method, absorption method, biological treatment etc., but owing to multiple reason, at present domestic and international prevailing, the most widely used chemical precipitation method that is still of heavy metal containing wastewater treatment technology.And chemical precipitation method processing electroplating effluent effect is undesirable, do not reach existing emission request, and have that processing efficiency is low, sediment weight greatly, easily causes secondary pollution problems, therefore the efficient chemical treatment medicament of development of new how is the emphasis that people study all the time.
Kai Fa macromolecular heavy metal chelating agent relies on the extremely strong huge legendary turtle of itself and metal to close ability in recent years, for electroplating wastewater improvement has brought new life, high-molecular chelating agent is to be parent with the macromolecular material, on its macromolecule matrix, introduce some by chemical reaction and have the group of metal-chelating performance, drop in the water can be immediately with water in heavy metal ion generation selectivity chelatropic reaction, generate water-fast metal complex, under the synergy of flocculation agent, the precipitation by metallic ion in the waste water is removed again.High-molecular chelating agent water-soluble makes it have that reaction is fast, characteristics such as consumption is little, selectivity is strong, eliminating efficiency height, enjoys users to favor.But because such rule of origin in synthesized polymer material, costs an arm and a leg, processed in units amount cost is too high, and has the residual monomer toxicity problem, is difficult to apply.
People such as Hu Chunhong have developed a kind of heavy metal chelant of nontoxic, cheap and biodegradable starch-containing skeleton; this sequestrant is a graft acrylic acid methyl esters on starch; obtain with quadrol generation amidate action again; it has a plurality of amino and acyl group; can with heavy metal ion form inner complex and precipitation with reach the purpose of purifying waste water (starch graft acrylic acid methyl esters and quadrol synthetic macromolecule sequestrant. Hu Chunhong etc. applied chemistry; in June, 2007,716～719 pages of the 24th the 6th phases of volume).But the ability of the disclosed heavy metal chelant chelating of this article heavy metal ion is still waiting to improve.
Summary of the invention
The technical problem to be solved in the present invention is further to improve the ability of the heavy metal chelant processing metallic wastewater of starch-containing skeleton structure.
The technical scheme that the present invention addresses the above problem is:
A kind of starch and methyl acrylate graft copolymer that contains amino, the main chain of this graft copolymer is a starch, side chain is a polymethyl acrylate, it is characterized in that: the part formyl radical on the polymethyl acrylate side chain by the hydrazine hydrate amination is-CONHNH
2Percentage of grafting is 20%～82%, and nitrogen content is 1%～20%.
Percentage of grafting of the present invention is meant the mass percentage content of side chain in graft copolymer, and nitrogen content is the mass percentage content of nitrogen element in graft copolymer.
Multipolymer of the present invention can prepare by the following method:
Get starch, add in 5～15 times of water and stir into starch milk; Feed nitrogen, the methyl acrylate that the initiator of adding starch weight 0.5～5% and starch weight are 0.5～5 times is warming up to 25 ℃～65 ℃ reaction 2～10h, uses NaCO
3Solution is neutralized to neutrality, gets the starch graft acrylic acid methyl terpolymer; The hydrazine hydrate that adds 3～50 times of gained starch graft acrylic acid methyl terpolymer quality, stir, 95 ℃ of following condensing reflux 6～36h obtain white jelly, add dehydrated alcohol and separate out white precipitate, with getting final product in 45～85 ℃ of following vacuum-dryings behind the absolute ethanol washing.
Preparing the used starch of multipolymer of the present invention can be cheap raw materials such as tapioca (flour), yam starch, W-Gum.Multipolymer of the present invention can be used as metal traps and is used to handle electroplating wastewater.When multipolymer of the present invention is dissolved in electroplating wastewater, sequestering action takes place rapidly in functional group in the molecule and metal ion, generate insoluble product, the reticulated structure of himself can make the precipitation rapid flocculation sink again simultaneously, reach the purpose of removing metal ion in the waste water, the clearance of heavy metal ion is up to more than 99%.
Embodiment
Preparation example
The percentage of grafting of following example and nitrogen content are all measured as follows:
The mensuration of nitrogen content: adopt Kjeldahl determination, the nitrogen content in the working sample, calculate as follows again:
Nitrogen content %=[(V-V
0) N/W] * 0.014 * 100
In the formula: V-consumes the milliliter number of HCl, mL;
V
0The milliliter number mL of the HCl that-blank assay consumes;
The equivalent concentration of N-HCl
The W-sample weight, g
The measuring method of percentage of grafting: employing gravimetric determination percentage of grafting (G, %).Dried thick product is wrapped with filter paper, placed the extracting of 250ml Soxhlet extractor to remove homopolymer, washing, suction filtration vacuum-drying get pure graft copolymer to constant weight.
Calculation formula is as follows:
In the formula: m
S---the quality of reaction starch, g;
m
G---the quality of graft copolymer, g.
Example 1
Get tapioca (flour) 5g and distilled water 50mL and add in the 250mL there-necked flask, feed nitrogen after stirring into starch milk; Add 0.15g ceric ammonium nitrate and 15g methyl acrylate, be warming up to 30 ℃ of reaction 9h, use NaCO
3Solution is neutralized to neutrality, gets the starch graft acrylic acid methyl terpolymer.Get gained multipolymer 2g (butt), add hydrazine hydrate 30mL, stir, 85 ℃ of following condensing reflux 10h obtain white gluey product, separate out and washed product with dehydrated alcohol, and 50 ℃ of following vacuum-dryings promptly get the aminating starch graft acrylic acid methyl terpolymer of hydrazine hydrate.The percentage of grafting (G) that records multipolymer is 73.2%, and nitrogen content is 13.8%.
Example 2 is got yam starch 10g and distilled water 50mL and is added in the 250mL there-necked flask, feeds nitrogen after stirring into starch milk; Add 0.05g ammonium persulphate and 6.5g methyl acrylate, be warming up to 30 ℃ of reaction 2h, use NaCO
3Solution is neutralized to neutrality, gets the starch graft acrylic acid methyl terpolymer.Get gained multipolymer 2g (butt), add hydrazine hydrate 15mL, stir, 95 ℃ of following condensing reflux 6h obtain white gluey product, separate out and washed product with dehydrated alcohol, and 50 ℃ of following vacuum-dryings promptly get the aminating starch graft acrylic acid methyl terpolymer of hydrazine hydrate.The percentage of grafting (G) that records multipolymer is 29.12%, and nitrogen content is 1.88%.
Example 3 extracting corn starch 5g and distilled water 60mL add in the 250mL there-necked flask, feed nitrogen after stirring into starch milk; Add 0.25g potassium permanganate and 22.8g methyl acrylate, be warming up to 35 ℃ of reaction 4h, use NaCO
3Solution is neutralized to neutrality, gets the starch graft acrylic acid methyl terpolymer.Get gained multipolymer 2g (butt), add hydrazine hydrate 80mL, stir, 95 ℃ of following condensing reflux 15h obtain white gluey product, separate out and washed product with dehydrated alcohol, and 50 ℃ of following vacuum-dryings promptly get the aminating starch graft acrylic acid methyl terpolymer of hydrazine hydrate.The percentage of grafting (G) that records multipolymer is 80.62%, and nitrogen content is 18.02%.
The effect example
Example 4
Get the aminating starch graft acrylic acid methyl terpolymer of example 1 gained hydrazine hydrate 10mg, join Cu
2+Starting point concentration is containing in the ion plating waste water of 30ppm, stirs 45min post-absorption analyser under the room temperature and records Cu
2+Ionic concn is 0.003ppm, and clearance is near 100%.Difference by the forward and backward thermal weight loss of chelating starch absorption metal is calculated chelating Cu
2+Amount is 4.343mmolg
-1
Example 5
Get the aminating starch graft acrylic acid methyl terpolymer of example 1 gained hydrazine hydrate 15mg, add and contain Cu
2+, Pb
2+, Cd
2+, Ni
2+, Cr
6+Concentration is in the 30mL simulated wastewater of 100ppm, stirs 60min under the room temperature, records Cu with atomic absorption analyzer
2+Ionic concn is 0.009ppm, Ni
2+Concentration is 0.013, Cd
2+Concentration is 0.013, Pb
2+Concentration is 0.021, and the total clearance of metal ion is greater than 99%.
Comparative Examples:
Getting the starch-grafted methyl acrylate of 1g places logical N2 gas and has agitator and the there-necked flask of prolong, add acetone 25mL, stir, be heated to 55 ℃ with its dissolving with water-bath, add 0.01g KOH then, after stirring 2min, add the 15mL quadrol, with warming-in-water to 95 ℃, in 60 ℃ of loft drier, dry by the fire 24h behind the reaction 6h, substantially be neutral with distillation washed several times with water to washing lotion then, the solid after the washing in 60 ℃ of dry 24h, is obtained the aminating starch graft acrylic acid methyl terpolymer of quadrol.
Take by weighing the aminating starch graft acrylic acid methyl terpolymer of above-mentioned quadrol 10mg, join Cu
2+The ion starting point concentration is in the 30mL electroplating wastewater of 100ppm, stirs 45min post-absorption analyser under the room temperature and records Cu
2+Ionic concn is 0.23ppm, and clearance is near 77%.
Take by weighing the aminating starch graft acrylic acid methyl terpolymer of above-mentioned quadrol 10mg, the 30mL that joins starting point concentration and be 100ppm contains Ag
+In the ion plating waste water, record Ag with atomic absorption analyzer behind the stirring 30min under the room temperature
+Ionic concn is 0.26ppm, and clearance is near 74%.
Claims (2)
1. one kind contains amino starch and methyl acrylate graft copolymer, and the main chain of this graft copolymer is a starch, and side chain is a polymethyl acrylate, it is characterized in that: the part formyl radical on the polymethyl acrylate side chain by the hydrazine hydrate amination is-CONHNH
2Percentage of grafting is 20%～82%, and nitrogen content is 1%～20%.
2. the preparation method of the described multipolymer of claim 1, this method is made up of following steps:
Get starch, add in 5～15 times of water and stir into starch milk; Feed nitrogen, the methyl acrylate that the initiator of adding starch weight 0.5～5% and starch weight are 0.5～5 times is warming up to 25 ℃～65 ℃ reaction 2～10h, uses NaCO
3Solution is neutralized to neutrality, gets the starch graft acrylic acid methyl terpolymer; The hydrazine hydrate that adds 3～50 times of gained starch graft acrylic acid methyl terpolymer quality, stir, 95 ℃ of following condensing reflux 6～36h obtain white jelly, add dehydrated alcohol and separate out white precipitate, with getting final product in 45～85 ℃ of following vacuum-dryings behind the absolute ethanol washing;
In the above-mentioned steps, described initiator is ammonium persulphate, potassium permanganate or ceric ammonium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910213623A CN101717472A (en) | 2009-12-07 | 2009-12-07 | Graft copolymer of amino-containing starch and methyl acrylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910213623A CN101717472A (en) | 2009-12-07 | 2009-12-07 | Graft copolymer of amino-containing starch and methyl acrylate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626916A (en) * | 2013-11-08 | 2014-03-12 | 天津大学 | Method for preparing N-isopropylacrylamide-co-acylhydrazone adsorbent |
| CN107583614A (en) * | 2016-07-07 | 2018-01-16 | 天津工业大学 | A kind of novel amino starch chelating material and preparation method thereof |
| CN110040833A (en) * | 2019-04-23 | 2019-07-23 | 襄阳先创环保科技有限公司 | A kind of preparation method of the heavy metal capturing agent for electroplating wastewater |
-
2009
- 2009-12-07 CN CN200910213623A patent/CN101717472A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626916A (en) * | 2013-11-08 | 2014-03-12 | 天津大学 | Method for preparing N-isopropylacrylamide-co-acylhydrazone adsorbent |
| CN103626916B (en) * | 2013-11-08 | 2015-10-14 | 天津大学 | A kind of preparation method of NIPA-co-acylhydrazone sorbent material |
| CN107583614A (en) * | 2016-07-07 | 2018-01-16 | 天津工业大学 | A kind of novel amino starch chelating material and preparation method thereof |
| CN110040833A (en) * | 2019-04-23 | 2019-07-23 | 襄阳先创环保科技有限公司 | A kind of preparation method of the heavy metal capturing agent for electroplating wastewater |
| CN110040833B (en) * | 2019-04-23 | 2021-09-03 | 襄阳先创环保科技有限公司 | Preparation method of heavy metal ion trapping agent for electroplating wastewater |
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Open date: 20100602 |