CN102941070A - Polyethylene-methacrylic acid-polyethylene polyamine fiber and method for preparing same - Google Patents
Polyethylene-methacrylic acid-polyethylene polyamine fiber and method for preparing same Download PDFInfo
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- CN102941070A CN102941070A CN2012105047378A CN201210504737A CN102941070A CN 102941070 A CN102941070 A CN 102941070A CN 2012105047378 A CN2012105047378 A CN 2012105047378A CN 201210504737 A CN201210504737 A CN 201210504737A CN 102941070 A CN102941070 A CN 102941070A
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Abstract
The invention discloses a polyethylene-methacrylic acid-polyethylene polyamine fiber and a method for preparing the same, and belongs to the field of environmental material synthesis and application. Polyethylene fiber is taken as a base material, methacrylic acid and polyethylene polyamine are taken as monomers, and a porous fibrous adsorbing material is produced through foaming polymerization reaction. The synthesis method is simple, raw materials are low in price, the prepared porous fibrous adsorbing material has a porous structure and a hydrophilic surface, heavy metal ions in water can be quickly and efficiently removed through the action of surface amino, the time for the equilibrium adsorbing of divalent heavy metal ions of cadmium, lead, copper and the like is less than 30 minutes, the adsorbed fiber is easy to recycle and can be repeatedly used after regeneration and the polyethylene-methacrylic acid-polyethylene polyamine fiber is suitable for quickly removing the heavy metal ions in the water/wastewater.
Description
Technical field:
The invention discloses a kind of is the amido modified porous chelate fibre and preparation method thereof of matrix based on high polymer polyethylene fiber, is based in particular a kind of polyethylene-methacrylic acid-polyethylene polyamine fiber and preparation method thereof.
Background technology:
In recent years, China's heavy metal water pollutes and is on the rise, and how fast, efficiently particularly the heavy metal ion such as lead, cadmium do great damage to ecological environment, remove the hot issue that the heavy metal ion such as water/Pb In Exhausted Water, cadmium become the Study on Water Pollution Control field.Have the advantages such as adsorption capacity is large, regeneration can be regulated and control, be easy to structure based on the resin type adsorbent of macromolecule polymer material and be widely used in field of waste water treatment.Adopt fiber to cause at present people's attention as the disposal that sorbing material is applied to the outburst surroundings contamination accident, because fibrous sorbing material having in shape very strong plasticity, applicable to use occasion complicated and changeable, also is convenient to reclaiming.Research has reported based on wool to be the chelate fibre of matrix, and heavy metal ion is had certain Adsorption effect; And the road is vigorous and graceful etc., and the people has synthesized the sponge resin that the hydrophobicity oily substance is had good adsorption effect.But existing fiber adsorbing material all exists following deficiency: 1) adopt the animal hair such as wool as host material; not only the source is difficult; be not suitable for large-scale production; and cost of manufacture is higher; with processing and not easy operation control of synthesis condition; especially the adsorbing fiber counterweight metal biosorption capacity of preparation is lower; compare in addition a certain distance [1] M.Monier with traditional cationic ion-exchange resin; N.Nawar; D.A.Abdel-Latif; Preparation and characterization of chelating fibers based on natural wool for removal of Hg (II); Cu (II) and Co (II) metal ions from aqueous solutions; J.Hazard.Mater.184 (2010) 118 (Buddhist nun etc. not; be that fibrous matrix prepares chelate fibre and removes Hg solution (II) with wool; Cu (II) and Co (II), " noxious material ", 184 phases in 2010: 118 pages.); 2) most fiber adsorbing materials are mainly for the Adsorption of lyophobic dust, and do not consider hydroaropic substance, but the water of actual burst pollutes and mostly is heavy-metal pollution in recent years.Disclosed patent " a kind of amine-modified fibrous emergent sorbing material and preparation method thereof " (application number: 2011104274558 before this, publication number: although the emergent adsorbing fiber for preparing CN102489268A) can overcome the deficiency of animal hair matrix adsorbing fiber material, but still exist some and need improved place: 1) synthetic method in original patent is two step synthesis steps of first grafting reamination, process is loaded down with trivial details, is unfavorable for reducing cost and improves productive rate; 2) aminating reaction in original patent adopts the ethylenediamine infusion process, and amido content is difficult for improving; 3) fiber that makes of the synthetic method in original patent does not have loose structure, and specific area is lower, is unfavorable for absorption.
Therefore, utilize artificial synthetic high polymer fibrous material as matrix, adopt the fibrous sorbing material of more simple one-step synthesis reaction preparation porous, high-load functional group, remove fast the heavy metal ion such as water/Pb In Exhausted Water, cadmium and have important actual application value.
Summary of the invention:
1, invents the technical problem that will solve
Matrix source for the animal hair fibrous material of foreign literature report is difficult for, adsorption effect to heavy metal also is not so good as described ideal, and amine-modified fibrous emergent sorbing material amido content is low and without the defective such as loose structure and preparation process be loaded down with trivial details in the existing patent of invention, the invention provides a kind of polyethylene-methacrylic acid-polyethylene polyamine fiber and preparation method thereof, adopt step foaming polymerisation, prepare novel porous, the fibrous sorbing material of high amido content.This is invented, and not only synthesis step is simple, prepared polyethylene-methacrylic acid-ethyleneamine copolymer (is called for short: PE-MA-N) have loose structure, the high advantage of surperficial amido content, to the heavy metal ion equilibrium adsorption capacities such as lead, cadmium, copper in the water apparently higher than disclosed patent before this (application number: 2011104274558, publication number: the amine-modified fibrous emergent sorbing material of preparation CN102489268A).
2, technical scheme
Polyethylene-methacrylic acid provided by the present invention-ethyleneamine fiber is to adopt PE fiber and methacrylic acid, ethyleneamine to prepare through the foaming polymerisation.
A kind of polyethylene-methacrylic acid-ethyleneamine fiber synthesis flow and the basic structural formula of fiber are as follows:
X wherein, y, m and n represent construction unit quantity, all more than or equal to 2.
Prepared porous, fibrous copolymer diameter 55-65 μ m, amido content is greater than 10mmol/g, and pore diameter range is 2-8nm, and specific area is greater than 100m
2/ g.
The preparation process of polyethylene-methacrylic acid-ethyleneamine fiber is:
Step (1): polyethylene (English name: polyethylene, be called for short PE, CAS accession number: 9002-88-4) fiber preliminary treatment:
(a) extracting: PE with organic solvent extracting 4 hours in Soxhlet extractor, is then at room temperature dried;
(b) swelling: the PE fiber after will drying through extracting places the sweller swelling.The quality of fiber (g) is 1:20 with sweller volume (ml) usage ratio, and swelling temperature is 30 ℃, and swelling time is 4 hours;
Employed organic solvent is selected from and is ethanol (English name: Etanol in the step (1-a), CAS accession number: 64-17-5), acetone (English name: Acetone, CAS accession number: 67-64-1) or benzinum (English name: PETROLEUM ETHER, CAS accession number: 101316-46-5);
Employed sweller is selected from N in the step (1-b), dinethylformamide (English name: N, N-Dimethylformamide, be called for short DMF, CAS accession number: 68-12-2), dichloroethanes (English name: Dichloroethane, CAS accession number: 1300-21-6) or toluene (English name: Toluene, CAS accession number: 108-88-3).
Step (2): preparation reaction emulsion:
To be made into the reaction emulsion after methacrylic acid, polyethylene polyamine, organic solvent, emulsifying agent, blowing agent and the water mixing, wherein the volume proportion of methacrylic acid, polyethylene polyamine, organic solvent, emulsifying agent, blowing agent and water (is methacrylic acid: polyethylene polyamine: organic solvent: emulsifying agent: blowing agent: water=1:1～2:2～4:1～2:1～2:4～9) as shown in the table;
| Component | Methacrylic acid | Polyethylene polyamine | Organic solvent | Emulsifying agent | Blowing | Water |
| Proportioning | ||||||
| 1 | 1～2 | 2～4 | 1～2 | 1～2 | 4～9 |
In the step (2), organic solvent is DMF, dichloroethanes or toluene, and emulsifying agent is selected polyethenoxy sorbitan oleate (English name: Tween 80; Be called for short: Tween-80; CAS accession number: 9005-65-6), polyoxyethylene oleic acid ester (English name: Polyethylene glycol monooleate; Be called for short: OE-6; CAS accession number: 9004-96-0), diglycerol polypropylene glycol ether (English name: Polypropylene oxide diglycidyl ether; The CAS accession number: a kind of 26142-30-3), blowing agent is normal heptane.。
Step (3): foaming polymerisation
The described emulsion of PE fiber and step 2 is mixed the rear initator that adds, wherein the ratio of each component is PE fiber (quality g): emulsion (volume mL): initator (quality g)=5:1000～2000:1～2, at 85～95 ℃ of lower reaction 12～24h, obtain product polyethylene-methacrylic acid of the present invention-ethyleneamine fiber, acetone is washed rear 50 ℃ of lower vacuum drying.
Employed initator selects benzoyl peroxide or azo diethyl butyronitrile in the step (3).
3, beneficial effect
The invention provides a kind of polyethylene-methacrylic acid-ethyleneamine fiber and its preparation method, take polyethylene fibre as matrix, take methacrylic acid and polyethylene polyamine as monomer, prepare copolymer by the foaming polymerisation, overcome the emergent sorbing material preparation process of existing fiber lengthy and tedious, do not have loose structure, the relatively low deficiency of surperficial amido content, preparation method and prepared material possess following innovative point:
1) preparation technology's innovation: adopt step foaming polymerization, the synthesis technique step is simple, produces without high ammonia nitrogen waste liquid; Disclosed patent " a kind of amine-modified fibrous emergent sorbing material and preparation method thereof " (application number: 2011104274558 before this, publication number: synthesis step CN102489268A) needs through " preliminary treatment---graft polymerization reaction---aminating reaction ", and step is comparatively lengthy and tedious; And the amination process is difficult to reaction thoroughly, because the too high meeting of ammonia concn causes that the methacrylic acid of grafting is partly dissolved on the fiber, and ammonia concn is excessively low, can cause the amido content of finishing, and the waste liquid that reaction later can the high ammonia nitrogen of generating portion.And synthesis path provided by the invention is " preliminary treatment-foaming polymerization ", directly the polyethylene polyamine with high amido content joins in the polymerization reaction system, saved this process of adding ammoniacal liquor amination, not only reduced the generation of high ammonia nitrogen waste liquid, and the amido content of fiber obviously improves, this synthetic method is simple, cost of material is cheap, prepared porous, fibrous sorbing material has loose structure and hydrophilic surface, can be quick by surperficial amido effect, heavy metal ion in the efficient removal water, to cadmium, plumbous, the equilibrium adsorption time of the divalent heavy metal ions such as copper was less than 30 minutes, and the fiber after the absorption is easy to reclaim, reuse after renewable, be applicable to the quick removal of water/heavy metal ions in wastewater.
2) innovation of product: the fibrous material of preparation has loose structure, and specific area is large, and surperficial amido content is high, and counterweight cation equilibrium adsorption capacity is large.Disclosed patent " a kind of amine-modified fibrous emergent sorbing material and preparation method thereof " (application number: 2011104274558 before this, publication number: CN102489268A) fiber of preparation does not have loose structure, and specific area is lower, and high-specific surface area and loose structure are the key factors that improves the sorbing material absorption property, the fiber that the present invention synthesizes has higher specific area and loose structure, thus Effective Raise the adsorption capacity of fiber.
Description of drawings:
Fig. 1 is polyethylene-methacrylic acid of preparing of the present invention-ethyleneamine fibre chemistry structure chart.
Fig. 2 is the FT-IR collection of illustrative plates of polyethylene-methacrylic acid-ethyleneamine fiber, 3349.3cm among the figure
-1The strong absworption peak at place has proved there are a large amount of amidos on the fiber.According to list of references (Xing Qiyi, Pei Weiwei etc., basic organic chemistry, Higher Education Publishing House, the third edition in 2005, p184).
Fig. 3 among Fig. 3 (a) is the solid-state nuclear magnetic resonance carbon spectrum of polyethylene-methacrylic acid-ethyleneamine fiber; Fig. 3 (b) is PE-MA-N fibre solid nuclear magnetic resonance
13Structure chart corresponding to C NMR collection of illustrative plates characteristic peak, the corresponding structure of its characteristic peak is listed among Fig. 3 (b), according to list of references (organic chemistry), association reaction raw material, the reaction mechanism mechanism of reaction, and the infared spectrum of product, the characteristic peak positions in the nuclear magnetic resonance map, can identify the structure of determining material.According to list of references (Xing Qiyi, Pei Weiwei etc., basic organic chemistry, Higher Education Publishing House, the third edition in 2005, p216).
Fig. 4 is respectively the scanning electron microscope (SEM) photograph of PE fiber, polyethylene-methacrylic acid-ethyleneamine fiber, this shows that polyethylene-methacrylic acid-ethyleneamine fiberoptic fiber has loose structure and high-specific surface area, and this is conducive to improve fiber counterweight metal biosorption capacity.
Fig. 5 is respectively the contact angle of PE, polyethylene-methacrylic acid-ethyleneamine fiber and water, can find out that polyethylene-methacrylic acid-ethyleneamine fiber has preferably wellability, good hydrophily is namely arranged, and this is conducive to the quick adsorption to heavy metal ion in the water.
The reaction principle figure of Fig. 6 PE-MA-N of the present invention
The specific embodiment
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of ethanol, dry and be placed in the 3 neck bottles, add 100 milliliters of DMF, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion, PE fiber, reaction emulsion and ratio of initiator are as follows:
85 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 12 hours will react gained PE-MA-N and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain polyethylene-methacrylic acid-ethyleneamine fibrous finished product.Its physicochemical property is as follows:
Embodiment 2
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of ethanol, dry and be placed in the 3 neck bottles, add 100 milliliters of DMF, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion, each component addition is as follows in the reaction emulsion:
90 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 18 hours will react gained PE-MA-N and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain porous fibre shape sorbing material finished product polyethylene-methacrylic acid-ethyleneamine fiber, and its physicochemical property is as follows:
Embodiment 3
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of ethanol, dry and be placed in the 3 neck bottles, add 100 milliliters of DMF, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion, each component addition is as follows in the reaction emulsion:
95 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 24 hours will react gained PE-MA-N and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain porous fibre shape sorbing material finished product polyethylene-methacrylic acid-ethyleneamine fiber.Its physicochemical property is as follows:
Fiber molecule formula such as Fig. 1 of being prepared into, in Fig. 6, fiber reinforcement is polyethylene-methacrylic acid, ' CH-' (2) of methacrylic acid link to each other with ' CH-' (1) on the Polyethylene Chain, and ethyleneamine is that ' N ' (4) are connected with ' C ' (3) of methacrylic acid on the ethyleneamine with the methacrylic acid interface.And polymerisation has also occured as polymerization single polymerization monomer self in methacrylic acid and polyethylene polyamine, and its interface is ' CH-' (2) of ' CH2-' (5) and methacrylic acid on the ethyleneamine.Among infared spectrum Fig. 2, the PE-MA-N that is prepared into has obvious amido characteristic peak at δ 3349.3 places.The PE-MA-N that is prepared at solid-state nuclear magnetic resonance collection of illustrative plates such as Fig. 3 (a) (PE-MA-N).Characteristic of correspondence peak correspondence corresponding functional group on its nuclear magnetic resonance map.Fig. 3 (b) PE-MA-N fibre solid nuclear magnetic resonance
13Structure chart corresponding to C NMR collection of illustrative plates characteristic peak, PE-MA-N fiber ESEM such as Fig. 4 of preparation this shows new fibrous material rough surface, have the structure of porous.Fig. 4 (a) PE fiber scanning electron microscope (SEM) photograph (smooth surface, atresia), Fig. 4 (b) is the scanning electron microscope (SEM) photograph (rough surface, porous) of the PE-MA-N fiber of preparation, the PE-MA-N fiber of preparation and surface contact angle such as Fig. 5 of water.This shows that the contact angle of new fibrous material and water less than 90 degree, is hydrophilic sorbing material.The contact angle of Fig. 5 (a) PE fiber and water is that the contact angles of 119 degree (b) PE-MA-N fibers and water are 31 degree (upper strata projections be water droplet, bottom matrix is fibrous material).
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of acetone, dry and be placed in the 3 neck bottles, add 100 milliliters of dichloroethanes, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion,, each component addition is as follows:
85 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 12 hours will react gained PE-MA-N and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain porous fibre shape sorbing material finished product polyethylene-methacrylic acid-ethyleneamine fiber.Its physicochemical property is as follows:
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of acetone, dry and be placed in the 3 neck bottles, add 100 milliliters of dichloroethanes, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion,, each component addition is as follows:
90 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 18 hours will react gained PE-MA-N and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain porous fibre shape sorbing material finished product polyethylene-methacrylic acid-ethyleneamine fiber.Its physicochemical property is as follows:
Embodiment 6
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of acetone, dry and be placed in the 3 neck bottles, add 100 milliliters of dichloroethanes, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion, each component addition is as follows:
95 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 24 hours will react gained PE-MA-N and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain porous fibre shape sorbing material finished product PE-MA-N.Its physicochemical property is as follows:
Embodiment 7
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of benzinums, dry and be placed in the 3 neck bottles, add 100 milliliters of toluene, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion, each component addition is as follows:
85 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 12 hours will react gained PE-MA-N and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain porous fibre shape sorbing material finished product polyethylene-methacrylic acid-ethyleneamine fiber.Its physicochemical property is as follows:
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of benzinums, dry and be placed in the 3 neck bottles, add 100 milliliters of toluene, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion, each component addition is as follows in the reaction emulsion:
90 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 18 hours will react gained polyethylene-methacrylic acid-ethyleneamine fiber (PE-MA-N) and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain porous fibre shape sorbing material finished product polyethylene-methacrylic acid-ethyleneamine fiber.Its physicochemical property is as follows:
Embodiment 9
Adopt 5g PE to add the extracting 4 hours in Soxhlet extractor of 200 milliliters of benzinums, dry and be placed in the 3 neck bottles, add 100 milliliters of toluene, 30 degrees centigrade of swellings 4 hours.Add the reaction emulsion, each component addition is as follows:
95 ℃ of heating water baths, and with the rotating speed stirring reaction of 60r/min 24 hours will react gained polyethylene-methacrylic acid-ethyleneamine fiber and carry out solid-liquid and separate, and with the acetone washing, dry.50 ℃ of lower vacuum drying obtain porous fibre shape sorbing material finished product polyethylene-methacrylic acid-ethyleneamine fiber.Its physicochemical property is as follows:
Its diameter of the product that above-described embodiment 1-9 obtains is at 55-65 μ m, and specific area is at 101.9-147.4m
2/ g, amido content is at 10.5-13.9mmol/g.
Claims (6)
1. polyethylene-methacrylic acid-polyethylene polyamine fiber is characterized in that fibrous inside is the polyethylene polyamine base of polyethylene-methacrylic acid skeleton and finishing, and its basic structure formula is as follows:
X wherein, y, m and n are all more than or equal to 2.
2. polyethylene-methacrylic acid according to claim 2-polyethylene polyamine fiber is characterized in that being porous, fibrous copolymer, and its diameter range is 55-65 μ m, and amido content is greater than 10.0mmol/g, and specific area is greater than 100m
2/ g, pore diameter range 2-8nm.
3. the preparation method of polyethylene-methacrylic acid according to claim 1 and 2-polyethylene polyamine fiber the steps include:
(1) PE preliminary treatment
Extracting: PE with the extracting 4 hours in Soxhlet extractor of organic solvent extractant, is then at room temperature dried;
Swelling: the PE fiber after will drying through extracting places three-necked bottle, adds the sweller swelling 4 hours, and sweller volumetric usage (milliliter) is 20:1 with quality (gram) ratio of fiber, and swelling temperature is 30 degrees centigrade;
(2) preparation reaction emulsion
To be made into the reaction emulsion after methacrylic acid, polyethylene polyamine, organic solvent, emulsifying agent, blowing agent and the water mixing, each component volume proportion is methacrylic acid: polyethylene polyamine: organic solvent: emulsifying agent: blowing agent: water=1:1～2:2～4:1～2:1～2:4～9;
(3) foaming polymerization
The PE fiber is mixed the rear initator that adds with emulsion, PE fiber (gram) is 5:1000～2000: 1～2 with the ratio of emulsion (milliliter), initator (gram), at 85～95 ℃ of lower reaction 12～24h, make polyethylene-methacrylic acid-polyethylene polyamine fiber, acetone cleans rear 50 ℃ of vacuum drying.
4. the preparation method of porous fibre shape sorbing material according to claim 3 is characterized in that, employed organic solvent is ethanol, acetone or benzinum in the step 1, and employed sweller is DMF, dichloroethanes or toluene.
5. the preparation method of porous fibre shape sorbing material according to claim 3, it is characterized in that, in the described step 2, organic solvent is DMF, dichloroethanes or toluene, emulsifying agent is polyethenoxy sorbitan oleate, polyoxyethylene oleic acid ester or diglycerol polypropylene glycol ether, and blowing agent is normal heptane.
6. the preparation method of porous fibre shape sorbing material according to claim 3 is characterized in that, employed initator selects benzoyl peroxide or azo diethyl butyronitrile in the described step (3).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437360A (en) * | 2014-10-24 | 2015-03-25 | 重庆希尔康血液净化器材研发有限公司 | Preparation method of resin carbon for blood purification |
| CN106238022A (en) * | 2016-10-26 | 2016-12-21 | 泰州职业技术学院 | A kind of preparation method of oxidic polyethylene dispersion sewage-treating agent |
| CN111749016A (en) * | 2020-07-03 | 2020-10-09 | 江苏扬农化工集团有限公司 | Polyethylene polymerization grafting impregnation liquid and ultrahigh molecular weight polyethylene polymerization grafting modification method |
| WO2020216377A1 (en) * | 2019-04-26 | 2020-10-29 | 中国环境科学研究院 | Water pollutant emergency treatment apparatus and system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010002656A1 (en) * | 1999-12-03 | 2001-06-07 | Ulrich Schnegg | Process for preparing monodisperse adsorber resins and their use |
| CN102161758A (en) * | 2011-01-26 | 2011-08-24 | 大连理工大学 | Preparation method of novel silica gel-based hyperbranched PAMAM (polyamidoamine) chelating resin |
| CN102587133A (en) * | 2012-01-16 | 2012-07-18 | 天津工业大学 | Preparation method of functional fiber capable of adsorbing heavy metal ions and organic pollutants at same time |
-
2012
- 2012-11-30 CN CN201210504737.8A patent/CN102941070B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010002656A1 (en) * | 1999-12-03 | 2001-06-07 | Ulrich Schnegg | Process for preparing monodisperse adsorber resins and their use |
| CN102161758A (en) * | 2011-01-26 | 2011-08-24 | 大连理工大学 | Preparation method of novel silica gel-based hyperbranched PAMAM (polyamidoamine) chelating resin |
| CN102587133A (en) * | 2012-01-16 | 2012-07-18 | 天津工业大学 | Preparation method of functional fiber capable of adsorbing heavy metal ions and organic pollutants at same time |
Cited By (6)
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|---|---|---|---|---|
| CN104437360A (en) * | 2014-10-24 | 2015-03-25 | 重庆希尔康血液净化器材研发有限公司 | Preparation method of resin carbon for blood purification |
| CN106238022A (en) * | 2016-10-26 | 2016-12-21 | 泰州职业技术学院 | A kind of preparation method of oxidic polyethylene dispersion sewage-treating agent |
| CN106238022B (en) * | 2016-10-26 | 2019-04-19 | 泰州职业技术学院 | A kind of preparation method of oxidic polyethylene dispersion sewage-treating agent |
| WO2020216377A1 (en) * | 2019-04-26 | 2020-10-29 | 中国环境科学研究院 | Water pollutant emergency treatment apparatus and system |
| CN111749016A (en) * | 2020-07-03 | 2020-10-09 | 江苏扬农化工集团有限公司 | Polyethylene polymerization grafting impregnation liquid and ultrahigh molecular weight polyethylene polymerization grafting modification method |
| CN111749016B (en) * | 2020-07-03 | 2022-12-09 | 江苏扬农化工集团有限公司 | Polyethylene polymerization graft impregnation liquid and method for polymerization graft modification of ultrahigh molecular weight polyethylene |
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