CN103112937A - Ethyl polyethylene polyamine polymethacrylate chelating flocculant and preparation method thereof - Google Patents
Ethyl polyethylene polyamine polymethacrylate chelating flocculant and preparation method thereof Download PDFInfo
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- CN103112937A CN103112937A CN2013100756739A CN201310075673A CN103112937A CN 103112937 A CN103112937 A CN 103112937A CN 2013100756739 A CN2013100756739 A CN 2013100756739A CN 201310075673 A CN201310075673 A CN 201310075673A CN 103112937 A CN103112937 A CN 103112937A
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Abstract
The invention discloses an ethyl polyethylene polyamine polymethacrylate heavy metal chelating flocculant and a preparation method thereof. The method adopts a technical scheme comprising the following steps of: carrying out addition reaction on polyethylene polyamine and ethylene oxide under an alkaline condition to prepare N-ethyl polyethylene polyamine, carrying out ester exchange reaction on N-ethyl polyethylene polyamine and methyl methacrylate in the presence of a catalyst and a polymerization inhibitor to synthesize ethyl polyethylene polyamine methacrylate, synthesizing ethyl polyethylene polyamine polymethacrylate through free radical polymerization, and then performing reaction on ethyl polyethylene polyamine polymethacrylate and carbon disulfide under the alkaline condition to generate the ethyl polyethylene polyamine polymethacrylate chelating flocculant. The ethyl polyethylene polyamine polymethacrylate chelating flocculant overcomes defects such as low relative molecular mass and no functional groups on sectional chain links of high-polymer heavy-metal chelating flocculants. The ethyl polyethylene polyamine polymethacrylate chelating flocculant not only has a good chelating function, but also has an excellent flocculating property, is applicable to the treatment of various heavy metal wastewater, and has broad popularization application value.
Description
Technical field
The invention belongs to heavy metal-polluted water treatment and flocculation agent field, particularly a kind of polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent that integrates heavy metal ion chelating and flocculating function and preparation method thereof.
Background technology
Heavy metal can not be degraded by microorganisms, and easily enrichment and cause remarkable toxic effect in vivo, be a kind of persistent pollutant.In a single day environment is subject to heavy metal contamination and just is difficult to administer, and its improvement cost is quite painful.Section adds up according to national environmental protection, and since two thousand nine, China has recurred more than 30 particularly serious heavy metal contamination event, a lot of blood lead events, and serious threat is to the people's life security.Heavy metal contamination has become one of hot issue of Chinese society's concern.The control of heavy metal contamination, healthy concerning broad masses of the people especially children is stable concerning the harmony of society.Heavy metal wastewater thereby is a kind of principal mode that heavy metal moves and pollutes, be environmental pollution the most serious, the mankind are endangered one of maximum sewage.Researched and developed so far the various heavy method of wastewater treatment, as chemical precipitation method (oxyhydroxide, sulfide, the chelating precipitator method), ferrite process, absorption method, ion exchange method, membrane filtration (ultrafiltration, enhancing ultrafiltration method, nanofiltration, reverse osmosis, electroosmose process), flotation process and electrochemical method (electricity flocculation, electric flotation, galvanic deposit) etc.In these methods, some treatment effect is bad, is difficult to satisfy more and more stricter wastewater discharge standard; Some is infeasible economically, has limited to a great extent their actual application value.Compare additive method, the chelating precipitator method are easy and simple to handle, and treatment effect is good, are suitable for the processing of extensive heavy metal wastewater thereby, are one of methods of the tool application prospect that advances that the heavy metal containing wastewater treatment mass-producing processes.Its treatment effect depends on the performance of chelated flocculating agent used.
Chinese patent CN101585572A and CN102491473A have announced the amphiprotic high-molecule chelated flocculating agent of two types, solve to a certain extent the problem of the flco negative charge surplus that forms in the high-molecular chelating agent use procedure.But these two inventions are all to introduce positive charge by the form of diallyl quaternary ammonium salt on macromolecular chain, because the diallyl quaternary ammonium salt is chain growth mechanism polymerization by Cheng Huan in molecule-intermolecular growth, polymerization activity is lower, relative molecular mass is not high (Liu Lihua generally, Li Jing, Li Jiaqiu. the synthetic and advances of Basic Research of Diallyldialkyl quaternary ammonium polymer. the polymer circular, 2006, (5): 86-93), and the quality of flocculating property depends on the relative molecular mass of flocculation agent to a great extent.The high-molecule chelated flocculating agent of processing heavy metal wastewater thereby requires will have on macromolecular chain pair heavy metal ion to have the functional group of strong sequestering power on the one hand, can be with heavy metal ion firmly " binding ", require again on the other hand thick the and closely knit floc sedimentation of small flco gathering formation that can form after " binding " heavy metal ion, be beneficial to that it is settlement separate.Therefore, the two family macromolecule chelated flocculating agents that patent CN101585572A and CN102491473A announce have open defect aspect relative molecular mass, the flco of formation is still thick not closely knit, causes subsidence rate fast not, the sediment volume is bigger than normal, and water ratio is higher.In addition, patent CN101585572A is the amide group-CONH that utilizes on molecular chain
2React to connect active amino with formaldehyde and polyethylene polyamine by Mannich, can not realize that each amide group can connect the polyethylene polyamine group, and superfluous formaldehyde easily causes crosslinkedly, make its bad stability; Patent CN102491473A comes with the polyethylene polyamine reaction, active amino to be introduced in molecular chain by epoxide group, be beneficial to heavy metal ion is had the introducing of the dithio formyloxy of strong sequestering action, because reactive hydrogen source in reaction system is many, the part epoxy group(ing) easily is combined with other reactive hydrogen and open loop, therefore, still have quite a few to fail to connect the polyethylene polyamine group.So, all exist quite a few chain link there is no the situation of functional group in above-mentioned two family macromolecule chelated flocculating agents.
Summary of the invention
one of purpose of the present invention is the above-mentioned technical problem for existing high-molecule chelated flocculating agent existence, a kind of polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent is provided, the present invention utilizes the methyl acrylic ester monomer to have higher polymerization activity and is beneficial to synthetic polymkeric substance than high molecular weight, and introduce polyethylene polyamine by transesterification reaction be beneficial on high molecular each chain link, functional group is arranged in each monomer molecule, promote the gathering growth of chelating " binding " to heavy metal ion and flco, thereby improve the chelate for flocculation effect, reduce sediment volume and water ratio.
Polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent of the present invention consists of: the structural formula of main component is that compound, the ancillary component of formula I is xanthogenic acid and sodium hydroxide, and outward appearance is faint yellow or yellow transparent liquid;
In formula I, n is 1000～5000 integer, and x is 1～3 integer.
Second purpose of the present invention is to provide the preparation method of above-mentioned polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent, and it comprises the steps:
(1) polyethylene polyamine is added in autoclave, adding mass percentage concentration is 10% potassium hydroxide solution again, is heated to boiling, then passes into oxyethane, react 2～3h under 160～180 ℃, 0.5～0.8MPa, underpressure distillation obtains N-hydroxyethyl polyethylene polyamine; Wherein, the mol ratio of polyethylene polyamine and oxyethane is 2～2.1: 1, and the amount of potassium hydroxide is 0.4～0.6% of the polyethylene polyamine that adds and oxyethane total mass;
(2) be that 1: 2～2.5 ratio joins with agitator in molar ratio with step (1) gained N-hydroxyethyl polyethylene polyamine and methyl methacrylate, in the reactor of thermometer and separation column, press again calcium hydroxide, thiodiphenylamine and N-hydroxyethyl polyethylene polyamine mol ratio are 0.15～0.20: 0.014～0.016: 1 ratio adds calcium hydroxide and thiodiphenylamine, at 70～90 ℃ of reaction 3～4h, remove unreacted methyl methacrylate and N-hydroxyethyl polyethylene polyamine under reduced pressure, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets methacrylic acid polyethylene polyamine ethyl ester,
(3) step (2) gained methacrylic acid polyethylene polyamine ethyl ester being made into mass percentage concentration with polar solvent dissolving is 40～60% monomer solution, then logical N
2Drive oxygen 30min, be warming up to 55～65 ℃, then add radical initiator by 1～1.5% of monomer mass, reaction 4～6h, evaporating solvent, then precipitating gets faint yellow paste in methyl alcohol;
(4) step (3) gained paste being added deionized water be mixed with mass percentage concentration is 3～5% solution, then be 1.0: 1.2～1.5: 1～1.2 ratio in the mol ratio of N atom, sodium hydroxide and dithiocarbonic anhydride in the polyethylene polyamine molecule of access, first add sodium hydroxide, drip again dithiocarbonic anhydride and at room temperature react 5～6h, then be warmed up to 40 ℃ of reaction 1h, namely get product polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent.
Preferably, polyethylene polyamine described in step (1) is any in quadrol, diethylenetriamine and triethylene tetramine.
Preferably, the sorbent material that column chromatography described in step (2) is used in separating is alkali alumina, and eluent is ethyl acetate.
Preferably, polar solvent described in step (3) is any in tetrahydrofuran (THF), methyl-sulphoxide and DMF.
Preferably, radical initiator described in step (3) is any in Diisopropyl azodicarboxylate, azo-bis-isobutyrate hydrochloride and azo two isobutyl imidazoline salt hydrochlorates.
The present invention adopts elder generation, and addition under alkaline condition prepares N-hydroxyethyl polyethylene polyamine with polyethylene polyamine and oxyethane, carry out under catalyzer and stopper exist with methyl methacrylate again transesterification reaction the polyethylene polyamine group is incorporated into molecule in preparation methacrylic acid polyethylene polyamine ethyl ester monomer, then adopt the free crowd mode to synthesize polymethyl acrylic acid polyethylene polyamine ethyl ester, then react strong chelation group-CSS with sodium hydroxide and dithiocarbonic anhydride
-Be incorporated into the technical scheme on macromolecular chain.Realized that synthetic chelated flocculating agent has than high-molecular weight, and on macromolecular chain, each chain link has functional group.Therefore, the present invention has overcome Chinese patent CN101585572A and the CN102491473A relative molecular mass is not high, the shortcoming that there is no functional group on the part chain link, be conducive to promote chelating " binding " to heavy metal ion and the growth of flco, make flco closely knit and thick, improve the treatment effect of heavy metal wastewater thereby, reduce volume and the water ratio of sediment, be beneficial to the further processing of sediment.
The present invention has following technique effect compared to existing technology:
(1) the present invention is based on the methyl acrylic ester monomer and have higher polymerization activity, and polyethylene polyamine is easy to introduce the group-CSS that contents of many kinds of heavy metal ion is had strong sequestering power
-Characteristics design the product molecular structure, the two-part structure amalgamation in a part, is made it to be easy to synthetic polymer than high molecular weight and is beneficial to the introducing of functional group.
(2) the present invention will be easy to access function base-CSS by the transesterification reaction of N-polyethylene polyamine and methyl methacrylate
-Amino introduce in monomer molecule, synthesize polymethyl acrylic acid polyethylene polyamine ethyl ester by Raolical polymerizable, with dithiocarbonic anhydride and sodium hydroxide reaction preparation polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent, making on high molecular each chain link has functional group again.
(3) product of the present invention not only has than high-molecular weight, and each chain link of macromolecular chain has the chelating function group, be beneficial to the chelating " binding " to heavy metal ion, simultaneously molecular chain is long and be beneficial to adsorption bridging between micro-floccule, promote that flco becomes thick closely knit, be beneficial to settlement separate, reduce sediment volume and water ratio, be convenient to the further processing to sediment.Overcome and taken Chinese patent CN101585572A and the CN102491473A relative molecular mass is not high, there is no the shortcoming of functional group on the part chain link.
(4) product of the present invention is applied widely, can be at normal temperatures with common heavy metal ion such as Cu in waste water
2+, Ni
2+, Pb
2+, Cd
2+, Hg
2+, Mn
2+And Zn
2+Deng chelating and remove; And treatment process is simple, only needs product of the present invention and heavy metal containing sewage are fully mixed, and gets final product through settlement separate and filtration, does not need to increase complicated equipment and operation.
(5) technology of preparing conceptual design of the present invention is reasonable, and technique is simple, is easy to operate and control; " three wastes " are few, and required equipment is conventional equipment, is easy to realize suitability for industrialized production, has broad application prospects.
Product of the present invention is fit to the processing of the various heavy metal wastewater therebies of generation in industrial and agricultural production and people's life.
Description of drawings
Fig. 1 is preparation technology's schema of product of the present invention.
Fig. 2 is the IR spectrogram of product polymethyl acrylic acid quadrol ethoxycarbonyl chelated flocculating agent of the present invention.
When Fig. 3 is use product of the present invention and other sequestrant processing heavy metal wastewater thereby, upper strata liquid turbidity is with the changing conditions of settling time.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
Referring to Fig. 1, be preparation technology's schema of the present invention, its specific embodiment is as follows:
The sorbent material that column chromatography in embodiment 1～8 is used in separating is alkali alumina, and eluent is ethyl acetate.
Embodiment 1:
(1) in the mol ratio of quadrol and oxyethane be the ratio of 2: 1, the 301g quadrol is joined in the 1L autoclave, adding the 16.4g mass percentage concentration is 10% potassium hydroxide solution again, be heated to boiling, then pass into 110.1g oxyethane, react 3h under 160 ℃, 0.5MPa, be decompressed to 1333Pa, collect the cut of 102～104.5 ℃, get the 242.5gN-hydroxyethylethylene diamine;
(2) step (1) gained N-hydroxyethyl-ethylenediamine and 467g methyl methacrylate are joined in the reactor of 1.5L with agitator, thermometer and separation column, add again 25.9g calcium hydroxide and 6.5g thiodiphenylamine, at 70 ℃ of reaction 4h, being decompressed to 1333Pa steams except unreacted methyl methacrylate and N-hydroxyethyl-ethylenediamine, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets 347.9g methacrylic acid quadrol ethyl ester;
(3) step (2) gained methacrylic acid quadrol ethyl ester being made into mass percentage concentration with 520g tetrahydrofuran (THF) dissolving is that 40% solution is placed in 1.5L with the three-necked bottle of reflux condensing tube, agitator and ventilating pit, logical N
2Drive oxygen 30min, be warming up to 55 ℃, then add the 5.2g azo-bis-isobutyrate hydrochloride to make initiator, reaction 6h, evaporating solvent, then precipitating gets the faint yellow paste of 332g in methyl alcohol;
(4) getting 50g step (3) gained paste, to be mixed with mass percentage concentration with the 1.62L deionized water be that 3% solution joins in the three-necked bottle that 3L is equipped with prolong, agitator and dropping funnel, adding 29g quality percentage composition is 96% sodium hydroxide, slowly dropping 44.6g mass percentage concentration is 99% dithiocarbonic anhydride, at room temperature react 6h, then be warmed up to 40 ℃ of reaction 1h, get light yellow transparent liquid, i.e. product polymethyl acrylic acid quadrol ethoxycarbonyl chelated flocculating agent.
Product is revolved after inspissation contracting in anhydrous propanone precipitating 3 times, to constant weight, at upper its infrared spectra (KBr compressing tablet) of measuring of Spectrum One (B) FTIR infrared spectrometer (U.S. PE company), the results are shown in Figure 2 40 ℃ of lower vacuum-dryings.Each peak ownership (cm
-1): the absorption peak that 3339.30 places are strong and wide is the stretching vibration peak of N-H and O-H, and 2970.06,2932.51 and 2869.86 are-CH
2-and
Asymmetric and symmetrical stretching vibration peak, 1737.37 is C=O stretching vibration peak in ester group, 1623.83 is the formation vibration peak of N-H, 1454.81 is C in the aminodithioformic acid group-N stretching vibration peak, 1393.84 and 1365.53 places are-CH
2-and
Corresponding C-H formation vibration peak, 1294.52,1277.40 is the stretching vibration peak of C-N, and 1228.20,1217.03,1147.26 is the stretching vibration peak of C-O, and the stronger spike at 1073.58 and 933.23 places can be attributed to-CSS
-The stretching vibration peak of middle C=S and C-S is between the characteristic absorbance (1501～1200cm of the two keys of C=S
-1) and the characteristic absorbance (700～600cm of C-S singly-bound
-1), showing that the C-S key also has the character of partial double bond, 828.77 places can be attributed to-CSS
-Formation vibration.More than show in polymer and successfully connected-CSS
-
Quality percentage composition through determination of elemental analysis S is 31.37%, and relative molecular mass is 1.99 * 10
6
Embodiment 2:
(1) in the mol ratio of quadrol and oxyethane be the ratio of 2.05: 1, the 308.5g quadrol is joined in the 1L autoclave, adding the 21g mass percentage concentration is 10% potassium hydroxide solution again, be heated to boiling, then pass into 110.1g oxyethane, react 2.5h under 170 ℃, 0.65MPa, be decompressed to 1333Pa, collect the cut of 102～104.5 ℃, get the 243.6gN-hydroxyethylethylene diamine;
(2) step (1) gained N-hydroxyethyl-ethylenediamine and 515.4g methyl methacrylate are joined in the reactor of 1.5L with agitator, thermometer and separation column, add again 29.5g calcium hydroxide and 7g thiodiphenylamine, at 80 ℃ of reaction 3.5h, being decompressed to 1333Pa steams except unreacted methyl methacrylate and N-hydroxyethyl-ethylenediamine, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets 352.2g methacrylic acid quadrol ethyl ester;
(3) step (2) gained methacrylic acid quadrol ethyl ester being made into mass percentage concentration with 352.2g tetrahydrofuran (THF) dissolving is that 50% solution is placed in 1.5L with the three-necked bottle of reflux condensing tube, agitator and ventilating pit, logical N
2Drive oxygen 30min, be warming up to 55 ℃, then add the 4.6g azo-bis-isobutyrate hydrochloride to make initiator, reaction 5.5h, evaporating solvent, then precipitating gets the faint yellow paste of 333.4g in methyl alcohol;
(4) getting 50g step (3) gained paste, to be mixed with mass percentage concentration with the 1.2L deionized water be that 4% solution joins in the three-necked bottle that 2.5L is equipped with prolong, agitator and dropping funnel, adding 31.4g quality percentage composition is 96% sodium hydroxide, slowly dropping 49g mass percentage concentration is 99% dithiocarbonic anhydride, at room temperature react 5.5h, then be warmed up to 40 ℃ of reaction 1h, get light yellow transparent liquid, i.e. product polymethyl acrylic acid quadrol ethoxycarbonyl chelated flocculating agent.
Quality percentage composition through determination of elemental analysis S is 31.86%, and relative molecular mass is 8.97 * 10
5
Embodiment 3:
(1) in the mol ratio of quadrol and oxyethane be the ratio of 2.1: 1, the 316g quadrol is joined in the 1L autoclave, adding the 26g mass percentage concentration is 10% potassium hydroxide solution again, be heated to boiling, then pass into 110.1g oxyethane, react 2h under 180 ℃, 0.8MPa, be decompressed to 1333Pa, collect the cut of 102～104.5 ℃, get the 243.2g N-hydroxyethyl-ethylenediamine;
(2) step (1) gained N-hydroxyethyl-ethylenediamine and 561.1g methyl methacrylate are joined in the reactor of 1.5L with agitator, thermometer and separation column, add again 31.1g calcium hydroxide and 7.45g thiodiphenylamine, at 90 ℃ of reaction 3h, being decompressed to 1333Pa steams except unreacted methyl methacrylate and N-hydroxyethyl-ethylenediamine, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets 349.5g methacrylic acid quadrol ethyl ester;
(3) step (2) gained methacrylic acid quadrol ethyl ester being made into mass percentage concentration with 286g DMF dissolving is that 55% solution is placed in 1.5L with the three-necked bottle of reflux condensing tube, agitator and ventilating pit, logical N
2Drive oxygen 30min, be warming up to 60 ℃, then add the 3.5g azo-bis-isobutyrate hydrochloride to make initiator, reaction 5h, evaporating solvent, then precipitating gets the faint yellow paste of 316.3g in methyl alcohol;
(4) getting 50g step (3) gained paste, to be mixed with mass percentage concentration with the 0.95L deionized water be that 5% solution joins in the three-necked bottle that 2L is equipped with prolong, agitator and dropping funnel, adding 33.8g quality percentage composition is 96% sodium hydroxide, slowly dropping 53g mass percentage concentration is 99% dithiocarbonic anhydride, at room temperature react 5h, then be warmed up to 40 ℃ of reaction 1h, get light yellow transparent liquid, i.e. product polymethyl acrylic acid quadrol ethoxycarbonyl chelated flocculating agent.
Quality percentage composition through determination of elemental analysis S is 32.03%, and relative molecular mass is 4.35 * 10
5
Embodiment 4:
(1) in the mol ratio of quadrol and oxyethane be the ratio of 2.1: 1, the 316g quadrol is joined in the 1L autoclave, adding the 26g mass percentage concentration is 10% potassium hydroxide solution again, be heated to boiling, then pass into 110.1g oxyethane, react 3h under 170 ℃, 0.7MPa, be decompressed to 1333Pa, collect the cut of 102～104.5 ℃, get the 244.5g N-hydroxyethyl-ethylenediamine;
(2) step (1) gained N-hydroxyethyl-ethylenediamine and 588.5g methyl methacrylate are joined in the reactor of 1.5L with agitator, thermometer and separation column, add again 34.8g calcium hydroxide and 7g thiodiphenylamine, at 80 ℃ of reaction 4h, being decompressed to 1333Pa steams except unreacted methyl methacrylate and N-hydroxyethyl-ethylenediamine, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets 357g methacrylic acid quadrol ethyl ester;
(3) step (2) gained methacrylic acid quadrol ethyl ester being made into mass percentage concentration with 238g tetrahydrofuran (THF) dissolving is that 60% solution is placed in 1.5L with the three-necked bottle of reflux condensing tube, agitator and ventilating pit, logical N
2Drive oxygen 30min, be warming up to 65 ℃, then add 5.35g azo two isobutyl imidazoline salt hydrochlorates to make initiator, reaction 5h, evaporating solvent, then precipitating gets the faint yellow paste of 325.3g in methyl alcohol;
(4) getting 50g step (3) gained paste, to be mixed with mass percentage concentration with the 1.62L deionized water be that 3% solution joins in the three-necked bottle that 3L is equipped with prolong, agitator and dropping funnel, adding 36.3g quality percentage composition is 96% sodium hydroxide, slowly dropping 53g mass percentage concentration is 99% dithiocarbonic anhydride, at room temperature react 5h, then be warmed up to 40 ℃ of reaction 1h, get light yellow transparent liquid, i.e. product polymethyl acrylic acid quadrol ethoxycarbonyl chelated flocculating agent.
Quality percentage composition through determination of elemental analysis S is 32.11%, and relative molecular mass is 3.99 * 10
5
Embodiment 5:
(1) in the mol ratio of diethylenetriamine and oxyethane be the ratio of 2: 1, the 361.1g diethylenetriamine is joined in the 1L autoclave, adding the 17.5g mass percentage concentration is 10% potassium hydroxide solution again, be heated to boiling, then pass into 77.1g oxyethane, react 3h under 160 ℃, 0.5MPa, be decompressed to 133Pa, collect the cut of 159～162.5 ℃, get 239.5g N-hydroxyethyl diethylenetriamine;
(2) step (1) gained N-hydroxyethyl diethylenetriamine and 326.4g methyl methacrylate are joined in the reactor of 1.5L with agitator, thermometer and separation column, add again 24.2g calcium hydroxide and 5.2g thiodiphenylamine, at 80 ℃ of reaction 4h, being decompressed to 133Pa steams except unreacted methyl methacrylate and N-hydroxyethyl diethylenetriamine, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets 312.9g methacrylic acid diethylenetriamine ethyl ester;
(3) step (2) gained methacrylic acid diethylenetriamine ethyl ester being made into mass percentage concentration with 469.4g DMF dissolving is that 40% solution is placed in 2L with the three-necked bottle of reflux condensing tube, agitator and ventilating pit, logical N
2Drive oxygen 30min, be warming up to 65 ℃, then add the 4.7g Diisopropyl azodicarboxylate to make initiator, reaction 6h, evaporating solvent, then precipitating gets the faint yellow paste of 267.8g in methyl alcohol;
(4) getting 50g step (3) gained paste, to be mixed with mass percentage concentration with the 1.62L deionized water be that 3% solution joins in the three-necked bottle that 3L is equipped with prolong, agitator and dropping funnel, adding 34.5g quality percentage composition is 96% sodium hydroxide, slowly dropping 52.5g mass percentage concentration is 99% dithiocarbonic anhydride, at room temperature react 6h, then be warmed up to 40 ℃ of reaction 1h, get light yellow transparent liquid, i.e. product polymethyl acrylic acid diethylenetriamine ethoxycarbonyl chelated flocculating agent.
Quality percentage composition through determination of elemental analysis S is 33.79%, and relative molecular mass is 5.42 * 10
5
Embodiment 6:
(1) in the mol ratio of diethylenetriamine and oxyethane be the ratio of 2.1: 1, the 379.2g diethylenetriamine is joined in the 1L autoclave, adding the 27.4g mass percentage concentration is 10% potassium hydroxide solution again, be heated to boiling, then pass into 77.1g oxyethane, react 2h under 180 ℃, 0.8MPa, be decompressed to 133Pa, collect the cut of 159～162.5 ℃, get 240.2g N-hydroxyethyl diethylenetriamine;
(2) step (1) gained N-hydroxyethyl diethylenetriamine and 408.5g methyl methacrylate are joined in the reactor of 1.5L with agitator, thermometer and separation column, add again 18.1g calcium hydroxide and 4.5g thiodiphenylamine, at 70 ℃ of reaction 4h, being decompressed to 133Pa steams except unreacted methyl methacrylate and N-hydroxyethyl diethylenetriamine, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets 293g methacrylic acid diethylenetriamine ethyl ester;
(3) step (2) gained methacrylic acid diethylenetriamine ethyl ester being made into mass percentage concentration with 195.4g methyl-sulphoxide dissolving is that 60% solution is placed in 1L with the three-necked bottle of reflux condensing tube, agitator and ventilating pit, logical N
2Drive oxygen 30min, be warming up to 60 ℃, then add 3.52g azo two isobutyl imidazoline salt hydrochlorates to make initiator, reaction 5h, evaporating solvent, then precipitating gets the faint yellow paste of 252.9g in methyl alcohol;
(4) getting 50g step (3) gained paste, to be mixed with mass percentage concentration with the 0.95L deionized water be that 5% solution joins in the three-necked bottle that 2L is equipped with prolong, agitator and dropping funnel, adding 43.1g quality percentage composition is 96% sodium hydroxide, slowly dropping 63g mass percentage concentration is 99% dithiocarbonic anhydride, at room temperature react 6h, then be warmed up to 40 ℃ of reaction 1h, get light yellow transparent liquid, i.e. product polymethyl acrylic acid diethylenetriamine ethoxycarbonyl chelated flocculating agent.
Quality percentage composition through determination of elemental analysis S is 35.07%, and relative molecular mass is 2.11 * 10
6
Embodiment 7:
(1) in the mol ratio of triethylene tetramine and oxyethane be the ratio of 2: 1, the 438.7g triethylene tetramine is joined in the 1.5L autoclave, adding the 30.3g mass percentage concentration is 10% potassium hydroxide solution again, be heated to boiling, then pass into 66.1g oxyethane, react 3h under 170 ℃, 0.6MPa, decompression 1.33Pa, collect the cut of 174～178.5 ℃, get 260.3g N-hydroxyethyl triethylene tetramine;
(2) step (1) gained N-hydroxyethyl triethylene tetramine and 274.3g methyl methacrylate are joined in the reactor of 1.5L with agitator, thermometer and separation column, add again 20.3g calcium hydroxide and 4.4g thiodiphenylamine, at 90 ℃ of reaction 3.5h, being decompressed to 1.33Pa steams except unreacted methyl methacrylate and N-hydroxyethyl triethylene tetramine, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets 311.3g methacrylic acid triethylene tetramine ethyl ester;
(3) step (2) gained methacrylic acid triethylene tetramine ethyl ester being made into mass percentage concentration with 207.5g tetrahydrofuran (THF) dissolving is that 60% solution is placed in 1.5L with the three-necked bottle of reflux condensing tube, agitator and ventilating pit, logical N
2Drive oxygen 30min, be warming up to 60 ℃, then add the 4.05g Diisopropyl azodicarboxylate to make initiator, reaction 6h, evaporating solvent, then precipitating gets the faint yellow paste of 262.1g in methyl alcohol;
(4) getting 50g step (3) gained paste, to be mixed with mass percentage concentration with the 1.2L deionized water be that 4% solution joins in the three-necked bottle that 3L is equipped with prolong, agitator and dropping funnel, adding 42g quality percentage composition is 96% sodium hydroxide, slowly dropping 59.1g mass percentage concentration is 99% dithiocarbonic anhydride, at room temperature react 6h, then be warmed up to 40 ℃ of reaction 1h, get light yellow transparent liquid, i.e. product polymethyl acrylic acid triethylene tetramine ethoxycarbonyl chelated flocculating agent.
Quality percentage composition through determination of elemental analysis S is 36.54%, and relative molecular mass is 6.93 * 10
5
Embodiment 8:
(1) in the mol ratio of triethylene tetramine and oxyethane be the ratio of 2.1: 1, the 460.6g triethylene tetramine is joined in the 1.5L autoclave, adding the 26.3g mass percentage concentration is 10% potassium hydroxide solution again, be heated to boiling, then pass into 66.1g oxyethane, react 3h under 180 ℃, 0.8MPa, be decompressed to 1.33Pa, collect the cut of 174～178.5 ℃, get 262.8g N-hydroxyethyl triethylene tetramine;
(2) step (1) gained N-hydroxyethyl triethylene tetramine and 345.7g methyl methacrylate are joined in the reactor of 1.5L with agitator, thermometer and separation column, add again 20.5g calcium hydroxide and 4.4g thiodiphenylamine, at 75 ℃ of reaction 4h, being decompressed to 1.33Pa steams except unreacted methyl methacrylate and N-hydroxyethyl triethylene tetramine, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets 315.8g methacrylic acid triethylene tetramine ethyl ester;
(3) step (2) gained methacrylic acid triethylene tetramine ethyl ester being made into mass percentage concentration with 315.8g methyl-sulphoxide dissolving is that 50% solution is placed in 1.5L with the three-necked bottle of reflux condensing tube, agitator and ventilating pit, logical N
2Drive oxygen 30min, be warming up to 65 ℃, then add 4.74g azo two isobutyl imidazoline salt hydrochlorates to make initiator, reaction 6h, evaporating solvent, then precipitating gets the faint yellow paste of 288.3g in methyl alcohol;
(4) getting 50g step (3) gained paste, to be mixed with mass percentage concentration with the 1.62L deionized water be that 3% solution joins in the three-necked bottle that 3L is equipped with prolong, agitator and dropping funnel, adding 48.5g quality percentage composition is 96% sodium hydroxide, slowly dropping 70.9g mass percentage concentration is 99% dithiocarbonic anhydride, at room temperature react 6h, then be warmed up to 40 ℃ of reaction 1h, get light yellow transparent liquid, i.e. product polymethyl acrylic acid triethylene tetramine ethoxycarbonyl chelated flocculating agent.
Quality percentage composition through determination of elemental analysis S is 37.12%, and relative molecular mass is 2.71 * 10
6
Take embodiment 1 gained sample as medicament, preparation contains Cu respectively
2+, Ni
2+, Cd
2+, Pb
2+And Zn
2+The mass body volume concentrations be the simulation heavy metal water sample of 100mg/L.Floc test condition: get respectively 500mL simulation heavy metal water sample, on the intelligent color-screen coagulate examination stirring instrument of MY3000-6G (Wuhan City Mei Yu Instr Ltd.), add medicament, stir soon 5min under 200～220r/min, stir 10min under 100～120r/min, then stir slowly 10min under 50～60r/min, standing 35min, the clear liquid of getting 2cm under liquid level place is measured AA100 type Atomic Absorption Spectroscopy AAS (U.S. PE company) is upper, and treatment effect sees Table 1.
The removal effect of table 1 product of the present invention to heavy metal ion
As seen, product of the present invention is to free Cu
2+, Ni
2+, Cd
2+, Pb
2+And Zn
2+Plasma all has removal effect preferably, and survivor ion concentration is all far below national sewage comprehensive discharge primary standard (GB8978-1996).
Take embodiment 1 gained sample, ACPF(patent CN101585572A sample), PHMF(patent CN102491473A sample) and TMT-18 as medicament, 100mg/L Cu
2+Simulated wastewater is experimental subjects.First will contain Cu
2+Simulated wastewater joins in the coagulation cup, is placed in (Wuhan City Mei Yu Instr Ltd.) on the intelligent color-screen coagulate examination stirring instrument of MY3000-6G, and the optimum amount of the every kind of medicament that draws by floc test adds.Stir soon 5min under 200～220r/min, stir 10min under 100～120r/min, slowly stir again 10min under 50～60r/min, stop stirring and namely begin timing, press certain hour interval sampling at the upper turbidity of measuring of 2100P portable turbidimeter (U.S. HACH company), to time t mapping, the results are shown in accompanying drawing 3 with upper strata liquid turbidity.
Can find out from accompanying drawing 3, the turbidity that adopts sample preparation copper-containing wastewater of the present invention upper strata liquid in standing same time is low than PHMF and ACPF obviously, far below commercially available TMT-18, show that the chelate for flocculation effect of sample of the present invention is than ACPF(patent CN101585572A sample), PHMF(profit CN102491473A sample) and TMT-18 good.
It is only below preferred embodiment of the present invention, according to above-mentioned design of the present invention, those skilled in the art can also be in proportioning that the present invention provides and processing condition scope to make up such as proportioning and processing condition etc., conversion, similarly these conversion and revise and all belong to flesh and blood of the present invention.
Claims (6)
1. polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent, consist of: the structural formula of main component is that compound, the ancillary component of formula I is xanthogenic acid and sodium hydroxide, and outward appearance is faint yellow or yellow transparent liquid;
In formula I, n is 1000～5000 integer, and x is 1～3 integer.
2. the preparation method of polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent as claimed in claim 1, is characterized in that comprising the steps:
(1) polyethylene polyamine is added in autoclave, adding mass percentage concentration is 10% potassium hydroxide solution again, is heated to boiling, then passes into oxyethane, react 2～3h under 160～180 ℃, 0.5～0.8MPa, underpressure distillation obtains N-hydroxyethyl polyethylene polyamine; Wherein, the mol ratio of polyethylene polyamine and oxyethane is 2～2.1: 1, and the amount of potassium hydroxide is 0.4～0.6% of the polyethylene polyamine that adds and oxyethane total mass;
(2) be that 1: 2～2.5 ratio joins with agitator in molar ratio with step (1) gained N-hydroxyethyl polyethylene polyamine and methyl methacrylate, in the reactor of thermometer and separation column, press again calcium hydroxide, thiodiphenylamine and N-hydroxyethyl polyethylene polyamine mol ratio are 0.15～0.20: 0.014～0.016: 1 ratio adds calcium hydroxide and thiodiphenylamine, at 70～90 ℃ of reaction 3～4h, remove unreacted methyl methacrylate and N-hydroxyethyl polyethylene polyamine under reduced pressure, then remove by filter calcium hydroxide, the column chromatography separating-purifying gets methacrylic acid polyethylene polyamine ethyl ester,
(3) step (2) gained methacrylic acid polyethylene polyamine ethyl ester being made into mass percentage concentration with polar solvent dissolving is 40～60% monomer solution, then logical N
2Drive oxygen 30min, be warming up to 55～65 ℃, then add radical initiator by 1～1.5% of monomer mass, reaction 4～6h, evaporating solvent, then precipitating gets faint yellow paste in methyl alcohol;
(4) step (3) gained paste being added deionized water be mixed with mass percentage concentration is 3～5% solution, then be 1.0: 1.2～1.5: 1～1.2 ratio in the mol ratio of N atom, sodium hydroxide and dithiocarbonic anhydride in the polyethylene polyamine molecule of access, first add sodium hydroxide, drip again dithiocarbonic anhydride and at room temperature react 5～6h, then be warmed up to 40 ℃ of reaction 1h, namely get product polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent.
3. the preparation method of polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent according to claim 2, it is characterized in that: polyethylene polyamine described in step (1) is any in quadrol, diethylenetriamine and triethylene tetramine.
4. the preparation method of polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent according to claim 2, it is characterized in that: the sorbent material that column chromatography described in step (2) is used in separating is alkali alumina, and eluent is ethyl acetate.
5. the preparation method of polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent according to claim 2, it is characterized in that: polar solvent described in step (3) is any in tetrahydrofuran (THF), methyl-sulphoxide and DMF.
6. the preparation method of polymethyl acrylic acid polyethylene polyamine ethoxycarbonyl chelated flocculating agent according to claim 2, it is characterized in that: radical initiator described in step (3) is any in Diisopropyl azodicarboxylate, azo-bis-isobutyrate hydrochloride and azo two isobutyl imidazoline salt hydrochlorates.
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| CN106947084A (en) * | 2017-05-12 | 2017-07-14 | 天津医科大学 | Macromolecular material and its anticancer usage for complex copper ion |
| CN107511136A (en) * | 2017-08-23 | 2017-12-26 | 广州中国科学院工业技术研究院 | The treatment fluid of pigment adsorbent and its application |
| CN114106238A (en) * | 2021-12-14 | 2022-03-01 | 西南石油大学 | Zwitterionic flocculant and preparation method thereof |
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| CN114106238A (en) * | 2021-12-14 | 2022-03-01 | 西南石油大学 | Zwitterionic flocculant and preparation method thereof |
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