CN105152299B - A kind of hyper-branched polymer multi-function sewage treating agent and synthetic method - Google Patents
A kind of hyper-branched polymer multi-function sewage treating agent and synthetic method Download PDFInfo
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Abstract
The invention belongs to Treatment of Industrial Water technical field, more particularly to a kind of hyper-branched polymer multi-function sewage treating agent and synthetic method.The functional group that can largely realize the one removal such as heavy metal ion, suspension, colloid, oil slick is contained in hyper-branched polymer multi-function sewage treating agent of the invention, its hyper-branched polymer molecular skeleton and molecular end position；Hyper-branched polymer kernel is organosiloxane structural, and organosiloxane structural has low-surface-energy, it is easy to is positioned at the surface and interface of solid suspension particle and colloidal solution, and can reduce the water content of generation flco.
Description
Technical field
The invention belongs to Treatment of Industrial Water technical field, more particularly to a kind of hyper-branched polymer multi-function sewage treating agent
And synthetic method.
Background technology
In recent years, with plating and the fast development of printed circuit board process industry, discharge substantial amounts of cupric, zinc, it is violent,
The waste water of the heavy metal ion such as cadmium, town, in these waste water often containing can be combined with metal ion produce and its stable state it is new
Type complexing agent, such as complexing agent such as Chinese catalpa lemon hydrochlorate, EDTA, organic phospho acid, triethanolamine, tartrate, pyrophosphate, cause water
What matter composition became becomes increasingly complex.For the heavy metal of complex state, neutralization precipitation method treatment waste water is extremely difficult to country's discharge mark
Standard, so as to cause plurality of heavy metal to enter in environment water；The more organic sulfur class heavy metal chelating agent of Recent study（Two sulphur
For carbaminate（DTC) class heavy metal chelating agent, xanthan acids heavy metals trapping, TMT class heavy metal chelating agents）After treatment
Waste water, flco body is small, amount is big, water is more, easily produces secondary pollution, and the water environment survived to the mankind and its allogene brings pole
Big harm.
The content of the invention
It is an object of the present invention to overcome the deficiencies in the prior art, there is provided a kind of hyper-branched polymer multi-functional sewage
Inorganic agent, the inorganic agent is more with heavy metal ion action site, molecular weight is big, efficiency high, can realize heavy metal ion, suspend
The one such as thing, oil slick is removed, additionally, the wadding mud of generation is aqueous few, can mitigate the burden of flco treatment.Present invention also offers
A kind of synthetic method of hyper-branched polymer multi-function sewage treating agent.
In order to solve the above technical problems, the technical scheme is that：A kind of hyper-branched polymer Multifunctional Additive
Synthetic method, the method comprises the following steps：
（1）There is thiol-ene in vinylsiloxane and mercaptoethylmaine or trimethylolpropane tris (3-thiopropionate)
Reaction, the hyper-branched polymer kernel of the first one-step functional of generation；
（2）Step（1）Product elder generation and epichlorohydrin reaction, then again with organic amine react, generate it is hyperbranched
Macromolecule, described organic amine is polyethylene polyamine and triethylamine；
（3）By adding reaction kinetic type monomer reaction, high-molecule metal agent for capturing of the synthesis containing various functional groups.
Step（1）Described vinylsiloxane be 2,4,6- trimethyl -2,4,6- trivinyls cyclotrisiloxane, 2,4,
Any ratio mixing of one or more of 6,8- tetramethyl -2,4,6,8- tetravinyls cyclotetrasiloxane, vinyl silicone oil.
The step（1）The ratio between the vinylsiloxane medium vinyl functional group of addition and mercapto functional group mole are 1:
1-1.5。
The step（2）Middle added epoxychloropropane, organic amine and step（1）Middle added mercapto functional group mole
Than for（1-1.02）:（1-1.02）：1.The step（2）The mol ratio of middle added polyethylene polyamine and triethylamine is 10-
1:1。
The step（3）In, reaction kinetic type monomer includes CS2, TGA, one kind of O- acylurea intermediates or
Two or more arbitrary proportion mixing.
The mol ratio 1 of the vinylsiloxane and reaction kinetic type monomer:10-40.
The step（1）Reaction temperature be 0-25 oC, the time be 1 h-8 h.
The step（2）Reaction temperature be 5-110 oC, the time be 1 h-8 h, regulation pH in 8-11.
The step（3）Reaction temperature be 5-25 oC, the time be 1 h-8 h, regulation pH be 9-14.
According to a kind of hyper-branched polymer multi-function sewage treating agent prepared by above-mentioned synthetic method.
Polyethylene polyamine of the present invention is ethylenediamine, diethylenetriamine, triethylene tetramine, pentaethylene hexamine, six second
The amine of alkene seven, the amine of seven ethene eight, the amine of eight ethene nine, a kind of or arbitrarily several arbitrary proportion of the amine of nine ethene ten, the amine of triethylene five is mixed
Close.
The beneficial effects of the invention are as follows：Hyper-branched polymer multi-function sewage treating agent of the invention, its hyperbranched high score
The official that can largely realize the one removal such as heavy metal ion, suspension, colloid, oil slick is contained in sub- molecular skeleton and molecular end position
Can group；Hyper-branched polymer kernel is organosiloxane structural, and organosiloxane structural has low-surface-energy, it is easy to be positioned at solid
The surface and interface of body suspended particle and colloidal solution, and the water content of generation flco can be reduced.The inorganic agent and heavy metal ion
Action site is more, molecular weight is big, efficiency high, can realize that the one such as heavy metal ion, suspension, oil slick is removed, additionally, generation
Wadding mud is aqueous few, can mitigate the burden of flco treatment.
Specific embodiment
The experimental technique used in following embodiments, is conventional method；Material, reagent used etc., can be from
Commercial sources are obtained.
Heavy metal solution is prepared：
(1) effluent containing heavy metal ions solution is simulated：According to each heavy metal relative atomic mass and its place compound point
Son amount calculates weigh a certain amount of metallic compound respectively, configures certain density Cu2+、Zn2+、Hg2+、Cd2+ Pb2+、Cr3+
Deng solution.
Each simulation heavy metal wastewater thereby solution concentration is as follows：
Cu2+=70.3 mg/L; Zn2+=75.2 mg/L；Hg2+=193.5 mg/L；Pb2+=99.9 mg/L；
Cd2+=109.5 mg/L; Cr3+=85.7 mg/L； Ni2+=90.9 mg/L； Ag+=89.8 mg/L；
(2) heavy metal chelating agent of freshly synthesized good drying is weighed, a certain amount of ethanol is dissolved in（Industrial alcohol）In, it is dissolved in surely
In 1000 mL volumetric flasks, the concentration for making trapping agent ethanol solution is 0.002 g/mL.
The experimental procedure of trap heavy metals ion
(1) the above-mentioned effluent containing heavy metal ions sample 50-100mL for having simulated is taken in corresponding conical flask；
(2) pH, the mixing time of solution are controlled, heavy metal chelating agent is added and is trapped, react certain hour, stood
Sedimentation；
(3) supernatant liquid centrifugation centrifugation 15-20min is taken；
(4) supernatant liquid after centrifugation is taken again obtains settled solution to be measured with double-deck 0.22 miillpore filter suction filtration；
(5) take the clear liquid after appropriate filtering and prepare concentration of heavy metal ion of the analysis test after ICP tests trapping,
And calculate the clearance of heavy metal ion.
Embodiment 1
Step（1）：
To adding 0.05 mol 2,4,6- trimethyl -2,4,6- triethylene basic rings in the there-necked flask with magnetic agitation
The ethanol-toluene mixed solution of trisiloxanes, 0.2mol mercaptoethylmaines react at room temperature, reaction time 1-4h.
Step（2）：
By step（1）Reaction system be cooled to 0-5 °C, be then slowly added dropwise 0.4mol epoxychloropropane, course of reaction
Middle use 5-10% aqueous slkalis adjust pH after 8-11, completion of dropping, are stirred at room temperature 2-4 hours；After completion of the reaction, it is warming up to 80-
100 °C, the triethylamine solution of 0.35 mol pentaethylene hexamines and 0.05mol is added dropwise, is adjusted with 5-10% aqueous slkalis in course of reaction
PH was in 8-11, reaction time 4-10 hours；
Step（3）：
By step（2）The product of synthesis is soluble in water, is cooled to 5-10 °C, adds the g of the 50%NaOH aqueous solution 56, delays
It is slow that 0.7mol CS are added dropwise2, completion of dropping, by reaction system recover to room temperature continue stirring reaction 2-4h, obtain final product.
Medicament concentration 50mg/L, Cu2+Clearance 98.9%.
Embodiment 2
Step（1）：
To adding the ethene of 0.05 mol 2,4,6,8- tetramethyls -2,4,6,8- four in the there-necked flask with magnetic agitation
The ethanol-toluene mixed solution of basic ring tetrasiloxane, 0.2mol mercaptoethylmaines react at room temperature, reaction time 1-4h.
Step（2）
By step（1）Reaction system be cooled to 0-5 °C, be then slowly added dropwise 0.4mol epoxychloropropane, course of reaction
Middle use 5-10% aqueous slkalis adjust pH after 8-11, completion of dropping, are stirred at room temperature 2-4 hours；After completion of the reaction, it is warming up to 80-
100 °C, the triethylamine solution of 0.35 mol pentaethylene hexamines and 0.05mol is added dropwise, is adjusted with 5-10% aqueous slkalis in course of reaction
PH was in 8-11, reaction time 4-10 hours；
Step（3）:
By step（2）The product of synthesis is soluble in water, is cooled to 5-10 °C, adds the g of the 50%NaOH aqueous solution 60, delays
It is slow that 0.75 mol CS are added dropwise2, completion of dropping, by reaction system recover to room temperature continue stirring reaction 2-4h, finally produced
Thing.
Medicament concentration 50mg/L, Hg2+Clearance 99.3%.
Embodiment 3
Step（1）：
To adding 0.02 mol low molecular weight polycaprolactone methyl vinyl silicones in the there-necked flask with magnetic agitation（Mn=
602）Ethanol-toluene mixed solution, 0.15 mol mercaptoethylmaines react, reaction time 1-4h at room temperature.
Step（2）
By step（1）Reaction system be cooled to 0-5 °C, be then slowly added dropwise 0.3 mol epoxychloropropane, course of reaction
Middle use 5-10% aqueous slkalis adjust pH after 8-11, completion of dropping, are stirred at room temperature 2-4 hours；After completion of the reaction, it is warming up to 80-
100 °C, the triethylamine solution of 0.25 mol pentaethylene hexamines and 0.05mol is added dropwise, is adjusted with 5-10% aqueous slkalis in course of reaction
PH was in 8-11, reaction time 4-10 hours；
Step（3）:
By step（2）The product of synthesis is soluble in water, is cooled to 5-10 °C, adds the g of the 50%NaOH aqueous solution 40, delays
It is slow that 0.5 mol CS are added dropwise2, completion of dropping, by reaction system recover to room temperature continue stirring reaction 2-4h, obtain final product.
Medicament concentration 50mg/L, Ni2+Clearance 99.1%.
Embodiment 4
Step（1）：
To adding 0.02 mol low molecular weight polycaprolactone methyl vinyl silicones in the there-necked flask with magnetic agitation（Mn=
860）Ethanol-toluene mixed solution, 0.25 mol trimethylolpropane tris (3-thiopropionate) react at room temperature, react
Time 1-4h.
Step（2）
By step（1）Reaction system be cooled to 0-5 °C, be then slowly added dropwise 0.5 mol epoxychloropropane, course of reaction
Middle use 5-10% aqueous slkalis adjust pH after 8-11, completion of dropping, are stirred at room temperature 2-4 hours；After completion of the reaction, it is warming up to 80-
100 °C, the triethylamine solution of 0.45 mol pentaethylene hexamines and 0.05mol is added dropwise, is adjusted with 5-10% aqueous slkalis in course of reaction
PH was in 8-11, reaction time 4-10 hours；
Step（3）:
By step（2）The product of synthesis is soluble in water, is cooled to 5-10 °C, adds the g of the 50%NaOH aqueous solution 120,
It is slowly added dropwise 0.75 mol CS2, completion of dropping, by reaction system recover to room temperature continue stirring reaction 2-4h, then again upper
State in system, add EDC HCl, be slowly added dropwise 0.12mol TGAs, react 12-24 hours at room temperature, finally produced
Thing.EDC HCl play catalytic dehydration, and the mole of addition is the 0.5-1% of TGA consumption.
Medicament concentration 50mg/L, Cd2+Clearance 99.5%.
Embodiment 5
Step（1）：
To adding 0.02 mol low molecular weight polycaprolactone methyl vinyl silicones in the there-necked flask with magnetic agitation（Mn=
860）Ethanol-toluene mixed solution, 0.25 mol mercaptoethylmaines react, reaction time 1-4h at room temperature.
Step（2）
By step（1）Reaction system be cooled to 0-5 °C, be then slowly added dropwise 0.5 mol epoxychloropropane, course of reaction
Middle use 5-10% aqueous slkalis adjust pH after 8-11, completion of dropping, are stirred at room temperature 2-4 hours；After completion of the reaction, it is warming up to 80-
100 °C, the triethylamine solution of 0.45 mol pentaethylene hexamines and 0.05mol is added dropwise, is adjusted with 5-10% aqueous slkalis in course of reaction
PH was in 8-11, reaction time 4-10 hours；
Step（3）：
By step（2）The product of synthesis is soluble in water, is cooled to 5-10 °C, adds the g of the 50%NaOH aqueous solution 120,
It is slowly added dropwise 0.75 mol CS2, completion of dropping, by reaction system recover to room temperature continue stirring reaction 2-4h, then again upper
State in system, add EDC HCl, be slowly added dropwise 0.12mol TGAs, react 12-24 hours at room temperature, finally produced
Thing.EDC HCl play catalytic dehydration, and the mole of addition is the 0.5-1% of TGA consumption.
Medicament concentration 50mg/L, Pb 2+Clearance 98.8%.
Claims (9)
1. a kind of synthetic method of hyper-branched polymer multi-function sewage treating agent, the method comprises the following steps：
(1) there is thiol-ene reactions in vinylsiloxane and mercaptoethylmaine or trimethylolpropane tris (3-thiopropionate),
The hyper-branched polymer kernel of the first one-step functional of generation；
(2) the product elder generation of step (1) and epichlorohydrin reaction, then react with organic amine again, generate hyperbranched high score
Son, described organic amine is polyethylene polyamine and triethylamine；
(3) by adding reaction kinetic type monomer reaction, high-molecule metal agent for capturing of the synthesis containing various functional groups；
In the step (3), reaction kinetic type monomer includes CS2, TGA, O- acylurea intermediates one or two
Any of the above ratio mixes.
2. a kind of synthetic method of hyper-branched polymer multi-function sewage treating agent according to claim 1, its feature exists
In：Vinylsiloxane described in step (1) is 2,4,6- trimethyl -2,4,6- trivinyls cyclotrisiloxane, 2,4,6,8-
Any ratio mixing of one or more of tetramethyl -2,4,6,8- tetravinyls cyclotetrasiloxane, vinyl silicone oil.
3. a kind of synthetic method of hyper-branched polymer multi-function sewage treating agent according to claim 1, its feature exists
In：The ratio between the vinylsiloxane medium vinyl functional group of step (1) addition and mercapto functional group mole are 1:1-
1.5。
4. a kind of synthetic method of hyper-branched polymer multi-function sewage treating agent according to claim 1, its feature exists
In：The mercapto functional group mol ratio added in epoxychloropropane, organic amine and step (1) is added in the step (2) to be
(1-1.02):(1-1.02)：1, the polyethylene polyamine and the mol ratio of triethylamine added in the step (2) are 10-1:1.
5. a kind of synthetic method of hyper-branched polymer multi-function sewage treating agent according to claim 1, its feature exists
In：The vinylsiloxane is 1 with the mol ratio of reaction kinetic type monomer:10-40.
6. a kind of synthetic method of hyper-branched polymer multi-function sewage treating agent according to claim 1, its feature exists
In：The reaction temperature of the step (1) is 0-25 DEG C, and the time is 1h-8h.
7. a kind of synthetic method of hyper-branched polymer multi-function sewage treating agent according to claim 1, its feature exists
In：The reaction temperature of the step (2) is 5-110 DEG C, and the time is 1h-8h, and pH is in 8-11 for regulation.
8. a kind of synthetic method of hyper-branched polymer multi-function sewage treating agent according to claim 1, its feature exists
In：The reaction temperature of the step (3) is 5-25 DEG C, and the time is 1h-8h, and regulation pH is 9-14.
9. a kind of hyper-branched polymer multi-functional sewage treatment that prepared by the synthetic method according to any one of above-mentioned 1-8
Agent.
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| CN107399800B (en) * | 2017-08-08 | 2020-11-10 | 北京市理化分析测试中心 | Efficient complex-state heavy metal ion remover and synthesis method thereof |
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