CN110317337A - Over-branched polyamidoamine, preparation method and its application in terms of heavy mental treatment - Google Patents
Over-branched polyamidoamine, preparation method and its application in terms of heavy mental treatment Download PDFInfo
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- CN110317337A CN110317337A CN201910642000.4A CN201910642000A CN110317337A CN 110317337 A CN110317337 A CN 110317337A CN 201910642000 A CN201910642000 A CN 201910642000A CN 110317337 A CN110317337 A CN 110317337A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention discloses a kind of over-branched polyamidoamine, preparation method and its application in terms of heavy mental treatment, belong to the Treatment of Industrial Water technical field containing heavy metal.Its technical solution includes that fatty amine is dissolved in solvent, after mixing, citrate is added thereto, after reacting 3-10h at 50-80 DEG C, vacuumizes 5-10h, obtains over-branched polyamidoamine；The fatty amine is selected from aliphatic diamine or aliphatic polyamine；The solvent is selected from alcohol solvent or water.In terms of the present invention is applied to the Treatment of Industrial Water containing heavy metal; solves the dendroid daiamid preparation method complexity for being currently used for heavy mental treatment; reaction time is long; the high problem of energy consumption; it is mild with reaction condition; reaction time is short, easy to operate, convenient for product subsequent industrialization and large-scale production the characteristics of.
Description
Technical field
The invention belongs to containing heavy metal Treatment of Industrial Water technical field more particularly to a kind of over-branched polyamidoamine, its
Preparation method and its application in terms of heavy mental treatment.
Background technique
With the rapid development of industry, heavy metal is increasingly severe to the pollution of water resource, and heavy metal ion is with tired
The features such as product property and non-biodegradable, high risks are caused to the ecosystem and human health, so to a huge sum of money in water resource
The removal for belonging to ion has become a global problem.Currently, technology of the processing containing various effluent containing heavy metal ions is main
There are ion-exchange, membrane separation process, absorption method, chemical precipitation method etc..Its ion exchange methods invests big, complex process；Film point
It is at high cost from method, fouling membrane can be generated；Absorption method condition is stringent, is only applicable to low concentration wastewater, while there is also adsorbents
The problems such as regeneration；Cost is relatively low for the conventional chemical precipitation method, it is easy to operate, using relatively wide, but be difficult to meet increasingly strict discharge
Standard needs to carry out advanced treating with the combination of the techniques such as film process, ion exchange in actual process, and increase is processed into
This, it is difficult to it is commonly used.
Chinese patent CN203864654A discloses a kind of polyamidoamine dendrimers of carbodithioic acid sealing end, can
It is used using the stabilizer as incineration of refuse flyash, there is efficient stabilization to heavy metal in incineration of refuse flyash.But
The synthesis process of dendroid polyamide used in it is complicated, and the time is tediously long, limits the amplification industrialized production of the type product.
103506092 A of Chinese patent CN discloses a kind of support type polyamidoamine dendrimer cigarette smoke
Heavy metal absorbent and its preparation method and application, and specifically disclosing polyamidoamine dendrimer is by with second
Diamines is core, and the poly- of the amidation process formation of Micheal addition reaction and ester is repeated with ethylenediamine and methyl acrylate
Conjunction object chain is branch, high-molecular compound obtained.However, the daiamid for the product dendritic structure that the program obtains, from it
From the point of view of synthetic method, reaction process is complicated, and the reaction time is tediously long, and in practical operation, it is not anti-to need to carry out product washing removing
Otherwise the raw material answered can cause the defect of the structure of dendroid daiamid (grafting is incomplete).
Chinese patent CN201310526044.3 discloses a kind of dendroid daiamid and over-branched polyamidoamine is compound
The characteristics of heavy metal water treatment agent, reaction be under condition of different temperatures, vacuumized to obtain over-branched polyamidoamine it
It is compounded afterwards from the dendroid daiamid of different algebra, dissaving polymer needs anti-under 140 DEG C of hot conditions
5h is answered, energy consumption is relatively high.
Summary of the invention
Place in view of the shortcomings of the prior art, the main problem of solution to be solved by this invention is to overcome existing use
Complicated in the dendroid daiamid preparation method of heavy mental treatment, the reaction time is long, and the high problem of energy consumption proposes one kind
Mild with reaction condition, the reaction time is short, easy to operate, convenient for product subsequent industrialization and large-scale production it is hyperbranched
Daiamid, preparation method and its application in terms of heavy mental treatment.
To solve the technical problem, the technical solution adopted by the present invention are as follows:
The present invention provides a kind of preparation methods of over-branched polyamidoamine, comprising the following steps:
Fatty amine is dissolved in solvent, after mixing, citrate is added thereto, reacts 3-10h at 50-80 DEG C
Afterwards, 5-10h is vacuumized, over-branched polyamidoamine is obtained；
The fatty amine is selected from aliphatic diamine or aliphatic polyamine；The solvent is selected from alcohol solvent or water.
Preferably, the molar ratio of the fatty amine and the citrate is 12:5-12:3.
Preferably, the fatty amine is selected from ethylenediamine.
Preferably, any one of the solvent in methanol, ethyl alcohol or water.
Preferably, the citrate is selected from trimethyl citrate, triethyl citrate, methyl acrylate, metering system
Any one in sour methyl esters.
Preferably, ethylenediamine is dissolved in methanol, after mixing, citrate is added thereto, reacted at 50 DEG C
After 5h, 7h is vacuumized at 70 DEG C, obtains over-branched polyamidoamine；
The citrate is selected from methyl acrylate or methyl methacrylate.
Preferably, the molar ratio of the ethylenediamine and the citrate is 3:1.
The present invention also provides a kind of preparation methods of over-branched polyamidoamine as described in any one of the above embodiments to be prepared
Over-branched polyamidoamine.
Preferably, the over-branched polyamidoamine is the daiamid that the end group with dissaving structure is amino, described
Over-branched polyamidoamine has cavity structure and Amino End Group structure.
The present invention also provides a kind of over-branched polyamidoamines as described in any one of the above embodiments in heavy mental treatment side
The application in face.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention provides a kind of preparation methods of over-branched polyamidoamine, and this method is using fatty amine as core, with lemon
For lemon acid esters as chain extender, reaction condition is mild, and the reaction time is short, easy to operate, convenient for the subsequent industrialization of product and scale
Metaplasia produces；
2, the present invention provides a kind of over-branched polyamidoamine, which is the end with dissaving structure
Base is the daiamid of amino, has more cavity structures and Amino End Group structure；
3, the application the present invention provides a kind of over-branched polyamidoamine in terms of heavy mental treatment, the hyperbranched poly
Amide amine has stronger adsorption capacity and adsorbance to heavy metal ion, more to the capture ability and efficiency of heavy metal ion
It is high.
Detailed description of the invention
Fig. 1 is that the over-branched polyamidoamine that the embodiment of the present invention 1 is prepared obtains nuclear-magnetism figure；
Fig. 2 is that the over-branched polyamidoamine that the embodiment of the present invention 3 is prepared obtains nuclear-magnetism figure.
Specific embodiment
Below the technical solution in the specific embodiment of the invention will in detail, completely describe.Obviously, described
Embodiment is only the part specific embodiment of the total technical solution of the present invention, and not all embodiment.Based on this hair
Bright total design, those of ordinary skill in the art's every other embodiment obtained, all falls within the scope of protection of the invention.
The present invention provides a kind of preparation methods of over-branched polyamidoamine, comprising the following steps:
Fatty amine is dissolved in solvent, after mixing, citrate is added thereto, reacts 3-10h at 50-80 DEG C
Afterwards, 5-10h is vacuumized, over-branched polyamidoamine is obtained；
The fatty amine is selected from aliphatic diamine or aliphatic polyamine；The solvent is selected from alcohol solvent or water.
The preparation method use " one-step method " rapid synthesis it is a series of using fatty amine as core, using citrate as chain extension
The over-branched polyamidoamine of agent, reaction condition is mild, and the reaction time is short, easy to operate, is easy to implement the industrialized production of product.
The embodiment specifically defines reaction temperature, it should be noted that the reaction temperature can also be 55 DEG C, 60 DEG C, 65 DEG C, 70
DEG C, any point value in 75 DEG C and its range；The embodiment specifically defines the reaction time, it should be noted that when the reaction
Between can also be any point value in 4h, 5h, 6h, 7h, 8h, 9h and its range；The embodiment also specifically defines when vacuumizing
Between, it should be noted that the pumpdown time can also be any point value in 6h, 7h, 8h, 9h and its range.The embodiment
Using fatty amine as core, using citrate as chain extender, pass through defined reaction condition, one-step method rapid synthesis ultrabranching polyamide
Amine, compared to the preparation method of existing over-branched polyamidoamine, reaction condition is mild, and the reaction time is short, easy to operate, while not
It needs to wash reaction product, for realizing that the industrialized production of over-branched polyamidoamine is of great significance.The reaction
The reaction mechanism of process are as follows:
Ester exchange reaction occurs under heating conditions with lipoid substance for organic amine or Michael addition reaction is formed
AnBm type intermediate product (n >=1, m >=2).The AnBm type intermediate product is further continued for that ester exchange reaction occurs, and increases its degree of branching,
The target product with dissaving structure is formed, to be applied to the absorption and processing of heavy metal ion.
In a preferred embodiment, the molar ratio of the fatty amine and the citrate is 12:5-12:3.The embodiment
It specifically defines the molar ratio of fatty amine Yu the citrate, the reason is that, raw material availability is high under the molar ratio, and prepares
The structure of obtained product is more perfect, higher to the treatment effeciency of heavy metal ion.It should be noted that the molar ratio can be with
For 12:4.
In a preferred embodiment, the fatty amine is selected from ethylenediamine.The embodiment specifically defines that fatty amine is second two
Amine, the reason is that, ethylenediamine amine reactivity longer than carbochain is higher, four N-H keys on the primary amine in structure are certain
Under the conditions of ester exchange reaction or Michael addition reaction can all occur.
In a preferred embodiment, any one of the solvent in methanol, ethyl alcohol or water.The embodiment is specific
Define that solvent is any one in methanol, ethyl alcohol or water, any of the above-described solvent belongs to innoxious solvent, ensure that preparation
Process is environmentally protective.
In a preferred embodiment, the citrate is selected from trimethyl citrate, triethyl citrate, acrylic acid first
Any one in ester, methyl methacrylate.It should be noted that can be with for citrate cited by the present embodiment
It is that those skilled in the art pass through other substances for reasonably selecting and adjusting in this field in conjunction with common sense.
In a preferred embodiment, ethylenediamine is dissolved in methanol, after mixing, citrate is added thereto,
After reacting 5h at 50 DEG C, 7h is vacuumized at 70 DEG C, obtains over-branched polyamidoamine；
The citrate is selected from methyl acrylate or methyl methacrylate.
The embodiment specifically defines reaction raw materials and reaction condition, the reason is that, using ethylenediamine for core, with propylene
When sour methyl esters or methyl methacrylate are chain extender, the degree of branching of obtained product is more slightly lower than dendroid daiamid, but
Its inside configuration also contains more secondary amine groups, is conducive to product in inside configuration and provides more coordination nodes and a huge sum of money
Belong to ions binding, forms stronger coordination mode, obtain the capture ability and efficiency of higher heavy metal ion.
In a preferred embodiment, the molar ratio of the ethylenediamine and the citrate is 3:1.
The present invention also provides a kind of preparation methods of over-branched polyamidoamine as described in any one of the above embodiments to be prepared
Over-branched polyamidoamine.
In a preferred embodiment, the over-branched polyamidoamine is the polyamides that the end group with dissaving structure is amino
Amine amine, the over-branched polyamidoamine have cavity structure and Amino End Group structure.Over-branched polyamidoamine of structure is advantageous in this
In enhancing dissaving polymer to the adsorption capacity and adsorbance of heavy metal ion.
The present invention also provides a kind of over-branched polyamidoamines as described in any one of the above embodiments in heavy mental treatment side
The application in face.
In order to become apparent from introduce in detail over-branched polyamidoamine, preparation method provided by the embodiment of the present invention and its
Application in terms of heavy mental treatment, is described below in conjunction with specific embodiment.
Embodiment 1
1.2mol ethylenediamine is placed in the methanol of 10mol, after being completely dispersed, the trimethyl citrate of 0.4mol is added,
After 50 DEG C of reaction 10h, after vacuumizing 10h, over-branched polyamidoamine HP-1 is obtained.
Embodiment 2
1.2mol ethylenediamine is placed in the methanol of 10mol, after being completely dispersed, the triethyl citrate of 0.4mol is added,
After 60 DEG C of reaction 8h, after vacuumizing 8h, over-branched polyamidoamine HP-2 is obtained.
Embodiment 3
1.2mol ethylenediamine is placed in the methanol of 10mol, after being completely dispersed, the methyl acrylate of 0.3mol is added,
After 70 DEG C of reaction 6h, after vacuumizing 7h, over-branched polyamidoamine HP-3 is obtained.
Embodiment 4
1.2mol ethylenediamine is placed in the methanol of 10mol, after being completely dispersed, the methyl esters acrylic acid first of 0.5mol is added
Ester after vacuumizing 5h, obtains over-branched polyamidoamine HP-4 after 80 DEG C of reaction 5h.
Embodiment 5
1.2mol ethylenediamine is placed in the methanol of 10mol, after being completely dispersed, be added 0.3mol methyl acrylate and
The trimethyl citrate of 0.2mol after vacuumizing 7h, obtains over-branched polyamidoamine HP-5 after 60 DEG C of reaction 7h.
Embodiment 6
1.2mol diethylenetriamine is placed in the ethyl alcohol of 40mol, after being completely dispersed, the methyl acrylate of 0.3mol is added
After vacuumizing 7h, over-branched polyamidoamine HP-6 is obtained after 60 DEG C of reaction 4h with the trimethyl citrate of 0.2mol.
Embodiment 7
1.2mol triethylene tetramine is placed in the water of 40mol, after being completely dispersed, be added 0.3mol methyl acrylate and
The trimethyl citrate of 0.2mol after vacuumizing 7h, obtains over-branched polyamidoamine HP-7 after 60 DEG C of reaction 7h.
Embodiment 8
1.2mol ethylenediamine is placed in 10mol methanol, after being completely dispersed, the methyl acrylate of 0.4mol is added, 50
DEG C reaction 5h after, vacuumize 7h at 70 DEG C, obtain over-branched polyamidoamine HP-8.
Embodiment 9
The over-branched polyamidoamine that above-described embodiment 1-8 is prepared carries out heavy metals removal and recovery experiment test.
Testing procedure is as follows: first preparing the simulated wastewater of copper ions 10mg/L.
Step 1: the over-branched polyamidoamine that embodiment 1-8 is prepared according to effective component 30ppm additive amount,
It is added in simulated wastewater.Stirring, mixes them thoroughly；
Step 2: adjustment wastewater pH chelates over-branched polyamidoamine and heavy metal in waste water, and the sub- radius of graft content is big
Product, hydraulic detention time 30min；
Step 3: filtering.Clear water end outlet；Concentrated water end enters solution bothrium through pipeline；
Step 4: adjustment solution bothrium pH makes copper ion by releasing on over-branched polyamidoamine, hydraulic detention time
10min；
Step 5: filtering.Clear water end (copper concentrate) enters elemental copper recovery process；The recycling of concentrated water end and step
Two；Step 6: elemental copper recovery process waste water enters step a circulation.
Test result is shown in Table 1.
1 test result of table
By above-mentioned test result it can be found that the over-branched polyamidoamine being prepared by embodiment 1-8 is for a huge sum of money
When belonging to ion recovery processing, dendroid polyamides that treatment effect and the prior art (gradually being synthesized using divergent method) are prepared
Amine amine is not much different.And over-branched polyamidoamine provided by the present invention is with reaction condition is mild, the reaction time is short, at low cost
The characteristics of, there is great meaning for the industrialized production of the over-branched polyamidoamine for heavy mental treatment.
Claims (10)
1. the preparation method of over-branched polyamidoamine, which comprises the following steps:
Fatty amine is dissolved in solvent, after mixing, citrate is added thereto, after reacting 3-10h at 50-80 DEG C,
5-10h is vacuumized, over-branched polyamidoamine is obtained；
The fatty amine is selected from aliphatic diamine or aliphatic polyamine；The solvent is selected from alcohol solvent or water.
2. the preparation method of over-branched polyamidoamine according to claim 1, which is characterized in that the fatty amine with it is described
The molar ratio of citrate is 12:5-12:3.
3. the preparation method of over-branched polyamidoamine according to claim 1, which is characterized in that the fatty amine is selected from second
Diamines.
4. the preparation method of over-branched polyamidoamine according to claim 1, which is characterized in that the solvent is selected from first
Any one in alcohol, ethyl alcohol or water.
5. the preparation method of over-branched polyamidoamine according to claim 1, which is characterized in that the citrate is selected from
Trimethyl citrate, triethyl citrate, methyl acrylate, any one in methyl methacrylate.
6. the preparation method of over-branched polyamidoamine according to claim 1, which is characterized in that ethylenediamine is dissolved in methanol
In, after mixing, citrate is added thereto, after reacting 5h at 50 DEG C, vacuumizes 7h at 70 DEG C, obtain hyperbranched
Daiamid；
The citrate is selected from methyl acrylate or methyl methacrylate.
7. the preparation method of over-branched polyamidoamine according to claim 6, which is characterized in that the ethylenediamine with it is described
The molar ratio of citrate is 3:1.
8. the hyperbranched polyamides that the preparation method of over-branched polyamidoamine according to claim 1-7 is prepared
Amine amine.
9. over-branched polyamidoamine according to claim 8, which is characterized in that the over-branched polyamidoamine is with super
The end group of branched structure is the daiamid of amino, and the over-branched polyamidoamine has cavity structure and Amino End Group structure.
10. according to application of the described in any item over-branched polyamidoamines of claim 8-9 in terms of heavy mental treatment.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114988506A (en) * | 2022-06-26 | 2022-09-02 | 上海融达环境科技有限公司 | Compound medicament for advanced treatment of synthetic rubber industrial wastewater and preparation method thereof |
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| CN101323662A (en) * | 2008-07-24 | 2008-12-17 | 绍兴文理学院 | Biodegradable hyper branched aliphatic polyamide fiber daiamid and preparation thereof |
| CN105385137A (en) * | 2015-12-02 | 2016-03-09 | 威海晨源分子新材料有限公司 | Application of hyperbranched poly(amide amine)s in plastic processing |
| CN106622191A (en) * | 2016-12-13 | 2017-05-10 | 威海晨源分子新材料有限公司 | Hyperbranched poly(amide amine) crosslinking modified zeolite, preparation method of hyperbranched poly(amide amine) crosslinking modified zeolite and application of hyperbranched poly(amide amine) crosslinking modified zeolite in heavy metal wastewater treatment |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323662A (en) * | 2008-07-24 | 2008-12-17 | 绍兴文理学院 | Biodegradable hyper branched aliphatic polyamide fiber daiamid and preparation thereof |
| CN105385137A (en) * | 2015-12-02 | 2016-03-09 | 威海晨源分子新材料有限公司 | Application of hyperbranched poly(amide amine)s in plastic processing |
| CN106622191A (en) * | 2016-12-13 | 2017-05-10 | 威海晨源分子新材料有限公司 | Hyperbranched poly(amide amine) crosslinking modified zeolite, preparation method of hyperbranched poly(amide amine) crosslinking modified zeolite and application of hyperbranched poly(amide amine) crosslinking modified zeolite in heavy metal wastewater treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114988506A (en) * | 2022-06-26 | 2022-09-02 | 上海融达环境科技有限公司 | Compound medicament for advanced treatment of synthetic rubber industrial wastewater and preparation method thereof |
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Application publication date: 20191011 |