CN106905450B - A kind of preparation method of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal - Google Patents
A kind of preparation method of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal Download PDFInfo
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- CN106905450B CN106905450B CN201710169853.1A CN201710169853A CN106905450B CN 106905450 B CN106905450 B CN 106905450B CN 201710169853 A CN201710169853 A CN 201710169853A CN 106905450 B CN106905450 B CN 106905450B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a kind of preparation methods of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal, belong to water environment protection field.The present invention passes through spray drying process first and prepares chitosan microball, then the surface that methyl acrylate is grafted to chitosan microball is prepared by methyl acrylate grafted chitosan microballoon by Michael's addition, diethylenetriamine is finally grafted to the surface of methyl acrylate grafted chitosan microballoon by substitution reaction, separates, wash, be dried to obtain adsorbent for heavy metal.The present invention is grafted upper a large amount of amides and amino-functional group in adsorbent surface by the method that Hyperbranched Polymer with Terminal Amido is grafted, the strategy of microballoon grafting functional group again is first prepared simultaneously but also functional group is exposed to adsorbent surface to the greatest extent, enhances the adsorption effect of adsorbent for heavy metal.
Description
Technical field
The invention belongs to a kind of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon heavy metals in water environment protection field
The preparation method of ion adsorbent.
Background technique
Since heavy metal ion has high toxicity, non-biodegradable and enriching in vivo, into natural environment
Constantly accumulation later, and human body is further diverted by food chain, serious harm is brought to natural environment and human health.
Therefore, researching and developing environmentally safe and efficient heavy metal ion administering method is a urgent task.
Chitosan is the second largest natural polysaccharide that content is only second to cellulose in nature, is obtained by chitin is deacetylated,
It is widely distributed, it is cheap.Chitosan has many advantages, such as good biocompatibility, biodegradability, nontoxicity.In addition,
Contain a large amount of-OH and-NH in chitosan molecule2Active group can chelate contents of many kinds of heavy metal ion, therefore be widely studied
For heavy metal ion adsorbed field.Powder type or nanoscale chitosan are not easy to separate and recycle, therefore general
Chitosan is prepared into the absorption that heavy metal ion is used for after micron-sized particle.The study found that either Chitosan powder is also
It is chitosan particle, it, all can be because of-NH in molecule when adsorbing heavy metal ion in acid medium2It is protonated to form-NH3 +
And it is dissolved in the loss that water causes adsorbent, to limit its scope of application.The machinery of chitosan can be enhanced in addition crosslinking agent
Intensity and its stability in acid medium, but crosslinking agent can influence it to a huge sum of money by occupying the functional group of chitosan
The adsorption capacity of category.For the purpose of overcoming drawbacks described above, it is many research concentrate on to chitosan carry out functional group grafting after again
It is crosslinked, adds somewhat to the stability and absorption property of product, but still haveed the defects that certain: (1) being grafted
Functional group still some take part in crosslinking；(2) only have partial function group is exposed to play absorption work in microsphere surface
With most of functional groups are embedded in the inside of microballoon；(3) reason is not reached while increasing adsorbent preparation cost
The adsorption effect thought.Therefore, it is that pendulum exists that research and development, which have both the adsorbent for heavy metal of stability, low cost and high efficiency of additive capability,
An important issue in face of numerous scientific workers.
Summary of the invention
The purpose of the present invention is to provide a kind of suctions of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon heavy metal ion
Attached dose of preparation method makes up the deficiency of original technology.
Main raw material of chitosan used in the present invention is the natural polysaccharide that content is only second to cellulose in nature, and source is wide
It is general, it is cheap, effectively reduce production cost；Chitosan has good biocompatibility and nontoxicity, will not be to environment
Cause secondary pollution；Contain a large amount of-OH and-NH in shitosan macromolecule segment2Active group can be sent out with various metals ion
Raw complexation reaction, itself has excellent heavy metal ion adsorbed performance.The present invention has line shape by spray drying process preparation
The small particle microballoon of edge structure, effectively increases adsorption area, exposes more graft sites.Dissaving polymer is a kind of
With highly branched and three-dimensional structure polymer, a large amount of active group is contained in end.The present invention is super by Amino End Group
Branched polymer grafting is grafted upper a large amount of amides and amino-functional group in microsphere surface；Meanwhile it first preparing microballoon and being grafted function again
Can group strategy but also functional group is exposed to microsphere surface to the greatest extent, further enhance microballoon to heavy metal from
The adsorption effect of son.
The technical solution adopted by the present invention is that: a kind of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon heavy metal ion
Specific step is as follows for the preparation method of adsorbent: (1) being 3 ~ 6 × 10 by viscosity average molecular weigh5Da, deacetylation are 75% ~ 97%
Chitosan is dissolved in acetic acid or lactic acid aqueous solution of the concentration for 1% ~ 2%(v/v), obtains concentration as the chitosan of 1% ~ 3%(w/v)
Solution, unit g/mL；Inlet temperature be 160 ~ 220 DEG C, outlet temperature be 80 ~ 100 DEG C under conditions of to chitosan solution
It is spray-dried, chitosan microball is prepared；(2) using methanol as medium, in N2Protection, 40 ~ 60 DEG C of constant temperature, speeds of agitator
Under conditions of 400 ~ 1000 rpm, Michael addition reaction occurs for chitosan microball and methyl acrylate, and the reaction time is 36 ~ 60
H collects microballoon, and dehydrated alcohol washs 3 ~ 6 times, dries in 30 ~ 70 DEG C of baking ovens, obtains intermediate product methyl acrylate grafted chitosan
Microballoon.(3) using methanol as medium, in N2It protects, under conditions of 40 ~ 60 DEG C of constant temperature, 400 ~ 1000 rpm of speed of agitator, acrylic acid
Methyl esters grafted chitosan microballoon reacts 48 ~ 96 h with diethylenetriamine, collects microballoon, and dehydrated alcohol washs 3 ~ 6 times, 30 ~ 70 DEG C
It is dried in baking oven, obtains Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon.
In step (2), content of the chitosan microball in METHANOL MEDIUM is 1 ~ 6 g/100mL.
In step (2), the mass volume ratio of chitosan microball and methyl acrylate is 1:2 ~ 1:6, unit g:mL.
In step (3), content of the methyl acrylate grafted chitosan microballoon in METHANOL MEDIUM is 1 ~ 6 g/100 mL.
In step (3), the mass volume ratio of methyl acrylate grafted chitosan microballoon and diethylenetriamine is 1:8 ~ 1:40,
Unit is g:mL.
The positive effect of the present invention is as follows: main raw material of chitosan used in the present invention is that content is only second to fibre in nature
The natural polysaccharide of element is tieed up, it is from a wealth of sources, it is cheap；With good biocompatibility and nontoxicity, environment will not be caused
Secondary pollution；Contain a large amount of-OH and-NH in shitosan macromolecule segment2Active group can match with various metals ion
Position reaction, itself has excellent heavy metal ion adsorbed performance；There is striated border knot by the microballoon that spray drying process obtains
Structure, partial size effectively increase specific surface area less than 15 μm, expose more graft sites；The balling-up of adsorbent material elder generation, is followed by
Branch, can make grafted moiety be fully exposed to microsphere surface, effectively increase the utilization rate of grafted moiety；Amine-terminated hyperbrancedization polymerization
After object grafting, so that microsphere surface contains a large amount of amide and amino, effectively increases microballoon and the absorption of heavy metal ion is imitated
Fruit.The present invention is the Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon with efficient heavy ionic adsorption performance, preparation
Method is simple, process stabilizing, cheap, is convenient for industrialized production, and use is safe, and storage and transportation is convenient, has good society's effect
Benefit and economic benefit.
Specific embodiment:
A kind of preparation method of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal, feature
It is to include the following steps: that viscosity average molecular weigh is 3 ~ 6 × 10 by (1)5Da, the chitosan that deacetylation is 75% ~ 97% are dissolved in
In acetic acid or lactic acid aqueous solution of the concentration for 1% ~ 2%(v/v), concentration is obtained as the chitosan solution of 1% ~ 3%(w/v), unit is
g/mL；It is 160 ~ 220 DEG C in inlet temperature, outlet temperature does chitosan solution under conditions of being 80 ~ 100 DEG C by spraying
It is dry, chitosan microball is prepared；(2) using methanol as medium, in N2Protection, 40 ~ 60 DEG C of constant temperature, speed of agitator 400 ~ 1000
Under conditions of rpm, Michael addition reaction occurs for chitosan microball and methyl acrylate, and the reaction time is 36 ~ 60 h, collects micro-
Ball, dehydrated alcohol wash 3 ~ 6 times, dry in 30 ~ 70 DEG C of baking ovens, obtain intermediate product methyl acrylate grafted chitosan microballoon.(3)
Using methanol as medium, in N2It protects, under conditions of 40 ~ 60 DEG C of constant temperature, 400 ~ 1000 rpm of speed of agitator, methyl acrylate grafting
Chitosan microball reacts 48 ~ 96 h with diethylenetriamine, collects microballoon, and dehydrated alcohol washs 3 ~ 6 times, dries in 30 ~ 70 DEG C of baking ovens
It is dry, obtain Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon.
In step (2) of the present invention, content of the chitosan microball in METHANOL MEDIUM is 1 ~ 6 g/100mL；Chitosan microball
Mass volume ratio with methyl acrylate is 1:2 ~ 1:6, unit g:mL.In step (3), methyl acrylate grafted chitosan is micro-
Content of the ball in METHANOL MEDIUM is 1 ~ 6 g/100 mL；The quality of methyl acrylate grafted chitosan microballoon and diethylenetriamine
Volume ratio is 1:8 ~ 1:40, unit g:mL.
Following specific embodiment further provides preparation method of the invention.
Embodiment 1.
It is 3 × 10 by viscosity average molecular weigh5Da, 10 g of chitosan that deacetylation is 96%, being dissolved in 1000 mL concentration is
In acetic acid aqueous solution 1%(v/v), concentration is obtained as the chitosan solution of 1%(w/v)；It is 220 DEG C in inlet temperature, outlet temperature
Degree is spray-dried chitosan solution under conditions of being 100 DEG C, and collection obtains chitosan microball.Take 5 g chitosan microballs
It is added in 100 mL methanol, in N2Under conditions of protection, 40 DEG C of constant temperature, 800 rpm of speed of agitator, 20 mL acrylic acid are added
Methyl esters reacts 60 h, collects microballoon, and dehydrated alcohol washs 6 times, dries in 50 DEG C of baking ovens, obtains intermediate product methyl acrylate and connect
Branch chitosan microball.1.5 g methyl acrylate grafted chitosan microballoons are taken to be added in 100 mL methanol, in N2Protection, 40 DEG C
Under conditions of constant temperature, 800 rpm of speed of agitator, 20 mL diethylenetriamines are added and react 72 h, collect microballoon, dehydrated alcohol is washed
It washs 6 times, is dried in 70 DEG C of baking ovens, obtain Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon.The particle size range of the microballoon is 1 ~ 8
μm, 3.2 μm of average grain diameter, in the case where pH is 5.8,25 DEG C, in unitary system, to Pb2+Adsorption capacity be 233 ± 12.19 mg/
G, to Cu2+Adsorption capacity be 222 ± 14.33 mg/g, to Cd2+Adsorption capacity be 201 ± 11.19 mg/g.
Embodiment 2.
It is 6 × 10 by viscosity average molecular weigh5Da, 10 g of chitosan that deacetylation is 85%, being dissolved in 500 mL concentration is
In acetic acid aqueous solution 2%(v/v), concentration is obtained as the chitosan solution of 2%(w/v)；It is 180 DEG C in inlet temperature, outlet temperature
Degree is spray-dried chitosan solution under conditions of being 90 DEG C, and collection obtains chitosan microball.6 g chitosan microballs are taken to add
Enter into 100 mL methanol, in N2Under conditions of protection, 60 DEG C of constant temperature, 1000 rpm of speed of agitator, 18 mL acrylic acid first are added
Ester reacts 40 h, collects microballoon, and dehydrated alcohol washs 3 times, dries in 70 DEG C of baking ovens, obtains the grafting of intermediate product methyl acrylate
Chitosan microball.3 g methyl acrylate grafted chitosan microballoons are taken to be added in 100 mL methanol, in N2Protection, 60 DEG C of constant temperature,
Under conditions of 1000 rpm of speed of agitator, 30 mL diethylenetriamines are added and react 86 h, collects microballoon, dehydrated alcohol washing 6
It is secondary, it is dried in 70 DEG C of baking ovens, obtains Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon.The particle size range of the microballoon is 2 ~ 11 μ
M, 4.8 μm of average grain diameter, in the case where pH is 5.8,25 DEG C, in unitary system, to Pb2+Adsorption capacity be 212 ± 15.37 mg/
G, to Cu2+Adsorption capacity be 201 ± 11.43 mg/g, to Cd2+Adsorption capacity be 189 ± 9.13 mg/g.
Embodiment 3.
It is 5 × 10 by viscosity average molecular weigh5Da, 20 g of chitosan that deacetylation is 93%, being dissolved in 1000 mL concentration is
In lactic acid aqueous solution 2%(v/v), concentration is obtained as the chitosan solution of 2%(w/v)；It is 210 DEG C in inlet temperature, outlet temperature
Degree is spray-dried chitosan solution under conditions of being 100 DEG C, and collection obtains chitosan microball.Take 10 g chitosan microballs
It is added in 1000 mL methanol, in N2Under conditions of protection, 60 DEG C of constant temperature, 1000 rpm of speed of agitator, 60 mL propylene are added
Sour methyl esters reacts 60 h, collects microballoon, and dehydrated alcohol washs 3 times, dries in 60 DEG C of baking ovens, obtains intermediate product methyl acrylate
Grafted chitosan microballoon.5 g methyl acrylate grafted chitosan microballoons are taken to be added in 500 mL methanol, in N2Protection, 60 DEG C
Under conditions of constant temperature, 1000 rpm of speed of agitator, 200 mL diethylenetriamines are added and react 96 h, collect microballoon, dehydrated alcohol
It washs 6 times, is dried in 60 DEG C of baking ovens, obtain Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon.The particle size range of the microballoon is 2
~ 10 μm, 4.6 μm of average grain diameter, in the case where pH is 5.8,25 DEG C, in unitary system, to Pb2+Adsorption capacity be 255 ± 9.37
Mg/g, to Cu2+Adsorption capacity be 238 ± 9.86 mg/g, to Cd2+Adsorption capacity be 231 ± 16.53 mg/g.
Embodiment 4.
It is 3.5 × 10 by viscosity average molecular weigh5Da, 4.5 g of chitosan that deacetylation is 80%, is dissolved in 300 mL concentration
In acetic acid aqueous solution for 1%(v/v), concentration is obtained as the chitosan solution of 1.5%(w/v)；It is 190 DEG C in inlet temperature, out
Chitosan solution is spray-dried under the conditions of mouth is at a temperature of 90 °C, collection obtains chitosan microball.Take 3 g chitosans micro-
Ball is added in 100 mL methanol, in N2Under conditions of protection, 50 DEG C of constant temperature, 500 rpm of speed of agitator, 15 mL propylene are added
Sour methyl esters reacts 48 h, collects microballoon, and dehydrated alcohol washs 5 times, dries in 50 DEG C of baking ovens, obtains intermediate product methyl acrylate
Grafted chitosan microballoon.2 g methyl acrylate grafted chitosan microballoons are taken to be added in 100 mL methanol, in N2Protection, 60 DEG C
Under conditions of constant temperature, 500 rpm of speed of agitator, 40 mL diethylenetriamines are added and react 80 h, collect microballoon, dehydrated alcohol is washed
It washs 5 times, is dried in 50 DEG C of baking ovens, obtain Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon.The particle size range of the microballoon be 1 ~
10 μm, 3.8 μm of average grain diameter, in the case where pH is 5.8,25 DEG C, in unitary system, to Pb2+Adsorption capacity be 241 ± 13.26
Mg/g, to Cu2+Adsorption capacity be 224 ± 12.85 mg/g, to Cd2+Adsorption capacity be 219 ± 7.31 mg/g.
Claims (5)
1. a kind of preparation method of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal, feature exist
In including the following steps:
It (1) is 3 ~ 6 × 10 by viscosity average molecular weigh5 Da, it is 1% ~ 2%(v/ that the chitosan that deacetylation is 75% ~ 97%, which is dissolved in concentration,
V) in acetic acid or lactic acid aqueous solution, concentration is obtained as the chitosan solution of 1% ~ 3%(w/v), unit g/mL；In inlet temperature
It is 160 ~ 220 DEG C, outlet temperature is spray-dried chitosan solution under conditions of being 80 ~ 100 DEG C, and chitosan is prepared
Microballoon；
(2) using methanol as medium, in N2Under conditions of protection, 40 ~ 60 DEG C of constant temperature, 400 ~ 1000 rpm of speed of agitator, chitosan is micro-
Michael addition reaction occurs for ball and methyl acrylate, and the reaction time is 36 ~ 60 h, collects microballoon, dehydrated alcohol washing 3 ~ 6
It is secondary, it is dried in 30 ~ 70 DEG C of baking ovens, obtains intermediate product methyl acrylate grafted chitosan microballoon；
(3) using methanol as medium, in N2It protects, under conditions of 40 ~ 60 DEG C of constant temperature, 400 ~ 1000 rpm of speed of agitator, acrylic acid first
Ester grafted chitosan microballoon reacts 48 ~ 96 h with diethylenetriamine, collects microballoon, and dehydrated alcohol washs 3 ~ 6 times, 30 ~ 70 DEG C of bakings
It is dried in case, obtains Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon.
2. a kind of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal as described in claim 1
Preparation method, it is characterised in that in step (2), content of the chitosan microball in METHANOL MEDIUM is 1 ~ 6 g/100 mL.
3. a kind of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal as described in claim 1
Preparation method, it is characterised in that in step (2), the mass volume ratio of chitosan microball and methyl acrylate is 1:2 ~ 1:6, unit
For g:mL.
4. a kind of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal as described in claim 1
Preparation method, it is characterised in that in step (3), content of the methyl acrylate grafted chitosan microballoon in METHANOL MEDIUM is 1 ~ 6
g/100 mL。
5. a kind of Hyperbranched Polymer with Terminal Amido grafted chitosan microballoon adsorbent for heavy metal as described in claim 1
Preparation method, it is characterised in that in step (3), the mass volume ratio of methyl acrylate grafted chitosan microballoon and diethylenetriamine
For 1:8 ~ 1:40, unit g:mL.
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| CN112586712A (en) * | 2020-12-07 | 2021-04-02 | 安徽省美极调味食品有限公司 | Wet diced meat seasoning capable of being stored at normal temperature and preparation method thereof |
| CN112961344B (en) * | 2021-02-07 | 2022-10-11 | 威海金泓集团有限公司 | Chitosan-based hyperbranched polyamide compound and application thereof |
| CN114957650B (en) * | 2022-06-11 | 2024-05-10 | 新疆腾域鸿源农业科技有限公司 | Preparation method of potassium polyaspartate and application of potassium polyaspartate in plant growth promoter |
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| CN102604115A (en) * | 2012-02-22 | 2012-07-25 | 天津大学 | Carboxymethyl chitosan quaternary ammonium salt/PAMAM(Polyamidoamine) core-shell nanoparticles and preparation method |
| CN105669986A (en) * | 2016-03-14 | 2016-06-15 | 岭南师范学院 | Hyperbranched polyamide modified chitosan quaternary ammonium salt microsphere for wastewater treatment and preparation method and application thereof |
| CN105964227A (en) * | 2016-05-06 | 2016-09-28 | 福州大学 | Hyperbranched polyamide-grafted chitosan adsorbent and its preparation method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604115A (en) * | 2012-02-22 | 2012-07-25 | 天津大学 | Carboxymethyl chitosan quaternary ammonium salt/PAMAM(Polyamidoamine) core-shell nanoparticles and preparation method |
| CN105669986A (en) * | 2016-03-14 | 2016-06-15 | 岭南师范学院 | Hyperbranched polyamide modified chitosan quaternary ammonium salt microsphere for wastewater treatment and preparation method and application thereof |
| CN105964227A (en) * | 2016-05-06 | 2016-09-28 | 福州大学 | Hyperbranched polyamide-grafted chitosan adsorbent and its preparation method and use |
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