CN108659238A - A kind of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel of lead ion absorption and its preparation and application - Google Patents
A kind of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel of lead ion absorption and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel of lead ion absorption and its preparations and application, the mass percent that POSS hydridization polyacrylamide copolymer accounts for polyurethane in the hydrogel is 1 30wt%, and hydrogel has three-dimensional net structure；Preparation includes：The preparation of POSS hydridization polyacrylamide copolymers；The preparation of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel.Influence the invention avoids the use of crosslinking agent to its compound system each component performance, with the use of Vacuum Freezing ＆ Drying Technology, directly freezed is dry and achieve the purpose that form many stomatas in the structure of matter under vacuum conditions, solves the shortcomings of gap common in ternary system chemical crosslinking is not high, more hollow structures are unstable；And the characteristics of capable of keeping sample original chemical composition and physical property well during vacuum freeze drying, and avoid influence of the content of sample component to its formation problems.
Description
Technical field
The invention belongs to polymer composite and its preparation and application field, more particularly to a kind of lead ion absorption
POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel and its preparation and application.
Background technology
Heavy Metal Pollution is high, and has carcinogenicity, can not only destroy aquatic organism system, can also be detrimental to health.
These heavy metal main sources are cell manufacturer, hardware plating, process hides, paint and exploitation and oil refining etc..Heavy metal is main
It is enriched with by food chain and polluted drinking water enters human body and absorbed by liver.Lead ion be harmful to human 5 big heavy metals it
One, excessive lead ion can impair cardiac, bone, kidney and nervous system, lead to fatigue, even heart failure, under intelligence
The symptoms such as drop and anaemia.Especially for old man, pregnant woman, the crowd of the such hypoimmunity of child, therefore in discharging of waste liquid
The particularly significant of these heavy metal lead ions change is recycled in pre-treatment.At present to Pb2+The means of processing include mainly：Coagulation-flocculation
Method, ion-exchange and biological degradation method, the technologies such as chemistry redox method, but these technologies have some disadvantages, such as
Operating cost is high, secondary pollution caused by Toxic regeneration, and cannot remove completely pollutant.At the place of metal ion waste water
In reason method, biosorption process is widely used because easy to operate, treatment effeciency is high.
Polyacrylamide is absorption one of most common material of synthetic hydrogel, the hydrophilic radical carried on chain (-
CONH2), chelate is formd when interacting with metal ion, even the metal ion solution to low concentration also has height
Stability adsorption capacity and adsorptive selectivity.The hydrogel adsorption capacity that single polyacrylamide is formed under crosslinking agent effect has
Limit, therefore generally other heavy metals such as the gel adsorption lead being made are compounded with other synthesized gel rubbers or Native Gel.
Aqueous polyurethane, by the carbamate gradually polymerizeing, can be regarded as by dihydric alcohol and multicomponent isocyanate
It is a kind of block copolymer containing soft chain segment and hard segment, contains carboxylic acid increase hydrophily on general polymer chain.Aqueous poly- ammonia
Ester substitutes the high molecular material that organic solvent grows up as decentralized medium using water, has pollution small, hydrophily is strong, formation
The features such as gel rubber material, voidage height, internal voids structure-rich, itself has absorption property trapping and strainability, generally
After chemical modification, it can be used in sanitary sewage disposal serving as the heavy metal in vehicle treated sewage.
Polyhedral oligomeric silsesquioxane (POSS) is that a kind of novel organic-inorganic nanometer that structure is highly stable is miscellaneous in itself
Change material, POSS has many characteristics, such as good biocompatibility, preferable stability and nontoxicity, makes it in bio-medical and group
Knitting engineering field has a prodigious potential use, the effective recoverability for improving shape-memory material of introducing of POSS, water-fastness
The performances such as fastness and fastness to wet rubbing.- CONH contained by polyacrylamide (PAM)2N atoms carry lone pair electrons, can lead to
Absorption of the complexing realization to heavy metal ion is crossed, but due to the conjugation of N atoms and C=O, cloud density is made to drop
It is low, cause complexing decrease to thereby reduce adsorption capacity.To improve the ability that PAM adsorbs heavy metal ion, often in PAM
Introduce efficient, selective PAM class composite adsorbing material of the specific function group composition with high-adsorption-capacity.
As POSS, PAM, PU become respectively reveals different excellent properties, so there is many scholars to consider to tie three
The more excellent composite material of absorption property is prepared in conjunction.As patent No. CN201310410812.9 discloses gelatin/carboxymethyl
Chitosan/POSS photocrosslinkable hydrogels and preparation method, with glycidyl methacrylate to gelatin and carboxymethyl chitosan
Carry out double bond modification；Modified gelatin, modified carboxy methyl chitosan, eight vinyl oligomeric silsesquioxanes and crosslinking agent PEGDMA and
Photo-crosslinking prepares hydrogel after photoinitiator I2959 wiring solution-formings, patent No. CN201110381899.2 disclose acrylic acid with
Polyhedral silsesquioxane copolymer hydrogel and its preparation method and application, patent No. CN201110335297.3 are disclosed
A kind of preparation and its application of Novel alkyl cage-type silsesquioxane nano hybrid.Above-mentioned three patents are mainly that polyhedron is low
The application of polysilsesquioxane and the hybridization compounding hydrogel of other materials in terms of bioengineered tissue, and be used for heavy metal from
The research of sub- aspect is less.
Invention content
Technical problem to be solved by the invention is to provide a kind of POSS hydridization polyacrylamide/poly- ammonia of lead ion absorption
The porous composite hydrogel of ester and its preparation and application, the preparation method avoid the use of crosslinking agent to its compound system each component
The influence of performance is used cooperatively Vacuum Freezing ＆ Drying Technology, and directly freezed is dry and reach in the structure of matter under vacuum conditions
The middle purpose for forming many stomatas solves gap common in ternary system chemical crosslinking is not high, more hollow structures are unstable etc.
Disadvantage.
A kind of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel of lead ion absorption of the present invention, it is described
The mass percent that POSS hydridization polyacrylamide copolymer accounts for polyurethane in hydrogel is 1-30wt%, and hydrogel has three-dimensional
Network structure.
A kind of preparation of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel of lead ion absorption of the present invention
Method, the specific steps are：
(1) it is 12-14 with molar ratio by eight vinyl silsesquioxane OVPOSS and azodiisobutyronitrile:1 is dissolved in solvent
In, under nitrogen atmosphere, acrylamide solution reaction is added dropwise, washs, filters, vacuum drying obtains POSS hydridization polyacrylamides
The molar ratio of amine copolymer object, wherein OVPOSS and acrylamide is 1:7~8, OVPOSS in a solvent a concentration of 0.07~
0.08mmol/mL；
(2) POSS hydridization polyacrylamide copolymers in step (1) is soluble in water, stirring is added polyurethane, continues to stir
It mixes, addition saturation NaHCO3Solution is further continued for stirring, is transferred in mold and stands, and soaking flushing removes more in deionized water
Other small molecular weight impurities such as remaining alkali, vacuum freeze drying obtain POSS hydridization polyacrylamide/polyurethane cellular compound water congealing
The mass percent that glue, wherein POSS hydridization polyacrylamide copolymer account for polyurethane is 1-30wt%, polyurethane and saturation
NaHCO3The ratio of solution is 16g-500g:5mL.
Solvent is 1,4- dioxane in the step (1).
Time for adding is 3~5h in the step (1)；Reaction is：It is warming up to 60~65 DEG C of 36~48h of reaction.
Vacuum drying temperature is 50~55 DEG C in the step (1).
Washing is to be washed respectively three times with methanol, toluene successively in the step (1).
The mass percent concentration of OVPOSS is 98~99% in the step (1)；The quality percentage of azodiisobutyronitrile
Specific concentration is 98~99%.
The mass percent concentration of 1,4- dioxane is 98~99% in the step (1)；The quality hundred of acrylamide
It is 98~99% to divide specific concentration.
The mass percent concentration of polyurethane is 98~99% in the step (2)；NaHCO3Mass percent concentration
It is 97~98%.
The time for continuing to stir, be further continued for stirring in the step (2) is 2~4h.
Time of repose is 24~48h in the step (2).
Cryogenic temperature is not higher than -50 DEG C in vacuum freeze drying in the step (2), and the vacuum degree of vacuum freeze drying is not
Higher than 20Pa, the vacuum freeze drying time is 36~48h.
A kind of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel of the present invention is applied to adsorpting lead ion.
The POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel can qualitatively by Thermodynamic Adsorption and
Dynamic absorption obtains absorption heavy metal Pb2+Content.
The eight vinyl silsesquioxanes (OVPOSS) and acrylamide (AM) of cage type are copolymerized by the present invention first, obtain two
The composite system of first composite homogeneous；Then so that its binary compound system amide is hydrolyzed by alkaline condition, then pass through
The effect of hydrogen bond forms tri compound homogeneous system with polyurethane, avoids the use of crosslinking agent to its compound system each component
The influence of energy.And then coordinating Vacuum Freezing ＆ Drying Technology, directly freezed is dry and reach in the structure of matter under vacuum conditions
The purpose for forming many stomatas, solving in ternary system chemical crosslinking that common gap is not high, more hollow structures are unstable etc. lacks
Point.And the characteristics of vacuum freeze drying can keep sample original chemical composition and physical property well in the process is utilized, and keep away
Influence of the content of sample component to its formation problems is exempted from.
Advantageous effect
(1) influence the invention avoids the use of crosslinking agent to its compound system each component performance is used cooperatively vacuum
Freeze Drying Technique, directly freezed is dry and achieve the purpose that form many stomatas in the structure of matter under vacuum conditions, solves
The shortcomings of common gap is not high in ternary system of having determined chemical crosslinking, more hollow structures are unstable；And vacuum freeze drying mistake
Cheng Zhongneng keeps the characteristics of sample original chemical composition and physical property well, and avoids content of sample component and be molded to it and asked
The influence of topic.
(2) composite adsorption that the proportioning dosage of present invention regulation and control POSS hydridization polyacrylamide copolymer and polyurethane obtains
Material structure is stablized, and has more hollow structures, and has the effect of absorption heavy metal ion well, is adsorbed to the highest of lead ion
Amount reaches 195.21mg/g, hence it is evident that the sorbing material prepared higher than under equal conditions other conventional chemical cross-linking methods.
(3) present invention process it is simple, it is environmental-friendly, can largely prepare, and easy to operate, manufacturing cost is relatively low, can
To prepare the hydrogel of arbitrary size size according to demand.
Description of the drawings
Fig. 1 is the SEM figures of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel in embodiment 2.
Fig. 2 is that the compression of the more empty composite hydrogels of different proportion POSS hydridization polyacrylamide/polyurethane in embodiment 2 is strong
The relational graph of degree and displacement (wherein polyurethane concentration is 40g/L, 60g/L).
Fig. 3 is the adsorption dynamics adsorption kinetics figure of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel in embodiment 3.
Fig. 4 is that POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel is right in different time points in embodiment 3
Pb2+Removal rate curve.
Fig. 5 is the first order kinetics of POSS hydridization polyacrylamide/polyurethane hydrogel of the present invention.
Fig. 6 is the second-order kinetics of POSS hydridization polyacrylamide/polyurethane hydrogel of the present invention.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The preparation method of POSS hydridization polyacrylamide copolymers：By eight vinyl silsesquioxane OVPOSS (1.0g,
It 1.58mmol) is dissolved in 20mL Isosorbide-5-Nitraes-dioxane with azodiisobutyronitrile AIBN (0.02g, 0.12mmol), then in addition claims
It takes acrylamide (0.08g, 11.29mmol) to be dissolved in 30mL Isosorbide-5-Nitraes-dioxane, uses constant pressure under the atmosphere of nitrogen later
Acrylamide solution is slowly added dropwise in dropping funel, and about 3~5h is added dropwise, and is slowly warming up to 60 DEG C, reacts 48h, and reaction terminates
White precipitate is obtained later, is washed respectively three times with methanol, toluene successively, filtering, white solid is dried in vacuo at 50 DEG C and dries,
It is spare.
Embodiment 2
The preparation method of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel：By POSS hydridization in embodiment 1
Polyacrylamide copolymer 5.0g is dissolved in 33mL water, and dissolving is stirred at room temperature, and weighs polyurethane after dissolving respectively, and configuration POSS is miscellaneous
Change polyacrylamide copolymer additive amount account for 1wt%, 5wt% of polyurethane content, 10wt%, 15wt%, 20wt%,
The solution of 25wt%, 30wt% continue after stirring 2h, and addition 5mL is saturated NaHCO3Solution is further continued for stirring 2h, is transferred to mould
It is stood for 24 hours in tool.Hydrogel is obtained, soaking flushing removes other small molecular weight impurities such as extra alkali in deionized water, finally
Hydrogel is made, washing gained hydrogel product is subjected to vacuum freeze drying, vacuum refrigeration temperature is -57 DEG C, vacuum refrigeration
Dry vacuum degree is not higher than 20Pa, and the time of vacuum freeze drying is 48h.Up to POSS hydridization polyacrylamide/polyurethane
Porous composite hydrogel, it is spare；
Fig. 1 shows：The composite hydrogel of polyacrylamide/polyurethane of POSS hydridization is a kind of cross linked porous Compound Water
Gel.
Fig. 2 shows：With the increase of the polyurethane content in system, the compressive strength of material increases.When the content of polyurethane
When increasing to 60g/L, compressive strength at this time reaches maximum value.
Embodiment 3
The measurement of adsorption dynamics adsorption kinetics：At room temperature, 0.846g POSS hydridization polyacrylamide/polyurethane cellular is weighed respectively
Composite hydrogel (15wt%PAM, 20wt%PAM-OVPOSS) (PAM-OVPOSS/PU) xerogel, is placed in 500mL about 200ppm
Pb2+In solution, magnetic agitation, thermostatic absorption, setting adsorption time is 120min, at interval of being sampled after a period of time point
Analysis.Sampling time point is respectively：0min,1.5min,3min,5min,7min,9min,13min,17min,21min,30min,
40min,60min,90min,120min.Pb in aqueous solution is surveyed by plasma inductance linking atom emission spectrum (ICP)2+It is dense
Degree.Its hydrogel is to the calculation formula of adsorbance and removal rate under heavy metal ion different time points:
qt=(C0-Ct) × V/m St%=(C0-Ct)/C0× 100%
Wherein:qt(mg/g) be t time samplings when xerogel adsorb heavy metal ion content；C0(ppm (mg/L)) is initial
Heavy metal solution concentration；CtThe concentration for heavy metal ion that (ppm (mg/L)) is sample time when being t in solution；V (L) is solution
Volume；M (g) is the weight of xerogel；StFor t time samplings when gel removal rate.
Fig. 3 shows：POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel reaches adsorption equilibrium in 20min.
Fig. 4 shows：POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel reaches balance, Neng Gouyi in 30min
Except 82% heavy metal lead ion, show that composite hydrogel has preferable repeatability.
Embodiment 4
The measurement of Adsorption thermodynamics：Dry POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel is weighed respectively
(POSS acrylamides/polyurethane, m1/m0=0.01~0.3:1) sample number into spectrum 1-11.Different Pb is respectively configured again2+Solution
Various concentration gradient, be respectively (0,17.5495,44.333,62.393,105.297,174.771,185.71,
263.324,350.99,548.328,767.66ppm).Take the Pb of the various concentration gradient of 20mL2+Solution is in number 1-11
In sample bottle, the placement of the xerogel sample of reference numeral is entered, and constant temperature stirs at 25 DEG C of room temperature, adsorbs 1h.Pass through
Ion inductance linking atom emission spectrum (ICP) surveys Pb in the front and back aqueous solution of absorption2+Concentration.The then hydrogel pair of this kind of component
Adsorption capacity under the different initial concentration of heavy metal ion of heavy metal ion is：
qe=(C0-Ce)×V/m
Wherein：qe(mg/g) it is the adsorbance of the gel when a certain initial concentration assigns adsorption equilibrium；C0(ppm(mg/L))
Initial heavy metal solution concentration；CeHeavy metal in solution when (ppm (mg/L)) initial heavy metal solution concentration assigns adsorption equilibrium
Concentration；V (L) is the volume of solution；M (g) is xerogel quality.Obtained maximum adsorption capacity 195.21.
In order to verify the mechanism of adsorption process, the experimental data and power of adsorption process are simulated with pre- first order kinetics
Learn 1/qt=K1/(qet)+1/qe,ln(qe-qt)=lnqe-K1T, q in formulae(mg/g)：Adsorbance when adsorption equilibrium, qt(mg/
g)：Adsorbance when t, K1(min-1), representative is the rate constant for intending first order kinetics process, for first order kinetics process
K1And qeIt is by In (qe-qt) made to t straight line slope and intercept and calculate, as shown in Figure 5.
In order to verify the mechanism of adsorption process, the experimental data and power of adsorption process are simulated with pre- first order kinetics
Learn t/qt=1/ (k2qe 2)+t/qe, q in formulae(mg/g)：Adsorbance when adsorption equilibrium, qt(mg/g)：Adsorbance when t, K2
What (g/mg min) was respectively represented is the rate constant of quasi- second-order kinetics process, is t/q for second-order kinetics processtTo t
Mapping obtains what intercept calculated, as shown in Figure 6.
Fig. 5 and Fig. 6's the result shows that：It is fitted level-one second-order kinetic equation according to experiment adsorpting data, from data comparison
From the point of view of, the related coefficient of pseudo-first-order kinetic model square is less than corresponding quasi- secondary absorption kinetic model, quasi- two level
Kinetic model is balanced adsorbance and is close with experiment value.Therefore, hydrogel can be deduced to Pb2+Adsorption dynamics adsorption kinetics
Process is pseudo-second order kinetic Adsorption Model, and the rate of adsorption, which is chemisorbed, to be controlled.
Claims (9)
1. a kind of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel of lead ion absorption, which is characterized in that described
The mass percent that POSS hydridization polyacrylamide copolymer accounts for polyurethane in hydrogel is 1-30wt%, and hydrogel has three-dimensional
Network structure.
2. a kind of preparation method of POSS hydridization polyacrylamide/polyurethane cellular composite hydrogel of lead ion absorption, specifically
Step is：
(1) it is 12-14 with molar ratio by eight vinyl silsesquioxane OVPOSS and azodiisobutyronitrile:1 is dissolved in solvent,
Under nitrogen atmosphere, acrylamide solution reaction is added dropwise, washs, filters, vacuum drying obtains POSS hydridization polyacrylamide amine copolymers
The molar ratio of object, wherein OVPOSS and acrylamide is 1:A concentration of 0.07-0.08mmol/ of 7-8.0, OVPOSS in a solvent
mL；
(2) POSS hydridization polyacrylamide copolymers in step (1) is soluble in water, stirring is added polyurethane, continues to stir,
Saturation NaHCO is added3Solution is further continued for stirring, and stands, soaking flushing, vacuum freeze drying obtain POSS in deionized water
Hydridization polyacrylamide/polyurethane cellular composite hydrogel, wherein POSS hydridization polyacrylamide copolymer account for the matter of polyurethane
Amount percentage is 1-30wt%, polyurethane and saturation NaHCO3The ratio of solution is 16g-500g:5mL.
3. a kind of POSS hydridization polyacrylamide/polyurethane cellular Compound Water of lead ion absorption according to claim 2
The preparation method of gel, which is characterized in that solvent is Isosorbide-5-Nitrae-dioxane in the step (1).
4. a kind of POSS hydridization polyacrylamide/polyurethane cellular Compound Water of lead ion absorption according to claim 2
The preparation method of gel, which is characterized in that time for adding is 3~5h in the step (1)；Reaction is：It is warming up to 60~65 DEG C
React 36~48h.
5. a kind of POSS hydridization polyacrylamide/polyurethane cellular Compound Water of lead ion absorption according to claim 2
The preparation method of gel, which is characterized in that vacuum drying temperature is 50~55 DEG C in the step (1).
6. a kind of POSS hydridization polyacrylamide/polyurethane cellular Compound Water of lead ion absorption according to claim 2
The preparation method of gel, which is characterized in that the time for continuing to stir, be further continued for stirring in the step (2) is 2~4h.
7. a kind of POSS hydridization polyacrylamide/polyurethane cellular Compound Water of lead ion absorption according to claim 2
The preparation method of gel, which is characterized in that time of repose is 24~48h in the step (2).
8. a kind of POSS hydridization polyacrylamide/polyurethane cellular Compound Water of lead ion absorption according to claim 2
The preparation method of gel, which is characterized in that cryogenic temperature is not higher than -50 DEG C in vacuum freeze drying in the step (2), vacuum
The vacuum degree of freeze-drying is not higher than 20Pa, and the time of vacuum freeze drying is 36~48h.
9. a kind of POSS hydridization polyacrylamide/polyurethane cellular compound water congealing of lead ion absorption as described in claim 1
The application of glue, which is characterized in that be used for adsorpting lead ion.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535372A (en) * | 2018-10-31 | 2019-03-29 | 优美特（北京）环境材料科技股份公司 | A kind of aqueous polyurethane and preparation method thereof |
| CN110951081A (en) * | 2019-11-08 | 2020-04-03 | 东华大学 | Non-volatile multifunctional POSS-based tertiary amine catalyst and preparation and application thereof |
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