CN106977631A - A kind of modified polyacrylamide and its preparation method and application - Google Patents
A kind of modified polyacrylamide and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of modified polyacrylamide and preparation method thereof, its preparation includes：Using PAMA as parent, occur methylol reaction with formaldehyde, then occur graft reaction with the thiadiazoles of 2 amino of part, 5 sulfydryl 1,3,4, obtain the modified polyacrylamide.Preparation method of the present invention is simple, easy to operate, and yield is high.PAMA is modified, high mechanical strength, the characteristics of heat endurance is good is made it have.The invention also discloses application of the modified polyacrylamide in absorption basic fuchsin, modified polyacrylamide of the present invention is the functional material of separable enrichment, containing more functional group, there is preferable adsorptivity to basic fuchsin.
Description
Technical field
The invention belongs to adsorption technology field, it is related to a kind of modified polyacrylamide and its preparation method and application.
Background technology
In China, the trade effluent that enterprise discharges every year is about 19,900,000,000 tons, and wherein waste water from dyestuff is about 7,000,000,000 tons, therefore
Waste water from dyestuff is the main source of industrial wastewater.With the development of dyeing technology, waste water from dyestuff show biodegradability by
Gradual change difference trend, and waste water from dyestuff also have colourity depth, COD value height, strong toxicity, high concentration the characteristics of, be increasingly becoming it
The Major Difficulties of China's wastewater treatment.At present, the conventional method of processing waste water from dyestuff mainly has biodegradable, oxidation, membrane technology
And absorption.It is main using bioanalysis and Coagulation with Treatment waste water from dyestuff both at home and abroad, but processing waste water from dyestuff has difficult biochemistry at present
Degradability, is only difficult to make waste water from dyestuff qualified discharge by bioremediation, and adsorbing rule has preferable treatment effect, because
This, low stain, low cost, the adsorbent of high selectivity becomes the effective means for administering waste water from dyestuff.Industrially often adopt at present
Adsorbent is activated carbon.Activated carbon cost is high, is commonly used to the advanced treating of industrial wastewater.
Polyacrylamide (hereinafter referred to as PAM) is one of important high molecular polymer, and property is water-soluble, macromolecule,
It is homopolymerization or to be formed under given conditions with other monomers copolymerization by acrylamide, mass fraction is more than 50% linear water
The general name of the chemical substance of dissolubility.Character PAM products according to material mainly have three types：Emulsion, water-soluble liquogel, powder
Shape；Ion characteristic according to material is divided into cationic (CPAM), anionic (APAM), non-ionic (NPAM) and both sexes
Type, the polymer of four types has plenty of homopolymer, also has plenty of copolymer.
PAMA is conventional high polymer coagulant, extensive in fields such as sewage disposal, chemical industry, oil
Using.It is characterized in flocculability, cohesive.Therefore it is also that, most by of concern, its importance is production cost far below sun
Ion high polymer coagulant and Amphiphatic high polymer coagulant.
The synthetic method of anion-polyacrylamide mainly has Hydrolyze method, copolymerization method.Hydrolyze method：Homopolymerization posthydrolysis method,
Homopolymerization method.Copolymerization method：Monomer copolymerization method, grafting copolymerization process, aqueous solution polymerization, inverse emulsion polymerization and anti-phase suspension are poly-
Close.The production of current anion-polyacrylamide uses copolymerization method mostly.
Shen Lei (preparation of PAMA flocculant (APAM) and application [D] University Of Chongqing, 2011) is used
Aqueous solution copolymerization method, under conditions of inorganic initiator ammonium persulfate and sodium hydrogensulfite make initiator, polymerization of acrylamide list
Body and sodium hydroxide obtain PAMA (APAM), and it is 9,600,000 that experimental study, which has synthesized molecular weight, and residual monomer
Content is 0.072%；At the same time it is respectively 8,720,000 and 8,830,000, residual to obtain other two high molecular polymer APAM molecular weight
The content of monomeric substance is 0.050% and 0.043%.
By above-mentioned to water resources in china and the Current Description of water pollution, and polyacrylamide synthesis and modification and
The statement of application aspect, applying for PAMA flocculant is played an important role in water technology, and I
State is produced at present also in general level in PAMA flocculant in its species prepared.
Modified polyacrylamide can currently be applied to organic industry as a kind of hydrophilic polymer, biomedical,
The purified treatment of water, food industry, heavy metal recovery, the wadding of suspension sink.This polymer has a variety of function functional groups, such as carboxylic
Base, amino, hydroxyl or sulfonic group etc..It is that methylol reaction and graft reaction exist using Mannich reaction (Mannich reactions)
The group containing amino is introduced on PAMA main chain, when the group of introducing is amino or other groups, so that it may
To lift the feature of material in itself, the application in other respects of modified material is expanded.
The content of the invention
It is modified poly- there is provided one kind it is an object of the invention to solve above-mentioned technology present in prior art and Cost Problems
Acrylamide and its preparation method and application, using polyacrylamide as parent, with part (2- amino -5- sulfydryls -1,3,4- thiophenes two
Azoles) synthetic reaction is carried out, the modified polyacrylamide with higher functionality base conversion ratio is resulted in, the modified polyacrylamide
There is good selective absorption performance to basic fuchsin.
To solve above-mentioned technical barrier, the present invention uses following technical scheme：
A kind of modified polyacrylamide, includes the repeat unit as shown in formula (I)：
The inherent viscosity of the modified polyacrylamide is 700~800mg/mL.
Parent polyacrylamide is the linear polymer of energy adsorbent particles functional group, and particulate can be attached together
Dough polyacrylamide Long carbon chain is formed, bridging action is played between particles.Polyacrylamide can macromolecular scaffold pass through
Reacted linkage function group with reagent, so as to prepare the functional material of separable enrichment.Part 2- amino -5- sulfydryl -1,
There are multiple nitrogen-atoms in 3,4- thiadiazoles,
Lone pair electrons can be provided, such chemical constitution can preferably chelate basic fuchsin.
The preparation method of the modified polyacrylamide, including：It is poly- with the anion with the repeat unit as shown in (II)
Acrylamide is parent, occurs methylol reaction with formaldehyde, then occurs graft reaction with part of the structure as shown in (III), is obtained
With the modified polyacrylamide；
The preparation method is specifically included：
(1) it is PAMA is soluble in water, add formalin and carry out methylol reaction, obtain mixture；
(2) part is added in the mixture that step (1) is obtained and carries out graft reaction, polymer is obtained；
(3) the polymer immersion obtained step (2) in a solvent, after water washing, be freeze-dried the modification gathers
Acrylamide.
Preferably, in step (1), PAMA is soluble in water, and gained PAMA is water-soluble
The mass fraction of liquid is 0.5~5%.
Preferably, in step (1), the mass fraction of the formalin is 20~50%.
Preferably, in step (1), the ratio that adds of the PAMA and formalin is 1g：0.1~
8mL, in the proportion, the increase that the utilization rate of formaldehyde adds ratio with formaldehyde first increases to be reduced afterwards, because anion is poly-
Acrylamide and formaldehyde reaction generation hydroxymethyl polyacrylamide intermediate, then graft reaction is carried out with part, if content of formaldehyde
It is too high, easily crosslink, the stability of product can be reduced；Further preferably, the PAMA and formaldehyde are water-soluble
The ratio that adds of liquid is 1g：2~8mL；Optimally, the ratio that adds of the PAMA and formalin is
1g：3mL, now formaldehyde utilization rate highest, reach 87.6%.
Preferably, in step (1), the temperature of the methylol reaction is 25~35 DEG C.
Preferably, in step (1), the time of the methylol reaction is 2~5h.
Preferably, in step (2), the mass ratio of the part and PAMA in step (1) is 1：0.3~
1.1, as part adds the increase of ratio, the molecular weight of gained modified anion polyacrylamide first increases, and then increase becomes
Gesture tends towards stability.Because with the increase in reaction time, graft polymerization reaction is continuous to be carried out, and the strand of polymer constantly adds
Long, making the molecular weight of polymer constantly increases, and when reaction proceeds to certain time, due to graftable molecule on main chain
Chain limited amount, total molecular weight stops increase.
Preferably, in step (2), the temperature of the graft reaction is 50~100 DEG C, the modified polyacrylamide of preparation
Molecular weight is increased with the rise of temperature, is finally tended to balance；Because the rise of graft reaction temperature can be improved in solution
Part to the speed of the reactivity site diffusion on parent (PAMA) main chain, and increase active sites
The concentration of point part, promotes the progress of polymerisation.
Further preferably, the temperature of the graft reaction is 70~100 DEG C.In the temperature range, gained is modified poly- third
The molecular weight of acrylamide is maximum.
Preferably, in step (2), the pH of the graft reaction is 6~8, the molecular weight of gained modified polyacrylamide
With pH rise first increases and then decreases；Further preferably, the pH of the graft reaction is 7.5, under the pH, the trip of reaction environment
From hydrogen ion and hydroxide ion interaction do not interfere with polymerisation.
Preferably, in step (2), the time of the graft reaction is 8~15h.
Preferably, in step (3), the solvent is the formalin that mass fraction is 20~50%.
Preferably, in step (3), the temperature of the freeze-drying is -60~-40 DEG C.
Present invention also offers a kind of application of modified polyacrylamide in absorption basic fuchsin.
Compared with prior art, the modified polyacrylamide prepared using the method for the present invention, is had the following advantages that：Raw material
Wide material sources, it is cheap；
1st, preparation method of the present invention is simple, easy to operate, and yield is high；
2nd, PAMA is modified, makes it have high mechanical strength, the characteristics of heat endurance is good；
3rd, reaction dissolvent and reactant are green non-poisonous, cost-effective, and environmental protection reduces secondary pollution；
4th, modified polyacrylamide of the present invention is the functional material of separable enrichment, containing more functional group, to alkali
Property magenta has preferable adsorptivity；
5th, the nitrogen-atoms of modified polyacrylamide of the present invention is more, and nitrogen content is high more there is provided lone pair electrons, to basic fuchsin
There is preferable adsorption effect；
6th, the reaction scheme that the present invention is provided is simple, and synthetic method is easy to operate, it is only necessary to which parent reacts with formaldehyde to be generated
Occurs the step of graft reaction two after methylolation polyacrylamide intermediate and then with part, condition easily reaches, easily real
Now batch production and Automated condtrol, have a good application prospect
Brief description of the drawings
Fig. 1 is the infrared spectrum of modified polyacrylamide prepared by embodiment 1；
The thermogravimetric curve for the EAMTDP that Fig. 2 is APAM and prepared by embodiment 1；
The thermal weight loss rate analysis figure for the EAMTDP that Fig. 3 is APAM and prepared by embodiment 1；
The scanning electron microscope (SEM) photograph for the EAMTDP that Fig. 4 is APAM and prepared by embodiment 1, wherein, (a) is APAM ESEM
Figure, (b) is EAMTDP scanning electron microscope (SEM) photograph；
Fig. 5 is influence result figures of the system pH to basic fuchsin clearance；
Fig. 6 is influence result figure of the adsorption temp to basic fuchsin clearance.
Embodiment
The present invention is further depicted as with reference to specific embodiment, but present disclosure is not limited to this.
In the present invention, the method for determining polymer viscosity is as follows：
0.1g modified polyacrylamide samples accurately are weighed, is put into the beaker for filling 50mL deionized waters, is stirred in magnetic force
Several minutes of heating stirring on device are mixed, heater switch is turned off afterwards, beaker is then removed, room temperature are cooled to, then solution is transferred to
In the volumetric flask that 100mL is totally dried, add a certain amount of deionized water and carry out constant volume, it is standby.
" polyacrylamide characteristic is glued according to standard GB/T 12005.1-89 for the measuring method of experiment and specific measurement operation
Spend assay method "；The intrinsic viscosity of experiment test high molecular polymer is according to standard GB/T PT 12005.10-92
" Molecular Weight for Polyacrylamide is determined --- viscosimetry ", calculate the viscous equal average molecular that related data obtain high molecular polymer
Quality.
The relative molecular mass of polymer can be calculated according to by formula (1) (2) (3)：
ηr=t/to (1)
ηr--- relative viscosity；
The flow time of t --- sample solution, s；
to--- the flow time of 1.00mol/L sodium chloride solutions, s.
C=ms/v (2)
By the η tried to achieverTable look-up accordingly [η] c values divided by sample solution concentration c produces inherent viscosity [η].
In formula：
[η] --- inherent viscosity, mL/g；
The concentration of c --- sample solution, g/mL；
M --- sample mass, g；
S --- sample solid content, g；
The sample solution volume of V --- preparation, mL
The Mark-Houwink formula of this test condition are as follows：
[η]=kMa (3)
In formula：
The inherent viscosity of [η] --- solution, mL/g；
k——4.75×10-3, mL/g；
M --- relative molecular mass
a——0.80。
Embodiment 1
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA (APAM) 1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into,
Fully dissolved under normal temperature, add regulation pH to 7.5, add the formalin that 3mL mass fractions are 36.69%, at normal temperatures instead
3h is answered, mixture is obtained；By determining the amount of the residual formaldehyde in mixture, calculate analyze the utilization rate of formaldehyde is 87.6%.
(2) 0.80g (0.006mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 70 DEG C, pH is 7.5, the lower heating stirring reaction 10h of nitrogen protection, mixing speed is 300rpm/
Min, obtains polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 36.69% formalin, then with steaming
Distilled water is washed for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the modified polyacrylamide is obtained
(EAMTDP)。
After testing, the inherent viscosity of gained modified polyacrylamide is 786.49mg/mL, calculates the modified polypropene
The relative molecular mass 3.34 × 10 of acid amides6。
The infrared spectrum of gained modified polyacrylamide is as shown in figure 1,1600cm-1Locate as C=N flexural vibrations absworption peaks,
699cm-1Locate as C-S stretching vibration absworption peaks, 1400cm-1For C-N stretching vibration absworption peaks, 3350,3180cm-1Locate to stretch for N-H
Contracting vibration absorption peak；Compare modified polyacrylamide (EAMTDP), the infrared spectrum curve of PAMA (APAM)
Understand there is larger difference between them, the 699cm especially in modified spectrogram-1, 1600cm-1There is strong absworption peak appearance at place,
And 1400cm-1, 3000-3500cm-1Between peak value substantially strengthen, be indicated above synthesis after material in add C-S, C
=N, also demonstrating that the material of synthesis has abundant amino group.
The thermogravimetric curve of polyacrylamide (APAM) and modified polyacrylamide (EAMTDP) is as shown in Fig. 2 polypropylene
The thermal weight loss rate analysis of acid amides (APAM) and modified polyacrylamide (EAMTDP) is as shown in Figure 3.
When temperature rises to 100 DEG C or so, the thermal weight loss rate of polyacrylamide starts to be widely varied, after 500 DEG C
What is changed is unobvious.The thermal decomposition process of modified polyacrylamide is then divided into three phases.
APAM：First stage originates in 25 DEG C, terminates at 145 DEG C or so, thermal weight loss amount is 1.59%, thermal weight loss speed is
0.000217%s-1；Second stage is the fracture COO of branch chain link on main chain-, CONH2In C=O, C-O, C-N, N-H occurs disconnected
Split, result is that polyacrylamide quality substantially changes, and originates in 175~211 DEG C, terminates at 475 DEG C or so；Phase III is main
Chain is decomposed under high-temperature.
EAMTDP：First stage originates in 25 DEG C, terminates at 139 DEG C or so, weight-loss ratio is 0.81%, thermal weight loss rate speed
For 0.00011%s-1；Second stage is the cracking i.e. COO of the side chain on side chain and grafting on original main chain-WithIn C=O, C-O, C-N, N-H is broken, and result is that EAMTDP mass substantially changes, and rises
Start from 175 or so and terminate at 421 DEG C or so；Phase III is that main chain is decomposed under high-temperature.
From the point of view of Fig. 3 thermal weight loss speed, in APAM 55,271 DEG C, 343 DEG C；55 DEG C, 199 DEG C, 295 DEG C of EAMTDP
Hot speed peak value occur, to show that the fracture result that functional group occurs under corresponding temperature value is that weight changes in a short time very big.
EAMTDP bad stabilities, but be stable at normal temperatures at high temperature.
The scanning electron microscope (SEM) photograph of polyacrylamide (APAM) and modified polyacrylamide (EAMTDP) is as shown in figure 4, wherein, scheme
4 (a) is the scanning electron microscope (SEM) photograph of polyacrylamide (APAM), and Fig. 4 (b) is the ESEM of modified polyacrylamide (EAMTDP)
Figure, it can be seen that APAM and EAMTDP structure is significantly different, and the two granular size substantially changes, and EAMTDP particle is obvious
Less than APAM, the surface area of the two also changes therewith.Therefore show that the substance A PAM before and after synthesis is different with EAMTDP structure.
Embodiment 2
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA 1.0g accurately is weighed, is made into the aqueous solution that mass fraction is about 1%, at normal temperatures
Fully dissolving, adds regulation pH to 7.5, adds the formalin that 6mL mass fractions are 35%, reacts 2h, obtain mixture；Pass through
Determine mixture in residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 85.3%.
(2) 0.37g (0.005mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 70 DEG C, pH is 7.5, the lower heating stirring reaction 8h of nitrogen protection, mixing speed is 300rpm/min,
Obtain polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 35% formalin, then uses distilled water
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -60 DEG C, the modified polyacrylamide is obtained.
Calculate after testing, the relative molecular mass 3.28 × 10 of gained modified polyacrylamide6。
Embodiment 3
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA 1.0g accurately is weighed, is made into the aqueous solution that mass fraction is about 1%, at normal temperatures
Fully dissolving, adds regulation pH to 7, adds the formalin that 8mL mass fractions are 25%, reacts 5h, obtain mixture；By surveying
Determine the amount of the residual formaldehyde in mixture, calculate analyze the utilization rate of formaldehyde is 83.6%.
(2) 0.53g (0.004mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 70 DEG C, pH is 7.5, the lower heating stirring reaction 13h of nitrogen protection, mixing speed is 300rpm/
Min, obtains polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 25% formalin, then with distillation washing
Wash for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -40 DEG C, the modified polyacrylamide is obtained.
Calculate after testing, the relative molecular mass 3.25 × 10 of gained modified polyacrylamide6。
Embodiment 4
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA 1.0g accurately is weighed, is made into the aqueous solution that mass fraction is about 1%, at normal temperatures
Fully dissolving, adds regulation pH to 7.5, adds the formalin that 2mL mass fractions are 45%, reacts 2h, obtain mixture；Pass through
Determine mixture in residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 83.4%.
(2) 0.40g (0.003mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 70 DEG C, pH is 7.5, the lower heating stirring reaction 8h of nitrogen protection, mixing speed is 300rpm/min,
Obtain polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 45% formalin, then uses distilled water
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -60 DEG C, the modified polyacrylamide is obtained.
Calculate after testing, the relative molecular mass 3.14 × 10 of gained modified polyacrylamide6。
Embodiment 5
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA 1.0g accurately is weighed, is made into the aqueous solution that mass fraction is about 1%, at normal temperatures
Fully dissolving, adds regulation pH to 7.5, adds the formalin that 6mL mass fractions are 36.69%, reacts 2h, obtain mixture；
By determining the amount of the residual formaldehyde in mixture, calculate analyze the utilization rate of formaldehyde is 84.1%.
(2) 1.07g (0.008mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 70 DEG C, pH is 7.5, the lower heating stirring reaction 8h of nitrogen protection, mixing speed is 300rpm/min,
Obtain polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 36.69% formalin, then with distillation
Water washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -60 DEG C, the modified polyacrylamide is obtained.
Calculate after testing, the relative molecular mass 3.34 × 10 of gained modified polyacrylamide6。
Embodiment 6
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA 1.0g accurately is weighed, is made into the aqueous solution that mass fraction is about 3%, at normal temperatures
Fully dissolving, adds regulation pH to 7.5, adds the formalin that 8mL mass fractions are 50%, reacts 5h, obtain mixture；Pass through
Determine mixture in residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 87.3%.
(2) 0.80g (0.006mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 50 DEG C, pH is 7.5, the lower heating stirring reaction 15h of nitrogen protection, mixing speed is 300rpm/
Min, obtains polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 50% formalin, then uses distilled water
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the modified polyacrylamide is obtained.
Calculate after testing, the relative molecular mass 3.31 × 10 of gained modified polyacrylamide6。
Embodiment 7
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA 1.0g accurately is weighed, is made into the aqueous solution that mass fraction is about 3%, at normal temperatures
Fully dissolving, adds regulation pH to 7.5, adds the formalin that 8mL mass fractions are 50%, reacts 5h, obtain mixture；Pass through
Determine mixture in residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 87.3%.
(2) 0.80g (0.006mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 60 DEG C, pH is 7.5, the lower heating stirring reaction 13h of nitrogen protection, mixing speed is 300rpm/
Min, obtains polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 50% formalin, then uses distilled water
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the modified polyacrylamide is obtained.
Calculate after testing, the relative molecular mass 3.29 × 10 of gained modified polyacrylamide6。
Embodiment 8
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA 1.0g accurately is weighed, is made into the aqueous solution that mass fraction is about 1%, at normal temperatures
Fully dissolving, adds regulation pH to 7.5, adds the formalin that 3mL mass fractions are 36.69%, reacts 3h, obtain mixture；
By determining the amount of the residual formaldehyde in mixture, calculate analyze the utilization rate of formaldehyde is 87.6%.
(2) 0.80g (0.006mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 70 DEG C, pH is 8, the lower heating stirring reaction 8h of nitrogen protection, mixing speed is 300rpm/min, is obtained
Polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 36.69% formalin, then with steaming
Distilled water is washed for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the modified polyacrylamide is obtained.
After testing, the relative molecular mass 3.25 × 10 of gained modified polyacrylamide6。
Embodiment 9
A kind of preparation method of modified polyacrylamide, is followed the steps below successively：
(1) PAMA 1.0g accurately is weighed, is made into the aqueous solution that mass fraction is about 1%, at normal temperatures
Fully dissolving, adds regulation pH to 7.5, adds the formalin that 3mL mass fractions are 36.69%, reacts 3h, obtain mixture；
By determining the amount of the residual formaldehyde in mixture, calculate analyze the utilization rate of formaldehyde is 87.6%.
(2) 0.80g (0.006mol) part 2- amino -5- sulfydryl -1,3,4- thiophenes are added in mixture obtained by step (1)
Diazole (EAMTD), and at 70 DEG C, pH is 6, the lower heating stirring reaction 8h of nitrogen protection, mixing speed is 300rpm/min, is obtained
Polymer；
(3) the polymer mass fraction obtained by step (2) is soaked for 36.69% formalin, then with steaming
Distilled water is washed for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the modified polyacrylamide is obtained.
After testing, the relative molecular mass 3.22 × 10 of gained modified polyacrylamide6。
Embodiment 10
The modified polyacrylamide (EAMTDP) of the gained of 10.0mg embodiments 1 is weighed, totally dry 100mL iodine is positioned over
In measuring bottle, the deionized water of certain volume is added afterwards, modified polyacrylamide is fully dissolved, then add 30mL concentration
For 200mg/L basic fuchsin titer, system pH=7.5 is mixed up, in 30 DEG C of constant temperature oscillator and with certain
300rpm/min rotating speed shakes to balance and carries out adsorption test.After absorption terminates, after high speed centrifugation 15min, take away from liquid
Supernatant at the 30mm of face determines the absorbance of solution, the aqueous phase of analytical solution at basic fuchsin maximum absorption wavelength 542nm
The pinkish red concentration of middle residual alkalinity.Then the clearance of basic fuchsin is calculated with below equation：
D (%)=(Co-Ce)/Co
In formula：Ce be solution equilibria after Basic Fuchsin in Aqueous Solution concentration (mg/L)；Co is then the basic fuchsin before absorption
The concentration (mg/ml) of solution.
It is 83.79% to the clearance of basic fuchsin to extrapolate modified polyacrylamide (EAMTDP).
Embodiment 11~14
The operation of embodiment 10 is repeated, the pH value for differing only in system is adjusted to 5.0,6.0,7.0,8.0, to grind respectively
Study carefully influences of the system pH to basic fuchsin clearance, as a result as shown in Figure 5.
During modified polyacrylamide absorption basic fuchsin, the initial pH of solution is the important influence factor of adsorption experiment
One of.Hydrogen ion in reaction solution is tested easily to be adsorbed, and hydroxide ion can also influence adsorption site, therefore, probe into
PH is adsorbed with important meaning to basic fuchsin.
It can be seen from Fig. 5, the continuous increase modified polyacrylamide particle of system initial pH value is to basic fuchsin adsorbance
Value also increase.Slowly increase when pH value increases to 6 rear decoloring rates by 5.In neutral conditions, the hydrogen ion and hydrogen-oxygen in solution
Ion concentration is equal to reach the progress that balance does not interfere with absorption so that adsorbent is in the adsorption capacity of basic fuchsin
Rise.The percent of decolourization highest when the initial pH of solution reaches 7.5.
Embodiment 15~18
The operation of embodiment 10 is repeated, the temperature for differing only in system is changed to 15 DEG C, 20 DEG C, 25 DEG C, 35 DEG C, to study
Influence of the adsorption temp to basic fuchsin clearance, as a result as shown in Figure 6.
It can be drawn in curve in Fig. 6, reaction proceeds to after 30 DEG C, and adsorption experiment basically reaches balance.Therefore 30 DEG C
It is decided to be optimal adsorption temperature.The change of temperature can significantly affect the result of percent of decolourization before 30 DEG C, be influenceed not after 30 DEG C
Greatly, reason is that the functional group of temperature rise modified polyacrylamide adsorbent and adsorption site are more active, and molecular action is strong
It is strong, be greatly facilitated basic fuchsin molecule be progressively diffused into table in adsorbent by boundary layer and and its it is internal.
Above-described embodiment does not limit the present invention in any way, every to be obtained by the way of equivalent substitution or equivalent transformation
Technical scheme all fall within protection scope of the present invention.
Claims (8)
1. a kind of modified polyacrylamide, it is characterised in that the modified polyacrylamide includes the repetition list as shown in formula (I)
Member：
The inherent viscosity of the modified polyacrylamide is 700~800mg/mL.
2. a kind of preparation method of modified polyacrylamide according to claim 1, it is characterised in that including：With with
The PAMA of repeat unit as shown in (II) is parent, occurs methylol reaction with formaldehyde, then with structure such as
(III) graft reaction occurs for the part shown in, obtains the modified polyacrylamide；
3. the preparation method of modified polyacrylamide according to claim 2, it is characterised in that the preparation method is specific
Including：
(1) it is PAMA is soluble in water, add formalin and carry out methylol reaction, obtain mixture；
(2) part is added in the mixture that step (1) is obtained and carries out graft reaction, polymer is obtained；
(3) the polymer immersion obtained step (2) in a solvent, after water washing, is freeze-dried to obtain the modified polypropene
Acid amides.
4. the preparation method of modified polyacrylamide according to claim 3, it is characterised in that in step (1), described the moon
The ratio that adds of cationic polyacrylamide and formalin is 1g：0.1~8mL.
5. the preparation method of modified polyacrylamide according to claim 3, it is characterised in that described to match somebody with somebody in step (2)
The mass ratio of body and PAMA in step (1) is 1：0.3~1.1.
6. the preparation method of modified polyacrylamide according to claim 3, it is characterised in that described to connect in step (2)
The temperature of branch reaction is 50~100 DEG C.
7. the preparation method of modified polyacrylamide according to claim 3, it is characterised in that described to connect in step (2)
The pH of branch reaction is 6~8.
8. application of the modified polyacrylamide according to claim 1 in absorption basic fuchsin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114736071A (en) * | 2022-05-05 | 2022-07-12 | 白银丰宝农化科技有限公司 | Preparation method and application of attapulgite clay modified compound fertilizer |
| CN117089019A (en) * | 2023-10-18 | 2023-11-21 | 山东诺尔生物科技有限公司 | Modified aqueous solution polyacrylamide flocculant and preparation method thereof |
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| CA808729A (en) * | 1969-03-18 | L. Wisner Ralph | Cationic carbamoyl polymers | |
| RU2465287C1 (en) * | 2011-10-28 | 2012-10-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Method of producing sulphur-containing polyacrylamide derivatives |
| CN104558324A (en) * | 2014-12-25 | 2015-04-29 | 上海源育节能环保科技有限公司 | Resource recycling application of heavy metals in wastewater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CA808729A (en) * | 1969-03-18 | L. Wisner Ralph | Cationic carbamoyl polymers | |
| RU2465287C1 (en) * | 2011-10-28 | 2012-10-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Method of producing sulphur-containing polyacrylamide derivatives |
| CN104558324A (en) * | 2014-12-25 | 2015-04-29 | 上海源育节能环保科技有限公司 | Resource recycling application of heavy metals in wastewater |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736071A (en) * | 2022-05-05 | 2022-07-12 | 白银丰宝农化科技有限公司 | Preparation method and application of attapulgite clay modified compound fertilizer |
| CN117089019A (en) * | 2023-10-18 | 2023-11-21 | 山东诺尔生物科技有限公司 | Modified aqueous solution polyacrylamide flocculant and preparation method thereof |
| CN117089019B (en) * | 2023-10-18 | 2024-01-02 | 山东诺尔生物科技有限公司 | Modified aqueous solution polyacrylamide flocculant and preparation method thereof |
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