CN109553701A - A kind of preparation method of modification of chitosan polymer - Google Patents
A kind of preparation method of modification of chitosan polymer Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of modification of chitosan polymer, it is related to technical field of polymer materials, the following steps are included: acrylic acid AA is dissolved in a certain amount of deionized water, 10% NaOH solution is then added dropwise, makes pH=7.0 to ensure that complete neutralization forms corresponding salt NaAA；Preparation PHCSMA is dissolved in 5mLDMF, then acrylamide AM, function monomer (AMPS) and PHCSMA are dissolved in the solution neutralized by feed ratio, adding deionized water makes total amount of monomer be maintained at setting value；Lead to nitrogen deoxygenation 30min under water bath with thermostatic control stirring, oxidation-reduction initiator is added in total weight ratio, continue logical nitrogen, after reaction system becomes sticky, stops stirring and logical nitrogen, reaction system is placed in water bath with thermostatic control and reacts certain time；After the reaction was completed, reactant is cooled to room temperature, then will freezes gum-like product and is washed through dehydrated alcohol, dries, crushes to obtain white powder copolymer.
Description
Technical field
The present invention relates to technical field of polymer materials, are specifically a kind of preparation sides of modification of chitosan polymer
Method.
Background technique
Polymer flooding is to improve an important technology in recovery ratio.Partially hydrolyzed polyacrylamide (PHPA) (HPAM) is to be at present
The more universal polymer oil-displacing agent only used.But there is a problem of when using partially hydrolyzed polyacrylamide (PHPA) it is some, than
Such as by chemical degradation, mechanical shearing and porous media shear action, viscosity sharply declines in high salinity stratum, especially
It is Ca in water flooding2+And Mg2+Influence to HPAM viscosity is fairly obvious, and formation temperature is higher, and the influence to HPAM is got over
Greatly, finally work as Ca2+And Mg2+Concentration when reaching a certain level, can and the carboxyl in HPAM generate precipitating, then block oil reservoir,
Grievous injury is generated to oil reservoir.
Currently, oil field mainly uses polyacrylamide polymer solution as displacing fluid, it is therefore, useless in oil field mining liquid
In water, a large amount of HPAM can be contained, the viscosity of oil extraction waste water is substantially increased, also live containing a small amount of surface in oil extraction waste water
Property agent, the stability of Oil in Sewage Water water emulsion drop can be improved, at this point, the HPAM in waste water and surfactant act synergistically,
Interfacial film is formed at oil-water interfaces, this interface film strength is high, and elasticity is good, leads to the emulsification degree of water-oil emulsion very
Height, demulsification is difficult, and in subsequent processes, water-oil separating is of poor quality.Meanwhile HPAM present in waste water also will increase processing
Difficulty, the sedimentation time is elongated, and the demulsification of grease is difficult, increases oil content after processing, and HPAM concentration is got in oil extraction waste water
Height, the oil content of sewage is also higher after processing, and at present waste water treatment plant to treatment process technology used in oil extraction waste water and
The medicament used reaches the standard of oil field reinjection water and outer draining with being all difficult.
As the direction of exploitation towards low-carbon, the environmental protection of petroleum promotes, oilfield polymer needs economy, validity and green
Colour circle guaranteed cost organic unity, is provided simultaneously with biocompatibility and degradability.Chitosan (CS) is natural renewable material
Material, its materials is extensive, nontoxic, and the structure itself having makes it have preferable heat resistance, and the glucose of rigidity is hexa-atomic
Ring makes it have certain anti-shear performance, but the hydrogen bond action in CS is very strong, and this effect keeps the crystallinity of CS higher, water
Dissolubility is very poor nor is dissolved in organic solvent, it is difficult to carry out processing use to it, these disadvantages strongly limit CS's
Using.Currently, the physical and chemical modified technology of CS is widely paid close attention to, modified CS has many unique properties, makes
It puts greatly in food industry, medical and health use biomaterial, agricultural, textile industry, paper industry, cosmetics and environmental protection
Extraordinary splendor.Wherein, grafting, copolymerization and modification is the highly important modification mode of one of chitin modified method, it is in chitosan
A certain or several different macromolecules are introduced on chain obtains the graft copolymer of chitosan, it by this method, can be preferable
The physicochemical properties for improving CS, apply it in multiple fields.
Currently, the research that natural polymer is applied to polymer oil-displacing agent is had not been reported.Therefore, herein in tune early period
On the basis of grinding, there is environmentally protective property using the unique physicochemical properties of chitosan and natural polymer, it will
Main chain of the chitosan as polymer oil-displacing agent macromolecular after modification, being selectively introduced two or three kind has certain special function
Can monomer be copolymerized, carry out synthesis modification chitosan polymer, it is expected that a kind of with biodegradability to develop with this
Polymer oil-displacing agent, and can have certain superiority in terms of anti-shear performance.
The chemical structure of chitosan
For chitin in the shellfish such as shrimp, crab, shellfish and the content very abundant of fungal organisms body, it is yield
The only second largest polysaccharose substance present in the nature fewer than cellulose.Chitin is by acetylglucosamine structural unit
It constitutes, intermolecular existing hydrogen bond causes its water-soluble excessively poor, significantly limits its application field.Shell
Glycan is by chitin by partially deacetylated obtained, and chitosan can dissolve in an acidic solution, its application neck
Thus domain extends.Its structural formula is as follows:
The physicochemical properties of chitosan
Chitosan is unique naturally occurring alkaline polysaccharide, for white or flaxen powdery granule, raw material and
The difference of preparation method causes the relative molecular mass of chitosan that can also have differences.Chitosan has a large amount of hydroxyl, ammonia in containing
Base, makes intramolecular and intermolecular hydrogen bonding act on enhancing, and this hydrogen bond action with chitin different from, is had with chitosan again
Unique lattice structure and physicochemical properties.Chitosan is in alkalescent, is enabled it in dilute HCl, dilute HNO3It is molten in equal inorganic acids
Solution.There is very strong hydrogen bond action in chitosan structure, can not all dissolve in neutral aqueous solution, this restrict chitosans
It uses, therefore researcher proposes many methods to improve to the water solubility of chitosan.
The chemical modification method of chitosan
Researchers at home and abroad carry out the property to chitosan by the way of carrying out physical or chemical modification to chitosan with this
Matter is improved, and applies to every field.
(1) alkylated reaction
- NH in chitosan molecule2In N atom, have a pair of of lone pair electrons, by alkyl halide to the amino of chitosan
The modified available alkylated product of chitosan N-.Tommeraas is by N- alkylating, by trisaccharide 2- acetylaminohydroxyphenylarsonic acid 2-
Deoxidation-D- glucopyranose-β-(1 → 4) -2- acetylaminohydroxyphenylarsonic acid 2- deoxidation-D- glucopyranose-β-(1 → 4) -2,5-
Acid anhydride-mannose furans glycan molecule (A-A-M), the graft modification on low relative molecular mass and all chitosan molecule,
Obtained chitosan derivatives can dissolve in neutral, acid and alkaline solution.Wang Min is in NaOH solution with amphiphilic N-
Cetyl to be modified chitosan oligomer, and cetrimonium bromide is used to obtain as the catalyst of modified-reaction
N- alkyl derivative was obtained, provides important source material for exploitation self assembly capsule for medicine.
(2) acylation reaction
Have amino and hydroxyl on the aminoglucose saccharide residue of chitosan molecule chain, with certain acid anhydrides, carboxylic acid halides etc. can to it into
Row acylation modification, this is to introduce one preferable mode of carboxyl groups.Wang Qin etc. is first handled chitosan with alkali, then plus
Enter in DMSO and reacted with fumaric acid, obtains N- succinylation chitosan after purification is dry.Kurita is with DMF-H2O (volume
Than 95:5) it is reaction medium, chitosan is modified with phthalic anhydride, it is poly- that N- phthaloyl shell has successfully been obtained
Sugar.
Ying Guoqing is prepared for the Malaysia the N- acyl chitosan of different degree of substitution.And the moisture absorbability and moisture retentivity to product, inherent viscosity,
Relative molecular mass, degree of substitution are studied, it is found that the moisture absorbability and moisture retentivity of high substituted degree product and biocidal property all compare hyalomitome
Acid is excellent, is expected to replace expensive hyaluronic acid, widens the new application range of chitosan.
(3) carboxy-modified
Chitosan and glyoxalic acid reaction are formed schiff bases by Wang Cong etc., are adjusted after solution is strong basicity, then use sodium borohydride
Schiff bases are restored, by reactor product alcohol precipitation, obtain white powder N-CMC.Li Wanhai is prepared for carboxymethyl chitosan, and will
Product is used for the processing of industrial wastewater, the results showed that, compared with chitosan, carboxymethyl chitosan has decolourising property good, and effect is preferable,
Percent of decolourization is high.Huang Pan etc. has synthesized the different N- carboxymethyl chitosan of carboxylation degree using chitosan and glyoxalic acid as material, and to carboxylic
Change degree is determined, and has rated the biocompatibility of product, and resulting product is expected to apply in field of medical materials.
(4) quaternization
Chitosan quaternary ammonium salinization reaction is a kind of water-soluble important modification means for improving chitosan.Xu Chen etc. uses out-phase
Method is prepared for chitosan quaternary ammonium salt derivatives, and concurrently now in neutral conditions, quaternization reaction master carries out on amino.It is made
Standby product has certain water solubility, and the aqueous solution of n-trimethyl chitosan chloride can be with propylene glycol, glycerol under any proportion
It can be miscible.
Yang Fengke etc. summarise chitosan quaternary ammonium salt and its derivative drug delivery system, sensor, in terms of
Application status, in many fields, they are all being widely used, and chitosan quaternary ammonium salt can not only be used as medical and health use
Product, and stronger electrostatic attraction, the effect as the fields such as drug delivery and wastewater treatment are also more preferable.JiaZ chitosan with
Aldehyde forms schiff bases and protects to its amino, with sodium borohydride reduction, last same CH3I reaction obtains n-trimethyl chitosan chloride and spreads out
Biology.Sun reacts first by chitosan carboxy methylation, then with 2,3- epoxy ammonium, obtains quaternization with this
Carboxymethyl chitosan.ChoJ introduces hydroxypropyl-trimethyl ammonium chloride in chitosan molecule chain, and chitosan quaternary ammonium salt has been made.
(5) graft copolymerization
Shi Yunfeng etc. is prepared for 6-O- trityl -2- phthaloyl chitosan, and gathers with the grafting of D, L- lactide
It closes, with this synthetic copolymer, compared with polylactic acid and chitosan, the product of synthesis has excellent performance, is expected to be applied
In field of tissue engineering technology.
Yu Lina is prepared for hydroxypropyltrimethylammonium chloride chitosan (CTS-ETA) in neutral conditions, using obtained
Product handles pattern, has rated the physical property of paper.After CTS-ETA is added, the folding degree of paper is improved, anti-tensile refers to
Number, bursting strength, and can effectively enhance the resistance to ag(e)ing of paper.
Cui Jizhe poly glycol monomethyl ether obtains amphipathic graft modification chitosan derivatives to chitin modified,
Self assembly obtains all very weak amphipathic graft modification chitosan derivatives nano-micelle of crystallinity and thermal stability.
AA and AM monomer is grafted in chitosan macromolecular by Lee's silk floss Zhen, then is subject to different inorganic minerals respectively and is changed
Property, obtains different types of super moisture absorbing resin, and the water absorbing properties of the product of measurement show chitosan graft poly- (AA/AM)/receive
Rice SiO2Resin property is best, and the resin by the water absorption rate of the modified resin of kaolinite, illite all than not being modified
Want high.
The it is proposed of problem
There is the quick effect of salt, chemical degradation, shear degradation in now widely used polymer oil-displacing agent such as HPAM, make
With being restricted.With the expansion of field polymers technology of reservoir sweep application scale, amount containing polymer oilfield wastewater is also constantly increasing
Add, the treatment process technology and treatment agent that oil field generallyd use in the past, it is difficult to meet quality of water treatment requirement.Containing for generating is poly-
If sewage rationally cannot be handled and be utilized, outlet not only wastes valuable water resource, and would seriously pollute the environment, will band
Carry out serious consequence.Therefore, can by introducing a kind of natural polymer in polymer chain, find a kind of shear resistant compared with
It is good, and the polymer oil-displacing agent with certain biological degradability?
Summary of the invention
In view of the deficiencies in the prior art, the purpose of the present invention is to provide a kind of systems of modification of chitosan polymer
Preparation Method so that modification of chitosan polymer is better than HPAM in terms of shear resistant and biological degradability, and can be established
Higher resistance coefficient and residual resistance factor.
To achieve the above objectives, the technical solution adopted by the present invention is that: a kind of preparation method of modification of chitosan polymer,
The following steps are included: step S1. adds suitable N,N-dimethylformamide in flask；Step S2. is by suitable adjacent benzene two
Formic anhydride is added in flask, by magnetic stirrer, until being completely dissolved；Suitable chitosan is added step S3. burns
In bottle, and serpentine condenser is connected on flask, seal with rubber stopper port, then fill N to reaction system2；Step S4. is in N2
It is reacted in constant temperature oil bath under protection, until obtaining the first dark red-brown liquid；Step S5. waits for that the first dark red-brown liquid is cooling
It to room temperature, pours into ice water and is precipitated, obtain faint yellow fibrous material；Step S6. is using ethyl alcohol to yellowish color fibre
After shape substance is purified, faint yellow fibrous solids are obtained after filtering；Step S7. is dry to faint yellow fibrous solids
Afterwards, grinding obtains faint yellow solid particle；Step S8. adds suitable N,N-dimethylformamide in another flask；
Faint yellow solid particle obtained in appropriate step S7 and suitable maleic anhydride are sequentially added flask by step S9.
In, by magnetic stirrer, until being completely dissolved；Reaction system in step S10. step S9 fills N2Half an hour；Step
S11. in N2It is stirred to react under protection, obtains the second dark red-brown liquid；Step S12. waits for that the second dark red-brown liquid is cooled to
After room temperature, pours into precipitating in ice water and obtain White Flocculus；After step S13. filters White Flocculus, washed with ethyl alcohol
It washs；Step S14. is sufficiently dried to obtain brown solid in an oven；Step S15. take acrylic acid AA be dissolved in it is suitable go from
In sub- water, 10% NaOH solution is then added dropwise, forms the neutralization solution of pH=7.0；Step S16. will be obtained in step S14
Brown solid is dissolved in N,N-dimethylformamide；Step S17. is by solution made from step S16, suitable acrylamide AM, 2-
Acrylamido -2- methyl propane sulfonic acid sodium is dissolved in the neutralization solution, and adds deionized water；Step S18. is in step S17
Reaction system under water bath with thermostatic control stirring lead to N2Deoxygenation 30min；Step S19. adds suitable redox initiator
Agent then proceedes to logical N2, until reaction system becomes sticky；Step S20. stops stirring and logical N2, reaction system is placed in water bath with thermostatic control
In, until the reaction is complete；Reactant is cooled to room temperature by step S21., is generated and is frozen gum-like product；Step S22. produces frozen glue shape
Object washs through dehydrated alcohol, dries, crushing and to obtain white powder copolymer.
Based on the above technical solution, in step S1, the n,N-Dimethylformamide of 36mL is added in flask.
Based on the above technical solution, in step S2, the phthalic anhydride of 5.9882g is added in flask, is led to
Magnetic stirrer 15min is crossed, until being completely dissolved.
Based on the above technical solution, in step S3, the chitosan of 1.8032g is added in flask, and in flask
Upper connection serpentine condenser, seals with rubber stopper port, then fills N to reaction system2Half an hour.
Based on the above technical solution, in step S4, in N2It is reacted 8 hours in 120 DEG C of constant temperature oil baths under protection,
Until obtaining the first dark red-brown liquid.
Based on the above technical solution, in step S6, the faint yellow fibrous material is through each 100mL of two batches ethyl alcohol
Purification 4 hours, then faint yellow fibrous solids are obtained after filtering.
Based on the above technical solution, in step S8, the N of 30mL, N- dimethyl formyl are added in another flask
Amine.
Based on the above technical solution, in step S9, by faint yellow solid particle obtained in 1.1292g step S7
It is sequentially added in flask with the maleic anhydride of 0.6751g, by magnetic stirrer, until being completely dissolved.
Based on the above technical solution, in step S11, in N2It is stirred to react for 24 hours under protection in 120 DEG C, obtains
Two dark red-brown liquids.
Based on the above technical solution, the oxidation-reduction initiator is K2S2O8-NaHSO3。
The beneficial effects of the present invention are: modification of chitosan polymer is compared with HPAM, due to modification of chitosan polymer
Present in rigidity benzene radicals and natural polymer so that modification of chitosan polymer is in shear resistant and biodegrade
Property aspect be better than HPAM, can simplify sewage treatment (have biological degradability), and can establish higher resistance coefficient with
Residual resistance factor is used for polymer oil-displacing agent with potential advantage, this has a very big significance the production in oil field.
Detailed description of the invention
Fig. 1 is CS (A) and PHCS (B) infrared spectrogram in the embodiment of the present invention；
Fig. 2 is PHCS in the embodiment of the present invention1H-NMR schematic diagram；
Fig. 3 is PHCSMA (A) and PHCS (B) infrared spectrogram in the embodiment of the present invention；
Fig. 4 is PHCSMA in the embodiment of the present invention1H-NMR schematic diagram；
Fig. 5 is the infrared spectrogram of modification of chitosan polymer (PLCS) in the embodiment of the present invention；
Fig. 6 is modification of chitosan polymer (PLCS) in the embodiment of the present invention1H-NMR schematic diagram；
Fig. 7 is in the embodiment of the present invention
Fig. 8 is in the embodiment of the present inventionWithFigure is intended to；
Fig. 9 is the schematic diagram of PLCS shear resistant in the embodiment of the present invention；
Figure 10 is PLCS 0h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 11 is PLCS 3h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 12 is PLCS 6h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 13 is PLCS 17h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 14 is PLCS 21h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 15 is PLCS measurement result schematic diagram for 24 hours after biological enzyme effect in the embodiment of the present invention；
Figure 16 is PLCS 27h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 17 is PLCS 30h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 18 is PLCS 42h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 19 is PLCS 45h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 20 is PLCS 51h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 21 is PLCS 66h measurement result schematic diagram after enzyme effect biological in the embodiment of the present invention；
Figure 22 is influence schematic diagram of the biological enzyme to PLCS viscosity average molecular weigh in the embodiment of the present invention；
Figure 23 is the biodegradability schematic diagram of PLCS in the embodiment of the present invention；
Figure 24 is one-dimensional sandpack column experiment flow figure in the embodiment of the present invention；
Figure 25 is that HPAM solution injection pressure curve in the porous media that permeability is 2.7D shows in the embodiment of the present invention
It is intended to；
Figure 26 is that PLCS solution injection pressure curve in the porous media that permeability is 2.7D shows in the embodiment of the present invention
It is intended to；
Figure 27 is that HPAM solution injection pressure curve in the porous media that permeability is 1.6D shows in the embodiment of the present invention
It is intended to；
Figure 28 is that PLCS solution injection pressure curve in the porous media that permeability is 1.6D shows in the embodiment of the present invention
It is intended to.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and embodiments.
The synthesis and characterization of phthaloyl chitosan
Experimental drug and instrument
2.1 experimental drug of table
Test key instrument: FA1104 type electronic balance, JJ-1 electric mixer, DF-101S heat collecting type heated at constant temperature magnetic
Power blender, DZF-6050 type vacuum oven, 101-A type drying oven, WQF-520 Fourier infrared spectrograph etc..Three mouthfuls
Round-bottomed flask (100mL), serpentine condenser, beaker, glass bar, spoon etc..
The synthesis of phthaloyl chitosan
Contain a large amount of-NH in chitosan (CS)2, it is positively charged rare natural polymer, unique construction makes
It has unique activity, makes it a kind of biomaterial with wide application prospect, however, in chitosan molecule and dividing
Strong hydrogen bond action is generated between son, dissolve chitosan can only in acidic aqueous solution and certain organic solvents.N- neighbour's benzene
Diformazan acylation chitosan (PHCS) is a kind of important chitosan derivatives, dissolve in n,N-Dimethylformamide, dimethyl sulfoxide,
The organic solvents such as pyridine, and a good intermediate that can be modified as chitosan selective chemical, and then continue
A variety of modified-reactions of chitosan.
According to literature survey, phthaloyl has been carried out to chitosan first herein, chitosan is improved in part with this
Solubility property in organic solvent, convenient for the progress of subsequent reactions.
1. experimental principle:
Specific experimental procedure:
5.9882g phthalic anhydride, which is accurately weighed, with electronic balance (precision 0.0001g) is equipped with 36mLDMF's in prior
In 100mL three-necked flask, 15min is stirred on magnetic stirring apparatus, after its dissolution completely, by 1.8032gCS (glucose unit
Structure and phthalic anhydride molar ratio are 1:3) it is added in flask, upper serpentine condenser is connected on three-necked flask, uses rubber
Sealed port is filled in, then fills N to reaction system2Half an hour, in N2It reacts 8 hours, obtains in 120 DEG C of constant temperature oil baths under protection
Dark red-brown liquid is poured into a large amount of ice water and is precipitated after product is cooled to room temperature, and obtains a large amount of faint yellow fibrous materials
Matter, product purify 4 hours through each 100mL of two batches ethyl alcohol, and faint yellow fibrous solids are obtained after filtering, and do at 50 DEG C of normal pressure
Grinding obtains faint yellow solid particle after dry.
The characterization of phthaloyl chitosan
1. infrared spectrum analysis
(1) key instrument: WQF-520 type infrared spectrometer, Beijing Rayleigh Analytical Instrument Co., Ltd；The infrared pressure of FW-5 type
Piece machine, Tianjin win day victory and reach development in science and technology Co., Ltd；Potassium bromide (KBr, spectroscopic pure), Chengdu Ke Long chemical reagent factory.
(2) experimental method
A certain amount of chitosan and phthaloyl chitosan are sufficiently dried for 24 hours at 50 DEG C；After taking a small amount of drying
KBr, with infrared tabletting machine；IR spectrum scanning, acquisition instrument background are carried out with WQF-520 type infrared spectrometer；It takes
Sample after a small amount of drying is added KBr and is uniformly mixed, and the mass ratio of KBr and sample is in 50:1 or so；The KBr added with sample
With infrared tabletting machine；The sample strip made is subjected to IR spectrum scanning with WQF-520 type infrared spectrometer.
(3) result and analysis
The analysis of table 2.2PHCS infrared spectrum key data
Referring to shown in Fig. 1 and table 2.2, acylation reaction has occurred on the amino of the position C2 of CS, to confirm the to CS
The modification of one step is successful.
2. nuclear magnetic resonance spectroscopy
(1) instrument and reagent: BrukerAC-E200 nuclear magnetic resonance spectrometer, BrukerBiospin company, Switzerland；Nuclear magnetic tube,
WILMADLABGLASS company, the U.S.；Deuterated dimethyl sulfoxide, in wide core (Beijing) Application of Nuclear Technology Co., Ltd.
(2) experimental method
1) sample to be tested is placed in 50 DEG C of drying box and is dried for 24 hours；
2) certain product is added in nuclear magnetic tube；
3) deuterated dimethyl sulfoxide is added into the nuclear magnetic tube that sample is added；
4) with the hydrogen spectrum of BrukerAC-E200 nuclear magnetic resonance spectrometer scanning product, scan frequency 200Hz.
(3) result and analysis
Table 2.3PHCS's1The analysis of H-NMR key data
Referring to fig. 2 and shown in table 2.3, it was demonstrated that acylation reaction has occurred on the amino of chitosan, to further demonstrate,prove
Real is successful to the first step modification of CS.
The synthesis and characterization of maleylation phthalyl chitosan
Experimental drug and instrument: major experimental drug has phthaloyl chitosan (self-control), maleic anhydride, N,
Dinethylformamide (DMF), dehydrated alcohol etc..The synthesis instrument of laboratory apparatus and 2.1 phthaloyl chitosans
It is identical.
The synthesis of maleylation phthalyl chitosan
From the characterization of upper section it is found that successfully synthesizing phthaloyl chitosan, then, it is polymerize according to modification of chitosan
The requirement of object Molecular Model Design, to the first step, modified chitosan is further modified, can be with acrylamide (AM), third
The monomers such as olefin(e) acid (AA) are copolymerized.
(1) experimental principle:
(2) specific experimental procedure:
It accurately weighs 1.1292gPHCS with electronic balance to be added in the 100mL three-necked flask equipped with 30mLDMF in advance, so
Afterwards be added 0.6751g maleic anhydride (molar ratio of PHCS and MA: 1: 1.5), on magnetic stirring apparatus stirring to dissolve, to
Reaction system fills N2Half an hour, then in N2It is stirred to react for 24 hours under protection in 120 DEG C, obtains dark red-brown liquid, it is cooling to product
To room temperature, which is poured into precipitating in a large amount of ice water and obtains White Flocculus, is repeatedly washed with ethyl alcohol again after filtering, 30
Brown solid is sufficiently dried to obtain in DEG C baking oven.
The characterization of maleylation phthalyl chitosan
The analysis of table 2.4PHCSMA infrared spectrum key data
The 1H-NMR key data of table 2.5PHCSMA is analyzed
Referring to shown in Fig. 3 and Fig. 4 and table 2.4 and table 2.5, infrared and nuclear-magnetism characterization confirms the structure of PHCSMA.
The synthesis and characterization of modification of chitosan polymer
The synthesis of modification of chitosan polymer
PAM and its derivative are one kind in polyelectrolyte in extremely important product, they are passed through by acrylamide
Homopolymer or copolymer obtained from free radical polymerization.Aqueous solution polymerization is the primary synthetic methods of PAM and its derivative.This
Literary grace water solution polymerization process synthesis modification chitose graft copolymer is because this method has the advantages that
(1) heat transfer hooks, mass transfer is easy, and transmits heat in time, is conducive to the control of polymeric reaction temperature；
(2) for polymeric monomer concentration generally 20%~30% or so, the polymer concentration of generation is lower, can be to avoid polymerization
Implode in the process；
(3) concentration of the polyacrylamide obtained with water solution polymerization process is generally lower, can avoid chain tra nsfer well
The generation of phenomenon.
Synthesis step
Test primary drug acrylamide, acrylic acid, 2- acrylamido -2- methyl propane sulfonic acid sodium (AMPS), persulfuric acid
Potassium, sodium hydrogensulfite, sodium hydroxide, dehydrated alcohol are that analysis is pure, are provided by Chengdu Ke Long chemical reagent factory；Modification of chitosan
Function monomer is self-control；Experimental water is deionized water；Experiment initiator used is K2S2O8And NaHSO3, mole of the two
Than being 1: 1.
Synthesis step is as follows:
(1) acrylic acid AA is dissolved in a certain amount of deionized water, 10% NaOH solution is then added dropwise, makes pH=7.0
To ensure that complete neutralization forms corresponding salt NaAA；
(2) the modification of chitosan function monomer (PHCSMA) of preparation is dissolved in 5mLDMF, then presses feed ratio for propylene
Amide AM, function monomer (AMPS) and PHCSMA are dissolved in the solution neutralized, and adding deionized water keeps total amount of monomer
In setting value；
(3) lead to nitrogen (N under water bath with thermostatic control stirring2) deoxygenation 30min, oxidationreduction is added in total weight ratio and draws
Send out agent (K2S2O8-NaHSO3), continue logical N2, after reaction system becomes sticky, stop stirring and logical N2, reaction system is placed in constant temperature
Certain time is reacted in water-bath；
(4) after the reaction was completed, reactant is cooled to room temperature, jelly gum-like product is washed through dehydrated alcohol then, is dried,
White powder copolymer is crushed to obtain, and is put into spare in drier.
The optimum conditions of modification of chitosan polymer
Orthogonal test can reflect influence of the different influence factors to the extent of reaction, and the relatively excellent water for studying each factor is flat.It is logical
Literature survey is crossed, the quadrature factor of this paper is horizontal as follows: monomer gross mass concentration is the quality of 20.0%~26.0%, AM and AA
Than being 4.00~1.00, reaction temperature is 45 DEG C, and the dosage of initiator is the 0.1%~0.25% of system gross mass, solution
PH value is 6.0~7.0.The test of five factors, four horizontal quadrature is devised, orthogonal array is shown in Table 3.1.
3.1 modification of chitosan polymer orthogonal design table of table
Herein mainly using viscosity as evaluation criterion, by the calculated result of table 3.1 it can be seen that this experiment influences viscosity reservation
The factor primary and secondary sequence of rate are as follows: AA:AM mass ratio > modification of chitosan function monomer dosage > total monomer > AMPS dosage > is drawn
Send out agent concentration.
Optimal conditions can be obtained as a result, is, AA:AM mass ratio is 1: 1, modification of chitosan function monomer dosage position monomer total amount
0.1%, total monomer 26%, AMPS dosage be monomer total amount 0.1%, initiator dosage be 0.1%.
The characterization of modification of chitosan polymer
IR Characterization
IR Characterization means with it is identical above.The IR Characterization of modification of chitosan polymer is as shown in Figure 5.
The analysis of 3.2 modification of chitosan polymer infrared spectrum key data of table
Referring to shown in table 3.2, the characteristic peak of acid imide and chain ester structure is the distinctive absorption of modification of chitosan function monomer
Peak shows that copolyreaction has occurred in modification of chitosan function monomer and other polymerized monomers.
Nuclear-magnetism characterization
Nuclear-magnetism characterization method and identical above, solvent for use D2O.The nuclear-magnetism characterization such as Fig. 6 of modification of chitosan polymer
It is shown.
3.3 modification of chitosan polymer of table1The analysis of H-NMR key data
It referring to shown in table 3.3, is further demonstrated that by nmr analysis, modification of chitosan function monomer and other polymerized monomers are sent out
Copolyreaction is given birth to.
The measurement of viscosity average molecular weigh
(1) relationship of intrinsic viscosity and molecular weight
When high molecular polymer, which is dissolved in, forms solution in aqueous solvent, the viscosity of solution commonly greater than aqueous solvent viscosity,
Contribution of the polymer molecule to solution viscosity is usually indicated with intrinsic viscosity.The definition of intrinsic viscosity is polymer concentration
Level off to zero when reduced viscosity limiting value.Expression formula is that expression formula is as follows:
Or
In formula: ηsSolvent viscosity, mPas；
ηrRelative viscosity,Zero dimension；
ηRReduced viscosity,Unit is the inverse of concentration, dl/g or ml/g；
The viscosity for the polymer solution that η-is measured under low-down shear rate, mPas；
[η]-polymer intrinsic viscosity, unit are the inverse of concentration, dl/g or ml/g.
The relational expression of high molecular intrinsic viscosity and molecular weight is related with the form of macromolecule in the solution, and high molecular
Form is the reflection of the interaction force between macromolecule and solvent molecule between polymer segment, therefore intrinsic viscosity and molecular weight close
System is different with solvent for use, measuring temperature difference.Currently, common Mark-Houwink empirical formula indicates:
[η]=KMα (3-4)
In formula, K, α need the absolute method calibration of molecular weight after measured.For most of Polymer Solution, the numerical value of α
Between 0.5~1.0, and for common polymer solution system, value can be found from related handbook.
(2) measurement of viscosity average molecular weigh
1) laboratory apparatus and drug
Dilution type Ubbelohde viscometer, 10ml pipette, 100ml volumetric flask, assay balance, water bath with thermostatic control, stopwatch, glass sand
Core funnel, 100ml beaker, syringe, ear washing bulb；Modification of chitosan polymeric colloid (purification), NaCl (analysis is pure), the concentrated sulfuric acid
(concentration 99.0%), potassium bichromate (analysis is pure).
2) experimental method
It is poly- using Dilution chitosan according to GB12005.1-1989 polyacrylamide Intrinsic Viscosity Measurements method
Close the intrinsic viscosity of object.The polymer sodium chloride solution of 1mol/L is prepared, it is viscous with Ubbelohde under the conditions of 30 DEG C of bath temperatures
Degree meter measurement, model 4-0.58.
(3) experimental result
3.4 measurement result of table
Referring to shown in Fig. 7 and table 3.4,
This experiment steady temperature tables look-up to obtain, K=1.25 × 10 at 30 DEG C-2, α=0.78 brings the side Mark-Houwink into
The viscosity average molecular weigh M of modification of chitosan polymer can be obtained in journeynIt is 2.94 × 106。
The solution property of modification of chitosan polymer is studied
The tackifying of modification of chitosan polymer
The high-effective viscosity performance of polymer is an important performance of polymer.The polymer of 5000mg/L is prepared with pure water
Mother liquor, it is to be dissolved completely after, mother liquor is diluted to 500mg/L, 750mg/L, 1000mg/L, 1250mg/L, 1500mg/ with pure water
L, the weak solution of 1750mg/L, 2000mg/L, 2500mg/L concentration is measured at 60 DEG C with BrookfiledDV-III viscosimeter
The viscosity of various concentration polymer solution, measurement result are as shown in Figure 8.
Dense relation curve is glued it follows that with HPAM phase by the PLCS solution and HPAM solution prepared in Fig. 8 with pure water
Than when concentration is 500~750mg/L, the thickening Amplitude Ratio HPAM of PLCS is big；Comparison solution viscosity is from 500mg/L to 2500mg/
The change rate of L viscosity, HPAM viscosity increases about 4.1 times, and the viscosity of PLCS increases about 4.9 times.At the same concentration, though
The concentration of right PLCS is smaller than HPAM, but at low concentrations, the thickening amplitude of PLCS is larger.According to the analysis, since modified shell is poly-
There are aminoglucose sugar chain and rigid benzene radicals in glycopolymers, so that the polymerization of PLCS is anti-in polymerization process
The influence of steric hindrance should be received, molecular weight is lower.And since there are a plurality of polysaccharide branches in polymer molecule, so that polymerization
Object at low concentrations, relatively unfold by strand, and tackifying ability is preferable.
The shear resistant of modification of chitosan polymer
During polymer flooding, ground injection (blender, transport line, valve) and preforation tunnel can cause polymer
Mechanical degradation effect, causes polymer solution viscosity to lose.Shear action can damage polymer molecular chain, and polymer is molten
The viscosity of liquid will be greatly reduced, and the ability that polymer improves sweep efficiency, which also will receive, to be seriously affected, currently, Wu Yin can be used
(Warning) the mechanical shearing effect that blender simulating polymer solution is subject in process of injection allocation.
With pure water prepare 5000mg/L polymer mother liquor, it is to be dissolved completely after, mother liquor is diluted to 500mg/ with pure water
L, the weak solution of 750mg/L, 1000mg/L, 1250mg/L, 1500mg/L, 1750mg/L, 2000mg/L, 2500mg/L concentration,
It is different dense with the measurement of BrookfiledDV-III viscosimeter at 60 DEG C with 1 grade of Wu Yin blender (3000r/min) shearing 30s
The polymer solution viscosity after polymer solution is not clipped and shearing is spent, measurement result is as shown in Figure 9.
After HPAM solution is sheared half a minute, viscosity retention ratio between 68.6%~80.0%, PLCS 52.5%~
Between 95.3%, and compared with HPAM, after polymer solution concentration is greater than 1000mg/L, under same concentrations, PLCS has
Higher viscosity retention ratio shows certain anti-shear ability.According to the analysis, it is linear structure that this, which is primarily due to HPAM,
And modification of chitosan polymer is since with rigid glucosamine unit structure and benzene radicals, solution viscosity is by shearing work
Influence is relatively small, so PLCS has higher viscosity retention ratio.
The biological degradability of modification of chitosan polymer
That there are viscosity is big for polymer-bearing waste-water, emulsifiability is high, is difficult to the problems such as biodegrade, previous sewage treatment technology
And medicament, quality of water treatment standard requirements can not be properly arrived at.As the direction of exploitation towards the low-carbon, environmental protection of petroleum pushes away
Into oilfield polymer needs economy, validity and environmentally protective performance organic unity, is provided simultaneously with biocompatibility and can drop
Solve performance.Therefore, study PLCS biological degradability be very it is necessary to.
Currently, the biodegrading process of chitosan is mainly physics, chemical degradation method and enzyme edman degradation Edman.Compared to other two kinds of sides
Method, enzyme edman degradation Edman just can be carried out in mild condition, and too big pollution will not be caused to environment.More than 30 kinds are had now been found that
Specificity and non-specific enzyme can be used to be catalyzed the degradation reaction of chitosan, wherein non-specific enzyme includes protease, carbohydrase, rouge
Fat enzyme etc..Since the cost of non-specific enzyme is low, stability is good, to the good degrading effect of chitosan, therefore before having industrialization very much
Scape.Therefore, have studied herein alpha-amylase (50~70 DEG C of optimum temperature, optimal pH 5.5~7.5, the extensive and profound in meaning star biotechnology in Beijing
Co., Ltd) to the biodegradation of modification of chitosan polymer.
Biological enzyme effect is to modification of chitosan polymer MηInfluence
It is different using Dilution biological enzyme according to GB12005.1-1989 polyacrylamide Intrinsic Viscosity Measurements method
The intrinsic viscosity of the modification of chitosan polymer of action time.The instrument and drug used is the same as modification of chitosan polymer above
The measuring method of viscosity average molecular weigh is identical.
1. experimental procedure
(1) the modification of chitosan polymer solution that 1000mg/L is prepared with pure water, is stirred at room temperature dissolution, object to be polymerized
After dissolution completely, prepared polymer concentration is 400mg/L in 100mL volumetric flask, and NaCl concentration is the solution of 1mol/L, measurement
Do not add the original viscosity average molecular weigh of the polymer of biological enzyme at this time；
(2) taking 200mL concentration is that alphalise starch is added in 250mL wide-mouth bottle in 1000mg/L modification of chitosan polymer solution
Enzyme 0.004g (enzyme bottom is than 1: 50), sealing are placed in 60 DEG C of waters bath with thermostatic control, in the time interval of setting, are measured respectively in life
The viscosity average molecular weigh of modification of chitosan polymer under the object enzyme different role time.
2. experimental data
The measurement result of PLCSS after the biological enzyme effect 0h of table 4.1
The measurement result of PLCS after the biological enzyme effect 3h of table 4.2
The measurement result of PLCS after the biological enzyme effect 6h of table 4.3
The measurement result of PLCS after the biological enzyme effect 17h of table 4.4
The measurement result of PLCS after the biological enzyme effect 21h of table 4.5
The biological enzyme effect of table 4.6 for 24 hours after PLCS measurement result
The measurement result of PLCS after the biological enzyme effect 27h of table 4.7
The measurement result of PLCS after the biological enzyme effect 30h of table 4.8
The measurement result of PLCS after the biological enzyme effect 42h of table 4.9
The measurement result of PLCS after the biological enzyme effect 45h of table 4.10
The measurement result of PLCS after the biological enzyme effect 51h of table 4.11
The measurement result of PLCS after the biological enzyme effect 66h of table 4.12
It is as shown in FIG. 10 to 21 to test the data obtained figure:
3. result and analysis
Influence of 22 biological enzyme of analysis chart to PLCS viscosity average molecular weigh, the viscosity average molecular weigh of modification of chitosan polymer is by first
Initial value 2,940,000, after alpha-amylase is degraded 42 hours, viscosity average molecular weigh is reduced to 2,380,000, it is seen that alpha-amylase is although right
Its molecular weight is influenced, but influence it is unobvious, need further to verify biological enzyme effect to modification of chitosan polymer its
Influence in terms of him.
Influence of the biological enzyme effect to modification of chitosan polymer viscosity
1. experimental procedure:
(1) modification of chitosan and HPAM solution for preparing 5000mg/L with pure water respectively, are stirred at room temperature dissolution, to
Mother liquor is diluted to the weak solution that concentration is 2000mg/L with pure water again after polymer dissolution completely, is uniformly mixed；
(2) take respectively 2000mg/L modification of chitosan polymer solution and each 100mL of HPAM solution (respectively taking two groups) in
In 250mL wide-mouth bottle, sealing, respectively as experimental group, blank group (such as table 4.13)；
(3) four groups of test bottles are placed in 60 DEG C of water-baths, are stood, under the time interval determination biology enzyme effect of setting
Solution apparent viscosity (with the viscosity of BrookfiledDV-III viscosimeter measurement polymer solution at 60 DEG C).
4.13 biodegradability test table of table
2. result and analysis
The apparent viscosity of solution and the action time of biological enzyme are as shown in figure 23.
The biodegradability of 4.14 modification of chitosan polymer of table
It is found by Figure 23 and 4.14 analysis of table, viscosity retention ratio is from big to small successively are as follows: PLCS (blank group) > HPAM is (empty
White group) > HPAM (experimental group) > PLCS (experimental group)；After biological enzyme effect 46h, experimental group modification of chitosan solution it is apparent
Viscosity drops to 65.2mPa.s by initial 263.0mPa.s, and viscosity retention ratio is only 24.8%, blank group (not plus biological enzyme)
The viscosity retention ratio of modification of chitosan solution is up to 83.1%, illustrates that modification of chitosan polymer shows good degradable spy
Property；And for HPAM, being added after biological enzyme also has certain viscosity reducing effect, but fall and little；Analysis also can be obtained,
Constant temperature 57 hours under 60 DEG C of water-baths, comparison do not add the viscosity retention ratio of the blank group solution of bioactive enzyme, modification of chitosan
The viscosity retention ratio of polymer is higher than HPAM, illustrates that modification of chitosan polymer shows good thermal stability.
Polymer establishes flow resistance ability
Flow resistance characterization parameter
Resistance coefficient and residual resistance factor are the important fingers for describing the control of polymer solution mobility and reducing penetrating power
Mark, while being also the important parameter of polymer flooding numerical simulation and conceptual design.Resistance coefficient RF refers to that polymer reduces mobility
The ability of ratio, it is the ratio of the mobility of water and the mobility of polymer solution.
Residual resistance factor RRF describes the ability that polymer reduces permeability, it is the water phase of rock before and after polymer flooding
The ratio of permeability.That is permeability decrease coefficient.
Due to Kp=Kwa, Kw=KWb, so
In formula: RF RRF- is characteristic, respectively resistance coefficient and residual resistance factor；
λw, λpIt is respectively the mobility for injecting water and polymer solution, mD/ (mPas)；
Kw, KpIt is respectively water phase and polymer solution permeability, mD；
Kwb, KwaIt is respectively the water phase permeability before and after polymer injection, mD；
μw, μpIt is respectively the viscosity for injecting water and polymer solution, mPas.
Study condition and experimental procedure
1. study condition
(1) temperature: 60 DEG C；
(2) inject flow velocity: water filling flow velocity 3mL/min for the first time, note gathers and subsequent waterflooding flow velocity 1mL/min；
(3) experimental water: pure water
(4) experiment polymer: modification of chitosan polymer, HPAM；
(5) polymer solution concentration: 1000mg/L；
(6) laboratory apparatus: micro pump: HBS-2000/20B1 type, the continuous high pressure constant speed and constant pressure pump of twin-tub, highest work pressure
Power is 20MPa, minimum injection rate 0.01mL/min, maximum pump discharge 50.00mL/min, Haian County, Jiangsu Province petroleum scientific research apparatus
Co., Ltd.Intermediate receptacle: intermediate receptacle 2, maximum capacity 500mL and 1000mL, maximum working pressure 20MPa, Jiang Suhai
An County petroleum scientific research Instrument Ltd..Insulating box: SG-3 insulating box, Jiangsu Haian Oil Scientific Research Apparatus Co., Ltd..Pressure
Force snesor: range 0~0.1MPa and 0~1.0MPa each 1, precision is the 0.1% of range, in the complete well rock-electric test in Chengdu
The heart.One-dimensional sandpack column: internal diameter 2.5cm, length 25cm fill different meshes according to real permeability in one-dimensional sandpack column
Quartz sand.
2. experimental procedure
(1) preparation of polymer solution
The modification of chitosan polymer and HPAM mother liquor for being 5000mg/L with pure water compound concentration, solution temperature 25.0
DEG C, mother liquor is diluted to the weak solution that concentration is 1000mg/L with pure water again after object dissolution completely to be polymerized, is uniformly mixed.
(2) pretreatment of quartz sand
In order to exclude the influence of the impurity such as carbonate and shale in quartz sand, mass concentration is used to wash stone for 15% salt
Sand, then the quartz sand after pickling is cleaned with a large amount of tap water, then quartz sand is dried, finally presses different meshes
It is sieved.
(3) one-dimensional sandpack column flowing experiment step
Fill out sand tube back-up sand: quartz sand is inserted in pipe (25cm × 2.5cm), is suppressed by hydraulic press；
Saturated water: injecting pure water to one-dimensional sandpack column with the flow velocity of 3mL/min, after pressure to be implanted is steady, calculates one
Tie up the permeability of quartz sand in sandpack column；The pore volume of quartz sand in one-dimensional sandpack column is measured by " weight method ", is counted
Calculate its porosity.
Polymer waterflooding: the pressure of one-dimensional sandpack column inlet, the flow velocity note of 1mL/min are acquired with pressure sensor
Enter polymer solution, until injection pressure is basicly stable；Injection pressure after record is steady at one-dimensional sandpack column calculates resistance
Coefficient.
Subsequent waterflooding: acquiring the pressure of one-dimensional sandpack column inlet with pressure sensor, with the flow velocity of 1mL/min to one
It ties up sandpack column and injects pure water, until injection pressure is stablized；The pressure of one-dimensional sandpack column inlet after record is steady, calculates residual
Residual resistance coefficient.
One-dimensional sandpack column experiment flow schematic diagram is as shown in figure 24:
Resistance coefficient and residual resistance factor measurement
Copolymer solution is the injection pressure curve in 2.7D porous media as shown in Figure 25, Figure 26 in permeability.Copolymerization
Object solution is the injection pressure curve in 1.6D porous media as shown in Figure 27, Figure 28 in permeability.
As shown in Figure 25~Figure 28, in injection HPAM solution processes, compared with HPAM solution, inject under the same conditions
When PLCS solution, rate of pressure rise ratio HPAM is fast, and injection pressure when reaching steady is higher, and it is higher to illustrate that PLCS can be established
Resistance coefficient；When subsequent waterflooding pressure reaches steady, the smooth pressure highest of modification of chitosan polymer.
4.15HPAM and PLCS resistance coefficient and residual resistance factor
By table 4.15 according to the analysis, PLCS solution is due to stronger anti-shear ability, in injection allocation and in porous Jie
In matter migration process, shear action is small to the extent of the destruction ratio HPAM of PLCS molecular structure, so in the injection of note PLCS solution
Press the resistance coefficient established and residual resistance factor higher.
Conclusion
(1) in order to break in chitosan molecule with intermolecular hydrogen bond, improve chitosan dissolubility in organic solvent,
Convenient for the progress of subsequent graft copolymerization, phthaloyl has been carried out to chitosan first herein, can be dissolved in DMF,
In DMSO, the maleic anhydride with carbon-carbon double bond is gathered with by the modified phthaloyl shell of phthalic anhydride
Sugar reaction, the carbon-carbon double bond with reactivity is connected on phthaloyl chitosan, can participate in polymerization reaction,
And by it is infrared,1H-NMR confirms the structure of modification of chitosan；
(2) modification of chitosan and AA, AM and AMPS are copolymerized, polymer chain is connected on modification of chitosan；Using orthogonal
The synthesis condition of modification of chitosan is optimized in the method for test, obtained synthesis condition are as follows: monomer gross mass concentration is
26%, modification of chitosan function monomer and AMPS dosage are that the mass ratio of 0.1%, AA:AM of monomer gross mass is 1, K2S2O8-
NaHSO3(molar ratio 1:1) initiator dosage is the 0.1% of system gross mass, and reaction temperature is 45 DEG C；
(3) thickening property and mechanical shearing for having studied modification of chitosan polymer are acted on to modification of chitosan polymer
The influence of viscosity, tackifying is poor, but shear resistant is preferable, is able to maintain under the shearing condition of high shear rates higher viscous
Retention rate is spent, when concentration is 2000mg/L, the viscosity retention ratio of solution is up to 95.3%；
(4) biological enzyme (alpha-amylase) is had studied to the shadow of modification of chitosan polymer viscosity average molecular weigh and apparent viscosity
It rings.For modification of chitosan polymer after biological enzyme effect 57h, the apparent viscosity of solution is reduced to 65.2mPa 〃 by 263.0mPa 〃 s
S, viscosity retention ratio are only 24.8%；
(5) ability for establishing flow resistance that modification of chitosan polymer is had studied using one-dimensional sandpack column, shows this
Polymer can establish higher resistance coefficient and residual resistance factor, can effectively establish filtrational resistance, to improve displacement
The sweep efficiency of liquid.
Molecular Design of the invention:
The present invention is not limited to the above-described embodiments, for those skilled in the art, is not departing from
Under the premise of the principle of the invention, several improvements and modifications can also be made, these improvements and modifications are also considered as protection of the invention
Within the scope of.The content being not described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.
Claims (10)
1. a kind of preparation method of modification of chitosan polymer, which comprises the following steps:
Step S1. adds suitable N,N-dimethylformamide in flask；
Suitable phthalic anhydride is added in flask step S2., by magnetic stirrer, until being completely dissolved；
Suitable chitosan is added in flask step S3., and serpentine condenser is connected on flask, seals with rubber stopper end
Mouthful, then N is filled to reaction system2；
Step S4. is in N2It is reacted in constant temperature oil bath under protection, until obtaining the first dark red-brown liquid；
Step S5. is poured into ice water and is precipitated after the first dark red-brown liquid is cooled to room temperature, and obtains faint yellow threadiness
Substance；
After step S6. purifies faint yellow fibrous material using ethyl alcohol, faint yellow fibrous solids are obtained after filtering；
After step S7. is dry to faint yellow fibrous solids, grinding obtains faint yellow solid particle；
Step S8. adds suitable N,N-dimethylformamide in another flask；
Faint yellow solid particle obtained in appropriate step S7 and suitable maleic anhydride are sequentially added burning by step S9.
In bottle, by magnetic stirrer, until being completely dissolved；
Reaction system in step S10. step S9 fills N2Half an hour；
Step S11. is in N2It is stirred to react under protection, obtains the second dark red-brown liquid；
Step S12. pours into precipitating in ice water and obtains White Flocculus after the second dark red-brown liquid is cooled to room temperature；
After step S13. filters White Flocculus, washed with ethyl alcohol；
Step S14. is sufficiently dried to obtain brown solid in an oven；
Step S15. takes acrylic acid AA to be dissolved in suitable deionized water, and 10% NaOH solution is then added dropwise, forms pH=7.0
Neutralization solution；
Brown solid obtained in step S14 is dissolved in N,N-dimethylformamide by step S16.；
Step S17. is by solution made from step S16, suitable acrylamide AM, 2- acrylamido -2- methyl propane sulfonic acid sodium
It is dissolved in the neutralization solution, and adds deionized water；
Step S18. leads to N to the reaction system in step S17 under water bath with thermostatic control stirring2Deoxygenation 30min；
Step S19. adds suitable oxidation-reduction initiator, then proceedes to logical N2, until reaction system becomes sticky；
Step S20. stops stirring and logical N2, reaction system is placed in water bath with thermostatic control, until the reaction is complete；
Reactant is cooled to room temperature by step S21., is generated and is frozen gum-like product；
Step S22. will freeze gum-like product and wash through dehydrated alcohol, dries, crush to obtain white powder copolymer.
2. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that: in step S1, in flask
The N,N-dimethylformamide of middle addition 36mL.
3. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that:, will in step S2
The phthalic anhydride of 5.9882g is added in flask, by magnetic stirrer 15min, until being completely dissolved.
4. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that:, will in step S3
The chitosan of 1.8032g is added in flask, and serpentine condenser is connected on flask, port is sealed with rubber stopper, then to anti-
System is answered to fill N2Half an hour.
5. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that: in step S4, in N2Protection
Under reacted 8 hours in 120 DEG C of constant temperature oil baths, until obtain the first dark red-brown liquid.
6. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that: described light in step S6
Yellow fibrous substance purifies 4 hours through each 100mL of two batches ethyl alcohol, then faint yellow fibrous solids are obtained after filtering.
7. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that: in step S8, another
The N,N-dimethylformamide of 30mL is added in flask.
8. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that:, will in step S9
The maleic anhydride of faint yellow solid particle and 0.6751g obtained sequentially adds in flask in 1.1292g step S7, passes through
Magnetic stirrer, until being completely dissolved.
9. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that: in step S11, in N2It protects
It is stirred to react for 24 hours under shield in 120 DEG C, obtains the second dark red-brown liquid.
10. the preparation method of modification of chitosan polymer as described in claim 1, it is characterised in that: the oxidationreduction draws
Hair agent is K2S2O8-NaHSO3。
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| CN114316926A (en) * | 2022-01-11 | 2022-04-12 | 陕西科技大学 | Chitosan oil field clay stabilizer based on Mannich reaction and preparation method thereof |
| CN114316926B (en) * | 2022-01-11 | 2022-12-20 | 陕西科技大学 | Chitosan oil field clay stabilizer based on Mannich reaction and preparation method thereof |
| CN115888815A (en) * | 2022-10-25 | 2023-04-04 | 湖北工程学院 | Preparation of N-maleylation chitosan copper catalyst and application of N-maleylation chitosan copper catalyst in boron addition reaction |
| CN115888815B (en) * | 2022-10-25 | 2024-03-19 | 湖北工程学院 | Preparation of N-maleylation chitosan copper catalyst and application of catalyst in boron addition reaction |
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