CN106046258A - Chitosan cross-linked and modified acrylamide compound as well as preparation method thereof and application thereof - Google Patents

Chitosan cross-linked and modified acrylamide compound as well as preparation method thereof and application thereof Download PDF

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CN106046258A
CN106046258A CN201610456694.9A CN201610456694A CN106046258A CN 106046258 A CN106046258 A CN 106046258A CN 201610456694 A CN201610456694 A CN 201610456694A CN 106046258 A CN106046258 A CN 106046258A
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chitosan
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amide compound
modified propylene
propylene amide
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杨隽
王芬
潘小杰
范志玮
徐黎刚
徐恩松
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Wuhan Institute of Technology
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    • C09K8/504Compositions based on water or polar solvents
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    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
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    • C08J2351/00Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/02Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides

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Abstract

The invention discloses a chitosan cross-linked and modified acrylamide compound as well as a preparation method thereof and application thereof, and belongs to the field of oilfield chemistry. The preparation method for the chitosan cross-linked and modified acrylamide compound comprises the following steps: 1) at a temperature being 50-70 DEG C, completely dissolving 0.04-0.12g of a biological type cross-linking agent chitosan into 50 mL of acid, adding 0.05-0.25g of an initiator, adding 50 mL of a solution with 6-8.5g of the acrylamide after certain time, and carrying out free radical polymerization reaction at certain stirring speed, thereby synthesizing a first product; and putting a product obtained in the step 1) at a temperature being 90-110 DEG C to carry out nucleophilic reaction, thereby obtaining polymer gel. The gel prepared by the preparation method is economical and environmental-friendly, has a cross-linked net-shaped structure, further has good shearing resistance, temperature and salt resistance, and can be used as a gel profile control agent.

Description

Chitosan crosslinked modified propylene amide compound and preparation method thereof, application
Technical field
The present invention relates to a kind of chitosan crosslinked modified propylene amide compound and preparation method thereof, application, belong to oil field Chemical field.
Technical background
Oil is one of grand strategy goods and materials of country, is the most also the important foundation raw material of development petrochemical industry, relation The overall situation to national economy.Current whole petroleum industry all suffers from this huge predicament of imbalance between supply and demand, and society is to petroleum resources Demand increasing, and crude oil production amount all have passed through conventional exploitation rank in the past along with the exploitation in major part oil field Section (uses the crude oil that once about can only exploit 20%~40% with secondary oil recovery technology), and the yield initially entering High water cut is passed Derogatory section and decline, the new oil field that determines of prospecting, the whole nation is the most fewer and feweri.How improving oneself warp of oil recovery factor is institute of the whole society The problem paid close attention to.
At present, each elephant of China enters the middle and late stage of aqueous exploitation successively, needs to be carried by tertiary oil recovery means High oil recovery factor.Wherein, the displacement of reservoir oil host with polyacrylamide polymer as representative increasingly receives the concern of people. How to improve the temperature-resistant anti-salt performance of separan polymer, need into being allowed to be adapted to the exploitation of high temperature and high salt oil deposit Emphasis for the work of vast oil researcher.
The method improving acrylic amide profile control agent heat and salt resistance mainly has: (1) introduces temperature-resistant anti-salt monomer, such as: 2- Acrylamide-2-methylpro panesulfonic acid etc.;(2) add cross-linking agent, be allowed to form tridimensional network, improve its temperature-resistant anti-salt Property.Conventional function monomer can improve the heat and salt resistance of acrylamide profile control agent to a certain extent, but expensive.Conventional Cross-linking agent have: inorganic crosslinking agent such as potassium dichromate, aluminium citrate, various chromic salts and organic crosslinking agent such as phenol, formaldehyde, thiourea Deng, but these materials pollute the environment.
Its raw material sources of natural macromolecule carbohydrate are extensive, cheap, renewable, biodegradable.Research table Bright have the high swelling property of low concentration, efficient suspension, high pseudoplastic behavior, the characteristic such as high temperature resistant as environment-friendly material so that Natural polymer not only improves intake profile and the Flooding Efficiency of water injection well as Water Shutoff Agents Used In Oil Fields, expands oil well Responding layer position and direction, improve oil recovery factor on the whole;And economic effect is greatly improved compared with other blocking agent Benefit.
Chitosan is the product of de-acetyl chitin, i.e. Chitosan, formal name used at school poly-glucosamine, and having another name called can Dissolubility chitin, chitosan.It has the architectural characteristic being analogous to dextran amine, containing abundant hydroxyl in its macromolecular structure And amino, these active groups can be with the molecule generation chemical reaction of other material, by acylated, hydroxylating, cyaniding, ether Change, alkylation, esterification, imidizate, Azide, one-tenth salt, chelate, hydrolyze, aoxidize, halogenation, the reaction such as branch and crosslinking, can prepare Chitosan derivatives.As a kind of chemical modification of polymer, chitosan the most all demonstrates the functional characteristic of uniqueness, There is the highest practical value in the fields such as the process of food, agricultural, water, daily use chemicals and biomedical engineering, and its natural resources is the richest Rich, it is estimated that yield is 109~1011t/a, is the second largest organic resource being only second to cellulose.
Summary of the invention
It is an object of the invention to provide a kind of chitosan crosslinked modified propylene amide compound and preparation method thereof, the method Raw material and technique are simple, low cost, and the chitosan crosslinked modified propylene amide compound obtained has relatively as gel profile control agent Good heat-resistant salt-resistant, and will not be to environment.
To achieve these goals, the technical solution used in the present invention is as follows: chitosan crosslinked modified propylene amide compound Thing, it has a general structure represented by following formula I:
Wherein: chitosan molecule amount is 2~300,000, n is n=5~36.
The preparation method of described chitosan crosslinked modified propylene amide compound, it is characterised in that comprise the steps:
1) at 50~70 DEG C, 0.04~0.12g biotype cross-linking agent chitosan is dissolved completely in 50mL acid, adds 0.05~0.25g initiator, after certain time, adds the solution 50mL of 6~8.5g acrylamides, in certain mixing speed Under carry out Raolical polymerizable, synthesize first step product;
2) by the 1st) step products therefrom is placed at 90~110 DEG C and carries out necleophilic reaction, obtains polymer gel.
By such scheme, described acid be mass fraction be the glacial acetic acid of 2%.
By such scheme, described initiator is (NH4)2S2O8、K2S2O8、Na2SO3/(NH4)2S2O8、NaHSO3/(NH4)2S2O8、Na2SO3/K2S2O8、NaHSO3/K2S2O8In any one.
By such scheme, step 1) described in reaction temperature be 60 DEG C.
By such scheme, step 1) described in certain time be 10min.
By such scheme, described mixing speed is 50~200 revolutions per seconds, the most most preferably 100 revolutions per seconds.
By such scheme, the time of described polyreaction is 1.5-4h.
By such scheme, the time of described polyreaction is 2h.
By such scheme, the temperature of described necleophilic reaction is 100 DEG C, and the response time is 3~4h.
Described chitosan crosslinked modified propylene amide compound is as the application of gel profile control agent.
The reaction principle of chitosan crosslinked modified propylene amide compound of the present invention is as follows:
1, first step free radical grafting reaction mechanism
At a certain temperature, decomposition of initiator forms primary group of free radicals, causes chitosan (CS) to form macromolecular radical, Then free radical grafting copolymerization is carried out with acrylamide (AM).Graft copolymerization is broadly divided into the following steps: (1) potassium peroxydisulfate divides Split formation primary group of free radicals;(2) primary group of free radicals reacts with CS molecule, by radical transfer to CS molecule, obtains CS Macromolecular radical;(3) CS macromolecular radical and AM carry out chain propagation reaction, form AM/CS graft polymers.
2, second step necleophilic reaction mechanism
Amide groups (-NH on AM molecule2) can be with the methylol (-CH on CS2OH) there is necleophilic reaction, and CS is as life Thing type macromole, containing more than one-CH in a molecule2OH, i.e. has multiple crosslinking points, under certain reaction condition, enters Row cross-linking reaction i.e. can get the chitosan crosslinked modified propylene amide compound of tridimensional network.
Present invention have the advantage that
(1) chitosan crosslinked modified propylene amide compound prepared by the present invention is as gel profile control agent, crosslinking used Agent is a kind of polysaccharide biotype macromolecule, and raw material is biodegradable, is extensively easy to get, with low cost, more common inorganic crosslinking Agent such as potassium dichromate, aluminium citrate, various chromic salts and organic crosslinking agent such as phenol, formaldehyde, thiourea etc., have good environmental protection Property;
(2) the environmental protective polymer gel profile control agent that prepared by the present invention, reacts with water as disperse medium, monomer and cross-linking agent And the low raw-material cost such as initiator, be extensively easy to get, production cost can be substantially reduced;
(3) the environmental protective polymer gel profile control agent that prepared by the present invention, uses water solution polymerization process, and course of reaction is simple, Easily operated.
(4) the environmental protective polymer gel profile control agent that prepared by the present invention, can be by changing monomer, cross-linking agent and initiator Concentration, the performance of gel after the viscosity of control system and plastic;
(5) the environmental protective polymer gel profile control agent that prepared by the present invention, when ambient temperature range is 100 DEG C~140 DEG C, Not havinging obvious degradation, retention of viscosity rate is higher;It is 0~2.5 × 10 in crude salt concentration range5Have the most steady during mg/L Qualitative, do not have brokenly the phenomenon such as glue, precipitation;The intake profile of water injection well can be effectively improved, improve the swept volume injecting water, Thus improve oil recovery factor.
(6) method preparing environmental protective polymer gel profile control agent in the present invention, synthesizes, it is achieved underground crosslinked in two steps; The product of first step synthesis has good endurance of cutting, and the polymer gel intensity that second step finally synthesizes is not produced by the first step The impact sheared in thing injection process.
Accompanying drawing explanation
Fig. 1 is the cross-linking modified acrylamide compound of chitosan and the infrared spectrum pair of chitosan in the embodiment of the present invention 1 Than figure, wherein curve a is the infrared spectrogram of chitosan (CS), and curve b is chitosan crosslinked modified propylene amide compound The infrared spectrogram of (AM/CS cross linked polymer);
Fig. 2 is the acrylamide consumption curve to system viscosity in the embodiment of the present invention 2;
Fig. 3 is the dosage of crosslinking agent curve to system viscosity in the embodiment of the present invention 3;
Fig. 4 is the initiator amount curve to system viscosity in the embodiment of the present invention 4.
Fig. 5 is the resistant to shearing test curve of the embodiment of the present invention 5 gained environment-friendly type profile control agent;
Fig. 6 is the heatproof test curve of the embodiment of the present invention 6 gained environment-friendly type profile control agent;
Fig. 7 is the anti-salt test curve of the embodiment of the present invention 6 gained environment-friendly type profile control agent.
Detailed description of the invention
For being more fully understood that the present invention, the following examples are to further illustrate the present invention, but present disclosure It is not limited solely to the following examples.
Embodiment 1
A kind of preparation method of chitosan crosslinked modified propylene amide compound, its preparation process is as follows:
1) at 60 DEG C, it is in 2% glacial acetic acid that 0.08g chitosan is dissolved completely in 50mL mass fraction, adds 0.15g Potassium peroxydisulfate, after 10min, adds the solution 50mL of 8g acrylamide, carries out free radical under the mixing speed of 100 revolutions per seconds Polyreaction 2h, synthesizes first step product;
2) by the 1st) step products therefrom is placed at 100 DEG C and carries out necleophilic reaction 4h, obtains end product polymer gel.
Chitosan and the polymer gel after ethyl alcohol purification are carried out examination of infrared spectrum.Obtain infrared spectrogram, as Shown in accompanying drawing 1, spectrum figure analysis the results are shown in Table 1.
The infrared spectrogram analysis result of table 1 CS and AM/CS cross linked polymer
From Fig. 1 with Biao 1: compared with a spectrogram in Fig. 1, in spectrogram b, wave number 1410.20cm-1The bending of place C-N is shaken Dynamic peak occurs, meanwhile, and wave number 1099.69cm-1The stretching vibration of place-OH and 561.76cm-1The wagging vibration of place-OH Characteristic peak weakens, and thus may certify that, it is poly-that chitosan and acrylamide there occurs that reaction, Success in Experiment have prepared AM/CS crosslinking Compound.
Embodiment 2
With the consumption of acrylamide as variable, carry out 6 groups of experiments and prepare chitosan crosslinked modified propylene amide compound, its Preparation process is as follows:
1) at 60 DEG C, it is in 2% glacial acetic acid that the chitosan of 0.08g is dissolved completely in 50mL mass fraction, adds 0.15g Ammonium persulfate., after 10min, adds the solution 50mL of a certain amount of acrylamide, under the mixing speed of 100 revolutions per seconds Carry out Raolical polymerizable 2h, synthesize first step product;
2) by the 1st) step products therefrom is placed at 100 DEG C and carries out necleophilic reaction 3h, and (second step produces to obtain polymer gel Thing);
Wherein, the consumption of acrylamide is shown in Table 1.
Test process measures this first step product and the viscosity of second step product with NDJ-8S viscosimeter, acrylamide Consumption is on the impact of system viscosity as shown in Figure 2.
Table 1
Experiment 1 Experiment 2 Experiment 3 Experiment 4 Experiment 5 Experiment 6
The consumption of acrylamide 6g 6.5g 7.0g 7.5g 8.0g 8.5g
From accompanying drawing 2, along with acrylamide consumption increases, the viscosity of first step product and second step product is all in rising Trend, but when acrylamide consumption is more than 8g, second step product viscosity steeply rises.
Embodiment 3
With the consumption of chitosan as variable, carry out 5 groups of experiments and prepare chitosan crosslinked modified propylene amide compound, its system Standby step is as follows:
1) at 60 DEG C, it is in 2% glacial acetic acid that a certain amount of chitosan is dissolved completely in 50mL mass fraction, adds 0.15g potassium peroxydisulfate-sodium sulfite (both mol ratios are 1:1), after 10min, adds the solution 50mL of 8g acrylamide, Under the mixing speed of 100 revolutions per seconds, carry out Raolical polymerizable 2h, synthesize first step product;
2) by the 1st) step products therefrom is placed at 100 DEG C and carries out necleophilic reaction 3.5h, obtains chitosan crosslinked modified third Enamides (second step product);
Wherein, the consumption of chitosan is shown in Table 2.
Test process measures this first step product and the viscosity of second step product, chitosan dosage with NDJ-8S viscosimeter On the impact of system viscosity as shown in Figure 3.
Table 2
Experiment I Experiment II Experiment III Experiment IV Experiment V
The consumption of chitosan 0.04g 0.06g 0.08g 0.10g 0.12g
From accompanying drawing 3, along with the increase of chitosan dosage, the viscosity of first step product produces without significant change, second step The viscosity of thing finally tends towards stability in drastically declining after the most slowly declining.
Embodiment 4
With initiator potassium persulfate consumption as variable, carry out 7 groups of experiments and prepare chitosan crosslinked modified propylene amide compound Thing, its preparation process is as follows:
1) at 60 DEG C, being dissolved completely in 50mL mass fraction by chitosan crosslinked dose of 0.08g is in 2% glacial acetic acid, Until completely dissolved, add a certain amount of potassium peroxydisulfate, after 10min, add the solution 50mL of 8g acrylamide, 100 turns/ Carry out Raolical polymerizable 2h under the mixing speed of second, synthesize first step product;
2) by the 1st) step products therefrom is placed at 100 DEG C and carries out necleophilic reaction 3h, and (second step produces to obtain polymer gel Thing);
Wherein, the consumption of potassium peroxydisulfate is shown in Table 3.
Test process measures this first step product and the viscosity of second step product with NDJ-8S viscosimeter, potassium peroxydisulfate Consumption is on the impact of system viscosity as shown in Figure 4.When potassium peroxydisulfate consumption is 0.2g and 0.25g, the polymerization being finally synthesizing Thing becomes bulk.
Table 3
Experiment i Experiment ii Experiment iii Experiment iv Experiment v Experiment vi Experiment vii
The consumption of potassium peroxydisulfate 0.05g 0.075g 0.1g 0.125g 0.15g 0.2g 0.25g
Embodiment 5
At 60 DEG C, it is in 2% glacial acetic acid that 0.08g chitosan is dissolved completely in 50mL mass fraction, adds 0.15g mistake Potassium sulfate-sodium sulfite (both mol ratios are 1:1), after 10min, adds the solution 50mL of 8g acrylamide, 100 Revolutions per second mixing speed under carry out Raolical polymerizable 2h, synthesize first step product, by gained first step product at 100S-1 Shear rate down cut different time, shear time scope: 30~180min, gradient is 30min;Each product is placed At 100 DEG C, carry out necleophilic reaction 4h, obtain polymer gel (second step product).
Test process measures this first step product and the viscosity of second step product, shear time pair with NDJ-8S viscosimeter The impact of system viscosity is as shown in Figure 4, it is known that the product of first step synthesis has good endurance of cutting, and be finally synthesizing is poly- Compound gel strength is not affected by shearing in first step product injection process.
Embodiment 6
At 60 DEG C, it is in 2% glacial acetic acid that 0.08g chitosan is dissolved completely in 50mL mass fraction, adds 0.15g mistake Potassium sulfate, after 10min, adds the solution 50mL of 8g acrylamide, carries out radical polymerization under the mixing speed of 100 revolutions per seconds Close reaction 2h, synthesize first step product, gained first step product is placed at 100 DEG C and carries out necleophilic reaction 4h, be polymerized Thing gel.
Resulting polymers gel is carried out resistance to gentle salt tolerant test.The temperature of heatproof testing setup be respectively 100 DEG C, 110 DEG C, 120 DEG C, 140 DEG C, when reaching design temperature, place and survey viscosity after 2h;The salt concentration range of salt tolerant testing setup is: 0~25 ×104(proportioning of the most various salt is mg/L: CaCl2:MgCl2: KCl:NaCl=2:1:2:5).
Measure the viscosity of this polymer gel in test process with NDJ-8S viscosimeter, heat resistance is as shown in Figure 5, resistance to Temperature scope is 100~140 DEG C;As shown in Figure 6, the crude salt concentration range being suitable for is 0~2.5 × 10 to salt resistant character5mg/L。
Embodiment 7
At 50 DEG C, it is in 2% glacial acetic acid that 0.08g chitosan is dissolved completely in 50mL mass fraction, adds 0.15g mistake Potassium sulfate, after 10min, adds the solution 50mL of 8g acrylamide, carries out radical polymerization under the mixing speed of 50 revolutions per seconds Reaction 4h, synthesizes first step product, is placed at 110 DEG C by gained first step product and carries out necleophilic reaction 2h, obtain polymer Gel.
Embodiment 8
At 70 DEG C, it is in 2% glacial acetic acid that 0.08g chitosan is dissolved completely in 50mL mass fraction, adds 0.15g mistake Potassium sulfate, after 10min, adds the solution 50mL of 8g acrylamide, carries out radical polymerization under the mixing speed of 200 revolutions per seconds Close reaction 1.5h, synthesize first step product, gained first step product is placed at 90 DEG C and carries out necleophilic reaction 4h, be polymerized Thing gel.

Claims (10)

  1. The most chitosan crosslinked modified propylene amide compound, it has a general structure represented by following formula I:
    Wherein: chitosan molecule amount is 2~300,000, n is n=5~36.
  2. 2. the preparation method of the chitosan crosslinked modified propylene amide compound described in claim 1, it is characterised in that include as Lower step:
    1) at 50~70 DEG C, 0.04~0.12g biotype cross-linking agent chitosan is dissolved completely in 50mL acid, adds 0.05 ~0.25g initiator, after certain time, add the solution 50mL of 6~8.5g acrylamides, enter under certain mixing speed Row Raolical polymerizable, synthesizes first step product;
    2) by the 1st) step products therefrom is placed at 90~110 DEG C and carries out necleophilic reaction, obtains polymer gel.
  3. The preparation method of chitosan crosslinked modified propylene amide compound the most according to claim 2, it is characterised in that institute Stating acid is the glacial acetic acid of 2% for mass fraction.
  4. The preparation method of chitosan crosslinked modified propylene amide compound the most according to claim 2, it is characterised in that institute Stating initiator is (NH4)2S2O8、K2S2O8、Na2SO3/(NH4)2S2O8、NaHSO3/(NH4)2S2O8、Na2SO3/K2S2O8、NaHSO3/ K 2S2O8In any one.
  5. The preparation method of chitosan crosslinked modified propylene amide compound the most according to claim 2, it is characterised in that step Rapid 1) reaction temperature described in is 60 DEG C.
  6. The preparation method of chitosan crosslinked modified propylene amide compound the most according to claim 2, it is characterised in that institute Stating mixing speed is 50~200 revolutions per seconds.
  7. The preparation method of chitosan crosslinked modified propylene amide compound the most according to claim 2, it is characterised in that institute The time stating polyreaction is 1.5-4h.
  8. The preparation method of chitosan crosslinked modified propylene amide compound the most according to claim 7, it is characterised in that institute The time stating polyreaction is 2h.
  9. The preparation method of chitosan crosslinked modified propylene amide compound the most according to claim 2, it is characterised in that institute The temperature stating necleophilic reaction is 100 DEG C, and the response time is 3~4h.
  10. 10. the chitosan crosslinked modified propylene amide compound described in claim 1 is as the application of gel profile control agent.
CN201610456694.9A 2016-06-21 2016-06-21 Chitosan cross-linked and modified acrylamide compound as well as preparation method thereof and application thereof Pending CN106046258A (en)

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CN109825176A (en) * 2018-12-27 2019-05-31 安徽伊法拉电力科技有限公司 A kind of preparation method of super-hydrophobic insulator anticorrosive paint
CN113214809A (en) * 2021-04-15 2021-08-06 长江大学 Environment-friendly profile control and water shutoff system, preparation method thereof and application thereof in medium-low temperature high water-cut oil reservoir
CN113214809B (en) * 2021-04-15 2023-05-23 长江大学 Environment-friendly profile control water plugging system, preparation method thereof and application thereof in medium-low-temperature high-water-content oil reservoir
CN113265056A (en) * 2021-05-21 2021-08-17 陕西万朗石油工程技术服务有限公司 Preparation method of modified acrylamide polymer fracturing fluid

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Application publication date: 20161026