CN103435750A - Hydrophobic associated polymer containing capsaicin activated monomer and preparation method thereof - Google Patents
Hydrophobic associated polymer containing capsaicin activated monomer and preparation method thereof Download PDFInfo
- Publication number
- CN103435750A CN103435750A CN2013103825730A CN201310382573A CN103435750A CN 103435750 A CN103435750 A CN 103435750A CN 2013103825730 A CN2013103825730 A CN 2013103825730A CN 201310382573 A CN201310382573 A CN 201310382573A CN 103435750 A CN103435750 A CN 103435750A
- Authority
- CN
- China
- Prior art keywords
- acrylamide
- monomer
- benzyl
- hydrophobic
- associated polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a hydrophobic associated polymer containing a capsaicin activated monomer and a preparation method thereof. The method comprises the following step: by taking an acrylamide monomer containing capsaicin activity as a hydrophobic monomer, carrying out polymerization reaction on the acrylamide monomer and acrylamide and (methyl) crylic acid under initiation of a water-soluble initiator when in preparation, wherein the weight part ratio of the acrylamide monomer containing capsaicin activity to the acrylamide to the (methyl) crylic acid is (1-20) to (60-90) to (9-20), the reaction temperature is 30-80 DEG C, and the reaction time is 2-20 hours. The hydrophobic associated polymer macromolecule disclosed by the invention simultaneously contains a carboxyl group and a hydrophobic unit containing capsaicin activity with a rigid benzene ring structure, displays good viscosifying capacity, solubleness, salt resistant and temperature-resistance, and antimicrobial properties, is low in price, and can be used as a novel oil-displacing agent to be applied in tertiary oil recovery of an oil field.
Description
[technical field]
The invention belongs to polymeric material field.More specifically, the present invention relates to a kind of hydrophobic associated polymer that contains the capsaicine activity monomer and preparation method thereof.
[background technology]
Oil is the important energy and industrial chemicals, and along with the world economy fast development, people constantly increase the demand of oil, and its reserves constantly reduce, and oil is more and more valuable as non-renewable resource.Yet the main force oil fields such as China's grand celebration at present successively enter high moisture later stage mining period, in oil reservoir, nearly 60% crude oil can not, with conventional oil recovery technique exploitation, restrict the development of national economy.In order to stablize China's field output, adopt tertiary oil recovery technology to improve recovery ratio, become the grand strategy measure of petroleum industry, wherein polymer flooding is to improve the important method of waterflooding oil field oil recovery factor in tertiary oil recovery.Polymer flooding is by injecting molecular weight water-soluble polymers solution in oil reservoir, reduce water-oil mobility ratio, improving the sweep efficiency that drives liquid, thereby improves oil recovery factor.Present stage, two the most frequently used base polymers of oil field are respectively partially hydrolyzed polyacrylamide (HPAM) and xanthan gum, they have obtained good result of use at most of block in oil field, yet all have the problem that is difficult to overcome for high temperature and high salt oil deposit the time: HPAM depends on high molecular and molecular chain-COO
-electrostatic repulsion, molecular chain is stretched, thereby reaches Efficient Adhesive Promotion, but under the conditions such as high temperature and high salt, high-shear, HPAM facile hydrolysis, degraded, chain are curling etc., cause the solution property cataclysm and do not reach the requirement of engineering construction; Although the xanthan gum salt resistance is good, its thermostability and biologically stable are poor, stop up oil reservoir thereby degraded easily occurs, and cost are higher.For this reason, polymkeric substance in the urgent need to development temperature resistant antisalt, antibiont degraded meets the demands, wherein the most frequently used method is to take acrylamide copolymer as basis, introduce by polymer modification or copolymerization the structural unit that other have specific function, make its acquisition stand the ability of severe condition, what development at present relatively rapidly, research is the most popular is hydrophobic associated water-soluble polymer.
Hydrophobic associated water-soluble polymer (Hydrophobically Associating Water-soluble Polymer, HAWP) refers to the class water-soluble polymers that a small amount of hydrophobic grouping is arranged on the polymer hydrophilicity macromolecular chain.In the aqueous solution, when polymkeric substance surpasses finite concentration, due to the interaction between molecular chain, hydrophobic association can occur form reversible physical cross-linked network structure, make polymers soln there is high-effective viscosity, anti-salt, unique rheological property such as anti-shearing, thereby all show important application prospect at aspects such as tertiary oil recovery, water treatment, water-based paint, medicine preparations.
20th century the mid-80, Evani and Rose have proposed concept (the S Evani of HAWP first, G D Rose.Water soluble hydrophobic association polymers[J] .Polym Mat Sci Eng-Prepr, 1987,57:477-481), find that this base polymer has shown a kind of special heterogeneous gathering behavior by hydrophobic grouping generation association in the aqueous solution.1988, the McCormick professor research group of American South University of Mississippi has carried out a large amount of research (McCormick C L to the hydrophobic association polyacrylamide multipolymer of heatproof, anti-salt, Nonaka T, Johnson C B.Water-soluble copolymers synthesis and aqueous solution behavior of associative acrylamide/N-alkylacrylamide copolymers[J] .Polymer, 1988,29:731-739.), result shows that these copolymer sheets reveal obvious tackifying and salt resistance.1997; the Mitchell of University of Toronto cooperates the hydrophobic associated polymer of polyoxyethylene class is studied with the people such as Richard of Nanyang Technological University; the association performance of finding this base polymer can increase along with the increase of hydrophobic chain length (Kumacheva, E.; Rharbi, Y.W.; Nik, M.A.Fluorescence studies of an alkaline sellable associative polymer in aqueous solution[J] .Langmuir, 1997,13:182-186.).The Jeanne Francois team of France starts to carry out the polyoxyethylated research of hydrophobically modified at the mid-80; the imagination that telechelic type hydrophobically modified polymers forms " fancy structure " model in the aqueous solution has been proposed; and used many modern Molecular tools such as comprising fluorescence spectrum, small-angle neutron scattering, little angle X-ray diffraction and little angle laser light scattering to confirm this model (Chiarelli, PA.; Johal, M.S.; Holmes, D.J.Polyelectrolyte spin-assembly[J] .Langmuir, 2002,18:168-173).After a while, Francoise Caudau professor has started the comprehensive research to AM/CnAM hydrophobically associating polymkeric substance on the basis of AM polymerization process research, by the synthetic model compound, has intactly proposed the mechanism of micellar copolymerization.
And at home hydrophobic associated polymer research is started late, nineteen ninety-five, petroleum exploration and development research institute started of oiling was to the research of hydrophobic associated water-soluble polymer, find that this base polymer has good temperature resistance, anti-salt and anti-shear ability, but, while using, need to add stablizer in salt solution.With oneself, synthetic cationic surfactivity hydrophobic monomer MEDMDA and AM copolymerization obtained hydrophobic associated water-soluble polymer to the people such as professor Huang Ronghua of Sichuan University in 1997, but polymers obtained viscosity is very low, critical association is dense, is difficult to meet application requiring.1999, the inferior academician in Southwest Petroleum Institute Luoping is from the actual needs of oil-gas mining, the multiple models of structure that can form in solution such as hydrophobic associated polymer have been proposed, and the hydrophobic associated polymer oil-displacement mechanism is done to further investigation always, develop the water-soluble hydrophobic associated polymer for the industrialization displacement of reservoir oil (AP-P4) with good heat and salinity tolerance performance.2004, the people such as Zhang Xi have synthesized non-ionic hydrophobic association polymer PBAM by the micellar free radical copolymerization method, study discovery existence due to surfactant micelle in polymerization process, hydrophobic monomer is very high in the embedding rate of initial reaction stage, and the later stage mainly be take methacrylamide homopolymer as main, cause serious microtexture heterogeneity, the thickening property of multipolymer is had a great impact.2007, Jiang Liding, Gao Baojiao etc. were with Anionic surface-active monomer NaAMC
14s and AM carry out the homogeneous phase copolymerization in the aqueous solution, have prepared two analog copolymers with random structure and micro-block structure.Result of study shows, the multipolymer with micro-block structure has very strong Hydrophobic association property, and shows strong anti-shear performance and unique quick property of positivity salt.2009, Lv Xin etc. were at C
18introduce the monomer styrene that contains aromatic group on two kinds of monomer bases of DMAAC and AM, obtain AM/C
18the DMAAC/Styrene hydrophobic associated polymer, research shows that the temperature resistant antisalt and the shear resistant that increase multipolymer along with chain rigidity obviously increase, and critical association concentration reduces.Recently, the use fluorochemical monomers such as Yang Qinhuan, butyl acrylate, cationic monomer have carried out emulsifier-free emulsion polymerization, and synthetic polymer stabilizing is better with this understanding.Song Chunlei etc. are with AM, DMC, C
11aM is raw material, synthetizing hydrophobic associated polyamphoteric electrolyte P (AM/DMC/C in water medium
11aM), because it has hydrophobic association character and anti-polyelectrolyte effect concurrently, thereby show salt resistant character preferably.
Hydrophobic associated polymer developed in recent years very fast, relevant research and had obtained remarkable progress, had obtained in a lot of fields fruitful achievement, but also had many problems to need further research.For example domestic most oil field enters or is about to enter high water-cut stage or runs into concentrated water, and HAWP viscosity can decline to a great extent, and even produces precipitation, affects its use range.In addition, along with the intensification of domestic petroleum mining depth, in oil well, temperature is higher, and the heat resistance of polymkeric substance has to be strengthened.Again, in the oil recovery process, sulphate reducing bacteria, saprophytic microorganism etc. bacterium may stick on duct wall and contact with the HAWP constantly injected for a long time, makes the ability of bacterial degradation polymkeric substance greatly improve, make the polymer solution viscosity loss larger, cause oil displacement efficiency to reduce.In addition, the hydrophobic monomer building-up process of most of modification is loaded down with trivial details, expensive, and large-scale application does not have practical significance on oilfield exploitation.Therefore, develop the challenge that well behaved, cheap hydrophobic associated polymer is still an arduousness.
The present invention strengthens the heat-resistant salt-resistant performance of polymers soln and antimicrobial properties during for the oil field displacement of reservoir oil and designs research and development.The inventor introduces the acrylamide hydrophobic monomer containing capsaicine activity in polymer molecular chain, improve on the one hand tackifying ability and the saline-alkaline tolerance of polymkeric substance by hydrophobic association character, hydrophobic monomer containing capsaicine activity has the antibiont characteristic on the other hand, give the polymeric anti-microbial performance, reduce the viscosity loss that it causes because of microbiological deterioration, benzene ring structure in hydrophobic monomer increases the molecular chain rigidity in addition, and then improves thermostability and the anti-shear ability of polymkeric substance.Introduce hydroxy-acid group simultaneously in molecular chain and improve the water-soluble of polymkeric substance, meet the practice of construction needs.
[summary of the invention]
The object of the present invention is to provide a kind of hydrophobic associated polymer that contains the capsaicine activity monomer with good temperature resistant antisalt, antimicrobial properties and preparation method thereof, described polymkeric substance is the efficient oil field of a class oil-displacing agent.
The present invention is achieved through the following technical solutions:
The present invention relates to a kind of hydrophobic associated polymer that contains the capsaicine activity monomer, its structural formula is as follows:
Wherein: R is CH
3or H; R
1and R
2f, Cl, Br, OH, SH, OCH respectively do for oneself
3, SCH
3, OCH
2cH
3, CH
3, CH
2cH
3, CH (CH
3)
2or C (CH
3)
3; R
3for CH (CH
3)
2, CH
2cH=CH
2, CH
3, OH or H; R
4for CH
3or H; The weight-average molecular weight of described multipolymer is 50000～3000000; X, y, z is structural unit molecular fraction scope, x=70～92.5mol% wherein, y=7～20mol%, z=0.5～10mol%.
Further, the invention provides the preparation method of the above-mentioned hydrophobic associated polymer that contains the capsaicine activity monomer, it is characterized in that, described preparation method comprises the steps:
Step 1: add successively acrylamide monomer, (methyl) Acrylic Acid Monomer and distilled water in reactor, three's weight part is respectively 60～90:9～20:300～480, is stirred to after monomer dissolves and uses NaOH regulation system pH value to 5～7; It is 10～30% that regulating pondage makes the total monomer quality percentage concentration;
Step 2: add the Surfactant SDS of 12～30 weight parts, add the acrylamide hydrophobic monomer containing capsaicine activity of 1～20 weight part after stirring; Logical N
2add the water soluble starter of 0.12～1.2 weight part after 20 minutes, react 2～12 hours at 30～80 ℃ of temperature, obtain transparent polymeric articles;
Step 3: use the dehydrated alcohol deposition and purification, 30～50 ℃ of lower vacuum-dryings, to constant weight, obtain the hydrophobic associated polymer that contains the capsaicine activity monomer of the present invention;
The described acrylamide hydrophobic monomer containing capsaicine activity is N-(4-hydroxy-3-methoxy-benzyl) acrylamide, the fluoro-benzyl of N-(4-hydroxyl-3-) acrylamide, the chloro-benzyl of N-(4-hydroxyl-3-) acrylamide, the bromo-benzyl of N-(4-hydroxyl-3-) acrylamide, N-(4-hydroxyl-3-methylthio group-benzyl) acrylamide, N-(3, 4-diethoxy phenyl) acrylamide, N-(3, the 4-Dimethoxyphenyl) acrylamide, the chloro-benzyl of N-(4-sulfydryl-3-) acrylamide, N-(4-sulfydryl-3-ethylmercapto group-benzyl) one or more in acrylamide,
Described water soluble starter is water-soluble azo compounds initiator or redox system initiator; Described water-soluble azo compounds is azo diisobutyl amidine hydrochloride or azo di-isopropyl tetrahydroglyoxaline; Described redox system is K
2s
2o
8and NaHSO
3, K
2s
2o
8and Na
2sO
3, K
2s
2o
8and Na
2s
2o
3, KMnO
4and NaHSO
3, KMnO
4and Na
2sO
3or KMnO
4and Na
2s
2o
3.
Preferably, in step 1, the weight part of acrylamide monomer, (methyl) vinylformic acid and distilled water is respectively: 65～85:12～16:350～480; More preferably, its weight part is respectively: 70:14:400;
Preferably, the amount of the acrylamide hydrophobic monomer containing capsaicine activity added in step 2 is 5～15 weight parts, more preferably 7～12 weight parts;
Preferably, the described acrylamide hydrophobic monomer containing capsaicine activity is N-(4-hydroxy-3-methoxy-benzyl) acrylamide, the bromo-benzyl of N-(4-hydroxyl-3-) acrylamide, N-(4-hydroxyl-3-methylthio group-benzyl) acrylamide or N-(4-sulfydryl-3-ethylmercapto group-benzyl) acrylamide; N-(4-hydroxy-3-methoxy-benzyl more preferably) acrylamide and N-(4-hydroxyl-3-methylthio group-benzyl) acrylamide.
Further, the invention provides the purposes as the oil field oil-displacing agent by the above-mentioned hydrophobic associated polymer that contains the capsaicine activity monomer.
Compared with prior art, the above-mentioned hydrophobic associated polymer that contains the capsaicine activity monomer that the present invention synthesizes has following beneficial effect:
(1) in copolymer chain, introduced carboxylate anion's group, make polymkeric substance there is good water-soluble and polymer viscosity and be greatly improved;
(2) containing the capsaicine activity hydrophobic units in the introducing of polymerizable molecular chain, make polymkeric substance have hydrophobic association character cause tackify and saline-alkaline tolerance stronger, on engineering, consumption obviously reduces, can be cost-saving;
(3) hydrophobic units containing capsaicine activity of introducing copolymer chain has the antibiont characteristic, makes polymkeric substance have good antimicrobial properties; The contribution of benzene ring structure in hydrophobic units to the rigidity of polymer molecular chain simultaneously, also make polymkeric substance show good temperature tolerance and shear resistant;
(4) this polymer production cost is low, is beneficial to suitability for industrialized production, can be used as emerging oil-displacing agent and applies in the tertiary oil recovery in oil field.
[accompanying drawing explanation]
The infrared spectrogram that accompanying drawing 1 is the hydrophobic associated polymer that contains the capsaicine activity monomer in the embodiment of the present invention 1.
Accompanying drawing 2 is polymers soln apparent viscosity in the embodiment of the present invention 1 and controlled trial and the relation of concentration.
Accompanying drawing 3 is polymers soln apparent viscosity in the embodiment of the present invention 1 and embodiment 2 and controlled trial and the relation of temperature.
The solution apparent viscosity that accompanying drawing 4 is the polymkeric substance in the embodiment of the present invention 1 and controlled trial and the relation of additional inorganic salt concentration.
Accompanying drawing 5 is polymer solution viscosity rate of loss in the embodiment of the present invention 1 and controlled trial and the relation of PM-2 Hydrolyzed Polyacrylamide Degrading Bacteria incubation time.
[embodiment]
Below in conjunction with specific embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited by the following examples.
One, Preparation Example
Preparation Example 1: the hydrophobic associated polymer that contains the capsaicine activity monomer synthetic
7.1g acrylamide, 2.16g vinylformic acid are dissolved in to 40 ml distilled waters, slowly dripping the NaOH solution regulation system pH that massfraction is 10% is 6.4, adding distilled water control total monomer is 15% (massfraction), add afterwards 2.35g Surfactant SDS (SDS), add 1.12gN-(4-hydroxy-3-methoxy-benzyl after fully stirring) acrylamide, continuously stirring, fully be dissolved in the SDS micella it, forms diaphanous homogeneous system.Logical nitrogen deoxygenation, after 20 minutes, adds 0.052g azo diisobutyl amidine hydrochloride, and 56 ℃ of lower isothermal reactions 8 hours, obtain the transparent polymeric articles with certain viscosity.By the dehydrated alcohol precipitation, then with scissors, throw out is cut into small pieces, uses soaked in absolute ethyl alcohol 3 days, 45 ℃ of lower vacuum-dryings obtain the hydrophobic associated polymer that contains the capsaicine activity monomer, and its intrinsic viscosity is 623.1mL/g.
Structural characterization:
The infrared spectrogram of the prepared above-mentioned hydrophobic associated polymer that contains the capsaicine activity monomer of Preparation Example 1 as shown in Figure 1.The charateristic avsorption band frequency has as we know from the figure: 3430cm
-1place is the stretching vibration peak of amide group N-H; 1658cm
-1stretching vibration for amide group C=O; 2863cm
-1, 2928cm
-1, 2781cm
-1place is-CH
3,-CH
2, the stretching vibration peak of-CH; 1454cm
-1, 1358cm
-1, 1347cm
-1for-CH
3,-CH
2, the flexural vibration peak of-CH; 1564cm
-1place in-COO-the C=O charateristic avsorption band; 1655,1609,1450cm
-1for phenyl ring skeletal vibration absorption peak, 3195.01cm
-1for on phenyl ring=stretching vibration peak of C-H, 762,812cm
-1for on phenyl ring=the out-of-plane deformation vibration peak of C-H.The polymkeric substance that can determine synthesized is by hydrophobic monomer N-(4-hydroxy-3-methoxy-benzyl) acrylamide and acrylamide, acrylic acid copolymer form.
Preparation Example 2: the hydrophobic associated polymer that contains the capsaicine activity monomer synthetic
7.1g acrylamide, 2.16g2-acrylamide-2-methylpro panesulfonic acid are dissolved in to 40 ml distilled waters, slowly dripping the NaOH solution regulation system pH that massfraction is 10% is 6.4, adding distilled water control total monomer is 15% (massfraction), add afterwards 2.37g Surfactant SDS (SDS), add 1.20gN-(4-hydroxyl-3-methylthio group-benzyl after fully stirring) acrylamide, continuously stirring, it fully is dissolved in the SDS micella, forms diaphanous homogeneous system.Logical nitrogen deoxygenation, after 20 minutes, adds 0.052g azo diisobutyl amidine hydrochloride, and 56 ℃ of lower isothermal reactions 8 hours, obtain the transparent polymeric articles with certain viscosity.By the dehydrated alcohol precipitation, then with scissors, throw out is cut into small pieces, uses soaked in absolute ethyl alcohol 3 days, 45 ℃ of lower vacuum-dryings obtain the hydrophobic associated polymer that contains the capsaicine activity monomer, and its intrinsic viscosity is 646.3mL/g.
Preparation Example 3:
Controlled trial 1: acrylamide-acrylicacid copolymer (calling HPAM in the following text) synthetic
By the 7.1g acrylamide, 2.16g vinylformic acid is dissolved in 50 ml distilled waters, slowly dripping the NaOH solution regulation system pH that massfraction is 10% is 6.4, adding distilled water control total monomer is 15% (massfraction), logical nitrogen deoxygenation 20 minutes, add 0.046g azo diisobutyl amidine hydrochloride (total monomer quality 0.5%), 56 ℃ of lower isothermal reactions are after 8 hours, with dehydrated alcohol, precipitate, with scissors, throw out is cut into small pieces again, soaked in absolute ethyl alcohol 3 days, 45 ℃ of lower vacuum-dryings obtain aforesaid propylene acid amides-vinylformic acid copolymer, its intrinsic viscosity is 670.1mL/g.
Controlled trial 2: acrylamide-acrylicacid-N-octyl acrylamide multipolymer (PAAC) synthetic
7.1g acrylamide, 2.16g vinylformic acid are dissolved in to 40 ml distilled waters, slowly dripping the NaOH solution regulation system pH that massfraction is 10% is 6.4, adding distilled water control total monomer is 15% (massfraction), add afterwards 2.32g Surfactant SDS (SDS), add the 0.99gN-octyl acrylamide after fully stirring, continuously stirring, fully be dissolved in the SDS micella it, forms diaphanous homogeneous system.Logical nitrogen deoxygenation, after 20 minutes, adds 0.051g azo diisobutyl amidine hydrochloride, and 56 ℃ of lower isothermal reactions 8 hours, obtain the transparent polymeric articles with certain viscosity.By the dehydrated alcohol precipitation, then with scissors, throw out is cut into small pieces, uses soaked in absolute ethyl alcohol 3 days, 45 ℃ of lower vacuum-dryings obtain acrylamide-acrylicacid-N-octyl acrylamide multipolymer, and its intrinsic viscosity is 651.2mL/g.
Two, performance test embodiment
Performance test embodiment 1: the rheological of the hydrophobic associated polymer that contains the capsaicine activity monomer
Prepare the aqueous solutions of polymers that a series of polymkeric substance (being respectively the hydrophobic associated polymer that contains the capsaicine activity monomer, reference examples HPAM and the PAAC of embodiment 1 preparation) concentration is 0.05-0.85%, measure the apparent viscosity of solution under 30 ℃, data as shown in Figure 2.From Fig. 2, can find: it is little that HPAM aqueous solution apparent viscosity increases amplification with concentration, and the basic linearity that keeps rises; And reference examples PAAC and Preparation Example 1 polymkeric substance increase slowly when lower concentration, but after concentration reaches certain value (critical association concentration), apparent viscosity rises rapidly, illustrate that polymkeric substance the hydrophobic association effect occurs when this concentration and forms the space reticulated structure, the hydrodynamic volume of molecule increases, and viscosity significantly increases.By Fig. 2, found out, the critical association concentration of PAAC polymkeric substance is in about 0.35g/dL, and containing the critical association concentration of the hydrophobic associated polymer of capsaicine activity monomer in the 0.30g/dL left and right, show that it has tackifying ability preferably.
Performance test embodiment 2: the temperature resistance of the hydrophobic associated polymer that contains the capsaicine activity monomer
The hydrophobic associated polymer that contains the capsaicine activity monomer in Preparation Example 1 and 2 and reference examples PAAC multipolymer are made into respectively to 0.5% the aqueous solution, at 20 ℃-100 ℃ of temperature, measure the apparent viscosity changing conditions of polymers soln, data are as Fig. 3.From Fig. 3, can find: three kinds of polymer solution viscosities are along with the rising of temperature is all on a declining curve; When temperature reaches 90 ℃, PAAC multipolymer viscosity degradation trend obviously slows down, and work as temperature, reaches 80 ℃, and the polymer viscosity downtrending that contains the capsaicine activity monomer obviously slows down; In the time of 100 ℃, the viscosity retention ratio of PAAC multipolymer is 36%, and the polymer viscosity retention rate of Preparation Example 1 and 2 reaches respectively more than 52% and 55%, illustrate that the hydrophobic associated polymer that contains the capsaicine activity monomer has viscosity save power preferably under comparatively high temps.
Performance test embodiment 3: the salt resistance of the hydrophobic associated polymer that contains the capsaicine activity monomer
The hydrophobic associated polymer that contains the capsaicine activity monomer, reference examples HPAM and PAAC in Preparation Example 1 are made into respectively to 0.5% the aqueous solution, are to measure the apparent viscosity of above-mentioned polymers soln under the 300-40000mg/L condition in NaCl concentration, as shown in Figure 4.As can be seen from Figure 4, the HPAM polymer solution viscosity is along with descend to adding sharply of NaCl, the PAAC polymer solution viscosity is along with decline to a great extent adding first of NaCl, the viscosity that adds along with NaCl after 20000mg/L tends towards stability, when NaCl concentration reaches 40000mg/L, two polymer viscosity retention rates are respectively 20.8% and 32.7%.Sharply rise after first slightly descending adding of NaCl containing the polymer solution viscosity of capsaicine activity monomer, salt thickening phenomenon occurs, illustrate that the polarity of solution increases, and impels the Interpolymer Association effect to strengthen due to the adding of inorganic salt, thus the soltion viscosity increase; After NaCl concentration surpasses 2700mg/L, soltion viscosity again descends and tends to be steady gradually, and when NaCl concentration reaches 40000mg/L, the polymer viscosity retention rate reaches 57%.Illustrate that the hydrophobic associated polymer that contains the capsaicine activity monomer has good salt resistant character.
Performance test embodiment 4: the microbial resistance of the hydrophobic associated polymer that contains the capsaicine activity monomer
The hydrophobic associated polymer that contains the capsaicine activity monomer, reference examples HPAM and PAAC in Preparation Example 1 are made into respectively to 0.2% the aqueous solution, by 10% inoculum size, the PM-2 Hydrolyzed Polyacrylamide Degrading Bacteria is proceeded in aqueous solutions of polymers, 37 ℃ of constant-temperature shaking culture, the results of regular determination soltion viscosity over time, obtains the relation of incubation time and soltion viscosity rate of loss.
As seen from Figure 5, the viscosity loss rate of shaking culture three kinds of aqueous solutions of polymers after 2 days all increases fast, after 9 days, tend towards stability, the viscosity loss rate of HPAM after 11 days of cultivating reaches 24%, the viscosity loss rate of PAAC reaches 21%, and in Preparation Example 1, the viscosity loss rate of polymkeric substance is 11%, illustrate contain the capsaicine activity monomer hydrophobic associated polymer there is good antimicrobial properties.
Hydrophobic associated polymer that contains the capsaicine activity monomer of the present invention and preparation method thereof is described by concrete example, those skilled in the art can use for reference content of the present invention, the links such as appropriate change raw material, processing condition realize corresponding other purpose, its relevant change does not all break away from content of the present invention, within all similar replacements and change will become apparent to those skilled in the art that and all be deemed to be included in scope of the present invention.
Claims (10)
1. a hydrophobic associated polymer that contains the capsaicine activity monomer, its structural formula is as follows:
Wherein: R is CH
3or H; R
1and R
2f, Cl, Br, OH, SH, OCH respectively do for oneself
3, SCH
3, OCH
2cH
3, CH
3, CH
2cH
3, CH (CH
3)
2or C (CH
3)
3; R
3for CH (CH
3)
2, CH
2cH=CH
2, CH
3, OH or H; R
4for CH
3or H; The weight-average molecular weight of described multipolymer is 50000～3000000; X, y, z is structural unit molecular fraction scope, x=70～92.5mol% wherein, y=7～20mol%, z=0.5～10mol%.
2. the preparation method of the hydrophobic associated polymer that contains the capsaicine activity monomer according to claim 1, is characterized in that, described preparation method comprises the steps:
Step 1: add successively acrylamide monomer, (methyl) Acrylic Acid Monomer and distilled water in reactor, three's weight part is respectively 60～90:9～20:300～480, is stirred to after monomer dissolves and uses NaOH regulation system pH value to 5～7; It is 10～30% that regulating pondage makes the total monomer quality percentage concentration;
Step 2: add the Surfactant SDS of 12～30 weight parts, add the acrylamide hydrophobic monomer containing capsaicine activity of 1～20 weight part after stirring; The logical water soluble starter of 0.12～1.2 weight part that adds after N220 minute reacts 2～12 hours at 30～80 ℃ of temperature, obtains transparent polymeric articles;
Step 3: use the dehydrated alcohol deposition and purification, 30～50 ℃ of lower vacuum-dryings, to constant weight, obtain the hydrophobic associated polymer that contains the capsaicine activity monomer of the present invention;
The described acrylamide hydrophobic monomer containing capsaicine activity is N-(4-hydroxy-3-methoxy-benzyl) acrylamide, the fluoro-benzyl of N-(4-hydroxyl-3-) acrylamide, the chloro-benzyl of N-(4-hydroxyl-3-) acrylamide, the bromo-benzyl of N-(4-hydroxyl-3-) acrylamide, N-(4-hydroxyl-3-methylthio group-benzyl) acrylamide, N-(3, 4-diethoxy phenyl) acrylamide, N-(3, the 4-Dimethoxyphenyl) acrylamide, the chloro-benzyl of N-(4-sulfydryl-3-) acrylamide, N-(4-sulfydryl-3-ethylmercapto group-benzyl) one or more in acrylamide.
3. method according to claim 2, is characterized in that, described water soluble starter is water-soluble azo compounds initiator or redox system initiator; Described water-soluble azo compounds is azo diisobutyl amidine hydrochloride or azo di-isopropyl tetrahydroglyoxaline; Described redox system is K
2s
2o
8and NaHSO
3, K
2s
2o
8and Na
2sO
3, K
2s
2o
8and Na
2s
2o
3, KMnO
4and NaHSO
3, KMnO
4and Na
2sO
3or KMnO
4and Na
2s
2o
3.
4. method according to claim 2, is characterized in that, in step 1, the weight part of acrylamide monomer, (methyl) vinylformic acid and distilled water is respectively: 65～85:12～16:350～480.
5. method according to claim 4, is characterized in that, in step 1, the weight part of acrylamide monomer, (methyl) vinylformic acid and distilled water is respectively: 70:14:400.
6. method according to claim 2, is characterized in that, the amount of the acrylamide hydrophobic monomer containing capsaicine activity added in step 2 is 5～15 weight weight parts.
7. method according to claim 6, is characterized in that, the amount of the acrylamide hydrophobic monomer containing capsaicine activity added in step 2 is 7～12 weight parts.
8. method according to claim 2, it is characterized in that, the described acrylamide hydrophobic monomer containing capsaicine activity is N-(4-hydroxy-3-methoxy-benzyl) acrylamide, the bromo-benzyl of N-(4-hydroxyl-3-) acrylamide, N-(4-hydroxyl-3-methylthio group-benzyl) acrylamide or N-(4-sulfydryl-3-ethylmercapto group-benzyl) acrylamide.
9. method according to claim 8, is characterized in that, the described acrylamide hydrophobic monomer containing capsaicine activity is N-(4-hydroxy-3-methoxy-benzyl) acrylamide and N-(4-hydroxyl-3-methylthio group-benzyl) acrylamide.
10. the hydrophobic associated polymer that contains the capsaicine activity monomer claimed in claim 1 is used as to the purposes of oil field oil-displacing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310382573.0A CN103435750B (en) | 2013-08-27 | 2013-08-27 | Hydrophobic associated polymer containing capsaicine activity monomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310382573.0A CN103435750B (en) | 2013-08-27 | 2013-08-27 | Hydrophobic associated polymer containing capsaicine activity monomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103435750A true CN103435750A (en) | 2013-12-11 |
| CN103435750B CN103435750B (en) | 2015-10-21 |
Family
ID=49689477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310382573.0A Active CN103435750B (en) | 2013-08-27 | 2013-08-27 | Hydrophobic associated polymer containing capsaicine activity monomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435750B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152130A (en) * | 2014-07-03 | 2014-11-19 | 西南石油大学 | AM /NaAA/NIDA hydrophobic association polymer oil displacement agent and synthetic method thereof |
| CN105085800A (en) * | 2015-09-06 | 2015-11-25 | 华鼎鸿基采油技术服务（北京）有限公司 | Heat-resistant and salt-tolerant polymer oil-displacing agent and preparation method thereof |
| CN105524215A (en) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | Heatproof salt-resistant acrylamide polymer microsphere dispersed system and preparation method and use thereof |
| CN105566565A (en) * | 2015-12-17 | 2016-05-11 | 中国海洋大学 | Hydrophobic association polymer with double bonds on side chains, method for preparing hydrophobic association polymer and application thereof |
| CN106496411A (en) * | 2016-11-04 | 2017-03-15 | 中国海洋大学 | A kind of purposes of the hydrophobic associated polymer with multiple ring structure side chains and preparation method thereof with it |
| CN108424491A (en) * | 2017-02-14 | 2018-08-21 | 中国石油化工股份有限公司 | A kind of acrylamide copolymer and its preparation method and application |
| CN108587286A (en) * | 2018-03-22 | 2018-09-28 | 福建师范大学 | A kind of preparation method of the coating of anti-marine biofouling |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405266A (en) * | 2002-10-28 | 2003-03-26 | 四川大学 | Method for preparing oil-displacing agent of high-tack-producing hydrophobic association polymer |
| CN1513890A (en) * | 2003-07-28 | 2004-07-21 | 西南石油学院 | AM/NaAA/AHAC trielement hylrophobic association polymer and its synthesis method |
| CN101486782A (en) * | 2008-11-22 | 2009-07-22 | 中国海洋大学 | Hydrophobic association polymer with carboxyl and capsaicine activity and preparation thereof |
-
2013
- 2013-08-27 CN CN201310382573.0A patent/CN103435750B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405266A (en) * | 2002-10-28 | 2003-03-26 | 四川大学 | Method for preparing oil-displacing agent of high-tack-producing hydrophobic association polymer |
| CN1513890A (en) * | 2003-07-28 | 2004-07-21 | 西南石油学院 | AM/NaAA/AHAC trielement hylrophobic association polymer and its synthesis method |
| CN101486782A (en) * | 2008-11-22 | 2009-07-22 | 中国海洋大学 | Hydrophobic association polymer with carboxyl and capsaicine activity and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 于良民等: ""新型疏水缔合聚合物的合成与性能评价"", 《石油地质与工程》, vol. 22, no. 3, 31 May 2008 (2008-05-31), pages 106 - 109 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152130A (en) * | 2014-07-03 | 2014-11-19 | 西南石油大学 | AM /NaAA/NIDA hydrophobic association polymer oil displacement agent and synthetic method thereof |
| CN104152130B (en) * | 2014-07-03 | 2016-12-07 | 西南石油大学 | AM/NaAA/NIDA hydrophobic associated polymer oil displacement agent and synthetic method thereof |
| CN105524215A (en) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | Heatproof salt-resistant acrylamide polymer microsphere dispersed system and preparation method and use thereof |
| CN105524215B (en) * | 2014-10-24 | 2019-07-05 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt acrylamide copolymer microballoon dispersion and its preparation method and application |
| CN105085800B (en) * | 2015-09-06 | 2017-06-16 | 华鼎鸿基采油技术服务（北京）有限公司 | A kind of Heat Resistant and Salt Tolerant Polymer oil displacement agent and preparation method thereof |
| CN105085800A (en) * | 2015-09-06 | 2015-11-25 | 华鼎鸿基采油技术服务（北京）有限公司 | Heat-resistant and salt-tolerant polymer oil-displacing agent and preparation method thereof |
| CN105566565A (en) * | 2015-12-17 | 2016-05-11 | 中国海洋大学 | Hydrophobic association polymer with double bonds on side chains, method for preparing hydrophobic association polymer and application thereof |
| CN106496411B (en) * | 2016-11-04 | 2018-11-23 | 中国海洋大学 | A kind of purposes of the hydrophobic associated polymer with a variety of ring structure side chains and preparation method thereof with it |
| CN106496411A (en) * | 2016-11-04 | 2017-03-15 | 中国海洋大学 | A kind of purposes of the hydrophobic associated polymer with multiple ring structure side chains and preparation method thereof with it |
| CN108424491A (en) * | 2017-02-14 | 2018-08-21 | 中国石油化工股份有限公司 | A kind of acrylamide copolymer and its preparation method and application |
| CN108424491B (en) * | 2017-02-14 | 2019-09-27 | 中国石油化工股份有限公司 | A kind of acrylamide copolymer and its preparation method and application |
| CN108587286A (en) * | 2018-03-22 | 2018-09-28 | 福建师范大学 | A kind of preparation method of the coating of anti-marine biofouling |
| CN108587286B (en) * | 2018-03-22 | 2020-10-30 | 福建师范大学 | Preparation method of marine organism fouling prevention coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103435750B (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435750B (en) | Hydrophobic associated polymer containing capsaicine activity monomer and preparation method thereof | |
| CN104448127B (en) | Polymer mobility control agent suitable for special high salinity reservoirs and preparation method thereof | |
| CN104448128B (en) | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent | |
| CN105566565B (en) | A kind of side chain contains the hydrophobic associated polymer of double bond, preparation method and the usage | |
| CN101293944B (en) | High adhesion-promotion salt resistant water-soluble copolymer, preparation method and application thereof | |
| CN106866878B (en) | Polymer-type profile control agent and preparation method thereof suitable for high temperature and high salt harshness oil reservoir | |
| CN104449636B (en) | Oil displacement agent of recovery ratio and preparation method thereof is improved suitable for high temperature and high salt harshness oil reservoir | |
| CN104650301B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN103483498B (en) | A kind of hydrophobic association amphoteric ion polymer and preparation method thereof | |
| CN106496411B (en) | A kind of purposes of the hydrophobic associated polymer with a variety of ring structure side chains and preparation method thereof with it | |
| CN101274974A (en) | Temperature-resistant water-soluble copolymer, preparation and use thereof | |
| CN106397694B (en) | A kind of micro- block hydrophobic associated polymer of high salt tolerance combed and preparation method thereof | |
| CN102260489A (en) | Branch-shaped comb polymer thickener, preparation method thereof and application thereof | |
| CN101205281A (en) | Water-soluble hydrophobic associated copolymer and preparation thereof | |
| CN104672408B (en) | A kind of water-soluble flooding polymers for having rigid core shell structure and preparation method thereof | |
| CN108676129A (en) | A kind of comb-type structure amphoteric ion polymer fluid loss additive and preparation method thereof | |
| CN102372820B (en) | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof | |
| CN115572347A (en) | High-temperature-resistant high-salt-resistant tackifying and shearing-improving agent for water-based drilling fluid and preparation method and application thereof | |
| CN102453252A (en) | Acrylamide macromonomer and comb type copolymer and preparation method and application thereof | |
| CN106084125B (en) | Copolymer suitable for extracting and cutting agent and its preparation method and application and saturated salt-water drilling fluid and its application | |
| CN102807503B (en) | Polymerizable monomer with surface activity and tackifying copolymer with surface activity as well as preparation methods and application thereof | |
| CN104628943A (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN102373051B (en) | Binary composite oil displacement agent and preparation method thereof | |
| CN102372647B (en) | Free radical polymerization functional monomer and synthesis method thereof | |
| CN100386403C (en) | Braided comb-shaped thickener for salt-resistant polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |