CN103483496A - Random copolymer, and preparation method and application thereof, and oil-displacing agent composition and preparing method of oil-displacing agent composition - Google Patents
Random copolymer, and preparation method and application thereof, and oil-displacing agent composition and preparing method of oil-displacing agent composition Download PDFInfo
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Abstract
The invention relates to a random copolymer, and a preparation method and an application thereof. The random copolymer contains a structural unit A and a structural unit B, wherein the structure of the structure unit A is selected from one or more structures represented by a formula (1) to a formula (4), and the structural unit B has the structure represented by a formula (5). With the total mole number of the structural units in the copolymer as a benchmark, the content of the structural unit A is 10-99.8 mol%, and the content of the structural unit B is 0.2-90 mol%; the viscosity average molecular weight of the copolymer is 12000000 to 30000000. The invention also relates to an oil-displacing agent composition and a preparation method thereof. The oil-displacing agent composition contains the random copolymer provided by the invention and a surfactant. The oil-displacing agent composition according to the invention has higher apparent viscosity, excellent temperature resistance and excellent salt resistance under conditions of high temperature and high degree of mineralization, and can greatly improve the recovery rate of petroleum.
Description
Technical field
The present invention relates to a kind of random copolymers, a kind of preparation method of random copolymers and the random copolymers prepared by the method, and described random copolymers the invention still further relates to a kind of oil-displacing agent composition and method of making the same as the application of polymer oil-displacing agent.
Background technology
In the whole bag of tricks that improves recovery ratio, polymer flooding occupies critical role.The effect of polymkeric substance is the rheological of regulating water filling, increases the viscosity that drives liquid, improves the water drive sweep efficiency.Reduce the local water phase permeability, water and oil can be flowed forward evenly.Polymer flooding is by add the polyacrylamide of a certain amount of high molecular in water filling, increase the viscosity of injected water, improve the flowing water mobility ratio, but there are some defects in polyacrylamide and the partially hydrolyzed polyacrylamide aqueous solution, as poor as the mechanical shearing stability, while being particularly useful for three class oil reservoir oil displacement agent, high temperature and high salt can cause that viscosity significantly loses.These defects have had a strong impact on the application of polyacrylamide under three class reservoir conditions.In order further to improve the viscosity of polyacrylamide, improve its temperature resistant antisalt, by with the novel functional monomer copolymerization process be an effective approach.
At present, the research salt-resistant polymer has two main paties both at home and abroad: the one, improve the hydromeehanics size that polymericular weight increases single polymer molecular chain as far as possible, consider that increasing the molecular chain rigidity increases the hydromeehanics size of polymkeric substance in the high salinity aqueous solution simultaneously, the 2nd, utilize the interaction between molecular chain, form by association the hydromeehanics size that supramolecular structure increases the molecule chain bundle, reach the purpose of high-effective viscosity.
Even increase the purpose of molecular weight, be to guarantee that although polymer solution viscosity can lose, because polymericular weight is high, corresponding its absolute viscosity will be higher, thereby meet the requirement of working fluid to the polymer viscosified ability under high salinity media.Yet there are some defects in this method: be at first the synthetic difficulty of high-molecular weight polymer, secondly polymericular weight is higher, and the polymer dissolution problem has difficulties.At present, this base polymer both domestic and external, under clear water and lesser temps, can meet the requirement of oil field to displacement of reservoir oil product.But can not meet the requirement of oil field to displacement of reservoir oil product in high-salinity water quality.
Introduce the monomeric unit of some high thermal stability monomeric units, larger skeleton and the group of strong hydratability on polymer molecular chain, thereby strengthen polymer thermostable and molecule chain rigidity, make polymer molecule can keep larger ydrodynamics size in the high salinity aqueous solution, this has strengthened the polymkeric substance salt resistance ability to a certain extent.Simultaneously, the introducing of function monomer, make polymkeric substance be restricted in high-salinity water quality Water Under solution, not there will be the phenomenon that precipitation occurs with calcium ions and magnesium ions, thereby reach the purpose of anti-salt.Therefore, study and develop good, heat-resisting, the anti-salt of thickening property, use properties is good and the good polymer oil-displacing agent of over-all properties such as cheap has become the emphasis direction of industry member, academia's research and development.
In addition, in the chemical flooding of used for tertiary oil recovery, tensio-active agent also occupies very consequence, and it can reduce oil water interfacial tension, and irreducible oil " is come out by force ", to improving recovery ratio, plays immeasurable effect.But, existing decreasing by surfactant interfacial tension limited in one's ability, oil displacement efficiency is still as one wishes not to the utmost.
Summary of the invention
The objective of the invention is, in order to overcome the defect of above-mentioned prior art, provides random copolymers that a kind of molecular weight is large, apparent viscosity is high, heat-resisting and salt tolerance is high and its preparation method and application.
Another object of the present invention is the defect that overcomes above-mentioned prior art, and the oil-displacing agent that a kind of apparent viscosity is high, heat-resisting and anti-salt property is excellent composition and method of making the same is provided.
The invention provides a kind of unregulated polymer, wherein, this unregulated polymer contains structural unit A and structural unit B, and described structural unit A is selected from formula (1) to one or more in structure shown in formula (4), and described structural unit B is the structure shown in formula (5); And the total mole number of structural unit in described polymkeric substance of take is benchmark, and the content of described structural unit A is 10-99.8 % by mole, is preferably 70-99.8 % by mole, more preferably 99-99.8 % by mole; The content of described structural unit B is 0.2-90 % by mole, is preferably 0.2-30 % by mole, more preferably 0.2-1 % by mole; The viscosity-average molecular weight of described polymkeric substance is 1,200 ten thousand-3,000 ten thousand, is preferably 1,500 ten thousand-2,600 ten thousand;
Wherein, R
1for hydrogen or C
1-C
4alkyl; R
2and R
3identical or different, and the C that respectively does for oneself
1-C
4alkyl; R
4for C
1-C
4alkylidene group; R
5for C
11-C
24alkyl; M
1for hydrogen, sodium or potassium; N is 0 or 1.
The present invention also provides a kind of preparation method of random copolymers, wherein, the method is included under the solution polymerization condition, under the existence of initiator, make monomer mixture carry out polyreaction in water, it is 1,200 ten thousand-3,000 ten thousand that the condition of polyreaction makes the viscosity-average molecular weight of the polymkeric substance that obtains, is preferably 1,500 ten thousand-2,600 ten thousand; Described monomer mixture contains monomer C and monomer D, described monomer C is selected from formula (6) to one or more in structure shown in formula (9), described monomer D is the structure shown in formula (10), and the total mole number of described monomer mixture of take is benchmark, the content of described monomer C is 10-99.8 % by mole, be preferably 70-99.8 % by mole, more preferably 99-99.8 % by mole; The content of described monomer D is 0.2-90 % by mole, is preferably 0.2-30 % by mole, more preferably 0.2-1 % by mole;
Wherein, R
6for hydrogen or C
1-C
4alkyl; R
7and R
8identical or different, and the C that respectively does for oneself
1-C
4alkyl; R
9for C
1-C
4alkylidene group; R
10for C
11-C
24alkyl; M
2for hydrogen, sodium or potassium; N is 0 or 1.
In addition, the present invention also provides the application as polymer oil-displacing agent of the random copolymers that made by above-mentioned preparation method and above-mentioned random copolymers.
The present invention also provides a kind of oil-displacing agent composition, and this oil-displacing agent composition contains described random copolymers provided by the invention and tensio-active agent.
The present invention also provides a kind of preparation method of oil-displacing agent composition, and the method comprises random copolymers and tensio-active agent are mixed, and wherein, described random copolymers is described random copolymers provided by the invention.
The present invention also provides a kind of oil-displacing agent composition made by aforesaid method.
Random copolymers provided by the invention has very high viscosity-average molecular weight, and the apparent viscosity of the solution made by it is high: the viscosity-average molecular weight of the ternary atactic copolymer that embodiment 1-4 makes all reaches more than 1,200 ten thousand; And the solution that the concentration that the salt solution that is 32868mg/L by salinity is mixed with corresponding multipolymer is 1500mg/L is 7.34s in shearing rate
-1, under the temperature condition that is 85 ℃, still there is higher apparent viscosity value.Itself and tensio-active agent are used in conjunction with, give full play to synergistic effect, the oil-displacing agent composition of gained has higher apparent viscosity, and more excellent heatproof and anti-salt property can improve the recovery ratio of oil greatly.
The accompanying drawing explanation
Fig. 1 is the infrared spectrum of the random copolymers that prepared by embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of random copolymers, wherein, this unregulated polymer contains structural unit A and structural unit B, wherein, described structural unit A is selected from formula (1) to one or more in structure shown in formula (4), and described structural unit B is the structure shown in formula (5); And the total mole number of structural unit in described polymkeric substance of take is benchmark, and the content of described structural unit A is 10-99.8 % by mole,, be preferably 70-99.8 % by mole, more preferably 99-99.8 % by mole; The content of described structural unit B is 0.2-90 % by mole, is preferably 0.2-30 % by mole, more preferably 0.2-1 % by mole; The viscosity-average molecular weight of described polymkeric substance is 1,200 ten thousand-3,000 ten thousand, is preferably 1,500 ten thousand-2,600 ten thousand,
Wherein, R
1can be hydrogen or C
1-C
4alkyl, particularly, R
1be selected from a kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl; R
2and R
3identical or different, and can be C separately
1-C
4alkyl, particularly, R
2and R
3a kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl; R
4can be C
1-C
4alkylidene group, particularly, R
4a kind of in methylene radical, ethylidene, trimethylene, tetramethylene; R
5can be C
11-C
24alkyl, preferably, R
5for C
11-C
24straight chained alkyl or C
11-C
24the straight monoene alkyl; M
1can be hydrogen, sodium or potassium; N can be 0 or 1.Preferably, R
5for undecyl or 8-17 thiazolinyls.
According to the present invention, in random copolymers, structural unit A can at random be combined by formula (1) to the structural unit shown in formula (4).In the preferred case, described structural unit A comprises the structural unit shown in formula (1) and is selected from formula (2) at least one in the structural unit shown in formula (4).Further preferably, described structural unit A comprises the structural unit shown in formula (1) and is selected from formula (2) to any one in the structural unit shown in formula (4).The present invention is not particularly limited the ratio of the said structure unit that comprises in structural unit A, and preferably, the structural unit shown in described formula (1) and formula (2) to the ratio of the structural unit shown in formula (4) is 8-12:1.
The present inventor is through in depth research discovery, and described structural unit A is the structural unit shown in the structural unit shown in formula (1) and formula (3), and the oil displacement efficiency of the random copolymers of gained is fabulous.
The present invention also provides a kind of preparation method of random copolymers, wherein, the method is included under the solution polymerization condition, under the existence of initiator, make monomer mixture carry out polyreaction in water, it is 1,200 ten thousand-3,000 ten thousand that the condition of polyreaction makes the viscosity-average molecular weight of the polymkeric substance that obtains, is preferably 1,500 ten thousand-2,600 ten thousand; Described monomer mixture contains monomer C and monomer D, described monomer C is selected from formula (6) to one or more in structure shown in formula (9), described monomer D is the structure shown in formula (10), and the total mole number of described monomer mixture of take is benchmark, the content of described monomer C is 10-99.8 % by mole, be preferably 70-99.8 % by mole, more preferably 99-99.8 % by mole; The content of described monomer D is 0.2-90 % by mole, is preferably 0.2-30 % by mole, more preferably 0.2-1 % by mole;
Wherein, R
6for hydrogen or C
1-C
4alkyl; R
7and R
8identical or different, and the C that respectively does for oneself
1-C
4alkyl; R
9for C
1-C
4alkylidene group; R
10for C
11-C
24alkyl; M
2for hydrogen, sodium or potassium; N is 0 or 1.Preferably, R
5for undecyl or 8-17 thiazolinyls.
According to the present invention, monomer C can at random be combined by the monomer to structure shown in formula (9) by formula (6).In the preferred case, described monomer C comprises the monomer of structure shown in formula (6) and is selected from formula (7) at least one in the monomer of structure shown in formula (9).Further preferably, described monomer C comprises the monomer of structure shown in formula (6) and is selected from formula (7) to any one in the monomer of structure shown in formula (9).The present invention is not particularly limited the ratio of the above-mentioned monomer that comprises in monomer C, and preferably, the monomer of structure shown in described formula (6) and formula (7) to the ratio of the monomer of structure shown in formula (9) is 8-12:1.
The present inventor finds through in depth research, and when the monomer of structure shown in the described monomer C monomer that is structure shown in formula (6) and formula (8), the oil displacement efficiency of the random copolymers prepared is fabulous.
According to the present invention, when described polyreaction starts, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture can in very large range change, and under preferable case, described ratio is 0.1-0.4:1.
The present invention is not particularly limited the consumption of described initiator, but, in order to take into account the size of trigger rate and copolymerization molecular weight of product, the consumption of described initiator is preferably the 0.01-0.1% of monomer mixture gross weight, more preferably 0.03-0.08%.Described initiator can be one or more in the various radical initiators in this area, and described radical initiator comprises azo initiator, peroxide initiator and redox initiator.The present inventor is surprised to find that, while adopting any two kinds of trigger monomer polymerizations in radical initiator, can obtain the polymerisate that molecular weight is higher, therefore, in the preferred case, described initiator is selected from any two kinds in azo initiator, peroxide initiator and redox initiator.
According to the present invention, described azo initiator is selected from one or more in azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline salt hydrochlorate, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile).Described peroxide initiator is selected from hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, one or more in benzoyl peroxide and the benzoyl peroxide tert-butyl ester.Described redox initiator is selected from one or more in vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide.Wherein, described vitriol-sulphite can be selected from one or more in sodium sulfate-S-WAT, vitriolate of tartar-potassium sulfite, ammonium sulfate-ammonium sulphite; Persulphate-thiocarbamide can be selected from one or more in Sodium Persulfate-thiocarbamide, Potassium Persulphate-thiocarbamide, ammonium persulphate-thiocarbamide; Persulphate-organic salt can be selected from one or more in Sodium Persulfate-Potassium ethanoate, Potassium Persulphate-Potassium ethanoate, ammonium persulphate-ammonium acetate; Ammonium persulphate-aliphatic amide can be selected from ammonium persulphate-N, one or more in N-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
According to the present invention, the condition of polyreaction can be the condition of this area routine.In order to overcome the inhibition of oxygen, obtain having the copolymerization product of larger molecular weight, in the preferred case, described polyreaction is carried out in inert atmosphere, such as can in reaction system, passing into the rare gas elementes such as nitrogen.The condition of polyreaction can comprise that temperature of reaction is 0-80 ℃, and preferred temperature of reaction is 0-60 ℃; Reaction times is 1-24 hour, and the preferred reaction times is 4-18 hour; The pH value of reaction system solution is 4-11, and preferred pH value is 8-11.Wherein, the pH value of reaction system solution is regulated by the amount that adds alkali, the various alkali that described alkali can select this area common regulator solution pH value to use, and preferred described alkali is sodium hydroxide and/or sodium carbonate.
The present inventor finds under study for action, takes following condition can access the ultra-high molecular weight random copolymers,, preferably, described polyreaction comprises two stages of carrying out successively, and the reaction conditions of first stage comprises that temperature of reaction is 0-20 ℃, and the reaction times is 1-8 hour; The reaction conditions of subordinate phase comprises that temperature of reaction is 40-80 ℃, and the reaction times is 1-4 hour.
According to the present invention, the monomer D shown in formula (10) can prepare by the preparation method who comprises the following steps:
(1) under the condensation reaction condition, the carboxylic acid that aromatic diamines that general formula is (11) is R-COOH with general formula is contacted, obtain intermediate M, wherein, n be 0 or 1, R be C
11-C
24alkyl, intermediate M as the formula (12):
(2) under amidation reaction condition, MALEIC ANHYDRIDE is contacted with described intermediate M, obtain the monomer D shown in formula (10).
According to the preparation method of monomer D of the present invention, particularly, the aromatic diamines that general formula is (11) can Ursol D or p dimethylamine; The carboxylic acid that general formula is R-COOH can be C for R
11-C
24alkyl or C
11-C
24the carboxylic acid of alkylene, preferably R is C
11-C
24straight chained alkyl or C
11-C
24the carboxylic acid of monoene alkyl.In further preferred situation, the aromatic diamines that general formula is (11) is Ursol D, and the carboxylic acid that general formula is R-COOH is lauric acid/or oleic acid; The aromatic diamines that perhaps general formula is (11) is the p dimethylamine, and the carboxylic acid that general formula is R-COOH is lauric acid/or oleic acid.
The mol ratio that the aromatic diamines that the present invention is (11) to step (1) formula of and the carboxylic acid that general formula is R-COOH add is not particularly limited, as long as meet and can obtain the intermediate M shown in formula (12), in the preferred case, the mol ratio that the aromatic diamines that general formula is (11) and the carboxylic acid that general formula is R-COOH add is 1:1-1.2.Similarly, the present invention is not particularly limited the amount of the MALEIC ANHYDRIDE that adds in step (2), as long as meet and can obtain the monomer D shown in formula (10), in the preferred case, the aromatic diamines that step (1) formula of is (11) and the mol ratio that the MALEIC ANHYDRIDE described in step (2) adds are 1:1-1.2.
According to the present invention, above-mentioned amidation reaction condition and condensation reaction condition can be all the condition of this area routine, as described in the condensation reaction condition comprise that temperature of reaction is 110-160 ℃, the reaction times is 2-6 hour; Described amidation reaction condition comprises that temperature of reaction is 80-110 ℃; Reaction times is 4-8 hour.
According to the present invention, for conditioned reaction speed, in the preferred case, described amidate action and/or condensation reaction are carried out under organic solvent exists, and the add-on of organic solvent can be selected within a large range.For example: add organic solvent in step (1), the aromatic diamines that general formula is (11) and the mol ratio that organic solvent adds are 1:5-20, more preferably 1:10-15; Add organic solvent in step (2), the aromatic diamines that general formula is (11) and the mol ratio that organic solvent adds are 1:20-30, more preferably 1:20-25.
According to the present invention, above-mentioned organic solvent can be the organic solvent of various routines known in those skilled in the art, in the preferred case, described organic solvent is selected from one or more in acetone, ethyl acetate, benzene, dimethylbenzene, methylene dichloride and trichloromethane.
According to the present invention, the preparation method of monomer D can also comprise monomer D is carried out to the recrystallization purification, and the solvent that recrystallization is used can be one or more in ethanol, acetone, hexane.The condition of carrying out the re-crystallization step of polymerisable monomer adopts condition well known in the art.
The amidate action and the condensation reaction that due to the preparation method of polymerisable monomer provided by the invention, relate to are reaction known in this field and that the Direction of Reaction is very clear and definite, so the structure of the structure of polymerisable monomer and intermediate M can be confirmed by raw material association reaction principle.Also can be confirmed by nuclear-magnetism and/or infrared spectrum.
According to the present invention, above-mentioned reaction is carried out in reactor, and described reactor can be the organic reaction container of various routines, can be for example various flasks or polymerization bottle.In order to make reaction system more even, the preferred above-mentioned reaction of the present invention is carried out under agitation condition.
The present invention also provides the random copolymers made according to aforesaid method.
In addition, the present invention above-mentioned random copolymers also is provided and the random copolymers for preparing by aforesaid method as the application of polymer oil-displacing agent.
According to oil-displacing agent composition of the present invention, this oil-displacing agent composition contains random copolymers of the present invention and tensio-active agent.
According to oil-displacing agent composition provided by the invention, above-mentioned random copolymers and the content of tensio-active agent can change within a large range.In the preferred case, the consumption of described random copolymers and tensio-active agent makes, and the gross weight of oil-displacing agent composition of take is benchmark, and the content of described random copolymers is the 30-90 % by weight, more preferably the 60-90 % by weight; The content of described tensio-active agent is the 10-70 % by weight, more preferably the 10-40 % by weight.
According to the present invention, described tensio-active agent can be the various tensio-active agents that can be used for improving oil recovery known in those skilled in the art, under preferable case, described tensio-active agent is selected from alkylaryl sulfonate surfactants, the alkylaryl sulfonate tensio-active agent, the polyethenoxy ether sulphonate tensio-active agent, the sulphosuccinates tensio-active agent, petroleum sulfonate surfactant, petroleum carboxylate surfactant, the amido-carboxylic acid salt surfactant, one or more in polyethenoxy ether carboxylate tensio-active agent and polyoxyethylene phosphate surfactant active.Metal ion in preferred described tensio-active agent is preferably a kind of in sodium, potassium, calcium.In addition, described alkyl carbon atoms number is 6-28, and described aromatic ring number is 1-5.
Described alkylaryl sulfonate surfactants can be for example one or more in dodecyl diphenyl oxide sodium sulfonate, dialkyl group phenyl ether disulfonic acid sodium, sodium dialkyl diphenyl ether monosulfonate.
Described alkylaryl sulfonate tensio-active agent can be for example phenyl sodium laurylsulfonate and/or alkyl phenolic group sodium laurylsulfonate.
Described polyethenoxy ether sulphonate tensio-active agent can be for example one or more in aliphatic alcohol polyoxyethylene sulfonate tensio-active agent, alkylphenol polyoxyethylene sulfosalt surfactant, alkyl phenyl polyethenoxy ether sulphonate tensio-active agent.
Described sulphosuccinates tensio-active agent can be for example mono succinate sodium sulfonate and/or sodium sulfosuccinic diester.
Described amido-carboxylic acid salt surfactant can be for example one or more in 2,4-dichloro-5-sulfonyl benzoic acid sodium, the chloro-5-sulfamoylbenzoic acid of 4-sodium, the chloro-3-sulfamoylbenzoic acid of 4-sodium.
Described polyethenoxy ether carboxylate tensio-active agent can be for example one or more in aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent, alkylphenol polyoxyethylene carboxylate surface active agent, alkyl phenyl polyethenoxy ether carboxylate tensio-active agent.
The molecular weight that described polyoxyethylene phosphate surfactant active is polyoxyethylene groups wherein is at the polyoxyethylene phosphate surfactant active of 100-400.
According to the preparation method of oil-displacing agent composition of the present invention, the method comprises random copolymers and tensio-active agent mixed, and wherein, described random copolymers is described random copolymers provided by the invention.
To the mixing temperature of random copolymers and tensio-active agent and mixing time, there is no particular limitation in the present invention, as long as make to mix between component, preferably, mixing temperature is 10-40 ℃, more preferably 20-30 ℃; Described mixing time is 60-150min, is preferably 90-120min.
The oil-displacing agent composition that aforesaid method according to the present invention makes.
The present invention is described in detail by the following examples.
Unless stated otherwise, in preparation example of the present invention, embodiment and Comparative Examples, agents useful for same all can be commercially available.
Preparation example 1
This preparation example is for illustrating the preparation of the polymerisable monomer that the present invention is used.
(1) preparation of intermediate
Measure 150 milliliters of dimethylbenzene, join in the there-necked flask of the Ursol D that is added with 0.1mol and 0.1mol oleic acid, be heated to 130 ℃, react 2 hours, obtain containing the product of intermediate as the formula (13).
(2) preparation of polymerisable monomer
In step (1) products therefrom, add the MALEIC ANHYDRIDE of 0.1mol, under 80 ℃, reaction was filtered after 6 hours, then with acetone solvent, the product that filters gained was carried out to recrystallization, obtained the polymerisable monomer D1 of 0.09mol.
Preparation example 2
This preparation example is for illustrating the preparation of the polymerisable monomer that the present invention is used.
(1) preparation of intermediate
Measure 150 milliliters of dimethylbenzene, join in the there-necked flask of the p dimethylamine that is added with 0.1mol and 0.1mol oleic acid, be heated to 150 ℃, react 6 hours, obtain containing the product of intermediate as the formula (14).
(2) preparation of polymerisable monomer
In step (1) products therefrom, add the MALEIC ANHYDRIDE of 0.1mol, under 110 ℃, back flow reaction, after 8 hours, steams solvent, and drying obtains free radical polymerizable functional monomer product, is designated as polymerisable monomer D2.With infrared spectroscopy, D2 is characterized, IR spectrogram and Fig. 1 are similar as a result.
Preparation example 3
This preparation example is for illustrating the preparation of polymerisable monomer provided by the invention.
(1) preparation of intermediate
Measure 150 milliliters of dimethylbenzene, join in the there-necked flask that the Ursol D that is added with 0.1mol mixes with the 0.1mol lauric acid, be heated to 140 ℃, react 4 hours, obtain containing the product of intermediate as the formula (15).
(2) preparation of polymerisable monomer
In step (1) products therefrom, be added dropwise to the MALEIC ANHYDRIDE of 0.1mol, under 90 ℃, reaction steamed solvent after 5 hours, and drying, obtain free radical polymerizable functional monomer product, is designated as monomer D3.With infrared spectroscopy, D3 is characterized, IR spectrogram and Fig. 1 are similar as a result.
Preparation example 4
(1) preparation of intermediate
Measure 150 milliliters of dimethylbenzene, join in the there-necked flask that the p dimethylamine that is added with 0.1mol mixes with the 0.1mol lauric acid, be heated to 140 ℃, react 4 hours, obtain containing the product of intermediate as the formula (16).
(2) preparation of polymerisable monomer
In step (1) products therefrom, be added dropwise to the MALEIC ANHYDRIDE of 0.1mol, under 90 ℃, reaction steamed solvent after 5 hours, and drying, obtain free radical polymerizable functional monomer product, is designated as monomer D4.With infrared spectroscopy, D4 is characterized, IR spectrogram and Fig. 1 are similar as a result.
Embodiment 1-4
These embodiment are the preparation by random copolymers provided by the invention for explanation.
Take acrylamide 4.75 grams, 5.25 gram 2-acrylamide-2-methyl propane sulfonic and 0.15 gram polymerisable monomer D1 are made into the aqueous solution, regulate the pH value to alkalescence (pH=6) with aqueous sodium hydroxide solution, add 3.0 milligrams of azo-bis-isobutyrate hydrochlorides (AIBA), under nitrogen protection, add 6.0 milligrams of ammonium persulphates, 20 ℃ of polymerizations of temperature are after 8 hours, be warming up to again 55 ℃, continue polymerization 4 hours, the gained colloid is taken out, granulation, dry, pulverize, obtain white powder acrylamide water-soluble polymers product, be designated as polymer P 1, the test polymer molecular weight is 1,900 ten thousand, at salinity 32868mg/L, apparent viscosity at 85 ℃ of temperature is 20.5mPas.
With infrared spectroscopy, P1 is characterized, result as shown in Figure 1, wherein, 3567.4cm
-1for-NH
2vibration absorption peak, 3482.1cm
-1for-the NH-vibration absorption peak; 2872.1cm
-1, 2933.8cm
-1for-CH
3with-CH
2-symmetry and asymmetric stretching vibration absorption peak, 1684.0cm
-1for the stretching vibration peak of-C=O, 1456.6cm
-1for typical-CH
2-scissoring vibration; 1541.0cm
-1for-the COO-vibration absorption peak; 1307.7cm
-1, 1188.0cm
-1and 1039.0cm
-1for-SO
3-symmetrical and asymmetric vibration absorption peak; 3208.8cm
-1with 1600 ~ 1450cm
-1three absorption peaks at place, illustrate the existence of phenyl ring.The charateristic avsorption band of three kinds of structural units all appears in infrared spectra, shows that this multipolymer is comprised of these three kinds of structural units.
Use respectively according to the method described above above-mentioned polymerisable monomer D2-D4 to prepare polymer P 2-P4.
Comparative Examples 1
The polymerisable monomer D1-D4 that this Comparative Examples does not add preparation example 1-4 of the present invention to prepare for explanation.
Take acrylamide 4.75 grams, 5.25 gram 2-acrylamide-2-methyl propane sulfonic is made into the aqueous solution, regulate the pH value to alkalescence (pH=8) with aqueous sodium hydroxide solution, add 3.0 milligrams of azo-bis-isobutyrate hydrochlorides (AIBA), under nitrogen protection, add 6.0 milligrams of ammonium persulphates, first select 20 ℃ of temperature, after polymerization 8 hours, be warming up to again 55 ℃, continue polymerization 4 hours, the gained colloid is taken out, granulation, dry, pulverize, obtain white powder acrylamide water-soluble polymers product, be designated as polymkeric substance DP, the test polymer molecular weight is 1,300 ten thousand, salinity 32868mg/L, apparent viscosity at 85 ℃ of temperature is 12.4mPas.
Embodiment 5-9
Embodiment 5
The present embodiment is for illustrating the preparation of oil-displacing agent composition provided by the invention.
By the polymer P of 0.3g 1 stirring and dissolving 1.5h in 200g salt brine solution (gross weight of salt brine solution of take is benchmark, and the content of calcium ion is 0.04 % by weight, and the content of magnesium ion is 0.0377 % by weight, and the content of sodium-chlor is 2.9 % by weight).Add 0.1g Sodium dodecylbenzene sulfonate (Beijing Chemical Plant) again in above-mentioned solution, under 25 ℃, be uniformly mixed 100min, obtain oil-displacing agent composition Q1.
Embodiment 6
According to embodiment 1, identical method prepares oil-displacing agent composition Q2, and different is uses polymer P 2 to replace polymer Ps 1, and dodecyl diphenyl oxide sodium sulfonate (the great global oilfield technology of grand celebration Services Co., Ltd produces) replaces Sodium dodecylbenzene sulfonate.
The present embodiment is for illustrating oil-displacing agent composition provided by the invention.
According to embodiment 1, identical method prepares oil-displacing agent composition Q3, different is to use polymer P 3 to replace polymer P 1, sulfonated petro-leum (to form: actives 60 % by weight, oil 20 % by weight, salt 1.5 % by weight, water 18.5 % by weight, in actives, single sulfonic acid accounts for 90 % by weight, and disulfonic acid and many sulfonic acid account for 10 % by weight; Producer: replace Sodium dodecylbenzene sulfonate the great global oilfield technology of grand celebration Services Co., Ltd).
Embodiment 8
The present embodiment is for illustrating oil-displacing agent composition provided by the invention.
According to embodiment 1, identical method prepares oil-displacing agent composition Q4, and different is to use polymer P 4 to replace polymer P 1, oil carboxylic acid sodium (to form: activeconstituents 58 % by weight, oily 18 % by weight, salt 2.5 % by weight, water 21.5 % by weight; Producer: replace Sodium dodecylbenzene sulfonate the great global oilfield technology of grand celebration Services Co., Ltd).
Embodiment 9
The present embodiment is for illustrating oil-displacing agent composition provided by the invention.
According to embodiment 1, identical method prepares oil-displacing agent composition Q5, different is to use polymer P 4 to replace polymer P 1, sulfonated petro-leum (to form: actives 60 % by weight, oil 20 % by weight, salt 1.5 % by weight, water 18.5 % by weight, in actives, single sulfonic acid accounts for 90 % by weight, and disulfonic acid and many sulfonic acid account for 10 % by weight; Producer: replace Sodium dodecylbenzene sulfonate the great global oilfield technology of grand celebration Services Co., Ltd).
Comparative Examples 2
Method according to embodiment 5 prepares oil-displacing agent composition DQ1, and different is to use polymkeric substance DP to replace polymer P 1.
The intrinsic viscosity of polymer P 1-P4 and DP is measured according to GB12005.1-89 For Intrinsic Viscosity Measurements method; Viscosity-average molecular weight is according to formula M
η=([η]/K)
1/ α, K=4.5 * 10 wherein
-3, α=0.80 is calculated; The apparent viscosity of aqueous solutions of polymers is 7.34s by BROOKFIELD DV-III viscosity apparatus in the rotating speed perseverance
-1, measure and obtain under the condition that temperature is 25 ℃ and 85 ℃, wherein, test condition comprises: polymer concentration is 1500mg/L, the solution total mineralization is 32868mg/L.Test result is as shown in table 1.The apparent viscosity of oil-displacing agent composition adopts the testing method identical with aqueous solutions of polymers to obtain, and result is as shown in table 2.
Table 1
| Mη(×10 4) | η25(mPa·s) | η85(mPa·s) | |
| P1 | 1900 | 36.8 | 20.5 |
| P2 | 1800 | 33.1 | 19.2 |
| P3 | 1600 | 30.9 | 17.6 |
| P4 | 1500 | 29.0 | 16.8 |
| DP | 1300 | 22.9 | 12.4 |
The viscosity-average molecular weight of M η representation polymer in table 1, η 25 represents the apparent viscosity of 25 ℃ of lower aqueous solutions of polymers, η 85 represents the apparent viscosity of 85 ℃ of lower aqueous solutions of polymers.The data of P1-P4 in table 1 and the data of contrast preparation example DP are compared, can find out adopt method of the present invention to prepare polymer P 1-P4 at normal temperatures (25 ℃) have the apparent viscosity of very high aqueous solutions of polymers, and still can keep the apparent viscosity of very high aqueous solutions of polymers when it under the condition of high temperature (85 ℃), high salinity (32868mg/L).
Table 2
| η25(mPa·s) | η85(mPa·s) | |
| Q1 | 37.3 | 21.6 |
| Q2 | 35.2 | 20.8 |
| Q3 | 34.0 | 19.4 |
| Q4 | 31.6 | 18.3 |
| Q5 | 33.6 | 19.8 |
| DQ1 | 25.6 | 13.1 |
In table 2, η 25 represents the apparent viscosity of 25 ℃ of lower oil-displacing agent compositions, and η 85 represents the apparent viscosity of 85 ℃ of lower oil-displacing agent compositions.By the data in table 2, with the data in table 1, compared, can find out the oil-displacing agent composition viscosity that adopts method of the present invention the to prepare viscosity higher than single polymerization oil-displacing agent, (25 ℃) have very high apparent viscosity at normal temperatures, and still can keep very high apparent viscosity when it under the condition of high temperature (85 ℃), high salinity (32868mg/L).
Claims (18)
1. a unregulated polymer, it is characterized in that, this unregulated polymer contains structural unit A and structural unit B, wherein, described structural unit A is selected from formula (1) to one or more in structure shown in formula (4), and described structural unit B is the structure shown in formula (5); And the total mole number of structural unit in described polymkeric substance of take is benchmark, and the content of described structural unit A is 10-99.8 % by mole, is preferably 70-99.8 % by mole, more preferably 99-99.8 % by mole; The content of described structural unit B is 0.2-90 % by mole, is preferably 0.2-30 % by mole, more preferably 0.2-1 % by mole; The viscosity-average molecular weight of described polymkeric substance is 1,200 ten thousand-3,000 ten thousand, is preferably 1,500 ten thousand-2,600 ten thousand,
Wherein, R
1for hydrogen or C
1-C
4alkyl; R
2and R
3identical or different, and the C that respectively does for oneself
1-C
4alkyl; R
4for C
1-C
4alkylidene group; R
5for C
11-C
24alkyl; M
1for hydrogen, sodium or potassium; N is 0 or 1.
2. random copolymers according to claim 1, wherein, described structural unit A comprises the structural unit shown in formula (1) and is selected from formula (2) at least one in the structural unit shown in formula (4); Preferably, described structural unit A comprises the structural unit shown in formula (1) and is selected from formula (2) to any one in the structural unit shown in formula (4).
3. random copolymers according to claim 1 and 2, wherein, described structural unit A is the structural unit shown in the structural unit shown in formula (1) and formula (3).
4. the preparation method of a random copolymers, it is characterized in that, the method is included under the solution polymerization condition, under the existence of initiator, make monomer mixture carry out polyreaction in water, it is 1,200 ten thousand-3,000 ten thousand that the condition of polyreaction makes the viscosity-average molecular weight of the polymkeric substance that obtains, is preferably 1,500 ten thousand-2,600 ten thousand; Described monomer mixture contains monomer C and monomer D, described monomer C is selected from formula (6) to one or more in structure shown in formula (9), described monomer D is the structure shown in formula (10), and the total mole number of described monomer mixture of take is benchmark, the content of described monomer C is 10-99.8 % by mole, be preferably 70-99.8 % by mole, more preferably 99-99.8 % by mole; The content of described monomer D is 0.2-90 % by mole, is preferably 0.2-30 % by mole, more preferably 0.2-1 % by mole;
Wherein, R
6for hydrogen or C
1-C
4alkyl; R
7and R
8identical or different, and the C that respectively does for oneself
1-C
4alkyl; R
9for C
1-C
4alkylidene group; R
10for C
11-C
24alkyl; M
2for hydrogen, sodium or potassium; N is 0 or 1.
5. method according to claim 4, wherein, described monomer C comprises the monomer of structure shown in formula (6) and is selected from least one in the monomer of structure shown in formula (7)-Shi (9), preferably, described monomer C comprises the monomer of structure shown in formula (6) and is selected from any one in the monomer of structure shown in formula (7)-Shi (9).
6. according to the described method of claim 4 or 5, wherein, the monomer of structure shown in the monomer that described monomer C is structure shown in formula (6) and formula (8).
7. method according to claim 4, wherein, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.1-0.4:1.
8. method according to claim 4, wherein, the 0.01-0.1% that the weight of described initiator is described monomer mixture gross weight; Described initiator is selected from least two kinds in azo initiator, peroxide initiator and redox initiator.
9. method according to claim 8, wherein, described azo initiator is selected from one or more in azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline salt hydrochlorate, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile); Described peroxide initiator is selected from hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, one or more in benzoyl peroxide and the benzoyl peroxide tert-butyl ester; Described redox initiator is selected from one or more in vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide.
10. method according to claim 4, wherein, described polymeric reaction condition comprises that the pH value is for 4-11, described polyreaction is carried out in inert atmosphere; Described polyreaction comprises two stages of carrying out successively, and the reaction conditions of first stage comprises: temperature is 0-20 ℃, and the time is 1-8 hour; The reaction conditions of subordinate phase comprises: temperature is 40-80 ℃, and the time is 1-4 hour.
11. according to the random copolymers that in claim 4-10, the described method of any one makes.
12. the application of the described random copolymers of any one in polymer oil-displacing agent in claim 1-3 and 11.
13. an oil-displacing agent composition, this oil-displacing agent composition contains the described random copolymers of any one and tensio-active agent in claim 1-3 and 11.
14. oil-displacing agent composition according to claim 13, wherein, the consumption of described random copolymers and tensio-active agent makes, and the gross weight of described oil-displacing agent composition of take is benchmark, the content of described random copolymers is the 30-90 % by weight, is preferably the 60-90 % by weight; The content of described tensio-active agent is the 10-70 % by weight, is preferably the 10-40 % by weight.
15. according to the described oil-displacing agent composition of claim 13 or 14, wherein, described tensio-active agent is selected from one or more in alkylaryl sulfonate surfactants, alkylaryl sulfonate tensio-active agent, polyethenoxy ether sulphonate tensio-active agent, sulphosuccinates tensio-active agent, petroleum sulfonate surfactant, petroleum carboxylate surfactant, amido-carboxylic acid salt surfactant, polyethenoxy ether carboxylate tensio-active agent and polyoxyethylene phosphate surfactant active.
16. the preparation method of an oil-displacing agent composition, the method comprises random copolymers and tensio-active agent is mixed, and it is characterized in that, described random copolymers is the described random copolymers of any one in claim 1-3 and 11.
17. method according to claim 16, wherein, described mixing temperature is 10-40 ℃, is preferably 20-30 ℃; Described mixing time is 60-150min, is preferably 90-120min.
18. the oil-displacing agent composition made by the described method of claim 16 or 17.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610496A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Random copolymer, preparation method and application thereof |
| CN106543351A (en) * | 2015-09-21 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of hydrophobic associated polymer and its preparation method and application |
| CN114075126A (en) * | 2020-08-14 | 2022-02-22 | 中国石油化工股份有限公司 | Compound and preparation method thereof, polymer and preparation method and application thereof |
| CN115725082A (en) * | 2021-09-02 | 2023-03-03 | 中国石油化工股份有限公司 | Viscosity-reducing oil displacement agent and preparation method and application thereof |
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| US20050014893A1 (en) * | 2001-10-17 | 2005-01-20 | Olivier Braun | Tris(hydroxymethyl) acrylamidomethane polmer, inverse latex and microlatex containing same, use of said polymer, inverse latex and microlatex |
| CN102030851A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Modified polyacrylamide and preparation method thereof |
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| US20050014893A1 (en) * | 2001-10-17 | 2005-01-20 | Olivier Braun | Tris(hydroxymethyl) acrylamidomethane polmer, inverse latex and microlatex containing same, use of said polymer, inverse latex and microlatex |
| CN102030851A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Modified polyacrylamide and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610496A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Random copolymer, preparation method and application thereof |
| CN106543351A (en) * | 2015-09-21 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of hydrophobic associated polymer and its preparation method and application |
| CN106543351B (en) * | 2015-09-21 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of hydrophobic associated polymer and its preparation method and application |
| CN114075126A (en) * | 2020-08-14 | 2022-02-22 | 中国石油化工股份有限公司 | Compound and preparation method thereof, polymer and preparation method and application thereof |
| CN115725082A (en) * | 2021-09-02 | 2023-03-03 | 中国石油化工股份有限公司 | Viscosity-reducing oil displacement agent and preparation method and application thereof |
| CN115725082B (en) * | 2021-09-02 | 2023-10-13 | 中国石油化工股份有限公司 | Viscosity-reducing oil displacement agent and preparation method and application thereof |
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