CN102875725A - Copolymer, and preparation method and application thereof - Google Patents
Copolymer, and preparation method and application thereof Download PDFInfo
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- CN102875725A CN102875725A CN201110200013XA CN201110200013A CN102875725A CN 102875725 A CN102875725 A CN 102875725A CN 201110200013X A CN201110200013X A CN 201110200013XA CN 201110200013 A CN201110200013 A CN 201110200013A CN 102875725 A CN102875725 A CN 102875725A
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Abstract
The invention discloses a copolymer, which is characterized by comprising a structural unit shown as a formula (1) and a structural unit shown as a formula (2). The invention also provides a preparation method for the copolymer, and application of the copolymer in preparation of an oil-displacing agent. When the copolymer is used for preparing the oil-displacing agent, because monomers having a stabilizer function participate in the polymerization of hydrolyzed polyacryamide (HPAM), a defect that chromatographic separation easily occurs is avoided.
Description
Technical field
The present invention relates to a kind of polymkeric substance and its preparation method and application, particularly, relate to a kind of multipolymer, the preparation method of this multipolymer, and this Application of copolymer.
Background technology
Polyacrylamide polymer (HPAM) is the main chemical agent that is used at present tertiary oil production in oil field, and the I class oil reservoir lower for temperature has good oil displacement efficiency, can greatly improve oil recovery.Yet, the use of HPAM is subjected to the impact of operating ambient temperature very large, for burying darker II class, III class oil reservoir, because the existence of high temperature and active impurity, the oxygen of trace also can cause the oxidative degradation that polymkeric substance is serious, cause the viscosity of solution sharply to descend, lose stickiness and high molecular chemical characters, lose its use value.This is present distinct issues very in II class, the practical application of III class oil reservoir.
Usually use the mode that adds stablizer, come so that HPAM can also keep stickiness and high molecular chemical characters under high temperature and oxidizing condition.Can be used for the retention of viscosity agent that the high molecular stablizer of the acrylic amide aqueous solution comprises the small molecules thermo-stabilizer and has crosslinked action, such as hindered phenol, Resorcinol, formaldehyde, alkali metal borohydride, basic metal hyposulfite etc., but above-mentioned existing stablizer can only add after the HPAM polymerization is finished, thereby has added the easily defective of generation chromatographic separation of the polymkeric substance existence behind the stablizer.
Summary of the invention
In order to overcome the existing defective that has added the easy generation chromatographic separation of the polymkeric substance existence behind the stablizer, this provides a kind of multipolymer and its preparation method and application.
The invention provides a kind of multipolymer, it is characterized in that, described multipolymer contains the structural unit shown in the structural unit shown in the formula (1) and the formula (2),
In the formula (1), W is selected from-CONH
2,-COOH and-CON (CH
3)
2In a kind of;
In the formula (2), R
1Be C
1-C
10Alkylidene group in any one, the chemical formula of X is suc as formula shown in (3),
In the formula (3), n is the integer of 0-11, and m is the integer of 0-11 and n and m's and be the integer of 1-11, R
2And R
3Be selected from independently of one another H and C
1-C
3Alkyl in any one, the R on the different carbon atoms
2Identical or different, the R on the different carbon atoms
3Identical or different.
In the described multipolymer, with respect to the structural unit shown in 1 mole of formula (1), the content of the structural unit shown in the formula (2) is the 0.0005-0.02 mole; With respect to the gross weight of multipolymer, the content sum of the structural unit shown in the structural unit shown in the formula (1) and the formula (2) is at least 75 % by weight; The intrinsic viscosity of described multipolymer is 500-3000ml/g.
The present invention also provides above-mentioned multipolymer in the application in the preparation oil-displacing agent.
The present invention also provides a kind of preparation method of multipolymer, it is characterized in that, the method comprises: in the presence of initiator and under the aqueous solution polymerization condition, the monomer shown in the formula (4) is contacted with the monomer shown in the formula (5),
Wherein, in the formula (4), identical in the definition of W and the formula (1); In the formula (5), R
1With identical in the definition of X and the formula (2).
The present invention also provides above-mentioned finger preparation method prepared multipolymer.
The present invention also provides the application of the prepared multipolymer of above-mentioned finger preparation method in the preparation oil-displacing agent.
For the preparation of oil-displacing agent the time, owing to having the polymerization that the monomer (namely having the monomer shown in the formula (4)) of stablizer function has participated in HPAM, therefore can not there be the defective that chromatographic separation easily occurs in multipolymer provided by the invention.In addition, this monomer is owing to connecting the existence of sulphur ring structure, thereby has and do not inhibit under the low temperature and possess efficient chain forwarding function under the high temperature; And owing to the existence of maleimide amine structure, suitably increased the rigidity of main polymer chain, the heat resistance that has therefore improved polymkeric substance also can stop the chain DeR of polymkeric substance effectively.So use the oil-displacing agent of monomer preparation provided by the invention under the high temperature and high salt environment, to have outstanding viscosity hold facility.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
In the present invention, in the situation that do not do opposite explanation, the volume numerical value of employed gas and liquid is the numerical value under the standard state.
In the present invention, in the situation that do not do opposite explanation, the scope of the term " solution " that uses is not limited to the particle dia of dispersate less than the dispersed system (true solution) of 1nm, but the liquid form mixt of general reference homogeneous can comprise colloidal dispersion (colloidal solution).
In the present invention, in the situation that do opposite explanation, the term of use " structural unit " refer to occur in the macromolecular chain take the atomic group of monomer structure as the basis.
In the present invention, do not do in the situation of opposite explanation, the numerical value of intrinsic viscosity is the numerical value of measuring by the one point method of stipulating among the standard GB/T 12005.1-89.
This provides a kind of multipolymer, it is characterized in that, described multipolymer contains the structural unit shown in the structural unit shown in the formula (1) and the formula (2),
In the formula (1), W can be selected from-CONH
2,-COOH and-CON (CH
3)
2In a kind of, be preferably-CONH
2Or-COOH and-CON (CH
3)
2, more preferably-CONH
2
In the formula (2), R
1Can be C
1-C
10Alkylidene group in any one, i.e. C
1-C
10Alkane lack the group that forms behind two hydrogen atoms; Be preferably C
2-C
6Alkylidene group in any one, more preferably a kind of in methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and the hexylidene further is preferably-(CH
2)
3-,-(CH
2)
4-or-(CH
2)
5-.
In the formula (2), the chemical formula of X is suc as formula shown in (3),
In the formula (3), n can be the integer of 0-11, and m can be the integer of 0-11 and n and m's and be the integer of 1-11; Under the preferable case, n is that 0, m is the integer of 1-7; Further under the preferable case, n is that 0, m is 2,3 or 4.
In the formula (3), R
2And R
3Can be selected from independently of one another H and C
1-C
3Alkyl (methyl, ethyl, n-propyl, sec.-propyl) in any one, the R on the different carbon atoms
2Can be identical or different, the R on the different carbon atoms
3Can be identical or different; Under the preferable case, R
2Be H or methyl, R
3Be H or methyl; Under the further preferable case, R
2Be H, R
3Be H.
In the described multipolymer, with respect to the structural unit shown in 1 mole of formula (1), the content of the structural unit shown in the formula (2) can be the 0.0005-0.02 mole, be preferably the 0.001-0.015 mole, more preferably the 0.003-0.01 mole further is preferably the 0.005-0.008 mole.
Among the present invention, do not make in the situation of opposite explanation the numerical value of the mol ratio between the structural unit of multipolymer for recording by magnetic nuclear resonance method.
In the described multipolymer, usage quantity according to the monomer that forms structural unit is calculated, gross weight with respect to multipolymer, the content sum of the structural unit shown in the structural unit shown in the formula (1) and the formula (2) can be at least 75 % by weight, preferably be at least 85 % by weight, further preferably be at least 95 % by weight, further preferably be at least 100 % by weight.The gross weight of multipolymer is calculated with the usage quantity sum of all monomers of being used to form structural unit.
The intrinsic viscosity of described multipolymer can be 500-3000ml/g, is preferably 1000-2500ml/g, and more preferably 1500-2300ml/g further is preferably 1800-2200ml/g.
Need to prove, above-mentioned multipolymer according to the difference of solid content, can be gelatinous multipolymer, also can be the multipolymer of the dry powder that obtains after gelatinous multipolymer drying, granulation and the pulverizing, also can be.
Described in standard GB/T 12005.2-89, solid content is defined as: with a certain amount of sample, dry to constant weight under certain temperature and vacuum condition, the quality of dry rear sample accounts for the percentage ratio of the quality of the sample before the drying.
The present invention also provides the application of this multipolymer in the preparation oil-displacing agent.Wherein, described multipolymer can directly use as oil-displacing agent, and described copolymerization product also can use as oil-displacing agent after adding other conventional additive.
The present invention also provides a kind of preparation method of multipolymer, it is characterized in that, the method comprises: in the presence of initiator and under the aqueous solution polymerization condition, the monomer shown in the formula (4) is contacted with the monomer shown in the formula (5),
Wherein, in the formula (4), identical in the definition of W and the formula (1), that is, W can be selected from-CONH
2,-COOH and-CON (CH
3)
2In a kind of, be preferably-CONH
2Or-COOH and-CON (CH
3)
2, more preferably-CONH
2
In the formula (5), R
1With identical in the definition of X and the formula (2).That is:
In the formula (5), R
1Can be C
1-C
10Alkylidene group in any one, i.e. C
1-C
10Alkane lack the group that forms behind two hydrogen atoms; Be preferably C
2-C
6Alkylidene group in any one, more preferably a kind of in methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and the hexylidene further is preferably-(CH
2)
3-,-(CH
2)
4-or-(CH
2)
5-.
In the formula (5), the chemical formula of X is suc as formula shown in (3).
According to method provided by the invention, wherein, monomer shown in the formula with respect to 1 mole (4), the consumption of the monomer shown in the formula (5) can be the 0.0005-0.02 mole, be preferably the 0.001-0.015 mole, more preferably the 0.003-0.01 mole further is preferably the 0.005-0.008 mole.
Wherein, the monomer shown in the formula with respect to 1 mole (4), the consumption of water can be the 0.3-0.5 liter, is preferably the 0.35-0.4 liter.
Wherein, the monomer shown in the formula with respect to 1 mole (4), the consumption of described initiator are 1 * 10
-6To 5 * 10
-5Mole is preferably 2 * 10
-6To 2.5 * 10
-6Mole.
Wherein, described initiator can be selected from the initiator of various routines known in the field, and for example, described initiator can be azo-type initiator and/or oxidation-reduction type initiator; Wherein, described azo-type initiator can and be preferably Diisopropyl azodicarboxylate and/or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described oxidation-reduction type initiator can and be preferably Potassium Persulphate-S-WAT initiator and/or ammonium sulfate-sodium bisulfite initiator.
Wherein, described aqueous solution polymerization condition can comprise polymerization temperature and polymerization time, and the selectable range of polymerization temperature is wider, the more high generation that more is beneficial to polyreaction of its polymerization temperature, but considering of comprehensive cost and effect, described polymerization temperature can be 0-70 ℃.The prolongation of polymerization time is conducive to the abundant copolymerization of monomer, but the long improvement amplitude to its performance of polymerization time is also not obvious, and therefore, polymerization time can be 5-10 hour, is preferably 6-8 hour.
In addition, under the preferable case, when selecting described azo-type initiator, described polymerization temperature is preferably 40-70 ℃; When selecting described oxidation-reduction type initiator, described polymerization temperature is preferably 0-30 ℃.
Polymerization system pH value is preferably neutrality or weakly alkaline, and described pH value is preferably 7.7-10, more preferably 8.5-9.5.Can adopt conventional method to regulate the pH of polymerization system, for example, can adopt sodium hydroxide or potassium hydroxide aqueous solution to regulate the pH value.
According to the present invention, the preparation method of the monomer shown in the formula (5) can comprise the steps:
(1) in the presence of the first solvent and under the amidation reaction condition, toxilic acid and/or maleic anhydride are carried out first with two thiophene amine contact.
(2) in the presence of catalyzer and under the second condensation reaction condition, the material after the first contact in the step (1) is carried out the 3rd with dewatering agent contact.
In the step (1), described two thiophene amine are at least a in the compound shown in the formula (6).
H
2N-R
1-X formula (6)
In the formula (6), R
1Definition and the middle R of formula (2) with X
1Identical with the definition of X, that is, in the formula (6), R
1Can be C
1-C
10Alkylidene group in any one, i.e. C
1-C
10Alkane lack the group that forms behind two hydrogen atoms; Be preferably C
2-C
6Alkylidene group in any one, more preferably a kind of in methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and the hexylidene further is preferably-(CH
2)
3-,-(CH
2)
4-or-(CH
2)
5-.
In the formula (6), the chemical formula of X is suc as formula shown in (3).
In the step (1), described the first solvent is as reaction medium, reacting environment is provided, as long as therefore can dissolve toxilic acid, maleic anhydride and described two thiophene amine, but under described amidation reaction condition, does not get final product with toxilic acid, maleic anhydride and the reaction of described two thiophene amine.Meet at least a that the first solvent of above-mentioned requirements can be in acetone, benzene, toluene and the hexanaphthene.The consumption of the first solvent is as long as guarantee toxilic acid, maleic anhydride and described two thiophene amine are fully dissolved, and generally, the mol ratio of toxilic acid and/or maleic anhydride and solvent can 1: 1-20.
In the step (1), with respect to 1 mole described two thiophene amine, the consumption of toxilic acid and/or maleic anhydride can be the 0.6-2 mole, is preferably the 0.8-1.8 mole, and more preferably the 1-1.6 mole further is preferably the 1.2-1.4 mole.
In the step (1), described amidation reaction condition does not have special requirement, can be for can be so that the normal condition of toxilic acid and/or maleic anhydride amidate action, for example, described amidation reaction condition can comprise: temperature is 30-80 ℃, be preferably 40-70 ℃, more preferably 50-65 ℃, further be preferably 58-62 ℃; Time can be 0.5-4 hour, is preferably 1-3 hour, more preferably 1.5-2.5 hour, further is preferably 1.8-2.2 hour.
In the step (1), because toxilic acid or maleic anhydride are subject to the impact of steric effect can only copolymerization and can not homopolymerization, so, described the first contact can be carried out under the non-existent condition of stopper, described the first contact also can in the situation that stopper exist and to carry out, toxilic acid with respect to every mole and/or maleic anhydride, the consumption of described stopper can be 0.01-0.1g.
In the step (2), with respect to 1 mole charging capacity of two thiophene amine described in the material after the first contact in the step (1), the consumption of described dewatering agent can be the 1-4 mole, is preferably the 1.5-3 mole, more preferably the 1.8-2.5 mole further is preferably the 2-2.2 mole.
In the step (2), described dewatering agent can be the dewatering agent that is used for condensation reaction of routine, and for example various energy include but not limited to diacetyl oxide and/or propionic anhydride as the carboxylic acid anhydride of dewatering agent.
In the step (2), described catalyzer can be the catalyzer that is used for condensation reaction of routine, and for example an alkali metal salt of carboxylic acid includes but not limited to one or more in sodium acetate, potassium acetate, Sodium Propionate and the potassium propionate.
In the step (2), with respect to every mole dewatering agent, the consumption of described catalyzer can be 0.1-1g, is preferably 0.2-0.8g, more preferably 0.4-0.6g.
In the step (2), described the second condensation reaction condition can be the condensation reaction condition of routine, for example, described the first condensation reaction condition can comprise: temperature is 30-80 ℃, be preferably 40-70 ℃, more preferably 50-65 ℃, further be preferably 58-62 ℃; Time can be 2-8 hour, is preferably 3-7 hour, more preferably 3.5-6 hour, further is preferably 4-4.5 hour.
After described the 3rd contact finishes, separate the material that described monomer can be obtained after the 3rd contact.The method of described separation can be the separation method of routine, for example: the material that obtains after the 3rd contact can be carried out underpressure distillation to remove solvent wherein; The material behind the solvent is removed in then at room temperature water and/or aqueous sodium carbonate washing, to remove at least a in wherein unreacted toxilic acid, maleic anhydride and the dewatering agent; With the material after the refining washing of the method for recrystallization, namely obtain the crystal of described monomer again; The used solvent of recrystallization can be the aqueous ethanolic solution of 55-75 volume % concentration.
The present invention also provides the multipolymer that is made by above-mentioned multipolymer preparation method.
Need to prove, above-mentioned multipolymer can be the product after the gelatinous copolymerization, also can be the multipolymer of the dry powder that obtains after super-dry, granulation, pulverizing of the product after the gelatinous copolymerization.
The present invention also provides the application of the multipolymer that is made by above-mentioned preparation method in the preparation oil-displacing agent.
Described multipolymer can directly use as oil-displacing agent, and described multipolymer also can use as oil-displacing agent after adding other conventional additive.
According to the purposes of described multipolymer in the preparation oil-displacing agent, wherein, described oil-displacing agent contains multipolymer provided by the invention, the content of described multipolymer can be known scope in the oil-displacing agent preparation field, and for example the weight ratio of the multipolymer of the gross weight of described oil-displacing agent and described dry powder can be 300-5000: 1.
Described oil-displacing agent can also with contain the materials such as alkaline matter, tensio-active agent and ion chelating agent; Thereby use as binary composite oil displacement agent and ternary composite driving finish.Described alkaline matter and tensio-active agent are the known content of oil-displacing agent preparation field, and the present invention repeats no more.
Among the present invention, intrinsic viscosity is measured according to standard GB/T 12005.1-89 acrylamide copolymer For Intrinsic Viscosity Measurements method; The copolymer solution apparent viscosity is used the Brookfield viscometer determining under the nominative testing temperature.
The present invention also provides above-mentioned preparation method prepared multipolymer.
The present invention also provides the application of the prepared multipolymer of above-mentioned preparation method in the preparation oil-displacing agent.
Need to prove, each the concrete technical characterictic described in above-mentioned embodiment in reconcilable situation, can make up by any suitable mode, and for example, in the formula (1), W is-CONH
2In the formula (2), R
1For-(CH
2)
3-,-(CH
2)
4-or-(CH
2)
5-; In the formula (3), R
2And R
3Be H, n is that 0, m is 2,3 or 4.For fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
The below will further describe in detail the present invention by specific embodiment.
Among the following embodiment 6,8-two thiophenes-1-octylame (is R
1For-(CH
2)
5-; R
2And R
3Be H, n is that 0, m is 2 formula (6) compound) and 6,9-, two thiophenes-1-nonyl amine (be R
1For-(CH
2)
5-; R
2And R
3Be H, n is that 0, m is 3 formula (6) compound) all available from the permanent scientific and technological development limited liability company far away in Nanjing.
Preparation Example 1
This Preparation Example is used for the preparation method of the monomer shown in the formula (5).
(6,8-, two thiophenes-1-octylame (is R with the maleic anhydride of 0.25mol, the toluene of 1.6mol, the stopper (p methoxy phenol) of 0.01g and the two thiophene amine of 0.15mol
1For-(CH
2)
5-; R
2And R
3Be H, n is that 0, m is 2 formula (6) compound)) after mixing under 60 ℃, under 60 ℃, kept 2 hours, obtain the first reaction solution.
Under 60 ℃, the acetic anhydride of above-mentioned the first reaction solution and 0.3mol and the sodium-acetate of 0.15g are mixed and kept under 60 ℃ 4 hours, obtain the second reaction solution.
With above-mentioned the second reaction solution under 60 ℃ and 20kPa condition underpressure distillation to removing toluene, then with the cold water mix of 4 ℃ of the material after the underpressure distillation and 200ml temperature evenly after filtration; After the aqueous sodium carbonate washing of the screening that filtration is obtained with 5 % by weight of 100ml, use again the water washing of 100ml, then dry; The solid that drying is obtained carries out recrystallization with the aqueous ethanolic solution of 67 volume %, obtains the solid behind the recrystallization of 34.2g, is the monomer C1 that this Preparation Example obtains, and with respect to the charging capacity of two thiophene amine, yield is 84.1%.
The above-mentioned solid that obtains behind the recrystallization carried out GC-MS detects and NMR detects, the molecular weight that detection obtains this solid is 271, and has chemical formula (wherein, the R shown in the formula (5)
1For-(CH
2)
5-; R
2And R
3Be H, n is that 0, m is 2).
Preparation Example 2
This Preparation Example is used for the preparation method of the monomer shown in the formula (5).
Prepare intermediate according to the method identical with Preparation Example 1, difference is that two used thiophene amine are that 6,9-, two thiophenes-1-nonyl amine (is R
1For-(CH
2)
5-; R
2And R
3Be H, n is that 0, m is 3 formula (6) compound).
The present embodiment has obtained the solid behind the recrystallization of 35.2g, is the monomer C2 that the present embodiment obtains, and with respect to the charging capacity of two thiophene amine, yield is 82.3%.
According to the method identical with embodiment 1, solid obtained above carried out GC-MS detects and NMR detects, the molecular weight that detection obtains this solid is 285, and has chemical formula (wherein, the R shown in the formula (5)
1For-(CH
2)
5-; R
2And R
3Be H, n is that 0, m is 3).
Embodiment 1
The present embodiment is used for illustrating multipolymer of the present invention and preparation thereof.
Under agitation, the monomer C1 shown in the formula (5) that makes of the Preparation Example 1 of 1 mole acrylamide and 0.0076 mole is dissolved in 0.394 liter the water.Under room temperature (25 ℃), after 30 minutes, the pH value of regulating the aqueous solution with sodium hydroxide is 9.2, under agitation adds 2.2 * 10 with the logical nitrogen deoxygenation of the aqueous solution
-6The initiator of mole (two (the 2-methyl-prop amidine) hydrochlorides (AIBA) of 2,2-azo) reacted 6 hours under normal pressure (0.1MPa) and 50 ℃ of constant temperature, obtained the gel multipolymer.The gel multipolymer drying, granulation, the pulverizing that obtain are obtained dry powder copolymer p 1.
Record according to standard GB/T 12005.1-89 acrylamide copolymer For Intrinsic Viscosity Measurements method: the intrinsic viscosity of dry powder copolymer p 1 is 1846ml/g.
Record by nucleus magnetic resonance: in the dry powder copolymer p 1, the acrylamide structural unit with respect to 1 mole, the content of monomer C1 structural unit is 0.0076 mole.
In the dry powder copolymer p 1, usage quantity according to the monomer that forms structural unit is calculated, with respect to multipolymer gross weight (being the usage quantity sum of acrylamide and monomer C1), the content sum of acrylamide structural unit and monomer C1 structural unit is 100 % by weight.
Embodiment 2
The present embodiment is used for illustrating multipolymer of the present invention and preparation thereof.
Prepare dry powder copolymer p 2 by the method identical with embodiment 1, difference is, the monomer C1 shown in the formula (5) that Preparation Example 1 is made replaces with the monomer C2 shown in the formula (5) that Preparation Example 2 makes.
According to embodiment 1 in identical measuring method record: in the dry powder copolymer p 2, intrinsic viscosity is 1852ml/g; Acrylamide structural unit with respect to 1 mole, the content of monomer C2 structural unit is 0.0076 mole; The content sum of acrylamide structural unit and monomer C2 structural unit is 100 % by weight.
Embodiment 3
The present embodiment is used for illustrating multipolymer of the present invention and preparation thereof.
Prepare dry powder copolymer p 3 by the method identical with embodiment 1, difference is that acrylamide is replaced with vinylformic acid.
According to embodiment 1 in identical measuring method record: in the dry powder copolymer p 3, intrinsic viscosity is 1893ml/g; Acrylic acid structure unit with respect to 1 mole, the content of monomer C1 structural unit is 0.0076 mole; The content sum of acrylic acid structure unit and monomer C1 structural unit is 100 % by weight.
Embodiment 4
The present embodiment is used for illustrating multipolymer of the present invention and preparation thereof.
Prepare dry powder copolymer p 4 by the method identical with embodiment 1, difference is that acrylamide is replaced with N,N-DMAA.
According to embodiment 1 in identical measuring method record: in the dry powder copolymer p 4, intrinsic viscosity is 1872ml/g; N,N-DMAA structural unit with respect to 1 mole, the content of monomer C1 structural unit is 0.0076 mole; The content sum of N,N-DMAA structural unit and monomer C1 structural unit is 100 % by weight.
Embodiment 5
The present embodiment is used for illustrating multipolymer of the present invention and preparation thereof.
Prepare dry powder copolymer p 5 by the method identical with embodiment 1, difference is, acrylamide is replaced with the mixture that the Methacrylamide of 0.8 mole acrylamide and 0.2 mole mixes.
According to embodiment 1 in identical measuring method record: in the dry powder copolymer p 5, intrinsic viscosity is 1883ml/g; Acrylamide structural unit with respect to 1 mole, the content of monomer C1 structural unit is 0.00596 mole; The content sum of acrylamide structural unit and monomer C1 structural unit is 78.6 % by weight.
Embodiment 6
The present embodiment is used for illustrating multipolymer of the present invention and preparation thereof.
Prepare dry powder copolymer p 6 by the method identical with embodiment 1, difference is that the consumption of the monomer C1 shown in the formula that Preparation Example 1 makes (5) is 0.019 mole.
According to embodiment 1 in identical measuring method record: in the dry powder copolymer p 6, intrinsic viscosity is 2965ml/g; Acrylamide structural unit with respect to 1 mole, the content of monomer C1 structural unit is 0.019 mole; The content sum of acrylamide structural unit and monomer C1 structural unit is 100 % by weight.
Comparative Examples 1
Prepare dry powder multipolymer Q1 by the method identical with embodiment 1, difference is, just the monomer C1 shown in the formula (5) that makes of Preparation Example 1 replaces with acrylamide.According to embodiment 1 in identical measuring method record: among the dry powder multipolymer Q1, intrinsic viscosity is 2146ml/g
Test implementation example 1
This test implementation example is used for explanation by the dry powder multipolymer Q1 of the dry powder copolymer p 1-P6 of embodiment 1-6 preparation and Comparative Examples 1 preparation during for the preparation of oil-displacing agent, the viscosity hold facility under the high temperature and high salt condition.
Respectively the dry powder copolymer p 1-P6 of 0.3g and Q1 are made into the solution (be equivalent to simulate and the dry powder multipolymer water of 0.3g joined the aqueous solution for 200mL as oil-displacing agent, the working condition of this oil-displacing agent under the high salt condition of salinity 32868mg/L (wherein divalent ion concentration 800mg/L)) of 200mL with simulation mineral reserve water (sodium chloride content is that 32068mg/L and calcium chloride content are the aqueous solution of 800mg/L).And on Brookfield DV-III type rotational rheometer, at shearing rate 7.34s
-1Under 10 minutes test condition of maintenance, measure respectively 25 ℃ down and the apparent viscosity under 85 ℃.Then above-mentioned each aqueous solution is after placing 60 days under 85 ℃, again at shearing rate 7.34s
-1With keep under 10 minutes the test condition, the apparent viscosity under measuring 85 ℃, the result is as shown in table 1.
Table 1
Can find out in the data from upper table 1, the multipolymer that obtains according to method of the present invention is as oil-displacing agent, and along with the apparent viscosity drop-out value under the condition of high temperature and high salt is obviously less, having preferably, viscosity keeps effect.And along with the growth in high temperature and high salt treatment time, apparent viscosity increases, and presents aging tackified phenomenon, therefore has excellent heat and salinity tolerance ability.
In addition, with respect to the structural unit shown in 1 mole of formula (1), when the content of the structural unit shown in the formula (2) was preferably the 0.003-0.01 mole, described multipolymer had better heat and salinity tolerance ability.
Claims (10)
1. a multipolymer is characterized in that, described multipolymer contains the structural unit shown in the structural unit shown in the formula (1) and the formula (2),
In the formula (1), W is selected from-CONB
2,-COOH and-CON (CH
3)
2In a kind of;
In the formula (2), R
1Be C
1-C
10Alkylidene group in any one, the chemical formula of X is suc as formula shown in (3),
In the formula (3), n is the integer of 0-11, and m is the integer of 0-11 and n and m's and be the integer of 1-11, R
2And R
3Be selected from independently of one another H and C
1-C
3Alkyl in any one, the R on the different carbon atoms
2Identical or different, the R on the different carbon atoms
3Identical or different;
In the described multipolymer, with respect to the structural unit shown in 1 mole of formula (1), the content of the structural unit shown in the formula (2) is the 0.0005-0.02 mole; With respect to the gross weight of multipolymer, the content sum of the structural unit shown in the structural unit shown in the formula (1) and the formula (2) is at least 75 % by weight; The intrinsic viscosity of described multipolymer is 500-3000ml/g.
2. multipolymer according to claim 1, wherein, with respect to the structural unit shown in 1 mole of formula (1), the content of the structural unit shown in the formula (2) is the 0.003-0.01 mole.
3. multipolymer according to claim 1 and 2, wherein, in the formula (1), W is-CONB
2Or-CON (CH
3)
2In the formula (2), R
1Be C
2-C
6Alkylidene group in any one; In the formula (3), R
2And R
3Be H or methyl, n is that 0, m is the integer of 1-7.
4. multipolymer according to claim 3, wherein, in the formula (1), W is-CONH
2In the formula (2), R
1For-(CH
2)
3-,-(CH
2)
4-or-(CH
2)
5-; In the formula (3), R
2And R
3Be H, n is that 0, m is 2,3 or 4.
5. the preparation method of a multipolymer is characterized in that, the method comprises: in the presence of initiator and under the aqueous solution polymerization condition, the monomer shown in the formula (4) is contacted with the monomer shown in the formula (5),
Wherein, in the formula (4), identical in the definition of W and the formula (1); In the formula (5), R
1With identical in the definition of X and the formula (2).
6. method according to claim 5, wherein, the monomer shown in the formula with respect to 1 mole (4), the consumption of the monomer shown in the formula (5) is the 0.0005-0.02 mole; Under the preferable case, the monomer shown in the formula with respect to 1 mole (4), the consumption of the monomer shown in the formula (5) is the 0.003-0.01 mole.
7. method according to claim 6, wherein, described aqueous solution polymerization condition comprises that polymerization temperature is 0-70 ℃, and polymerization time is 5-10 hour, and the pH value is 7.7-10.
8. the described method of any one according to claim 5-7, wherein, the monomer shown in the formula with respect to 1 mole (4), the consumption of water are the 0.3-0.5 liter, the consumption of described initiator is 1 * 10
-6To 5 * 10
-5Mole.
9. the multipolymer that the described method of any one makes among the claim 5-8.
10. the application of the described multipolymer of any one in the preparation oil-displacing agent among the claim 1-4 and 9.
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|---|---|---|---|---|
| US4681912A (en) * | 1984-06-07 | 1987-07-21 | Institut Francais Du Petrole | Process for manufacturing inverse microlatices of watersoluble copolymers, the resultant inverse microlatices and their use for improving the production of hydrocarbons |
| US5334287A (en) * | 1991-08-22 | 1994-08-02 | Basf Aktiengesellschaft | Graft polymers of natural substances containing saccharide structures or derivatives thereof and ethylenically unsaturated compounds and their use |
| CN101148582A (en) * | 2007-09-07 | 2008-03-26 | 成都理工大学 | Hydrophobic association micro-crosslinking polymer oil displacement agent and preparation method thereof |
| CN101260171A (en) * | 2008-04-22 | 2008-09-10 | 山东大学 | Comb-type structure activity polymer and its preparation technique and application |
-
2011
- 2011-07-14 CN CN201110200013.XA patent/CN102875725B/en active Active
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|---|---|---|---|---|
| US4681912A (en) * | 1984-06-07 | 1987-07-21 | Institut Francais Du Petrole | Process for manufacturing inverse microlatices of watersoluble copolymers, the resultant inverse microlatices and their use for improving the production of hydrocarbons |
| US5334287A (en) * | 1991-08-22 | 1994-08-02 | Basf Aktiengesellschaft | Graft polymers of natural substances containing saccharide structures or derivatives thereof and ethylenically unsaturated compounds and their use |
| CN101148582A (en) * | 2007-09-07 | 2008-03-26 | 成都理工大学 | Hydrophobic association micro-crosslinking polymer oil displacement agent and preparation method thereof |
| CN101260171A (en) * | 2008-04-22 | 2008-09-10 | 山东大学 | Comb-type structure activity polymer and its preparation technique and application |
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| Title |
|---|
| NAMBU, YOKO等: "Thermal and photoinitiated copolymerization of the cyclic disulfide lipoamide with styrene", 《MAKROMOLEKULARE CHEMIE》, vol. 189, no. 3, 31 December 1988 (1988-12-31), pages 495 - 500 * |
| SUZUKI, TATSUKI等: "Radical copolymerization of lipoamide with vinyl monomers", 《MACROMOLECULES》, vol. 23, no. 6, 31 December 1990 (1990-12-31), pages 1579 - 1582, XP002591020 * |
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