CN108424491B - A kind of acrylamide copolymer and its preparation method and application - Google Patents

A kind of acrylamide copolymer and its preparation method and application Download PDF

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CN108424491B
CN108424491B CN201710078168.8A CN201710078168A CN108424491B CN 108424491 B CN108424491 B CN 108424491B CN 201710078168 A CN201710078168 A CN 201710078168A CN 108424491 B CN108424491 B CN 108424491B
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monomer
structural unit
acrylamide copolymer
unit
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CN108424491A (en
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伊卓
胡晓娜
张文龙
祝纶宇
刘希
方昭
杜超
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]

Abstract

The present invention relates to petrochemical industry, a kind of acrylamide copolymer and its preparation method and application is disclosed.The acrylamide copolymer contains structural unit A, structural unit B and structural unit C, wherein, the structural unit A is the unit with structure shown in formula (1), the structural unit B is at least one of the unit with structure shown in formula (2)-formula (7), the structural unit C is the unit with structure shown in formula (8), and the weight ratio of three kinds of structural units is 1:0.001-10:0.001-10, the viscosity average molecular weigh of the acrylamide copolymer is 1,000,000-4,000 ten thousand.Copolymer good water solubility of the invention, residual monomer content are low, especially high temperature and it is with high salt under conditions of, apparent viscosity, thickening properties and the dispersed oil ability of solution are substantially improved compared with conventional polypropylene amide.

Description

A kind of acrylamide copolymer and its preparation method and application
Technical field
The present invention relates to petrochemical industries, and in particular, to a kind of acrylamide copolymer and preparation method thereof and answers With.
Background technique
Polymer displacement of reservoir oil is mainly the polymer solution for passing through injection certain scale, increases displacement fluid viscosity, reduces oil reservoir Water phase permeability come reduce mobility ratio, adjustment intake profile, with achieve the purpose that improve displacement phase volume, and then improve harvesting Rate.
As main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (PHPA) (HPAM) is in conventional oil reservoir tertiary oil recovery (EOB) in technology, large-scale promotion and application have been obtained, has played important function for oilfield stable production and volume increase.With routine The reduction of reservoir reserve, high temperature and high salt oil deposit make the application of HPAM be faced with many problems, and it is high to be mainly reflected in exploitation high temperature HPAM solution viscosity is greatly reduced in the compound action that dissolved oxygen generates in high temperature, with high salt and solution when salt oil deposit, causes HPAM oil displacement efficiency is not significant.Studies have shown that the acylamino- hydrolysis of HPAM generates carboxyl and significantly adds when temperature is higher than 70 DEG C Play, when degree of hydrolysis reaches 40% or more, carboxyl is just easy to and Ca in solution2+、Mg2+Ion generates precipitating, damages solution viscosity It loses.In addition, at high temperature, there are when dissolved oxygen, can also cause main polymer chain fracture to keep solution viscous in oxygen and solution in air Degree is remarkably decreased.
In order to improve the temperature-resistant anti-salt performance of polyacrylamide, a large amount of tackling key problem researchs have been carried out both at home and abroad, mainly around poly- Chain scale, chain size distribution, construction unit composition, the micro-sequential structure for closing object carry out a large amount of correlative study work, such as heatproof Salt resistance monomer-polymer, hydrophobic associated polymer, amphoteric polymer, composite polymer, comb polymer, template polymer and Surface-active polymer etc..Such as entitled " low temperature of AMPS/AM copolymer synthesizes and performance " (Chang Zhiying, polymer material science With engineering, 1997,13,16) with acrylamide (AM) and heat-resistant salt-resistant monomer 2- acrylamide-2-methylpro panesulfonic acid (AMPS) Copolymerization bipolymer.As CN101260171A discloses a kind of comb-type structure activity polymer and its preparation process and answers With by the monomer copolymerizables such as polyurethanes surface-active macromonomer and acrylamide at tackifying and reduction interfacial tension target Product.The polymer that above two method obtains respectively has its feature, certain performances for example temperature tolerance, salt-resistance, shear resistant and More traditional polyacrylamide increases really in surface-active index, but technological operation is relatively cumbersome, and obtains product point Son amount is small (being no more than 20,000,000), and the use of polymer is caused to be restricted.
Summary of the invention
It is an object of the invention to overcome the drawbacks described above of the prior art, a kind of acrylamide copolymer, Yi Zhongbing are provided The preparation method of acrylamide copolymer is answered by the acrylamide copolymer and the acrylamide copolymer of this method preparation With.
To achieve the goals above, the present invention provides a kind of acrylamide copolymers, wherein the acrylamide copolymer Contain structural unit A, structural unit B and structural unit C, wherein the structural unit A is the list with structure shown in formula (1) Member, the structural unit B are at least one of the unit with structure shown in formula (2)-formula (7), and the structural unit C is tool There is the unit of structure shown in formula (8), and the weight ratio of the structural unit A, the structural unit B and the structural unit C are 1:0.001-10:0.001-10 the viscosity average molecular weigh of the acrylamide copolymer is 1,000,000-4,000 ten thousand,
Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or the alkyl of C1-C4, R3For the alkylidene of C1-C14, R4And R5It is each independently hydrogen or the alkyl of C1-C16, R8And R9It is each independently the alkyl of C1-C4, R12For key or C6- The arlydene of C15, M1、M2And M4It is each independently H, Na or K, X is halogen.
It was found by the inventors of the present invention that the main chain of acrylamide copolymer strand of the invention is mainly by acrylamide The structural unit of structural unit and temperature-resistant anti-salt monomer is constituted, and is guaranteeing polymeric water-soluble simultaneously, polymer point can be improved The temperature-resistant anti-salt performance of son.In addition, copolymer branch is made of the structural unit of active function monomer, has and generate intermolecular form Cooperation is used, and the slack time of molecular motion is increased, and is improved solution viscoplasticity and is reduced the effect of oil water interfacial tension.
The present invention also provides a kind of methods for preparing acrylamide copolymer, this method comprises: in solution polymerization Under the conditions of, in the presence of initiator, monomer mixture is made to carry out polymerization reaction in water, wherein the monomer mixture contains Monomer E, monomer F and monomer G, the monomer E are the monomer with structure shown in formula (I), and the monomer F is with formula (II)- At least one of the monomer of structure shown in formula (VII), the monomer G are the monomer with structure shown in formula (VIII), and institute The weight ratio for stating monomer E, the monomer F and the monomer G is 1:0.001-10:0.001-10；The solution polymerization item Part makes the viscosity average molecular weigh of resulting polymers after polymerization reaction be 1,000,000-4,000 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or the alkyl of C1-C4, R3' it is C1-C14's Alkylidene, R4' and R5' it is each independently hydrogen or the alkyl of C1-C16, R8' and R9' it is each independently the alkyl of C1-C4, R12' it is key or the arlydene of C6-C15, M1’、M2' and M4' it is each independently H, Na or K, X ' is halogen.
The present invention also provides the acrylamide copolymers prepared by the above method.
In addition, the application the present invention also provides above-mentioned acrylamide copolymer as oil displacement agent and/or profile-controlling and plugging agent.
Acrylamide copolymer provided by the invention has the characteristics that good water solubility, residual monomer content are low, especially exists High temperature and it is with high salt under conditions of, apparent viscosity, thickening properties and the dispersed oil ability of solution have substantially compared with conventional polypropylene amide It is promoted, can be used as high temperature and high salt oil deposit Flooding Agent for EOR and/or profile-controlling and plugging agent.Moreover, propylene provided by the invention The preparation method step of amide copolymer is simple.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
Acrylamide copolymer provided by the invention contains structural unit A, structural unit B and structural unit C, wherein institute Stating structural unit A is the unit with structure shown in formula (1), and the structural unit B is with structure shown in formula (2)-formula (7) At least one of unit, the structural unit C are the unit with structure shown in formula (8), and the structural unit A, described The weight ratio of structural unit B and the structural unit C are 1:0.001-10:0.001-10, preferably 1:0.01-1.5:0.01- 0.2, further preferably 1:0.01-1:0.01-0.1；The viscosity average molecular weigh of the acrylamide copolymer is 1,000,000-4000 Ten thousand, preferably 20,000,000-3,000 ten thousand；
Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or the alkyl of C1-C4, R3For the alkylidene of C1-C14, R4And R5It is each independently hydrogen or the alkyl of C1-C16, R8And R9It is each independently the alkyl of C1-C4, R12For key or C6- The arlydene of C15, M1、M2And M4It is each independently H, Na or K, X is halogen (F, Cl, Br or I, preferably Cl).
In the present invention, the alkyl of the C1-C4 can be straight chain, be also possible to branch.The alkyl of the C1-C4 Example may include: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and tert-butyl.
In the present invention, the alkylidene of the C1-C14 can be linear chain or branched chain, the reality of the alkylidene of the C1-C14 Example can include but is not limited to: methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene With sub- tert-butyl, sub- n-pentyl, isoamylidene, sub- tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl, sub- n-octyl, Asia N-nonyl, sub- positive decyl, sub- positive hendecyl, sub- positive dodecyl, sub- positive tritriacontyl and sub- positive tetradecyl.The alkylidene refers to alkane Hydrocarbon loses the residue after two hydrogen atoms, and described two hydrogen atoms can be two hydrogen atoms on the same carbon atom, can also With two hydrogen atoms on different carbon atoms, can be straight chain, be also possible to branch, for example, the ethylidene can be- CH2CH2Or-CH (CH3)-。
In the present invention, the alkyl of the C1-C16 can be straight chain, be also possible to branch.The alkane of the C1-C16 The example of base can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, N-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, just Dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl.
In the present invention, although as long as containing structural unit A, structural unit B and structural unit C and meeting aforementioned proportion pass The purpose of the present invention can be realized in system, but under preferable case, on the basis of the total amount of the acrylamide copolymer, the structure The content of unit A is 30-99 weight %.
According to the present invention, in order to make acrylamide copolymer that there is good viscoplasticity, under preferable case, the structure list First B is the unit of structure shown at least one of unit with structure shown in formula (2)-formula (6) and formula (7-1):
Wherein, M2For K or Na, preferably Na；R1As hereinbefore defined.
The present invention does not specially require the content of the unit of structure shown in formula (7-1), for instance, it is preferred that shown in formula (1) The unit and formula (7-1) of structure shown at least one of unit of structure shown in the unit of structure, formula (2)-formula (6), formula (8) The weight ratio of the unit of shown structure is 1:0.001-10:0.001-10:0.1-1, more preferably 1:0.01-1.5:0.01- 0.2:0.1-1, further preferably 1:0.01-1:0.01-0.1:0.1-1.
Preferably, acrylates structural unit shown in the formula (7-1) can be gathered by acrylate monomers raw material Conjunction obtains or the structural unit as shown in some acrylamide structural unit i.e. formula (1) is obtained by hydrolysis, further preferably Ground, structural unit structural unit as shown in some acrylamide structural unit, that is, formula (1) shown in formula (7-1) is by hydrolyzing It arrives.Those skilled in the art could be aware that the process of hydrolysis includes reacting hydrolytic reagent with acrylamide copolymer, excellent Selection of land, the dosage of the hydrolytic reagent make the degree of hydrolysis of acrylamide copolymer be 10-30%.
In the present invention, the condition of the hydrolysis is not particularly limited, under preferable case, the condition packet of the hydrolysis Include: temperature is 50-110 DEG C, preferably 70-90 DEG C；Time is 0.5-6 hours, preferably 1-4 hours.
In the present invention, it is total to refer to that the molal quantity of acrylates structural unit accounts for acrylamide of the invention for the degree of hydrolysis The percentage of the total mole number of the structural unit of polymers.The degree of hydrolysis is determined by the inventory of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic base substances that can be realized above-mentioned purpose commonly used in the art, can Selected from one of sodium hydroxide, potassium hydroxide and sodium carbonate or a variety of.The dosage of the hydrolytic reagent can be according to acryloyl The degree of hydrolysis of amine copolymer object makes appropriate choice, so that the degree of hydrolysis of acrylamide copolymer meets subject to requirement.
Those skilled in the art could be aware that, by adjusting the dosage of inorganic base substance, available difference The acrylamide copolymer of degree of hydrolysis.In the present invention, the molal quantity of the inorganic base substance is equal to structure shown in formula (7-1) Acrylates structural unit molal quantity.
The present inventor has found under study for action, is made of specific structural unit A, structural unit B, structural unit C Polymer to obtain preferable oil displacement efficiency good when being used for oil displacement agent.For instance, it is preferred that R1、R2、R6、R7、R10、M1、M2And M4 It is each independently hydrogen, R3For the alkylidene (especially methylene) of C1-C4, R4And R11It is each independently hydrogen or methyl, R5For The straight chained alkyl of methyl or C8-C16；R8And R9It is each independently methyl or ethyl, R12(such as key or phenylene).It is highly preferred that R3For methylene, R4、R5、R8And R9Respectively It independently is methyl.It is further preferred that the structural unit B be the unit with structure shown in formula (2)-formula (6) in extremely Few one kind.
The method provided by the invention for preparing acrylamide copolymer includes: to cause under the conditions of solution polymerization (one kind) monomer mixture in the presence of agent, is set to carry out polymerization reaction in water, wherein the monomer mixture contains monomer E, list Body F and monomer G, the monomer E are the monomer with structure shown in formula (I), and the monomer F is with formula (II)-formula (VII) institute Show at least one of the monomer of structure, the monomer G is the monomer with structure shown in formula (VIII), and the monomer E, institute State the monomer F and monomer G weight ratio be 1:0.001-10:0.001-10, more preferably 1:0.01-1.5:0.01-0.2, Most preferably 1:0.01-1:0.01-0.1；The solution polymerization condition make resulting polymers after polymerization reaction it is viscous Molecular weight is 1,000,000-4,000 ten thousand, preferably 20,000,000-3,000 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or the alkyl of C1-C4, R3' it is C1-C14's Alkylidene, R4' and R5' it is each independently hydrogen or the alkyl of C1-C16, R8' and R9' it is each independently the alkyl of C1-C4, R12' it is key or the arlydene of C6-C15, M1’、M2' and M4' be each independently H, Na or K, X ' be halogen (F, Cl, Br or I, Preferably Cl).
In the present invention, monomer E is preferably the 30-99 weight % of monomer mixture gross mass.
In the present invention, the monomer F is temperature-resistant anti-salt monomer, and the example of the monomer F can be but be not limited to: propylene Acid, 2- acrylamide-2-methylpro panesulfonic acid, N, N- dimethylacrylamide, N, N- acrylamide, N- vinylpyridine Press against alkanone, diallyldimethylammonium chloride, p styrene sulfonic acid, vinyl sulfonic acid, ethylene methacrylic sulfonic acid, 2- acrylamido- One of dodecane sulfonic acid, 2- acrylamido-tetradecane sulfonic acid, 2- acrylamido-hexadecane sulfonic acid are a variety of.
The present inventor has found under study for action, when selecting specific monomer E, monomer F to be reacted with monomer G, The oil displacement efficiency of resulting polymer can be further increased.In the case of for example, it is preferable to, R1’、R2’、R6’、R7’、R10’、M1’、 M2' and M4' it is each independently hydrogen, R3' be C1-C4 alkylidene (especially methylene), R4' and R11' it is each independently hydrogen Or methyl, R5' it is methyl or the straight chained alkyl of C8-C16, R8' and R9' it is each independently methyl or ethyl, R12' it is key or Asia Phenyl.It is highly preferred that R3' it is methylene, R4’、R5’、R8' and R9' it is each independently methyl.It is further preferred that the list Body F is at least one of the monomer of structure shown in formula (II)-formula (VI).
In the present invention, the monomer G can be prepared according to the conventional method of this field, such as according to document Method synthesis in J.APPL.POLYM.SCI.2013, Lanni Jia etc..
According to the present invention, the solution polymerization carries out in water, when the solution polymerization starts, the monomer There is no particular limitation for the ratio of the total weight of the weight and water and monomer mixture of mixture, can become in a wider scope Dynamic, under preferable case, the ratio of the total weight of the weight and water and monomer mixture of the monomer mixture is 0.15-0.4:1, Further preferably 0.2-0.3:1.
In the present invention, the initiator can be the various initiators in this field.For example, the initiator can be selected from even Nitrogen series initiators and/or redox system initiator, preferably azo initiators and redox system initiator.It is described The dosage of azo initiators is 0.0001-0.1 weight %, preferably the 0.001-0.05 weight of the weight of monomer mixture Measure %；The dosage of the redox series initiators is the 0.0002-0.3 weight % of the weight of monomer mixture, preferably 0.002-0.15 weight %.The azo initiators are preferably water-soluble azo series initiators, and the redox system causes Agent includes Oxidizing and Reducing Agents, the reducing agent be inorganic reducing agent and/or organic reducing agent, and the oxidant with it is described The weight ratio of reducing agent is 0.1-1:1.
In the present invention, the water-soluble azo series initiators are preferably 2,2 '-azos bis- (2- amidine propanes) two hydrochloric acid Salt, 2, bis- (the 2- imidazoline propane) dihydrochlorides and 4 of 2 '-azos, at least one of 4'- azo bis- (4- cyanopentanoic acids), into One step is preferably bis- (2- amidine propane) dihydrochlorides of 2,2 '-azos.
In the present invention, the oxidant can in acyl peroxide, hydroperoxides and persulfate at least one Kind, preferably benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5- dimethyl -2,5- bis- (hydrogen peroxide) oneself At least one of alkane, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate, further preferably ammonium persulfate and/or potassium peroxydisulfate.
In the present invention, the reducing agent can be inorganic reducing agent and/or organic reducing agent, preferably inorganic reducing agent And organic reducing agent.The inorganic reducing agent can be selected from ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sulfurous At least one in sour sodium, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium hydrogensulfite Kind, preferably sodium hydrogensulfite；The organic reducing agent is preferably amine reducing agent, and the amine reducing agent is preferably N, N- bis- Methylethanolamine, N, N '-dimethyl piperazine, N, N, N ', N '-tetramethylurea element and N, N, N ', in N '-tetramethylethylenediamine extremely Few one kind, further preferably N, N, N ', N '-tetramethylethylenediamine.
In the preferred embodiment of the present invention, the initiator is bis- (2- amidine propane) disalts of 2,2 '-azos Hydrochlorate, ammonium persulfate, sodium hydrogensulfite and N, N, N ', N '-tetramethylethylenediamine.
In another embodiment of the invention, the initiator can be photoinitiator.The photoinitiator can be with Containing organic amine and water soluble compound, the water soluble compound is water-soluble thioxanthones compound and/or water solubility Benzophenone compound.The weight ratio of the organic amine and water soluble compound can be 1:0.0001-10000, preferably 1:0.002-500, more preferably 1:0.1-10, most preferably 1:0.1-1.The dosage of the photoinitiator can mix for monomer The 0.00001-0.5 weight % of the weight of object, preferably 0.0001-0.3 weight %, more preferably 0.0003-0.08 weight %.
In the photoinitiator that the present invention uses, the organic amine can restore auxiliary agent for the various common amines in this field, Under preferable case, the organic amine is at least one of compound shown in following formula (A):
Wherein, R21、R22And R23It is each independently hydrogen, straight chained alkyl (C1-C5), branched alkyl (C1-C5), naphthenic base (C1-C6), aromatic radical (C1-C6), alkoxy (C1-C6), halogen atom, nitro, sulfydryl, amino, alkylamino radical (C1-C6), arylamine Base (C1-C6), alkane hydroxyl (C1-C6) or R21、R22And R23In both any can be cyclized into (five yuan, hexa-atomic, seven yuan or eight yuan) Diazacyclo, and R21、R22And R23It is not simultaneously hydrogen.
It is highly preferred that R21、R22And R23From independently being hydrogen ,-CH3、-C2H5、-CH2CH2OH、-CH(OH)CH3、- CH2CH2NH2、-CH(NH2)CH3、-C2H4N(CH3)2、-CON(CH3)2Or R21、R22And R23In both any can be cyclized into pair Two piperazines, and R21、R22And R23It is not simultaneously hydrogen.
It is further preferred that the organic amine is N, N, N ', N '-tetramethylethylenediamine, N, N- dimethylethanolamine, N, N '-dimethyl piperazine, N, N, N ', at least one of N '-tetramethylurea and triethanolamine.
In the photoinitiator that the present invention uses, the water solubility benzophenone compound can be common each in this field Kind water solubility is using benzophenone as the compound of skeleton, for example, being obtained by using the hydrogen on water soluble group substituted benzene ring Various water-soluble benzophenone compounds.The water-soluble benzophenone compound that the present invention uses preferably has following formula (B) structure shown in:
Wherein, R is the group containing quaternary ammonium salt structure of C4-C12.
In formula (B), the position of substitution of R is not required particularly, it is preferable that (water solubility) hexichol first provided by the invention Ketone compounds have structure shown in following formula (B-1):
In formula (B) or formula (B-1), the quaternary ammonium salt group (R) of C4-C12 can refer to that substituent group on N is the season of linear chain or branched chain The example of ammonium salt groups, four substituent groups on N can include but is not limited to each independently: methyl, ethyl, n-propyl, different Propyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, just Octyl, n-nonyl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy and the above-mentioned group for being substituted (such as hydroxyl).
Preferably, R is-R24-N-(R25)3X11 -And R24For C1-C4 alkylidene (such as methylene or ethylidene),Or --- -- OCH2CH2CH2---, R25For the alkyl (such as-CH of C1-C43Or-C2H5), X11For halogen Plain (F, Cl, Br or I).
It is highly preferred that R is And X11For halogen (F, Cl, Br or I).
It is further preferred that R is
In the photoinitiator that the present invention uses, the water solubility thioxanthones compound can be common each in this field Kind water solubility is using thioxanthone as the compound of skeleton, for example, being obtained by using the hydrogen on water soluble group substituted benzene ring Various water-soluble thioxanthones compounds.The water-soluble thioxanthones compound that the present invention uses preferably has following formula (C) structure shown in:
Wherein, R31、R32、R33、R31’、R32' and R33' it is each independently hydrogen, alkyl, alkoxy, halogen, nitro, ammonia Base, alkylamino radical or carbon atom number are the ethoxy ether of 1-255 (preferably 1-250, more preferably 5-50, most preferably 10-20) Long-chain, n1 are the integer of 1-255 (preferably 1-250, more preferably 5-50, most preferably 15-20).
In the present invention, alkyl is preferably the alkyl of C1-C4, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group, tert-butyl etc..
Alkoxy can be the alkoxy of C1-C4, such as methoxyl group, ethyoxyl, propoxyl group.
Halogen can be F, Cl, Br or I.
The general formula of alkylamino radical can be-NH-R26, wherein R26It can be the alkyl of C1-C4, such as methyl, ethyl, positive third Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl etc..
The general formula of ethoxy ether long-chain is-O (CH2CH2O)m1-R27, wherein m1 can for 1-125 (preferably 1-120, more Preferably 5-50, most preferably 15-20), R27It can be the alkyl (such as methyl) of C1-C4.
Preferred embodiment according to the present invention, R31、R32、R33、R31’、R32' and R33' it is each independently hydrogen or first Base.
Most preferred embodiment according to the present invention, R31、R32、R33、R31’、R32' and R33' it is each independently hydrogen, or Person, R31And R31' it is hydrogen and R32、R33、R32' and R33' it is each independently methyl, n1 10-20.
According to the present invention, in order to further increase polymerization reaction efficiency, the photoinitiator can also be containing water-soluble even Nitrogen series initiators.The content of water-soluble azo series initiators is not required particularly, it is preferable that the organic amine and the water The weight ratio of soluble azo series initiators is 1:0.0001-10000, more preferably 1:0.002-500, further preferably 1: 0.1-10, most preferably 1:0.1-1.
The water-soluble azo series initiators can be the common water-soluble azo series initiators (as previously described) in this field, Under preferable case, the water-soluble azo series initiators are selected from 2,2 '-azos bis- (2- amidine propane) dihydrochlorides, 2, and 2 '-is even Bis- (the 2- imidazoline propane) dihydrochlorides and 4 of nitrogen, at least one of 4 '-azos bis- (4- cyanopentanoic acids), further preferably Bis- (2- amidine propane) dihydrochlorides of 2,2 '-azos.
A preferred embodiment of the invention, the photoinitiator also contain water-soluble azo series initiators, and The organic amine, the water soluble compound, water-soluble azo series initiators weight ratio be 1:0.1-10:0.1-10, it is described Organic amine is N, N, N ', N '-tetramethylethylenediamine, the water-soluble azo series initiators are bis- (the 2- amidino groups third of 2,2 '-azos Alkane) dihydrochloride.Polymerization efficiency can be further increased as initiator using the photoinitiator in the preferred embodiment.
According to the preferred embodiment of the present invention, the photoinitiator is made of mentioned component.Generally, the present invention uses Photoinitiator in each ingredient independently save, be added separately in polymerization reaction system when in use.
According to the present invention, the condition of the solution polymerization can be the condition of this field routine.For example, the polymerization Reaction carries out in the presence of an inert gas, and the polymeric reaction condition may include: that the initial temperature of polymerization reaction is 0-50 DEG C, It is preferred that 5 DEG C to 15 DEG C；Time is 2-12 hours, preferably 4-8 hours；PH value is 4-12, preferably 5-10.
The inert gas is the gas not reacted with raw material and product, such as can be the nitrogen of this field routine Or at least one of group 0 element gas in the periodic table of elements, preferably nitrogen.
The pH value can be obtained by the way that pH adjusting agent is added into polymerization system, and the pH adjusting agent can be this field Conventional various acidic ph modifiers and/or alkaline pH adjusting agent, the alkaline pH adjusting agent can be inorganic base substance, example Such as at least one of sodium hydroxide, potassium hydroxide and sodium carbonate, preferably sodium hydroxide；The acidic ph modifier can be One of hydrochloric acid, sulfuric acid and nitric acid are a variety of.
In accordance with the present invention it is preferred that the monomer F be the monomer with structure shown in formula (II)-formula (VI) at least When a kind of, the method also includes resulting polymers after polymerization reaction are hydrolyzed and are dried, the hydrolysis is so that polymerization is anti- The degree of hydrolysis of resulting polymers can be 10-30% after answering.Those skilled in the art could be aware that, the process packet of hydrolysis It includes hydrolytic reagent and polymer reaction.By hydrolysis, structural unit shown in some acrylamide structural unit, that is, formula (1) changes At acrylates structural unit, that is, the unit of structure shown in formula (7-1).
In the present invention, the condition of the hydrolysis is not particularly limited, under preferable case, the condition packet of the hydrolysis Include: temperature is 50-110 DEG C, preferably 70-90 DEG C；Time is 0.5-6 hours, preferably 1-4 hours.
In the present invention, it is total to refer to that the molal quantity of acrylates structural unit accounts for acrylamide of the invention for the degree of hydrolysis The percentage of the total mole number of the structural unit of polymers.The degree of hydrolysis is determined by the inventory of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic base substances that can be realized above-mentioned purpose commonly used in the art, can Selected from one of sodium hydroxide, potassium hydroxide and sodium carbonate or a variety of.The dosage of the hydrolytic reagent can be according to acryloyl The degree of hydrolysis of amine copolymer object makes appropriate choice, so that the degree of hydrolysis of acrylamide copolymer meets subject to requirement, it is excellent Select the dosage of inorganic base substance that the degree of hydrolysis of acrylamide copolymer is made to be 10-30%.
Those skilled in the art could be aware that, by adjusting the dosage of inorganic base substance, available difference The acrylamide copolymer of degree of hydrolysis.
In the present invention, the molal quantity of the inorganic base substance is equal to the molal quantity of acrylates structural unit.
According to the present invention, for the present invention to drying condition without particular/special requirement, the drying means can use hot-air seasoning, The heated-air drying temperature can be 40-120 DEG C, preferably 70-90 DEG C；Time is 0.2-4 hours, preferably 0.5-2 hours.
In addition, preparation method of the invention further includes that the product that will be dried to obtain is crushed and sieved, the crushing and The condition of screening can reasonably be selected according to the prior art, and details are not described herein.
In a preferred embodiment of the invention, the preparation method of the acrylamide copolymer includes following step It is rapid:
(1) that acrylamide monomer, temperature-resistant anti-salt monomer, active function monomer and water are mixed to form comonomer is water-soluble Liquid adjusts pH to 4-12 with inorganic base substance, and the initial temperature for controlling polymerisation in solution is 0-50 DEG C；
(2) the logical nitrogen progress deoxygenation into comonomer aqueous solution, deoxygenation 30 minutes or more；
(3) under logical condition of nitrogen gas, composite initiation system is added to monomer solution, carries out adiabatic polymerisation, is copolymerized Object gel；
(4) copolymer gel be once granulated, hydrolyzed, secondary granulation, drying, crushing and screening obtain temperature-resistant anti-salt Acrylamide copolymer product.
According to the present invention, in step (1), the temperature-resistant anti-salt monomer is monomer F of the present invention, the active function list Body is monomer G of the present invention, and the inorganic base substance contains acrylamide, temperature-resistant anti-salt monomer and surface for adjusting The pH value of the aqueous solution of activated monomer.The inorganic base substance can in sodium hydroxide, potassium hydroxide and sodium carbonate extremely Few one kind, preferably sodium hydroxide.
The present invention also provides the acrylamide copolymers according to made from the above method.
In addition, the application the present invention also provides the acrylamide copolymer in oil displacement agent.Provided by the invention third Acrylamide copolymer is particularly useful as high temperature and high salt oil deposit Flooding Agent for EOR.The method of application is referred to existing skill Art, details are not described herein.
The present invention will be described in detail by way of examples below.
In following embodiment, the performance of product (solid content, dissolution time, insolubles content, Residual acrylamide content, Apparent viscosity, shear viscosity retention rate, aging viscosity retention rate, dispersion crude oil ability) it tests using following methods progress: Q/ SH1020 1957-2008；
Intrinsic viscosity, bonded restorations Mη, according to People's Republic of China's oil and gas industry standard (SY/T5862-2008), using Dilution, intrinsic viscosity=H/C0, molecular weight M is calculated by formulaη=([η]/ 0.000373)1.515；
In following embodiment, acrylamide is commercially available from Bao Mo biochemical industry limited liability company, 2- acrylamido -2- first Base propane sulfonic acid is commercially available from Xiamen Changtian Enterprise Co., Ltd.；Bis- (the 2- amidine propanes) two of n-vinyl pyrrolidone, 2,2 '-azos Hydrochloride is commercially available from Aldrich；Monomer reference literature J.APPL.POLYM.SCI.2013, Lanni shown in formula (VIII) It is prepared by the method for Jia etc.；Commercial product is high molecular weight polyacrylamide (model: Japanese MO4000), and molecular weight is 22,000,000.
Embodiment 1
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention
1000 grams of acrylamides (AM), 10 grams of 2- acrylamide-2-methylpro panesulfonic acids and 10 grams are added such as in beaker The active function monomer of structure shown in formula (VIII), 4080 grams of deionized waters under stirring, control solution temperature with chilled brine 5 DEG C of degree is added sodium hydroxide and adjusts pH to 7.Monomer solution is transferred in polymerization bottle, 10.2 milligrams of water-soluble azos are added and draw Send out bis- (2- amidine propane) dihydrochlorides of 2,2 '-azo of agent and 10.2 milligrams of amines N, N, N ', N '-tetramethylethylenediamine leads to height Pure nitrogen gas deoxygenation 0.5 hour, 10.2 milligrams of sodium hydrogensulfites and 10.2 milligrams of ammonium persulfates are added, continue logical nitrogen until polymerization Thermocouple starts to warm up in bottle, and the reaction time 8 hours.Colloid is taken out, 4-6 millimeters of copolymer glue is granulated by pelletizer Grain.Obtained copolymer micelle is contacted with 113 grams of sodium hydroxide grain alkali kneading, hydrolyzes 0.5 hour, passes through at 90 DEG C of temperature It after secondary granulation, is dried, obtains the product of 20-80 mesh by crushing and screening.The performance of obtained acrylamide copolymer It is listed in Table 1 below.
Embodiment 2
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention
1000 grams of acrylamides (AM) of addition, 1000 grams of 2- acrylamide-2-methylpro panesulfonic acids and 100 grams in beaker The active function monomer of the structure as shown in formula (VIII), 4900 grams of deionized waters under stirring, control solution with chilled brine 15 DEG C of temperature, sodium hydroxide is added and adjusts pH to 7.Monomer solution is transferred in polymerization bottle, 1.05 grams of water-soluble azos are added Bis- (2- amidine propane) dihydrochlorides of 2,2 '-azo of initiator and 1.05 donaxine class N, N, N ', N '-tetramethylethylenediamine lead to height Pure nitrogen gas deoxygenation 0.5 hour, 1.05 grams of sodium hydrogensulfites and 1.05 grams of ammonium persulfates are added, continue logical nitrogen until in polymerization bottle Thermocouple starts to warm up, and the reaction time 4 hours.Colloid is taken out, 4-6 millimeters of copolymer micelle is granulated by pelletizer. Obtained copolymer micelle is contacted with 151.9 grams of sodium hydroxide grain alkali kneading, is hydrolyzed 4 hours under temperature 70 C, through two It after secondary granulation, is dried, obtains the product of 20-80 mesh by crushing and screening.The performance of obtained acrylamide copolymer arranges In table 1.
Embodiment 3
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention
1000 grams of acrylamides (AM), 100 grams of 2- acrylamide-2-methylpro panesulfonic acids and 50 grams are added such as in beaker The active function monomer of structure shown in formula (VIII), 3450 grams of deionized waters under stirring, control solution temperature with chilled brine 10 DEG C of degree is added sodium hydroxide and adjusts pH to 7.Monomer solution is transferred in polymerization bottle, 115 milligrams of water-soluble azos are added and draw Send out bis- (2- amidine propane) dihydrochlorides of 2,2 '-azo of agent and 115 milligrams of amines N, N, N ', N '-tetramethylethylenediamine leads to high-purity Nitrogen deoxygenation 0.5 hour, 115 milligrams of sodium hydrogensulfites and 115 milligrams of ammonium persulfates are added, continue logical nitrogen until in polymerization bottle Thermocouple starts to warm up, and the reaction time 6 hours.Colloid is taken out, 4-6 millimeters of copolymer micelle is granulated by pelletizer. Obtained copolymer micelle is contacted with 116.8 grams of sodium hydroxide grain alkali kneading, is hydrolyzed 2 hours at 80 DEG C of temperature, through two It after secondary granulation, is dried, obtains the product of 20-80 mesh by crushing and screening.The performance of obtained acrylamide copolymer arranges In table 1.
Embodiment 4
1000 grams of acrylamides (AM), 50 grams of 2- acrylamide-2-methylpro panesulfonic acids, 50 grams of N, N- are added in beaker The active function monomer of dimethylacrylamide (0.504mol) and 50 grams of structures as shown in formula (VIII), 3450 grams of deionizations Water under stirring, controls 10 DEG C of solution temperature with chilled brine, sodium hydroxide is added and adjusts pH to 7.Monomer solution is shifted Into polymerization bottle, bis- (2- amidine propane) dihydrochlorides of 115 milligrams of water-soluble azo initiators, 2,2 '-azo and 115 millis is added Donaxine class N, N, N ', N '-tetramethylethylenediamine leads to high pure nitrogen deoxygenation 0.5 hour, 115 milligrams of sodium hydrogensulfites and 115 is added Milligram ammonium persulfate, continues logical nitrogen until thermocouple starts to warm up in polymerization bottle, and the reaction time 6 hours.Colloid is taken out, is led to Cross the copolymer micelle that pelletizer is granulated into 4-6 millimeters.Obtained copolymer micelle is pinched with 118.9 grams of sodium hydroxide grain alkali Splice grafting touching, hydrolyzes 2 hours at 80 DEG C of temperature, after secondary granulation, is dried, obtain 20-80 purpose by crushing and screening Product.The performance of obtained acrylamide copolymer is listed in Table 1 below.
Embodiment 5
1000 grams of acrylamides (AM), 50 grams of 2- acrylamide-2-methylpro panesulfonic acids, 50 grams of N- second are added in beaker The active function monomer of alkenyl pyrrolidone and 50 grams of structures as shown in formula (VIII), 3450 grams of deionized waters, under stirring, 10 DEG C of solution temperature are controlled with chilled brine, sodium hydroxide is added and adjusts pH to 7.Monomer solution is transferred in polymerization bottle, is added Enter bis- (2- amidine propane) dihydrochlorides of 115 milligrams of water-soluble azo initiator 2,2 '-azos and 115 milligrams of amines N, N, N ', N '-tetramethylethylenediamine leads to high pure nitrogen deoxygenation 0.5 hour, 115 milligrams of sodium hydrogensulfites and 115 milligrams of ammonium persulfates is added, Continue logical nitrogen until thermocouple starts to warm up in polymerization bottle, the reaction time 6 hours.Colloid is taken out, is granulated by pelletizer At 4-6 millimeters of copolymer micelle.Obtained copolymer micelle is contacted with 118.4 grams of sodium hydroxide grain alkali kneading, in temperature It is hydrolyzed 2 hours at 80 DEG C of degree, after secondary granulation, is dried, obtains the product of 20-80 mesh by crushing and screening.It obtains The performance of acrylamide copolymer is listed in Table 1 below.
Embodiment 6
Acrylamide copolymer is prepared using method same as Example 2, unlike, without hydrolysis, that is, do not have Contacting obtained copolymer micelle with the kneading of sodium hydroxide grain alkali in embodiment 2 is carried out, 4 hours steps are hydrolyzed at 70 DEG C Suddenly.The performance of obtained acrylamide copolymer is listed in Table 1 below.
Embodiment 7
Acrylamide copolymer is prepared in the way of embodiment 1, unlike, monomer solution is transferred in polymerization bottle Later, 50 milligrams of water-soluble benzophenone compounds 1,50 milligrams of N, N, N are added ', N '-tetramethylethylenediamine, 50 milligrams of water Bis- (2- amidine propane) dihydrochlorides of 2,2 '-azo of soluble azo initiator are as initiator, and carrying out photopolymerization reaction, (100W is purple Outer light irradiates), reaction time 5h obtains polymer blob of viscose, (is granulated, hydrolysis, dry and crushing after polymerization through identical post-processing Deng) condition properties of product test result is shown in Table 1.
Wherein, water-soluble benzophenone compound 1 is chlorination [2- hydroxyl -3- (4- benzoyl phenoxy group)-N, N, N- The third ammonium of trimethyl -1-] (shown in structure such as formula (B-1) and R is), according to document: applying Material industry, 2005,35 (2): the method synthesis in 7-10.
Embodiment 8
Acrylamide copolymer is prepared in the way of embodiment 2, unlike, monomer solution is transferred in polymerization bottle Later, 100 milligrams of water-soluble benzophenone compounds 2,1000 milligrams of N, N, N are added ', N '-tetramethylethylenediamine, 500 millis Gram bis- (2- amidine propane) dihydrochlorides of 2,2 '-azo of water-soluble azo initiator carry out photopolymerization reaction as initiator (100W ultraviolet light), reaction time 5h obtain polymer blob of viscose, (are granulated, hydrolysis, do through identical post-processing after polymerization It is dry and crush etc.) condition properties of product test result is shown in Table 1.
Shown in water-soluble 2 structure of benzophenone compound such as formula (B-1) and R isSynthetic method are as follows: in there-necked flask be added 0.5g metallic sodium, 50.0mL without After fully reacting, 4 grams of 4- dihydroxy benaophenonels are added in water-ethanol, and stirring is warming up to 85 DEG C, 6 grams of 3- chloropropyl triethyl groups are added Ammonium bromide, reaction for 24 hours, are added dropwise 2mol/L hydrochloric acid aqueous isopropanol and adjust pH value to 4, cold filtration precipitates crystal, and is washed with ethyl alcohol Product is obtained after washing drying, which is subjected to infrared spectrum characterization, in infrared spectrum, 2700cm-1、1480cm-1Place occurs With the strong methylene characteristic absorption peak closed of nitrogen, 1250cm-1、1050cm-1Place is aryl ether absorption peak, 980cm-1、925cm-1Place is The characteristic absorption peak of quaternary ammonium salt cooperates nuclear-magnetism and mass spectral results, illustrates to have obtained target product.
Embodiment 9
Acrylamide copolymer is prepared in the way of embodiment 3, unlike, monomer solution is transferred in polymerization bottle Later, 0.315 milligram of water-soluble thioxanthones compound 1,1.575 milligrams of N, N, N are added ', N '-tetramethylethylenediamine, 1.575 milligrams of bis- (2- amidine propane) dihydrochlorides of 2,2 '-azo of water-soluble azo initiator carry out photopolymerization as initiator It reacts (100W ultraviolet light), reaction time 5h obtains polymer blob of viscose, (is granulated, water after polymerization through identical post-processing It is solution, dry and crush etc.) condition properties of product test result is shown in Table 1.
Shown in water-soluble 1 structure of thioxanthones compound such as formula (C) and R31、R32、R33、R31’、R32' and R33' it is hydrogen, N1 is 16, synthetic method are as follows: taking polyethylene glycol (number-average molecular weight 750) 10g, which is dissolved in toluene 50ml, adds pyridine 1ml and chlorine Change sulfoxide 6ml, 120 DEG C of reflux 2h, reaction solution is cooled to room temperature filtering, and filtrate decompression is evaporated off toluene and is cooled to room temperature, gained viscous fluid Methylene chloride 40ml and 25g Al are added in body2O32h filtering is stirred, filtrate decompression steaming vibrating dichloromethane, residue drops to cold nothing White precipitate is precipitated in water ether 300ml, filters, filter cake is dried under reduced pressure, and is obtained double chloro polyethylene glycol, is added in there-necked flask 4 grams of 2- hydroxyl thioxanthones are added in 0.5g sodium hydride, 50.0mL tolueneStirring heating To 85 DEG C, 7 grams of double chloro polyethylene glycol are added, reaction for 24 hours, is added dropwise 2mol/L hydrochloric acid aqueous isopropanol and adjusts pH value to 4, rotation is gone Most of solvent, is precipitated solid, and upper toluene of inclining solution is washed repeatedly with ether, ether is evaporated off, after vacuum drying, obtained The product is carried out infrared spectrum characterization, in infrared spectrum, 1625cm by product-1Place is carbonyl absorption peak in thioxanthone, 1600cm-1、1590cm-1For phenyl ring carbon-carbon double bond absorption peak, 1110cm-1Broad peak be C-O-C group in polyethylene glycol feature Absorption peak cooperates nuclear-magnetism and mass spectral results, illustrates to have obtained target product.
Embodiment 10
Acrylamide copolymer is prepared in the way of embodiment 4, unlike, monomer solution is transferred in polymerization bottle Later, 100 milligrams of water-soluble thioxanthones compounds 2,500 milligrams of N, N, N are added ', N '-tetramethylethylenediamine, 100 milligrams Bis- (2- amidine propane) dihydrochlorides of 2,2 '-azo of water-soluble azo initiator carry out photopolymerization reaction (100W as initiator Ultraviolet light), reaction time 5h obtains polymer blob of viscose, (is granulated, hydrolysis, dry and powder after polymerization through identical post-processing It is broken etc.) condition properties of product test result is shown in Table 1.
Shown in water-soluble 2 structure of thioxanthones compound such as formula (C) and R31And R31' it is hydrogen, R32、R33、R32' and R33’ For methyl, n1 16, synthetic method are as follows: taking polyethylene glycol (number-average molecular weight 750) 10g, which is dissolved in toluene 50ml, adds pyridine 1ml and thionyl chloride 6ml, 120 DEG C of reflux 2h, reaction solution are cooled to room temperature filtering, and filtrate decompression is evaporated off toluene and is cooled to room temperature, gained Methylene chloride 40ml and 25g Al are added in thick liquid2O3Stir 2h filtering, filtrate decompression steaming vibrating dichloromethane, residue drop It to white precipitate is precipitated in cold anhydrous ether 300ml, filters, filter cake is dried under reduced pressure, and double chloro polyethylene glycol is obtained, in there-necked flask 4.5 grams of 2- hydroxyl -3,4- dimethyl-thioxanthones are added in middle addition 0.5g sodium hydride, 50.0mL tolueneStirring is warming up to 85 DEG C, and 7 grams of double chloro polyethylene glycol are added, and reaction for 24 hours, is added dropwise 2mol/L hydrochloric acid aqueous isopropanol adjusts pH value to 4, and most of solvent is removed in rotation, and solid is precipitated, and upper toluene of inclining solution uses second Ether washs repeatedly, and ether is evaporated off, and after vacuum drying, obtains product, which is carried out infrared spectrum characterization, in infrared spectrum In, 1625cm-1Place is carbonyl absorption peak in thioxanthone, 1600cm-1、1590cm-1For phenyl ring carbon-carbon double bond absorption peak, 1440cm-1、1398cm-1And 1358cm-1Bending vibration, 1110cm for methyl and methylene-1Broad peak be C- in polyethylene glycol The characteristic absorption peak of O-C group cooperates nuclear-magnetism and mass spectral results, illustrates to have obtained target product.
Comparative example 1
Acrylamide copolymer is prepared using method same as Example 1, unlike, it is added without such as formula (VIII) institute Show the active function monomer of structure, the performance of obtained acrylamide copolymer is listed in Table 1 below.
Table 1
In conjunction with table 1 data it is found that the acrylamide copolymer solution apparent viscosity that embodiment 1 obtains can achieve 205.2mPas, shear viscosity retention rate are 94.1%, and dispersed oil ability is 90.2%, and comparative example 1 obtains acrylamide and is total to Copolymer solution apparent viscosity is only 14.5mPas, and shear viscosity retention rate is 74.5%, dispersed oil ability 80.5%, embodiment 1 greatly improves compared with the copolymer solution apparent viscosity that comparative example 1 obtains, shear viscosity retention rate and dispersed oil ability.Illustrate this The introducing of active function monomer is more advantageous to thickening properties, anti-shear performance and the dispersed oil energy for improving copolymer solution in invention Power.
Compared with Example 6 by embodiment 2, acrylamide copolymer solution apparent viscosity is obtained in embodiment 6 is 123mPas, lower than embodiment 2 index as a result, and insolubles content be substantially improved.Illustrate suitably to draw in copolymer structure Enter sodium acrylate structural unit to be more advantageous to the apparent viscosity for improving copolymer solution and reduce insolubles content.
By taking embodiment 1 as an example, acrylamide copolymer solution apparent viscosity that the present invention obtains up to 205.2mPas, And commercially available high molecular weight polyacrylamide solution apparent viscosity is only 11.5mPas, in addition, the acrylamide that embodiment 1 obtains Also relatively comparison commercial product has a clear superiority for copolymer solution anti-shear ability and dispersed oil ability.Accordingly, it is known that the present invention mentions The acrylamide copolymer of confession has good thickening properties, anti-shear performance and dispersed oil ability.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (21)

1. a kind of acrylamide copolymer, which is characterized in that the acrylamide copolymer contain structural unit A, structural unit B and Structural unit C, wherein the structural unit A is the unit with structure shown in formula (1), and the structural unit B is with formula (2) at least one of the unit of structure shown in-formula (7), the structural unit C are the unit with structure shown in formula (8), and The weight ratio of the structural unit A, the structural unit B and the structural unit C are 1:0.001-10:0.001-10, described The viscosity average molecular weigh of acrylamide copolymer is 1,000,000-4,000 ten thousand,
Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or the alkyl of C1-C4, R3For the alkylidene of C1-C14, R4With R5It is each independently hydrogen or the alkyl of C1-C16, R8And R9It is each independently the alkyl of C1-C4, R12For key or C6-C15 Arlydene, M1、M2And M4Be each independently H, Na or K, X is halogen, wherein the main chain of the acrylamide copolymer by Structural unit A and structural unit B is constituted, and branch is made of structural unit C.
2. acrylamide copolymer according to claim 1, wherein the structural unit B is with formula (2)-formula (6) institute Show the unit of structure shown at least one of unit of structure and formula (7-1):
Wherein, M3For K or Na.
3. acrylamide copolymer according to claim 2, wherein the unit of structure shown in formula (1), formula (2)-formula (6) The weight ratio of the unit of structure shown in the unit and formula (7-1) of structure shown at least one of unit of shown structure, formula (8) For 1:0.001-10:0.001-10:0.1-1；The viscosity average molecular weigh of the acrylamide copolymer is 20,000,000-3,000 ten thousand.
4. acrylamide copolymer according to claim 3, wherein the unit of structure shown in formula (1), formula (2)-formula (6) The weight ratio of the unit of structure shown in the unit and formula (7-1) of structure shown at least one of unit of shown structure, formula (8) For 1:0.01-1.5:0.01-0.2:0.1-1；The viscosity average molecular weigh of the acrylamide copolymer is 20,000,000-3,000 ten thousand.
5. acrylamide copolymer described in any one of -3 according to claim 1, wherein R1、R2、R6、R7、R10、M1、M2With M4It is each independently hydrogen, R3For the alkylidene of C1-C4, R4And R11It is each independently hydrogen or methyl, R5For methyl or C8-C16 Straight chained alkyl, R8And R9It is each independently methyl or ethyl, R12For key or phenylene.
6. a kind of method for preparing acrylamide copolymer, this method comprises: being deposited under the conditions of solution polymerization in initiator Under, monomer mixture is made to carry out polymerization reaction in water, which is characterized in that the monomer mixture contains monomer E, monomer F It is the monomer with structure shown in formula (I) with monomer G, the monomer E, the monomer F is with shown in formula (II)-formula (VII) At least one of monomer of structure, the monomer G are the monomer with structure shown in formula (VIII), and the monomer E, described The weight ratio of monomer F and the monomer G are 1:0.001-10:0.001-10；The solution polymerization condition makes polymerization anti- The viscosity average molecular weigh of resulting polymers is 1,000,000-4,000 ten thousand after answering, wherein the main chain of resulting polymers is by monomer E and monomer F Polymerization is constituted, and branch is made of monomer G polymerization,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or the alkyl of C1-C4, R3' be C1-C14 alkylene Base, R4' and R5' it is each independently hydrogen or the alkyl of C1-C16, R8' and R9' it is each independently the alkyl of C1-C4, R12' be The arlydene of key or C6-C15, M1’、M2' and M4' it is each independently H, Na or K, X ' is halogen.
7. according to the method described in claim 6, wherein, R1’、R2’、R6’、R7’、R10’、M1’、M2' and M4' be each independently Hydrogen, R3' be C1-C4 alkylidene, R4' and R11' it is each independently hydrogen or methyl, R5' it is methyl or the straight chain alkane of C8-C16 Base, R8' and R9' it is each independently methyl or ethyl, R12' it is key or phenylene.
8. according to the method described in claim 6, wherein, when the solution polymerization starts, the weight of the monomer mixture The ratio of amount and the total weight of water and monomer mixture is 0.15-0.4:1.
9. according to the method described in claim 8, wherein, when the solution polymerization starts, the weight of the monomer mixture The ratio of amount and the total weight of water and monomer mixture is 0.2-0.3:1.
10. according to the method described in claim 6, wherein, the initiator is selected from azo initiators and redox system draws Agent is sent out, the dosage of the azo initiators is the 0.0001-0.1 weight % of the weight of monomer mixture, the redox The dosage of series initiators is the 0.0002-0.3 weight % of the weight of monomer mixture；The azo initiators are water-soluble even Nitrogen series initiators, the redox series initiators include Oxidizing and Reducing Agents, the reducing agent be inorganic reducing agent and/or Organic reducing agent, and the weight ratio of the oxidant and the reducing agent is 0.1-1:1；
Alternatively, the initiator is the photoinitiator containing organic amine and water soluble compound, the water soluble compound is water Dissolubility thioxanthones compound and/or water-soluble benzophenone compound, the weight of the organic amine and water soluble compound For amount than being 1:0.0001-10000, the dosage of the photoinitiator is the 0.00001-0.5 weight % of the weight of monomer mixture.
11. according to the method described in claim 10, wherein, the water-soluble azo series initiators are selected from 2, the 2 '-bis- (2- of azo Amidine propane) dihydrochloride, bis- (the 2- imidazoline propane) dihydrochlorides of 2,2 '-azos and 4,4 '-azos it is bis- (4- cyanopentanoic acid) At least one of；The oxidant is selected from benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, dimethyl -2 2,5-, At least one of bis- (hydrogen peroxide) hexanes of 5-, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate；The inorganic reducing agent is selected from Ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, thiosulfuric acid At least one of sodium, potassium thiosulfate, rongalite and sodium hydrogensulfite；The organic reducing agent is selected from N, N- dimethyl ethanol Amine, N, N '-dimethyl piperazine, N, N, N ', N '-tetramethylurea element and N, N, N ', at least one of N '-tetramethylethylenediamine.
12. according to the method described in claim 10, wherein, the weight ratio of the organic amine and water soluble compound is 1: 0.0001-10000, the dosage of the photoinitiator are the 0.00001-0.5 weight % of the weight of monomer mixture.
13. according to the method for claim 12, wherein the weight ratio of the organic amine and water soluble compound is 1: 0.002-500, the dosage of the photoinitiator are the 0.0001-0.3 weight % of the weight of monomer mixture.
14. according to the method described in claim 10, wherein, the photoinitiator also contains water-soluble azo series initiators, and The weight ratio of the organic amine and the water-soluble azo series initiators is 1:0.0001-10000.
15. according to the method for claim 14, wherein the photoinitiator also contains water-soluble azo series initiators, and The weight ratio of the organic amine and the water-soluble azo series initiators is 1:0.002-500.
16. according to the method described in claim 6, wherein, the solution polymerization carries out under an inert atmosphere, the solution Polymeric reaction condition includes: that the initial temperature of polymerization reaction is 0-50 DEG C, and the time is 2-12 hours, pH value 4-12.
17. the method according to any one of claim 6-16, wherein the monomer F is with formula (II)-formula (VI) When at least one of the monomer of shown structure, the method also includes resulting polymers after polymerization reaction are hydrolyzed and are done Dry, the hydrolysis is so that the degree of hydrolysis of resulting polymers is 10-30% after polymerization reaction.
18. according to the method for claim 17, wherein the hydrolysising condition includes: that temperature is 50-110 DEG C, and the time is 0.5-6 hours.
19. according to the method for claim 17, wherein the condition of the drying includes: that temperature is 40-120 DEG C, and the time is 0.2-4 hours.
20. acrylamide copolymer made from method described in any one of claim 6-19.
21. acrylamide copolymer described in any one of claim 1-5 and 20 is as oil displacement agent and/or profile-controlling and plugging agent Application.
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