CN109232801A - Acrylamide copolymer and the preparation method and application thereof - Google Patents
Acrylamide copolymer and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109232801A CN109232801A CN201710556395.7A CN201710556395A CN109232801A CN 109232801 A CN109232801 A CN 109232801A CN 201710556395 A CN201710556395 A CN 201710556395A CN 109232801 A CN109232801 A CN 109232801A
- Authority
- CN
- China
- Prior art keywords
- monomer
- weight
- structural unit
- acrylamide
- acrylamide copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to oil field chemical fields, disclose a kind of acrylamide copolymer and its preparation method and application, wherein, the acrylamide copolymer contains structural unit A, structural unit B and structural unit C, wherein, structural unit A is with structural unit shown in formula (I), and structural unit B is with structural unit shown in formula (II), and structural unit C is with structural unit shown in formula (III)；And on the basis of the total weight of acrylamide copolymer, the content of structural unit A is 70-90 weight %, and the content of structural unit B is 8-28 weight %, and the content of structural unit C is 0.1-5 weight %.The acrylamide based copolymer of the invention can be used as high temperature and high salt oil deposit hot thickener used for tertiary oil recovery and use.
Description
Technical field
The present invention relates to oil field chemical fields, and in particular, to a kind of acrylamide copolymer and preparation method thereof with
Using.
Background technique
Polymer displacement of reservoir oil tech is an important raising petroleum recovery technology, the basic principle is that water-soluble polymeric
Object is added in water filling, to increase solution viscosity, is reduced water/oil mobility ratio, is expanded swept volume, improve sweep efficiency, reduces
The oil saturation of swept zone, to improve oil recovery.It was verified that petroleum can be increased substantially using polymer displacement of reservoir oil
Recovery ratio produces huge economic benefit and social benefit.For many years, polymer used in polymer displacement of reservoir oil is mainly people
The partially hydrolyzed polyacrylamide (PHPA) of work synthesis.The limitation of normal part hydrolyzed polyacrylamide is that heat-resistant salt-resistant performance is low, in height
Solution viscosity sharp fall under the conditions of temperature, high salinity, to significantly affect oil displacement efficiency.
For develop performance it is more excellent be able to satisfy high temperature oil field (temperature be higher than 85 DEG C) tertiary oil recovery requirement
Polymer oil-displacing agent, Chinese patent CN1240795A disclose a kind of heat-resistant salt-resistant thickening agent of copolymer, it be by initiator with
And copolymer made of monomer (A) and monomer (B) copolymerization, which is characterized in that monomer (A) is one or more water-soluble unsaturated
Monomer with alkene chain can be acrylic amide, vinyl pyrrolidone, 2- acrylamide-2-methylpro panesulfonic acid class, propylene
Acids, monomer (B) are flowed back by (polyoxyethylene) n alkanol ether, toluene, maleic acid and to a toluenesulfonic acid Hybrid Heating, azeotropic
Remove the paste obtained after the toluene of superfluous water and remnants；The copolymer is characterized in molecule containing amphipathic polymeric monomer chain
Section, shows temperature tolerance more better than normal part hydrolyzed polyacrylamide, but the amphipathic branch in the copolymer passes through ester
Key is connected with main chain, and ester bond easily hydrolyzes at high temperature, influences the stability of polymer.Chinese patent CN1317501A,
CN1414057A, CN1876751A etc. have invented the hydrophobic associated polymer oil displacement agent with different molecular structures, these polymerizations
Object is characterized on molecular backbone containing a certain number of hydrophobic molecule segments, in aqueous solution, thin between hydrophobic side chain
Water-hydrophobic interaction causes to be physical crosslinking between polymer molecular chain, to improve solution viscosity and anti-shear performance.
But it is difficult to form effective hydrophobic association thickening effect under lower polymer concentration not very obvious.
Hot thickening polymer is that its a kind of Aqueous Solution Viscosity is increased poly- with temperature raising in certain temperature range
Close object.Chinese patent CN101302267A (200810095791.5) discloses a kind of non-ionic thermal tackifying water-soluble polymers,
It is the polymer as made of monomer (A) and monomer (B) copolymerization, which is characterized in that monomer (A) is a kind of non-ionic monomer, single
Body (B) is the nonionic polymeric monomer for not having surface-active；Using a kind of molecular design method of thermal tackifying water-soluble polymers, benefit
It is copolymerized with non-ionic water-soluble polymeric monomer and nonionic monomer acrylamide, can not only increase the water solubility of copolymer, and
And copolymer can be made viscosity dramatically increases as the temperature increases；But from Fig. 1 and Fig. 2 of the patent can be seen that compared with
It is obviously thickened under low temperature, is unfavorable for the travel motion of polymer in the earth formation.
Therefore, the stability of acrylamide copolymer, the thickening effect of thickening effect especially at low temperature how to be improved
The problem of being still urgent need to resolve.
Summary of the invention
It is above-mentioned existing for the prior art the purpose of the invention is to overcome the problems, such as, a kind of acrylamide copolymerization is provided
Object and the preparation method and application thereof.
To achieve the goals above, one aspect of the present invention provides a kind of acrylamide copolymer, wherein the acrylamide
Copolymer contains structural unit A, structural unit B and structural unit C, wherein the structural unit A is with shown in formula (I)
Structural unit, the structural unit B are with structural unit shown in formula (II), and the structural unit C is with formula (III)
Shown in structural unit；And on the basis of the total weight of the acrylamide copolymer, the content of the structural unit A is 70-
The content of 90 weight %, the structural unit B is 8-28 weight %, and the content of the structural unit C is 0.1-5 weight %；
Wherein, R1And R2It is each independently hydrogen or the alkyl of C1-C4, R3For the alkylidene of C1-C12, R4、R5、R6And R7
It is each independently hydrogen or the alkyl of C1-C12.
Preferably, on the basis of the total weight of the acrylamide copolymer, the content of the structural unit A is 75-85
The content of weight %, the structural unit B are 14-24 weight %, and the content of the structural unit C is 0.2-2 weight %.
Preferably, the viscosity average molecular weigh of the acrylamide copolymer is 14,000,000-1,800 ten thousand；It is highly preferred that described third
The viscosity average molecular weigh of acrylamide copolymer is 15,500,000-1,750 ten thousand.
Preferably, R1And R2It is each independently H or methyl, R3For the alkylidene of C2-C6, R4、 R5、R6And R7Respectively solely
It is on the spot the alkyl of H or C1-C6.
Another aspect of the present invention additionally provides a kind of preparation method of acrylamide copolymer, wherein the preparation method packet
It includes under the conditions of the solution polymerization of alkene, in the presence of initiator, so that monomer mixture is carried out polymerization reaction in water, obtain
Acrylamide copolymer；Wherein, the monomer mixture contains monomer D, monomer E and monomer F, the D for formula (IV) institute
Show that the monomer of structure, the monomer E are monomer with structure shown in formula (V) and the monomer F for formula (VI) institute
Show the monomer of structure；And the weight ratio of the dosage of the monomer D, the monomer E and the monomer F is 1:(0.089-0.4):
(0.001-0.07)；
Wherein, R1' and R2' it is each independently hydrogen or the alkyl of C1-C4, R3' the alkylidene for being C1-C12, R4′、R5′、
R6' and R7' it is each independently hydrogen or the alkyl of C1-C12.
Preferably, on the basis of the water of 1000 parts by weight, the dosage of the monomer D is 175-225 parts by weight, the monomer
The dosage of E is 15.6-90 parts by weight, and the dosage of the monomer F is 0.19-16 parts by weight；Preferably, the dosage of the monomer D
For 180-200 parts by weight, the dosage of the monomer E is 29.6-72 parts by weight, and the dosage of the monomer F is 0.36-6 parts by weight.
Preferably, the initiator is selected from azo initiators and redox series initiators, the azo initiators
Dosage be monomer mixture in monomer total weight 0.0002-0.03 weight %, preferably 0.0015-0.01 weight %；
The dosage of the redox series initiators is the 0.0002-0.03 weight % of the total weight of monomer in monomer mixture, preferably
For 0.0015-0.01 weight %；The redox series initiators include Oxidizing and Reducing Agents, and the reducing agent is inorganic goes back
Former agent and/or organic reducing agent, and the weight ratio of the oxidant and the reducing agent is (0.1-1): 1；
Preferably, the azo initiators are water-soluble azo series initiators, the water-soluble azo series initiators choosing
From 2,2 '-azodiisobutyronitriles, 2,2 '-azo diisobutyl amidine dihydrochlorides, azobisisoheptonitrile, bis- (the 2- first of 2,2 '-azos
The third amidine of base) hydrochloride, 2,2 '-azos [2- (2- imidazoline -2- base) propane] dihydrochloride and bis- (the 4- cyano penta of 4,4 '-azos
At least one of acid)；
Preferably, the oxidant is benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5- dimethyl-
At least one of 2,5 bis- (hydrogen peroxide) hexanes, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate；The inorganic reducing agent is
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 N, N- dimethyl ethanol
Amine, N, N- lupetazin, tetramethylurea, N, at least one in N- dimethyl-ethylenediamine and N,N,N',N' tetramethylethylene diamine
Kind.
Preferably, the monomer D is acrylamide monomer, and the acrylamide monomer is acrylamide, methyl-prop
Acrylamide, N, N- dimethacrylamide, N, N- acrylamide, n-isopropyl acrylamide, N- methylol acryloyl
One of amine and N- hydroxyethyl acrylamide are a variety of；
Preferably, the monomer E is 2-hydroxyethyl methacrylate phosphate；
Preferably, the monomer F is shown in formula (VI), wherein R2' it is H, R3' the alkylidene for being C2-C6, R4′、R5′、R6′
And R7' it is each independently H or C1-C6 alkyl.
Preferably, the solution polymerization condition of the alkene includes: the solution polymerization of the alkene in indifferent gas
It is carried out under atmosphere, the initiator is azo initiators, and temperature is 40-70 DEG C, time 2-10h, pH value 6-8.
Preferably, the solution polymerization condition of the alkene includes: the solution polymerization of the alkene in indifferent gas
It is carried out under atmosphere, the initiator is redox series initiators, and temperature is 15-30 DEG C, time 5-10h, pH value 6-8.
Preferably, the method also includes resulting polymers after polymerization reaction are dried, the item of the drying
Part includes: that temperature is 40-120 DEG C, and the time is 0.2-4 hours.
Another aspect of the present invention additionally provides the acrylamide copolymer of method preparation described above as hot thickener
Application.
Acrylamide copolymer provided by the present invention, while introducing structural unit B shown in formula (II) and formula (III)
Shown in structural unit C preferable water-soluble and low-temperature stabilization made it have by structural unit B shown in introduction-type (II)
Property, and by having hydrophobic property borate structural unit C shown in introduction-type (III), make the propylene using hydrophobic effect
Association forms big space net structure between amide copolymer forms polymer molecule, i.e., " dynamic physical cross-linked network structure ",
Solution viscosity is significantly increased compared with acrylamide polymer；In addition, under conditions of formation temperature (85-95 DEG C), in structural unit C
Boric acid ester structure can partial hydrolysis at boric acid structure, generate new hydroxyl, the carboxyl in these new hydroxyls and structural unit B
And micro- cross-linking reaction can occur between each other at high temperature for the carboxyl of acrylamide hydrolysis, and then be conducive to further mention
The viscosity of high acrylamide copolymer aqueous solution, to achieve the purpose that thickening.
In addition, under 85-95 DEG C of hot conditions, using the aqueous solution of acrylamide copolymer provided by the present invention
Apparent viscosity is up to 19mPa.s or more, it can be seen that acrylamide copolymer of the invention, which has, substantially thickens advantage, using this
The acrylamide based copolymer provided by inventing can obtain that room temperature flowering structure is stable, viscosity is larger as thickener, height
(being higher than 85 DEG C) under temperature, viscosity does not drop, and has certain rising, and having reduces water/oil flow rate ratio, improves the effect of oil recovery,
It can be used as high temperature and high salt oil deposit hot thickener used for tertiary oil recovery to use.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
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.
One aspect of the present invention provides a kind of acrylamide copolymer, wherein the acrylamide copolymer contains structure list
First A, structural unit B and structural unit C, wherein the structural unit A is with structural unit shown in formula (I), the knot
Structure unit B is with structural unit shown in formula (II), and the structural unit C is with structural unit shown in formula (III)；And
On the basis of the total weight of the acrylamide copolymer, the content of the structural unit A can be 70-90 weight %, described
The content of structural unit B can be 8-28 weight %, and the content of the structural unit C can be 0.1-5 weight %；
Wherein, R1、R2It is each independently hydrogen or the alkyl of C1-C4, R3It can be the alkylidene of C1-C12, R4、R5、R6、
R7Hydrogen or the alkyl of C1-C12 can be each independently.
According to the present invention, the acrylamide copolymer, as long as containing structural unit A, structural unit B and structure list
First C, and meet aforementioned proportion relationship and can achieve the object of the present invention to a certain extent.
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 can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and tert-butyl.
In the present invention, the alkyl of the C1-C12 can be straight chain, be also possible to branch.The C1-C12's
The example of alkyl can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive hendecyl and
Positive dodecyl.
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 thickening effect good when being used for hot thickener.For instance, it is preferred that structural unit A shown in formula (I)
Middle R1R for H or methyl, in structural unit C shown in formula (III)2For H or methyl, R3For any in the alkylidene of C2-C6
Kind, R4、R5、R6And R7It is each independently any one of the alkyl of H or C1-C6, wherein R4、R5、R6And R7Can it is identical or
It is different.
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 weight of the acrylamide copolymer, the knot
The content of structure unit A is 75-85 weight %, and the content of the structural unit B is 14-24 weight %, and the structural unit C's contains
Amount is 0.2-2 weight %；It is highly preferred that the structural unit A's contains on the basis of the total weight of the acrylamide copolymer
Amount is 76-83 weight %, and the content of the structural unit B is 15-22 weight %, and the content of the structural unit C is 0.2-
1.8 weight %.
In the present invention, the viscosity average molecular weigh of the acrylamide copolymer is 14,000,000-1,800 ten thousand；Preferably, described
The viscosity average molecular weigh of acrylamide copolymer is 15,500,000-1,750 ten thousand.
In addition, the present invention also provides a kind of preparation methods of acrylamide copolymer, wherein the preparation method is included in
Under the conditions of the solution polymerization of alkene, in the presence of initiator, so that monomer mixture is carried out polymerization reaction in water, obtain propylene
Amide copolymer；Wherein, it is with knot shown in formula (IV) that the monomer mixture, which contains monomer D, monomer E and monomer F, the D,
The monomer of structure, the monomer E are that the monomer and the monomer F with structure shown in formula (V) are with knot shown in formula (VI)
The monomer of structure；And the weight ratio of the dosage of the monomer D, the monomer E and the monomer F is 1:(0.089-0.4):
(0.001-0.07)；
Wherein, R1' and R2' it is each independently hydrogen or the alkyl of C1-C4, R3' the alkylidene for being C1-C12, R4′、R5′、
R6' and R7' it is each independently hydrogen or the alkyl of C1-C12.
In the present invention, the alkyl of the C1-C4 can be straight chain, be also possible to branch.The alkane of the C1-C4
The example of base can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and tertiary fourth
Base.
In the present invention, the alkyl of the C1-C12 can be straight chain, be also possible to branch.The C1-C12's
The example of alkyl can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive hendecyl and
Positive dodecyl.
Preparation method according to the present invention, as long as by the monomer D, the monomer E and the monomer F according to above-mentioned ratio
Example relationship copolymerization, prepared acrylamide copolymer can achieve the object of the present invention to a certain extent.Under preferable case,
The weight ratio of the monomer D, the monomer E and the monomer F are 1:(0.16-0.32): (0.002-0.027).
Preparation method according to the present invention, the preferably described polymerization reaction are random copolymerization reaction.
Preparation method according to the present invention, wherein the monomer D with structure shown in formula (IV) can be acrylamide list
Body, the example that can be used include but is not limited to acrylamide, Methacrylamide, N,N-DMAA, N, N- bis-
One of ethyl acrylamide, n-isopropyl acrylamide, N hydroxymethyl acrylamide and N- hydroxyethyl acrylamide are more
Kind；Under preferable case, the monomer D is acrylamide or Methacrylamide.
Preparation method according to the present invention, wherein the monomer E with structure shown in formula (V) is 2- hydroxyethyl methyl third
Olefin(e) acid ester phosphate adds monomer E in the above-mentioned polymerization reaction of the present invention and is conducive to increase prepared acrylamide copolymerization
The water solubility of object, the monomer E and the monomer F is cooperateed with to be added in above-mentioned polymerization reaction is in proportion conducive to complex optimum
Water solubility and the high-temperature thickening effect of the acrylamide copolymer.
Preparation method according to the present invention, wherein the monomer F with structure shown in formula (VI) can be referred to as boracic list
Body, under preferable case, R in the formula (VI)2' it is H, R3' any one of the alkylidene for being C2-C6, R4′、R5′、R6' and R7′
It is each independently any one of H or C1-C6 alkyl.
Preparation method according to the present invention, by selecting the specific monomer D, the structures alone E and the structure
Monomer F is reacted, and the thickening effect of resulting polymer can be further increased.
Preparation method according to the present invention, the solution polymerization carry out in water, and the polymerisation in solution of the alkene is anti-
When should start, there is no particular limitation for the ratio of the total weight of the weight and water and monomer mixture of the monomer mixture, can
To change in a wider scope, as long as enabling to monomer dissolved mixture in water, convenient for the generation of solution polymerization
, it is preferable that the water is deionized water.Under preferable case, on the basis of the water of 1000 parts by weight, the use of the monomer D
Amount is 175-225 parts by weight, it is preferable that the dosage of the monomer D is 180-200 parts by weight.According to the aforementioned monomer D, institute
The weight ratio conversion for stating the monomer E and monomer F, while being equivalent to the monomer D for adding above-mentioned dosage in 1000 parts by weight,
The dosage of the monomer E is 15.6-90 parts by weight, it is preferable that the dosage of the monomer E is 29.6-72 parts by weight；The monomer
The dosage of F is 0.19-16 parts by weight, it is preferable that the dosage of the monomer F is 0.36-6 parts by weight.
Preparation method according to the present invention, for the selection of initiator, there is no particular/special requirements, as long as can promote described
The solution polymerization of alkene occurs for monomer D, the monomer E, the monomer F, such as can include but is not limited to azo
Series initiators or redox series initiators；Wherein, the dosage of the azo initiators can be monomer in monomer mixture
Total weight 0.0002-0.03 weight %, preferably 0.0015-0.01 weight %；The use of the redox series initiators
Amount can be the 0.0002-0.03 weight %, preferably 0.0015-0.01 weight % of the total weight of monomer in monomer mixture；
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 can be (0.1-1): 1；
Preferably, the azo initiators are water-soluble azo series initiators, the water-soluble azo series initiators choosing
From 2,2 '-azodiisobutyronitriles, 2,2 '-azo diisobutyl amidine dihydrochlorides, azobisisoheptonitrile, bis- (the 2- first of 2,2 '-azos
The third amidine of base) hydrochloride, 2,2 '-azos [2- (2- imidazoline -2- base) propane] dihydrochloride and bis- (the 4- cyano penta of 4,4 '-azos
At least one of acid)；It is highly preferred that the water-soluble azo series initiators are 2,2 '-azo diisobutyl amidine dihydrochlorides
Or 2,2 '-bis- (2- methyl-prop amidine) hydrochlorides of azo；
Preferably, the oxidant is benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5- dimethyl-
At least one of 2,5 bis- (hydrogen peroxide) hexanes, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate；It is highly preferred that the oxidation
Agent is ammonium sulfate, potassium peroxydisulfate or ammonium persulfate；
Preferably, the inorganic reducing agent is ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sulfurous acid
At least one in sodium, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium hydrogensulfite
Kind；The organic reducing agent is N, N- dimethylethanolamine, N, N- lupetazin, tetramethylurea, N, N- dimethyl-ethylenediamine
At least one of with N,N,N',N' tetramethylethylene diamine；It is highly preferred that the reducing agent is sodium sulfite or bisulfite
Sodium.
Preparation method according to the present invention, for the condition of the solution polymerization of alkene, there is no particular/special requirement, according to
The applicable elements of selected initiator reasonably adjust corresponding reaction condition.
Under preferable case, the solution polymerization condition of the alkene includes: the solution polymerization of the alkene lazy
Property atmosphere under carry out, the initiator be azo initiators, temperature be 40-70 DEG C, preferably 45-50 DEG C；Time is 2-
10h, preferably 4-6h；PH value is 6-8, preferably 6.5-7.5.
Under preferable case, the solution polymerization condition of the alkene includes: the solution polymerization of the alkene lazy
Property atmosphere under carry out, the initiator be redox series initiators, temperature be 15-30 DEG C, preferably 15-20 DEG C；Time is
5-10h, preferably 6-7h；PH value is 6-8, preferably 6.5-7.5.
Under preferable case, the pH value in the solution polymerization condition of the alkene is carried out by the way that alkali and/or acid is added
It adjusts, the alkali can be inorganic base or organic amine compound, can such as be selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, first
At least one of amine, ethamine, ethanol amine and triethanolamine, preferably sodium hydroxide.The acid is preferably inorganic acid, the nothing
Machine acid can be at least one of hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and phosphoric acid.
Under preferable case, the inert atmosphere (also referred to as protective atmosphere) refers to deposits in inert gas (protective gas)
Atmosphere, wherein inert gas (protective gas) is the gas not reacted with raw material and product, for example, can for this
At least one of group 0 element (helium, neon, argon, krypton, xenon) gas in the nitrogen or the periodic table of elements of field routine；It is preferred that
The inert gas is nitrogen.
Preparation method according to the present invention, in the solution polymerization condition of the alkene inert atmosphere by it is following optionally
Mode is realized: being continuously passed through inert gas during the solution polymerization of the alkene；Or the solution in the alkene
Polymerization reaction is passed through the inert gas predetermined time into the aqueous solution for be mixed with monomer mixture before starting, and it is poly- then to seal solution
Close reaction compartment；It is preferred that the predetermined time is 20-40min.
Preparation method according to the present invention, this method further include making gained acrylamide copolymer after polymerization reaction
The step of grain, drying, crushing, screening process.Wherein for dry step there is no particular/special requirement, use is well known in the art
Conventional method, such as 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.Wherein for granulation, crushing, screening process step
Suddenly also there is no particular/special requirements, and using conventional method known in the field, details are not described herein.
Meanwhile a kind of acrylamide copolymer as made from above-mentioned preparation method is additionally provided in the present invention.The propylene
Amide copolymer has the structural unit with the acrylamide copolymer same amount of foregoing description of the present invention, will no longer go to live in the household of one's in-laws on getting married herein
It states.
In addition, additionally providing a kind of application of above-mentioned acrylamide based copolymer as hot thickener in the present invention.It adopts
It uses the acrylamide based copolymer provided by the invention as thickener, can obtain that room temperature flowering structure is stable, viscosity is larger,
(being higher than 85 DEG C) under high temperature, viscosity does not drop, and has certain rising, and having reduces water/oil flow rate ratio, improves the effect of oil recovery
Fruit, is suitable for high temperature and high salt oil deposit tertiary oil recovery, and specific application method is referred to prior art progress.
It below will specific embodiments of the present invention will be described in detail by embodiment.
In the following example, the performance test of product is carried out using following methods:
1, viscosity average molecular weigh: according to formula Mv=([η]/K)1\αIt is calculated, wherein K=4.5 × 10-3, α=0.80, spy
Property viscosity number [η] is measured according to GB12005.1-1989 polyacrylamide Intrinsic Viscosity Measurements method；
2, polymer dissolution time: according to defined in Shengli Petroleum Administration Bureau company standard Q/SH10201572-2006
Method be measured.
3, poly- using the rich DV-III ULTRA type rotary viscosity measuring for strangling winged (Brookfield) company offer in the U.S.
The apparent viscosity of polymer solution at different temperatures.
Raw material employed in following embodiment is described as follows:
Acrylamide is commercially available from Bao Mo biochemical industry limited liability company；
2-hydroxyethyl methacrylate phosphate is commercially available from Japanese chemical drug company；
Bis- (the 2- methyl-prop amidine) hydrochlorides of 2,2 '-azos, 2,2 '-azo diisobutyl amidine dihydrochlorides and 4,4 '-azos
Bis- (4- cyanopentanoic acids) are commercially available from Aldrich；
Ammonium persulfate and sodium hydrogensulfite are commercially available from Beijing chemical reagents corporation.
Preparation example 1
According to document " Acs Macro Letters ", 2012,1 (5): 529-532) preparation method preparation formula (VI) institute
The structures alone F shown, structure are as follows:
That is, in the monomer F of the structure shown in formula (VI), R2' it is H, R3' it is ethylidene, R4′、R5′、 R6' and R7' respectively only
It is on the spot methyl.
Embodiment 1
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention.
(1) random copolymerization is reacted: under room temperature, stirring condition, acrylamide (AM, the monomer of 190g being added into beaker
D), the boracic monomer of the above-mentioned preparation example 1 of the 2-hydroxyethyl methacrylate phosphate (monomer E) of 50g and 2g preparation is (single
Body F) and 1000g deionized water；After dissolution of raw material, the pH to 7.5 that sodium hydroxide adjusts aqueous solution is added into aqueous solution；
Then sealed beaker forms inert atmosphere after being passed through nitrogen deoxygenation 30min to aqueous solution；Then it is added 0.01g's into aqueous solution
The sodium hydrogensulfite of ammonium persulfate and 0.01g are as redox initiation system, then in normal pressure, 15 DEG C of constant temperature (with freezing salt
Water control temperature) reaction 7 hours, obtain gum polymers solution product；
(2) granulation, dry, crushing and screening process: the gum polymers solution product is granulated by pelletizer
4-6 millimeters of copolymer micelle, it is 1 hour dry at 80 DEG C, it is then total by crushing and screening to obtain the acrylamide of 20-80 mesh
Copolymer product P1.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P1 is 1750 × 104, dissolution time is
82min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P1, structural unit A
(wherein R1Content for H) is 78.5 weight %, and the content of structural unit B is 20.7 weight % and structural unit C (wherein R2For
H, R3For ethylidene, R4、R5、R6And R7For methyl) content be 0.8 weight %.
Embodiment 2
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention.
(1) random copolymerization react: under room temperature, stirring condition, into beaker be added 180g acrylamide (AM, monomer D),
Boracic monomer prepared by the 2-hydroxyethyl methacrylate phosphate (monomer E) of 57.6g and the above-mentioned preparation example 1 of 2.4g is (single
Body F) and 1000g deionized water；After dissolution of raw material, the pH to 6.5 that sodium hydroxide adjusts aqueous solution is added into aqueous solution；
Then sealed beaker forms inert atmosphere after being passed through nitrogen deoxygenation 30min to aqueous solution；Then it is added 0.02g's into aqueous solution
Bis- (the 2- methyl-prop amidine) hydrochlorides (AIBA) of 2,2 '-azo of initiator, then in normal pressure, 50 DEG C of constant temperature (water-bath temperature control) reactions 4
Hour, obtain gum polymers solution product；
(2) granulation, dry, crushing and screening process: the gum polymers solution product is granulated by pelletizer
4-6 millimeters of copolymer micelle, it is 1 hour dry at 80 DEG C, it is then total by crushing and screening to obtain the acrylamide of 20-80 mesh
Copolymer product P2.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P2 is 1735 × 104, dissolution time is
84min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P2, structural unit A
(wherein R1Content for H) is 75 weight %, and the content of structural unit B is 24 weight % and structural unit C (wherein R2For H, R3
For ethylidene, R4、R5、R6And R7For methyl) content be 1 weight %.
Embodiment 3
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention.
(1) random copolymerization react: under room temperature, stirring condition, into beaker be added 200g acrylamide (AM, monomer D),
Boracic monomer prepared by the 2-hydroxyethyl methacrylate phosphate (monomer E) of 32.9g and the above-mentioned preparation example 1 of 2.4g is (single
Body F) and 1000g deionized water；After dissolution of raw material, the pH to 7 that sodium hydroxide adjusts aqueous solution is added into aqueous solution；It connects
Be passed through nitrogen deoxygenation 30min to aqueous solution after sealed beaker formed inert atmosphere；Then drawing for 0.01g is added into aqueous solution
2,2 '-azo diisobutyl amidine dihydrochloride of agent is sent out, is then reacted 5 hours in normal pressure, 45 DEG C of constant temperature (water-bath temperature control), obtains glue
Shaped polymer solution product；
(2) granulation, dry, crushing and screening process: the gum polymers solution product is granulated by pelletizer
4-6 millimeters of copolymer micelle, it is 1 hour dry at 80 DEG C, it is then total by crushing and screening to obtain the acrylamide of 20-80 mesh
Copolymer product P3.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P3 is 1720 × 104, dissolution time is
85min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P3, structural unit A
(wherein R1Content for H) is 85 weight %, and the content of structural unit B is 14 weight % and structural unit C (wherein R2For H, R3
For ethylidene, R4、R5、R6And R7For methyl) content be 1 weight %.
Embodiment 4
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention.
Acrylamide copolymer is prepared using preparation method same as Example 1, the difference is that: acrylamide
The dosage of (AM, monomer D) is 190g, and the dosage of 2-hydroxyethyl methacrylate phosphate (monomer E) is 36.3g, above-mentioned system
The dosage of boracic monomer (monomer F) prepared by standby example 1 is 0.45g, and acrylamide copolymer product P4 is prepared.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P4 is 1560 × 104, dissolution time is
102min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P4, structural unit A
(wherein R1Content for H) is 83.8 weight %, and the content of structural unit B is 16 weight % and structural unit C (wherein R2For H,
R3For ethylidene, R4、R5、R6And R7For methyl) content be 0.2 weight %.
Embodiment 5
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention.
(1) random copolymerization react: under room temperature, stirring condition, into beaker be added 185g acrylamide (AM, monomer D),
Boracic monomer prepared by the 2-hydroxyethyl methacrylate phosphate (monomer E) of 41.6g and the above-mentioned preparation example 1 of 4.6g is (single
Body F) and 1000g deionized water；After dissolution of raw material, the pH to 7 that sodium hydroxide adjusts aqueous solution is added into aqueous solution；It connects
Be passed through nitrogen deoxygenation 30min to aqueous solution after sealed beaker formed inert atmosphere；Then drawing for 0.05g is added into aqueous solution
Bis- (the 2- methyl-prop amidine) hydrochlorides (AIBA) of 2,2 '-azo of agent are sent out, it is then small in normal pressure, 60 DEG C of constant temperature (water-bath temperature control) reactions 6
When, obtain gum polymers solution product；
(2) granulation, dry, crushing and screening process: the gum polymers solution product is granulated by pelletizer
4-6 millimeters of copolymer micelle, it is 1 hour dry at 80 DEG C, it is then total by crushing and screening to obtain the acrylamide of 20-80 mesh
Copolymer product P5.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P5 is 1550 × 104, dissolution time is
100min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P5, structural unit A
(wherein R1Content for H) is 80 weight %, and the content of structural unit B is 18 weight % and structural unit C (wherein R2For H, R3
For ethylidene, R4、R5、R6And R7For methyl) content be 2 weight %.
Embodiment 6
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention.
Acrylamide copolymer is prepared using preparation method same as Example 1, the difference is that, it is used to contain
The structure of boron monomer (monomer F) is as follows:
That is, in the monomer F of the structure shown in formula (VI), R2' it is methyl, R3' it is ethylidene, R4′、 R5′、R6' and R7' each
From independently being methyl.
As a result acrylamide copolymer product P6 is obtained.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P6 is 1620 × 104, dissolution time is
90min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P6, structural unit A
(wherein R1Content for H) is 78.5 weight %, and the content of structural unit B is 20.7 weight % and structural unit C (wherein R2For
Methyl, R3For ethylidene, R4、R5、R6And R7For methyl) content be 0.8 weight %.
Embodiment 7
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention.
Acrylamide copolymer is prepared using preparation method same as Example 1, the difference is that, it is used to contain
The structure of boron monomer (monomer F) is as follows:
That is, in the monomer F of the structure shown in formula (VI), R2' it is H, R3' it is ethylidene, R4′、R5′、 R6' and R7' respectively only
It is on the spot H.
As a result acrylamide copolymer product P7 is obtained.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P7 is 1600 × 104, dissolution time is
88min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P7, structural unit A
(wherein R1Content for H) is 78.5 weight %, and the content of structural unit B is 20.7 weight % and structural unit C (wherein R2For
H, R3For ethylidene, R4、R5、R6And R7Content for H) is 0.8 weight %.
Embodiment 8
The present embodiment is used to illustrate the preparation method of acrylamide copolymer provided by the invention.
Acrylamide copolymer is prepared using preparation method same as Example 1, the difference is that, it is used to contain
The structure of boron monomer (monomer F) is as follows:
That is, in the monomer F of the structure shown in formula (VI), R2' it is H, R3' it is butylidene, R4′、R5′、R6' and R7' respectively only
It is on the spot H.
As a result acrylamide copolymer product P8 is obtained.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P8 is 1580 × 104, dissolution time is
95min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P8, structural unit A
(wherein R1Content for H) is 78.5 weight %, and the content of structural unit B is 20.7 weight % and structural unit C (wherein R2For
H, R3For butylidene, R4、R5、R6And R7Content for H) is 0.8 weight %.
Comparative example 1
Acrylamide copolymer is prepared using method same as Example 1, unlike, it is added without the preparation of preparation example 1
Obtained boracic monomer (monomer F), the acrylamide copolymer product P9 as a result obtained.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P9 is 1760 × 104, dissolution time is
82min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P9, structural unit A
(wherein R1Content for H) is 79.17 weight %, and the content of structural unit B is 20.83 weight %.
Comparative example 2
Acrylamide copolymer is prepared using method same as Example 1, unlike, it is added without 2- ethoxy first
Base acrylate phosphate (monomer E), the acrylamide copolymer product P10 as a result obtained.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P10 is 1640 × 104, dissolution time is
98min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P10, structural unit A
(wherein R1Content for H) is 98.86 weight %, structural unit C (wherein R2For H, R3For ethylidene, R4、R5、R6And R7For
Methyl) content be 1.04 weight %.
Comparative example 3
Acrylamide copolymer is prepared using method same as Example 1, unlike, the monomer D, the list
The weight ratio of the dosage of body E and the monomer F is 1:0.5:0.1, the acrylamide copolymer product P11 as a result obtained.
As a result the viscosity average molecular weigh for measuring acrylamide copolymer product P11 is 1080 × 104, dissolution time is
105min；And
It is calculated and is determined according to inventory, on the basis of the total weight of acrylamide copolymer product P11, structural unit A
(wherein R1Content for H) is 62.5 weight %, and the content of structural unit B is 31.25 weight %, structural unit C (wherein R2
For H, R3For ethylidene, R4、R5、R6And R7For methyl) content be 6.25 weight %.
Test case 1
Using acrylamide copolymer product P1-P8 and P9-P11 prepared by embodiment 1-8 and comparative example 1-3 as
Hot thickener uses, and measures the corresponding apparent viscosity of hot thickener at different temperatures.
Test method:
Firstly, the method preparation total salinity according to Shengli Petroleum Administration Bureau company standard Q/SH10201572-2006 is
The simulation mineral reserve water of 19334mg/L (wherein calcium ion and magnesium ion total concentration are 514mg/L)；
Secondly, (acrylamide copolymer produces the polymer that compound concentration is 3000mg/L using the simulation mineral reserve water as solvent
Product P1 is stirred 24 hours at room temperature to P11) solution；
Finally, strangling the DV-III ULTRA type rotary viscosity measuring for flying (Brookfield) company and providing using the U.S. is rich
The apparent viscosity of polymer solution at different temperatures, it is 25s that shear rate is constant when measurement-1, measurement temperature range is 30-
95 DEG C, heating rate is 2 DEG C/min.
Measurement result is as shown in table 1.
Table 1
The viscosity of the aqueous solution of acrylamide copolymer product P1-P8 provided by the invention it can be seen from data in table 1
At 50 DEG C or less, viscosity change is smaller, then increases and increases with temperature, maximum value is reached at 85 DEG C, further increases temperature
To 90 DEG C, viscosity is still able to maintain higher state.And the acrylamide copolymer product P9 of comparative example 1-3 preparation is not due to containing
Boron monomer, initial viscosity is although larger, with temperature it is upper it is long rise, viscosity is gradually reduced, acrylamide copolymer product P10 by
In being free of monomer E, molecular weight is lower, though overall viscosity rises with temperature and increased, viscosity is integrally lower, and acrylamide is total
Copolymer product P11 causes molecular weight small, overall viscosity is small since three kinds of monomer ratios are improper.
It can be seen that acrylamide copolymer product P1-P8 provided by the invention has apparent high warm thickening property matter,
Belong to a kind of typical hot thickening polymer, is particularly suitable for formation temperature higher than 85 DEG C of oil reservoir development fields.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
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 with structural unit shown in formula (I), and the structural unit B is with formula
(II) structural unit shown in, the structural unit C are with structural unit shown in formula (III)；And with the acrylamide
On the basis of the total weight of copolymer, the content of the structural unit A is 70-90 weight %, and the content of the structural unit B is 8-
The content of 28 weight %, the structural unit C is 0.1-5 weight %；
Wherein, R1And R2It is each independently hydrogen or the alkyl of C1-C4, R3For the alkylidene of C1-C12, R4、R5、R6And R7Respectively solely
It is on the spot hydrogen or the alkyl of C1-C12.
2. acrylamide copolymer according to claim 1, wherein using the total weight of the acrylamide copolymer as base
Standard, the content of the structural unit A are 75-85 weight %, and the content of the structural unit B is 14-24 weight %, the structure
The content of unit C is 0.2-2 weight %.
3. acrylamide copolymer according to claim 1 or 2, wherein the viscous equal molecule of the acrylamide copolymer
Amount is 14,000,000-1,800 ten thousand；Preferably, the viscosity average molecular weigh of the acrylamide copolymer is 15,500,000-1,750 ten thousand.
4. acrylamide copolymer described in any one of -3 according to claim 1, wherein R1And R2Be each independently H or
Methyl, R3For the alkylidene of C2-C6, R4、R5、R6And R7It is each independently the alkyl of H or C1-C6.
5. a kind of preparation method of acrylamide copolymer, which is characterized in that the preparation method includes the polymerisation in solution in alkene
Under reaction condition, in the presence of initiator, so that monomer mixture is carried out polymerization reaction in water, obtain acrylamide copolymer；Its
In, the monomer mixture contains monomer D, monomer E and monomer F, the monomer D be monomer with structure shown in formula (IV),
The monomer E is that the monomer and the monomer F with structure shown in formula (V) are the monomer with structure shown in formula (VI)；
And the weight ratio of the dosage of the monomer D, the monomer E and the monomer F is 1:(0.089-0.4): (0.001-0.07)；
Wherein, R1' and R2' it is each independently hydrogen or the alkyl of C1-C4, R3' the alkylidene for being C1-C12, R4′、R5′、R6' and
R7' it is each independently hydrogen or the alkyl of C1-C12.
6. according to the method described in claim 5, wherein, on the basis of the water of 1000 parts by weight, the dosage of the monomer D is
175-225 parts by weight, the dosage of the monomer E are 15.6-90 parts by weight, and the dosage of the monomer F is 0.19-16 parts by weight；
Preferably, the dosage of the monomer D is 180-200 parts by weight, and the dosage of the monomer E is 29.6-72 parts by weight, the monomer
The dosage of F is 0.36-6 parts by weight.
7. according to the method described in claim 5, wherein, the initiator is selected from azo initiators and redox system causes
Agent, the dosage of the azo initiators are the 0.0002-0.03 weight % of the total weight of monomer in monomer mixture, preferably
0.0015-0.01 weight %；The dosage of the redox series initiators is the total weight of monomer in monomer mixture
0.0002-0.03 weight %, preferably 0.0015-0.01 weight %；The redox series initiators include oxidant and go back
Former agent, the reducing agent is inorganic reducing agent and/or organic reducing agent, and the weight ratio of the oxidant and the reducing agent is
(0.1-1): 1；
Preferably, the azo initiators are water-soluble azo series initiators, and the water-soluble azo series initiators are selected from 2,
2 '-azodiisobutyronitriles, 2,2 '-azo diisobutyl amidine dihydrochlorides, azobisisoheptonitrile, bis- (the 2- methyl-props of 2,2 '-azos
Amidine) hydrochloride, in 2,2 '-azos [2- (2- imidazoline -2- base) propane] dihydrochloride and 4,4 '-azos bis- (4- cyanopentanoic acids)
At least one；The oxidant is benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5- dimethyl -2,5 pairs
At least one of (hydrogen peroxide) hexane, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate；The inorganic reducing agent is that sulfuric acid is sub-
Iron, iron ammonium sulfate, stannous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, sulphur
At least one of potassium thiosulfate, rongalite and sodium hydrogensulfite；The organic reducing agent is N, N- dimethylethanolamine, N, N-
Lupetazin, tetramethylurea, N, at least one of N- dimethyl-ethylenediamine and N,N,N',N' tetramethylethylene diamine.
8. method according to claim 5 or 6, wherein the monomer D is acrylamide monomer, the acrylamide
Be monomer be acrylamide, Methacrylamide, N, N- dimethacrylamide, N, N- acrylamide, N- isopropyl
One of acrylamide, N hydroxymethyl acrylamide and N- hydroxyethyl acrylamide are a variety of；
The monomer E is 2-hydroxyethyl methacrylate phosphate；And
The monomer F is shown in formula (VI), wherein R2' it is H, R3' the alkylidene for being C2-C6, R4′、R5′、R6' and R7' respectively only
It is on the spot H or C1-C6 alkyl.
9. the method according to claim 5 or 7, wherein the solution polymerization condition of the alkene includes: the alkene
Solution polymerization carry out under an inert atmosphere, the initiator is azo initiators, and temperature is 40-70 DEG C, and the time is
2-10h, pH value 6-8.
10. the method according to claim 5 or 7, wherein the solution polymerization condition of the alkene includes: the alkene
The solution polymerization of hydrocarbon carries out under an inert atmosphere, and the initiator is redox series initiators, and temperature is 15-30 DEG C,
Time is 5-10h, pH value 6-8.
11. the method according to any one of claim 5-10, wherein the method also includes to institute after polymerization reaction
It obtains polymer to be dried, the condition of the drying includes: that temperature is 40-120 DEG C, and the time is 0.2-4 hours.
12. the acrylamide copolymer of the preparation of method described in any one of claim 1-4 and 5-11 is as hot thickener
Application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710556395.7A CN109232801B (en) | 2017-07-10 | 2017-07-10 | Acrylamide copolymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710556395.7A CN109232801B (en) | 2017-07-10 | 2017-07-10 | Acrylamide copolymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109232801A true CN109232801A (en) | 2019-01-18 |
| CN109232801B CN109232801B (en) | 2020-12-18 |
Family
ID=65083325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710556395.7A Active CN109232801B (en) | 2017-07-10 | 2017-07-10 | Acrylamide copolymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109232801B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464781A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Thermothickening terpolymer, its preparation method and application |
| CN104448125A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
-
2017
- 2017-07-10 CN CN201710556395.7A patent/CN109232801B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464781A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Thermothickening terpolymer, its preparation method and application |
| CN104448125A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WILLIAM L. A. BROOKS ET AL.: "Triple Responsive Block Copolymers Combining pH-Responsive, Thermoresponsive, and Glucose-Responsive Behaviors", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109232801B (en) | 2020-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104650301B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN104628944B (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN106317308B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN109232803A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232810A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232801A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232805A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232799A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232806A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232808A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232800A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232807A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232797A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232798A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232809A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232804A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN107759728B (en) | A kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active | |
| CN109232802A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN105037621B (en) | A kind of modified bittern drag reducer and preparation method thereof | |
| CN107759727B (en) | A kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active | |
| CN106317311A (en) | Acrylamide copolymer, preparation method therefor and application of acrylamide copolymer | |
| CN106317314B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN104557587B (en) | A kind of polymerisable monomer and its preparation method and application | |
| CN107868173A (en) | A kind of acrylamide copolymer and preparation method and application | |
| CN107868189A (en) | A kind of acrylamide copolymer and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |