CN104650301B - 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 PDFInfo
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Abstract
The invention discloses a kind of acrylamide copolymer, the acrylamide copolymer contains construction unit A, construction unit B and construction unit C, wherein, the construction unit A is with formula（1）The unit of shown structure, the construction unit B is with formula（2）Formula（5）At least one of unit of shown structure, the construction unit C is with formula（6）The unit of shown structure, and the construction unit A, the construction unit B and the construction unit C mass ratio are 1：0.001‑3：0.001 0.5, the viscosity average molecular weigh of the acrylamide copolymer is 27,000,000 3,200 ten thousand.The acrylamide copolymer of the present invention has higher molecular weight and apparent viscosity, can be used as high temperature and high salt oil deposit Flooding Agent for EOR.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer and its preparation method and application.
Background technology
Polymer flooding is mainly the polymer solution by injecting certain scale, increases displacement fluid viscosity, reduces oil-reservoir water
Phase permeability come reduce mobility ratio, adjustment intake profile, with reach improve displacement phase volume purpose, and then improve recovery ratio.
It is used as main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (PHPA)（HPAM）In conventional oil reservoir tertiary oil recovery (EOB) technology,
Large-scale promotion and application have been obtained, has been that oilfield stable production and volume increase have played important function.With subtracting for conventional reservoir reserve
Few, high temperature and high salt oil deposit causes HPAM application to be faced with many problems, is mainly reflected in height during exploitation high temperature and high salt oil deposit
The compound action that dissolved oxygen is produced in temperature, high salt and solution causes HPAM solution viscosities to be greatly reduced, and causes HPAM oil displacement efficiencies
It is not notable.Research shows that, when temperature is higher than 70 DEG C, HPAM acylamino- hydrolysis generation carboxyl significantly aggravates, and works as degree of hydrolysis
More than 40% is reached, carboxyl is just easy to and Ca in solution2+、Mg2+Ion generation precipitation, loses solution viscosity.In addition, in height
Under temperature, when there is dissolved oxygen in oxygen and solution in air, main polymer chain fracture can be also caused to be remarkably decreased solution viscosity.
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 yardstick, chain size distribution, construction unit composition, the micro-sequential structure of compound carry out a large amount of correlative study work, such as heatproof
Salt resistance monomer-polymer, hydrophobic associated polymer, amphiphilic polymers, composite polymer, comb polymer, template polymer and
Surface-active polymer etc..Such as entitled " the low temperature synthesis of AMPS/AM copolymers and performance "（Chang Zhiying, polymer material science
With engineering, 1997,13,16）Article in acrylamide (AM) and heat-resistant salt-resistant monomer 2- acrylamido -2- methyl-prop sulphurs
Sour (AMPS) copolymerization bipolymer；CN200810015349.7 discloses a kind of comb-type structure activity polymer and its system
Standby technique and application, are synthesized with tackifying by monomer copolymerizations such as polyurethanes surface-active macromonomer and acrylamides and reduce boundary
Face tension force target product.The polymer that above two method is obtained respectively has its feature, some performances for example temperature tolerance, salt-resistance,
More traditional polyacrylamide increases really on shear resistant and surface-active index, but its to obtain molecular weight of product small
（No more than 20,000,000）, cause the use of polymer to be restricted.
The content of the invention
It is an object of the invention to the drawbacks described above for overcoming prior art, there is provided a kind of acrylamide copolymer and its preparation
Methods and applications.
The invention provides a kind of acrylamide copolymer, the acrylamide copolymer contains construction unit A, construction unit
B and construction unit C, wherein, the construction unit A is with formula（1）The unit of shown structure, the construction unit B be with
Formula（2）- formula（5）At least one of unit of shown structure, the construction unit C is with formula（6）The unit of shown structure,
And the construction unit A, the construction unit B and the construction unit C mass ratio are 1：0.001-3：0.001-0.5, it is excellent
Elect 1 as：0.01-1.5：0.01-0.2；The viscosity average molecular weigh of the acrylamide copolymer is 27,000,000-3,200 ten thousand, is preferably
29000000-3,100 ten thousand,
Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or C1-C4 alkyl, R3For C1-C14 alkylidene；
R4、R5、R8And R9It is each independently C1-C4 alkyl, R12For C1-C14 alkyl, M1For at least one of H, Na and K, n
For arbitrary integer in 1-20, x, y and z are each independently the arbitrary integer in 1-5.
Present invention also offers a kind of preparation method of acrylamide copolymer, the preparation method comprises the following steps,
Under the conditions of solution polymerization, in the presence of initiator, a kind of monomer mixture is set to carry out polymerisation in water, wherein, institute
State monomer mixture and contain monomer E, monomer F and monomer G, the monomer E for formula（8）The monomer of shown structure, the list
Body F is with formula（9）- formula（12）At least one of monomer of shown structure, the monomer G is with formula（13）Shown structure
Monomer, and the monomer E, the monomer F and the monomer G mass ratio be 1：0.001-3：0.001-0.5, preferably 1：
0.01-1.5：0.01-0.2；The solution polymerization condition make it that the viscosity average molecular weigh of resulting polymers after polymerisation is
27000000-3,200 ten thousand, preferably 29,000,000-3,100 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or C1-C4 alkyl, R3' for C1-C14's
Alkylidene；R4’、R5’、R8' and R9' it is each independently C1-C4 alkyl, R12' be C1-C14 alkyl, M3For in H, Na and K
At least one, n ' is arbitrary integer in 1-20, and x ', y ' and z ' are each independently the arbitrary integer in 1-5.
It is main by acrylamide and temperature-resistant anti-salt monomer knot on the main chain of the strand of the acrylamide copolymer of the present invention
Structure unit is constituted, and is being ensured polymeric water-soluble simultaneously, can improved the temperature-resistant anti-salt and anti-shear performance of polymer molecule.Altogether
Polymers side chain is made up of surface active function monomer, with Interpolymer Association effect is produced, increases the slack time of molecular motion,
Improve solution viscoplasticity and reduction oil water interfacial tension effect.
Temperature-resistant anti-salt product using the acrylamide based copolymer of the present invention has good water solubility, residual monomer content low
With molecular weight it is high the characteristics of.The acrylamide copolymer molecular weight of the present invention is up to more than 30,000,000, particularly in salinity
Under 32000mg/L, 95 DEG C of hot conditions, the apparent viscosity of solution is up to more than 22mPa.s, and commercially available high molecular weight polypropylene
The molecular weight of acid amides is only 20,000,000 or so, and the apparent viscosity of solution is only 8.9mPa.s, compared with commercially available prod, propylene of the invention
Amide copolymer, which has, significantly thickens advantage, can be used as high temperature and high salt oil deposit Flooding Agent for EOR.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of acrylamide copolymer, the acrylamide copolymer contains construction unit A, construction unit
B and construction unit C, wherein, the construction unit A is with formula（1）The unit of shown structure, the construction unit B be with
Formula（2）- formula（5）At least one of unit of shown structure, the construction unit C is with formula（6）The unit of shown structure,
And the construction unit A, the construction unit B and the construction unit C mass ratio are 1：0.001-3：0.001-0.5, it is excellent
Elect 1 as：0.01-1.5：0.01-0.2；The viscosity average molecular weigh of the acrylamide copolymer is 27,000,000-3,200 ten thousand, is preferably
29000000-3,100 ten thousand,
Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or C1-C4 alkyl, R3For C1-C14 alkylidene；
R4、R5、R8And R9It is each independently C1-C4 alkyl, R12For C1-C14 alkyl, M1For at least one of H, Na and K, n
For arbitrary integer in 1-20, x, y and z are each independently the arbitrary integer in 1-5.
In the present invention, the alkyl of the C1-C4 can be straight chain or side chain.The alkyl of the C1-C4
Example can include：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
In the present invention, the alkyl of the C1-C14 can be straight chain or side chain.The alkane of the C1-C14
The example of base can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group,
N-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive hendecyl, positive ten
Diyl, positive tritriacontyl and positive tetradecyl.
In the present invention, the alkylidene of the C1-C14 can be straight or branched, 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 the sub- tert-butyl group, 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 same carbon atom, also may be used
Can be straight chain or side chain with two hydrogen atoms on different carbon atoms, for example, the ethylidene can be-
CH2CH2- or-CH (CH3)-。
In the present invention, although as long as containing construction unit A, construction unit B and construction unit C and meeting aforementioned proportion pass
The purpose of the present invention can be achieved in system, but under preferable case, construction unit A amount accounts for the 30-99 of the acrylamide copolymer
Weight %.
According to the present invention, the acrylamide copolymer is also containing construction unit D, and the construction unit D is with formula（7）
The unit of shown structure：
Wherein, M2For potassium or sodium, preferably sodium.
The present invention is not specially required to construction unit D quality, for instance, it is preferred that the construction unit A, the knot
The mass ratio of structure unit B, the construction unit C and the construction unit D is 1：0.001-3：0.001-0.5：0.1-1, enters one
Step is preferably 1：0.01-1.5：0.01-0.2：0.1-1.
The present inventor has found under study for action, by specific construction unit A, construction unit B, construction unit C and knot
It is good that preferable oil displacement efficiency can be obtained when the quadripolymer of structure cells D composition is for oil displacement agent.For instance, it is preferred that the knot
Structure unit B is with formula（2）With（4）At least one of unit of shown structure, and R2And R7It is each independently hydrogen or first
Base；In the construction unit C, R12For C5-C10 alkyl, n is the arbitrary integer in 5-20, and x, y and z are each independently 1-3
In arbitrary integer when, the quadripolymer of composition is used to that during oil displacement agent preferable oil displacement efficiency can be obtained.Still more preferably
Ground, the construction unit C is with formula（14）The unit of shown structure：
Wherein, n is preferably the arbitrary integer in 8-12.
Present invention also offers a kind of preparation method of acrylamide copolymer, this method comprises the following steps, in solution
Under polymeric reaction condition, in the presence of initiator, a kind of monomer mixture is set to carry out polymerisation in water, wherein, the list
It is with formula that body mixture, which contains monomer E, monomer F and monomer G, the monomer E,（8）The monomer of shown structure, the monomer F is
With formula（9）- formula（12）At least one of monomer of shown structure, the monomer G is with formula（13）The list of shown structure
Body, and the monomer E, the monomer F and the monomer G mass ratio are 1：0.001-3：0.001-0.5, preferably 1：
0.01-1.5：0.01-0.2；The solution polymerization condition make it that the viscosity average molecular weigh of resulting polymers after polymerisation is
27000000-3,200 ten thousand, preferably 29,000,000-3,100 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or C1-C4 alkyl, R3' for C1-C14's
Alkylidene；R4’、R5’、R8' and R9' it is each independently C1-C4 alkyl, R12' be C1-C14 alkyl, M3For in H, Na and K
At least one, n ' is arbitrary integer in 1-20, and x ', y ' and z ' are each independently the arbitrary integer in 1-5.
The alkyl of the alkyl of the C1-C4, C1-C14 alkylidene and C1-C14 is identical with foregoing description.
In the present invention, monomer E is preferably the 40-99 weight % of monomer mixture gross mass.
The present inventor has found under study for action, when selecting specific monomer E, monomer F and monomer G to be reacted,
The oil displacement efficiency of the polymer of gained can further be improved.For instance, it is preferred that when the monomer F is with formula（9）And formula
（11）At least one of monomer of shown structure, and R2' and R7' it is each independently hydrogen or methyl；In the monomer G, R12’
For C5-C10 alkyl, n ' is the arbitrary integer in 5-20, when x ', y ' and z ' are each independently the arbitrary integer in 1-3, is closed
Into polymer have higher oil displacement efficiency, it is further preferred that the monomer G be with formula（15）The list of shown structure
Body：
Wherein, n ' is preferably the arbitrary integer in 8-12.
According to the present invention, the solution polymerization is carried out in water, when the solution polymerization starts, the monomer
There is no particular limitation for the ratio of the weight and water of mixture and the gross weight of monomer mixture, can become in wider scope
Dynamic, under preferable case, the ratio of the weight and water of the monomer mixture and the gross weight of monomer mixture is 0.15-0.4：1,
More preferably 0.2-0.3：1.
In the present invention, the initiator can be the various initiators in this area.For example, the initiator can be selected from even
Nitrogen series initiators and/or redox body class initiator, preferably azo series initiators and redox body class initiator.It is described
The consumption of azo series initiators is heavy for 0.0001-0.1 the weight %, preferably 0.001-0.05 of the gross weight of monomer mixture
Measure %；The consumption of the redox series initiators is the 0.0002-0.3 weight % of the gross weight of monomer mixture, is preferably
0.002-0.15 weight %.The azo series initiators are preferably water-soluble azo series initiators, the redox series initiators
Including Oxidizing and Reducing Agents, the reducing agent be inorganic reducing agent and/or organic reducing agent, and the oxidant with it is described also
The weight ratio of former agent is 0.1-1:1.
In the present invention, the water-soluble azo series initiators are preferably 2,2'- azo diisobutyl amidines dihydrochloride, 2,
At least one of 2'- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride and 4,4'- azo double (4- cyanopentanoic acids),
More preferably 2,2'- azos diisobutyl amidine dihydrochloride.
In the present invention, the oxidant can be in acyl peroxide, hydroperoxides and persulfate at least one
Kind, preferably benzoyl peroxide, hydrogen peroxide, TBHP, 2,5- dimethyl -2,5 pair (hydrogen peroxide) hexane,
At least one of ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate, are still more 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
Plant, 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- lupetazins, tetramethylurea, N, N-dimethyl-ethylenediamine and N, N, N ', in N '-tetramethylethylenediamine
At least one, more preferably N, N, N ', N '-tetramethylethylenediamine.
According to the present invention, the condition of the solution polymerization can be the conventional condition in this area.For example, the solution
Polymerisation is carried out in the presence of an inert gas, and the polymeric reaction condition can include：Temperature is -10 DEG C to 20 DEG C, preferably 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, for example, can be the conventional nitrogen in this area
Or at least one of group 0 element gas in the periodic table of elements, preferably nitrogen.
According to the present invention, methods described also includes resulting polymers after polymerisation are hydrolyzed and dried.This area
Technical staff could be aware that the process of hydrolysis is included hydrolytic reagent and polymer reaction.Pass through hydrolysis, part propylene acyl
Amine structure unit is formula（1）Shown construction unit is transformed into acrylates construction unit, i.e. Chinese style of the present invention（7）Shown
Construction unit.
In the present invention, the condition of the hydrolysis is not particularly limited, under preferable case, the condition bag 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；The hydrolysis causes poly-
The degree of hydrolysis for closing resulting polymers after reaction can be 10-30%.
In the present invention, the degree of hydrolysis refers to that the molal quantity of acrylates construction unit accounts for acrylamide of the invention and is total to
The percentage of the total mole number of the construction unit of polymers.The degree of hydrolysis is determined by the consumption of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent for it is commonly used in the art it is various can realize the inorganic alkaline compound of above-mentioned purpose,
Can be selected from least one of sodium hydroxide, potassium hydroxide and sodium carbonate.The consumption of the hydrolytic reagent can be according to acryloyl
The degree of hydrolysis of amine copolymer thing carries out appropriate selection, is defined so that the degree of hydrolysis of acrylamide copolymer meets use requirement, excellent
Inorganic alkaline compound consumption is selected so that the degree of hydrolysis of acrylamide copolymer is 10-30%.
Those skilled in the art could be aware that, by adjusting the consumption of inorganic alkaline compound, can obtain not
With the acrylamide copolymer of degree of hydrolysis.
In the present invention, the molal quantity of the inorganic alkaline compound is equal to the molal quantity of acrylates construction unit.
According to the present invention, the present invention is to drying condition without particular/special requirement, and 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.
The present invention it is a kind of preferred embodiment in, the preparation method of the acrylamide copolymer includes following step
Suddenly：
（1）Acrylamide monomer, temperature-resistant anti-salt monomer, surface active function monomer and water are mixed to form comonomer water
Solution, pH to 5-10 is adjusted with inorganic alkaline compound, controls -10 DEG C to 20 DEG C of solution temperature；
（2）Lead to nitrogen into the comonomer aqueous solution and carry out deoxygenation, control oxygen content in solution to be less than 1mg/L, it is preferably small
In 0.2mg/L；
（3）Under logical condition of nitrogen gas, composite initiation system is added to monomer solution, adiabatic polymerisation is carried out, obtains copolymerization
Thing gel；
（4）By copolymer gel progress, once granulation, hydrolysis, secondary granulation, drying, crushing and screening obtain temperature-resistant anti-salt
Acrylamide copolymer product.
According to the present invention, step（1）In, the temperature-resistant anti-salt monomer is monomer F of the present invention, the surface-active work(
Energy monomer is monomer G of the present invention, and the inorganic alkaline compound is used to adjust acrylamide and temperature-resistant anti-salt monomer water
The pH value of solution.The inorganic alkaline compound can be at least one of for sodium hydroxide, potassium hydroxide and sodium carbonate, preferably
For sodium hydroxide.
Present invention also offers the acrylamide copolymer according to made from the above method.
In addition, the application present invention also offers the acrylamide copolymer in oil displacement agent.
Below, by following examples, the present invention will be described in more detail
In following examples, the performance test of product is carried out using following methods：
1st, the method according to specified in the People's Republic of China (PRC) oil and gas industry standard SY/T5862-2008 is determined
Solid content, dissolution time, filtration ratio, insolubles content, AM residual monomer contents and the intrinsic viscosity of polymer.
2nd, polymer viscosity average molecular weigh method according to specified in SY/T5862-2008, using formula M=([η]/
0.000373)1.515To calculate, wherein, M is viscosity average molecular weigh, and [η] is intrinsic viscosity.
3rd, the apparent viscosity of polymer solution is that polymer is made into 1500mg/L's with salinity 32000mg/L salt solution
Solution, with Brookfield viscosimeters in 95 DEG C, 7.34s-1Under the conditions of determine.
In following examples, acrylamide is commercially available from Bao Mo biochemical industries limited company, 2- acrylamido -2- first
Base propane sulfonic acid is commercially available from Xiamen Changtian Enterprise Co., Ltd., and 2,2'- azo diisobutyl amidine dihydrochlorides are public commercially available from Aldrich
Department.Formula（15）The surface active function monomer of shown structure（Allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether ammonium sulfate）Purchase
From Foshan Kodi Gas Chemical Industry Co., Ltd., the trade mark is respectively SE-10, SE-15 and SE-20（" 10 ", " 15 " and " 20 " difference
Represent n ' numerical value.）
Embodiment 1
The present embodiment is used for the preparation method for illustrating the acrylamide copolymer that the present invention is provided
1000 grams of acrylamides, 10 grams of 2- acrylamide-2-methylpro panesulfonic acids are added in beaker, 10 grams such as formula（15）
The surface active function monomer of shown structure（N ' is 10）With 4080 grams of deionized waters, under stirring, chilled brine control is used
5 DEG C of solution temperature, adds sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, 10.2 milligram 2,2'- is added
Azo diisobutyl amidine dihydrochloride and 10.2 milligrams of N, N, N ', N '-tetramethylethylenediamine leads to high pure nitrogen deoxygenation 0.5 hour,
10.2 milligrams of sodium hydrogensulfites and 10.2 milligrams of ammonium persulfates are added, continue logical nitrogen until thermocouple starts to rise in polymerization bottle
Temperature, 8 hours reaction time.Colloid is taken out, 4-6 millimeters of copolymer micelle is a granulated into by comminutor.By degree of hydrolysis 20%,
The sodium hydroxide grain alkali of obtained copolymer micelle and respective amount is mediated and contacted, is hydrolyzed 0.5 hour at 90 DEG C of temperature, through two
After secondary granulation, it is dried, acrylamide copolymer the product P1, P1 of 20-80 mesh performance such as table 1 is obtained by crushing and screening
It is shown.Calculated and determined according to inventory, in acrylamide copolymer, construction unit A, construction unit B, construction unit C and structure
The mass ratio of cells D is 1：0.013：0.013：0.333.
Comparative example 1
Using process conditions same as Example 1, except that, it is added without such as formula（15）The surface active function of structure
Monomer（N ' is 10）, so that the performance for obtaining acrylamide copolymer product DP1, DP1 is as shown in table 1.
Embodiment 2
The present embodiment is used for the preparation method for illustrating the acrylamide copolymer that the present invention is provided
1000 grams of acrylamides, 1000 grams of 2- acrylamide-2-methylpro panesulfonic acids are added in beaker, 100 grams such as formula
（15）The surface active function monomer of shown structure（N ' is 10）With 4900 grams of deionized waters, under stirring, chilled brine is used
15 DEG C of solution temperature is controlled, sodium hydroxide regulation pH to 7 is added.Monomer solution is transferred in polymerization bottle, 1.05 gram 2 is added,
2'- azos diisobutyl amidine dihydrochloride and 1.05 grams of N, N, N ', N '-tetramethylethylenediamine leads to high pure nitrogen deoxygenation 0.5 small
When, 1.05 grams of sodium hydrogensulfites and 1.05 grams of ammonium persulfates are added, continue logical nitrogen until thermocouple is started to warm up in polymerization bottle,
4 hours reaction time.Colloid is taken out, 4-6 millimeters of copolymer micelle is a granulated into by comminutor.By degree of hydrolysis 20%, will
To the sodium hydroxide grain alkali of copolymer micelle and respective amount mediate and contact, hydrolyzed 4 hours under temperature 70 C, through secondary granulation
Afterwards, it is dried, the performance that acrylamide copolymer the product P2, P2 of 20-80 mesh are obtained by crushing and screening is as shown in table 1.
Calculated and determined according to inventory, in acrylamide copolymer, construction unit A, construction unit B, construction unit C and construction unit D
Mass ratio be 1：1.370：0.137：0.489.
Embodiment 3
The present embodiment is used for the preparation method for illustrating the acrylamide copolymer that the present invention is provided
1000 grams of acrylamides, 100 grams of 2- acrylamide-2-methylpro panesulfonic acids are added in beaker, 50 grams such as formula
（15）The surface active function monomer of shown structure（N ' is 10）With 3450 grams of deionized waters, under stirring, chilled brine is used
10 DEG C of solution temperature is controlled, sodium hydroxide regulation pH to 7 is added.Monomer solution is transferred in polymerization bottle, 115 milligram 2 is added,
2'- azos diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-tetramethylethylenediamine leads to high pure nitrogen deoxygenation 0.5 small
When, 115 milligrams of sodium hydrogensulfites and 115 milligrams of ammonium persulfates are added, continue logical nitrogen until thermocouple starts to rise in polymerization bottle
Temperature, 6 hours reaction time.Colloid is taken out, 4-6 millimeters of copolymer micelle is a granulated into by comminutor.By degree of hydrolysis 20%,
The sodium hydroxide grain alkali of obtained copolymer micelle and respective amount is mediated and contacted, is hydrolyzed 2 hours at 80 DEG C of temperature, through secondary
After granulation, it is dried, acrylamide copolymer the product P3, P3 of 20-80 mesh the performance such as institute of table 1 is obtained by crushing and screening
Show.Calculated and determined according to inventory, in acrylamide copolymer, construction unit A, construction unit B, construction unit C and structure list
First D mass ratio is 1：0.126：0.063：0.347.
Embodiment 4
The present embodiment is used for the preparation method for illustrating the acrylamide copolymer that the present invention is provided
1000 grams of acrylamides, 100 grams of 2- acrylamide-2-methylpro panesulfonic acids are added in beaker, 50 grams such as formula
（15）The surface active function monomer of shown structure（N ' is 15）With 3450 grams of deionized waters, under stirring, chilled brine is used
10 DEG C of solution temperature is controlled, sodium hydroxide regulation pH to 7 is added.Monomer solution is transferred in polymerization bottle, 115 milligram 2 is added,
2'- azos diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-tetramethylethylenediamine leads to high pure nitrogen deoxygenation 0.5 small
When, 115 milligrams of sodium hydrogensulfites and 115 milligrams of ammonium persulfates are added, continue logical nitrogen until thermocouple starts to rise in polymerization bottle
Temperature, 6 hours reaction time.Colloid is taken out, 4-6 millimeters of copolymer micelle is a granulated into by comminutor.By degree of hydrolysis 20%,
The sodium hydroxide grain alkali of obtained copolymer micelle and respective amount is mediated and contacted, is hydrolyzed 2 hours at 80 DEG C of temperature, through secondary
After granulation, it is dried, acrylamide copolymer the product P4, P4 of 20-80 mesh the performance such as institute of table 1 is obtained by crushing and screening
Show.Calculated and determined according to inventory, in acrylamide copolymer, construction unit A, construction unit B, construction unit C and structure list
First D mass ratio is 1：0.126：0.063：0.346.
Embodiment 5
The present embodiment is used for the preparation method for illustrating the acrylamide copolymer that the present invention is provided
1000 grams of acrylamides, 100 grams of 2- acrylamide-2-methylpro panesulfonic acids are added in beaker, 50 grams such as formula
（15）The surface active function monomer of the structure（N ' is 20）With 3450 grams of deionized waters, under stirring, chilled brine is used
10 DEG C of solution temperature is controlled, sodium hydroxide regulation pH to 7 is added.Monomer solution is transferred in polymerization bottle, 115 milligram 2 is added,
2'- azos diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-tetramethylethylenediamine leads to high pure nitrogen deoxygenation 0.5 small
When, 115 milligrams of sodium hydrogensulfites and 115 milligrams of ammonium persulfates are added, continue logical nitrogen until thermocouple starts to rise in polymerization bottle
Temperature, 6 hours reaction time.Colloid is taken out, 4-6 millimeters of copolymer micelle is a granulated into by comminutor.By degree of hydrolysis 20%,
The sodium hydroxide grain alkali of obtained copolymer micelle and respective amount is mediated and contacted, is hydrolyzed 2 hours at 80 DEG C of temperature, through secondary
After granulation, it is dried, acrylamide copolymer the product P5, P5 of 20-80 mesh the performance such as institute of table 1 is obtained by crushing and screening
Show.Calculated and determined according to inventory, in acrylamide copolymer, construction unit A, construction unit B, construction unit C and structure list
First D mass ratio is 1：0.126：0.063：0.346.
Embodiment 6
1000 grams of acrylamides, 50 grams of 2- acrylamide-2-methylpro panesulfonic acids, 50 grams of N, N- diformazans are added in beaker
Base acrylamide, 50 grams such as formula（15）The surface active function monomer of shown structure（N ' is 10）With 3450 grams of deionized waters, stir
Mix under state, 10 DEG C of solution temperature is controlled with chilled brine, add sodium hydroxide regulation pH to 7.Monomer solution is transferred to poly-
Close in bottle, add 115 milligrams of 2,2'- azos diisobutyl amidine dihydrochlorides and 115 milligrams of N, N, N ', N '-tetramethylethylenediamine,
Logical high pure nitrogen deoxygenation 0.5 hour, adds 115 milligrams of sodium hydrogensulfites and 115 milligrams of ammonium persulfates, continues logical nitrogen until poly-
Close thermocouple in bottle to start to warm up, 6 hours reaction time.Colloid is taken out, 4-6 millimeters of copolymer is a granulated into by comminutor
Micelle.By degree of hydrolysis 20%, obtained copolymer micelle is mediated with the sodium hydroxide grain alkali of respective amount and contacted, in 80 DEG C of temperature
Lower hydrolysis 2 hours, after secondary granulation, is dried, the acrylamide copolymer product of 20-80 mesh is obtained by crushing and screening
P6, P6 performance are as shown in table 1.Calculated and determined according to inventory, in acrylamide copolymer, construction unit A, construction unit B,
Construction unit C and construction unit D mass ratio are 1：0.127：0.063：0.355.
Embodiment 7
Using process conditions same as Example 6, except that, replaced with the vinyl pyrrolidone of equal mass
N,N-DMAA, so that the performance that acrylamide copolymer product P7, P7 is made is as shown in table 1.According to inventory
Calculate and determine, in acrylamide copolymer, construction unit A, construction unit B, construction unit C and construction unit D mass ratio are
1：0.127：0.063：0.354.
Embodiment 8
Using process conditions same as Example 2, except that, replace 2- acrylamides with the acrylic acid of equal mass
Base -2- methyl propane sulfonic acids, and without hydrolysis, i.e., do not carry out in embodiment 2 by obtained copolymer micelle and hydrogen-oxygen
Change sodium grain alkali and mediate contact, the step of being hydrolyzed 2 hours at 80 DEG C, so as to obtain acrylamide copolymer product P8, P8 property
Can be as shown in table 1.Calculated and determined according to inventory, in acrylamide copolymer, construction unit A, construction unit B and construction unit
C mass ratio is 1：1：0.1.
Embodiment 9
Using process conditions same as Example 2, except that, without hydrolysis, i.e., do not carry out in embodiment 2
Obtained copolymer micelle is mediated with sodium hydroxide grain alkali and contacted, the step of being hydrolyzed 2 hours at 80 DEG C, so as to obtain propylene
Amide copolymer product P9, P9 performance are as shown in table 1.Calculated and determined according to inventory, in acrylamide copolymer, structure list
First A, construction unit B and construction unit C mass ratio are 1：1：0.1.
Table 1
Understand that the molecular weight for the acrylamide copolymer product that embodiment 1 is obtained can with comparative example data in conjunction with the embodiments
To reach 30,800,000, and the molecular weight that comparative example 1 obtains acrylamide copolymer product is only 26,100,000, and embodiment 1 is relatively contrasted
The molecular weight of copolymer that example 1 is obtained improves nearly 4,700,000, and corresponding 95 DEG C of apparent viscosities improve 9.8mPas.Illustrate table in the present invention
The introducing of face active function monomer is more beneficial for the apparent of copolymer solution under the molecular weight of raising copolymer and hot conditions and glued
Degree.
By embodiment 2 compared with Example 9, the molecular weight that acrylamide copolymer product is obtained in embodiment 9 is 2700
Ten thousand, 95 DEG C of apparent viscosity 14.9mPas, both of which are less than the result of the products obtained therefrom of embodiment 2.Illustrate in copolymer structure
It is suitably introduced into molecular weight and copolymer solution under hot conditions that PAA construction unit is more beneficial for improving copolymer
Apparent viscosity.
By taking embodiment 1 as an example, the obtained temperature-resistant anti-salt acrylamide copolymer of the present invention in high salinity 32000mg/L,
Under the conditions of 95 DEG C of high temperature, the apparent viscosity of solution is up to 22.9mPas, and commercially available high molecular weight polyacrylamide solution apparent
Viscosity is only 8.9mPas, relatively contrast commercially available prod, and acrylamide copolymer of the invention, which has, significantly thickens advantage.Accordingly,
Understand that the acrylamide copolymer that the present invention is provided has good temperature-resistant anti-salt performance.
Claims (22)
1. a kind of acrylamide copolymer, it is characterised in that the acrylamide copolymer contain construction unit A, construction unit B and
Construction unit C, wherein, the construction unit A is the unit with structure shown in formula (1), and the construction unit B is with formula
(2) at least one of unit of structure shown in-formula (5), the construction unit C is the unit with structure shown in formula (6), and
The construction unit A, the construction unit B and the construction unit C mass ratio are 1：0.001-3：0.001-0.5；It is described
The viscosity average molecular weigh of acrylamide copolymer is 27,000,000-3,200 ten thousand,
Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or C1-C4 alkyl, R3For C1-C14 alkylidene；R4、
R5、R8And R9It is each independently C1-C4 alkyl, R12For C1-C14 alkyl, M1For at least one of H, Na and K, n is
Arbitrary integer in 1-20, x, y and z are each independently the arbitrary integer in 1-5.
2. acrylamide copolymer according to claim 1, wherein, the construction unit A, the construction unit B and institute
The mass ratio for stating construction unit C is 1：0.01-1.5：0.01-0.2；The viscosity average molecular weigh of the acrylamide copolymer is 2900
Ten thousand -3,100 ten thousand.
3. acrylamide copolymer according to claim 1, wherein, the acrylamide copolymer also contains construction unit
D, the construction unit D are the unit with structure shown in formula (7)：
Wherein, M2For potassium or sodium.
4. acrylamide copolymer according to claim 3, wherein, it is the construction unit A, the construction unit B, described
Construction unit C and the construction unit D mass ratio are 1：0.001-3：0.001-0.5：0.1-1.
5. acrylamide copolymer according to claim 3, wherein, it is the construction unit A, the construction unit B, described
Construction unit C and the construction unit D mass ratio are 1：0.01-1.5：0.01-0.2：0.1-1.
6. the acrylamide copolymer according to any one in claim 1-5, wherein, the construction unit B be with
At least one of unit of structure shown in formula (2) and (4), and R2And R7It is each independently hydrogen or methyl；The construction unit
In C, R12For C5-C10 alkyl, n is the arbitrary integer in 5-20, and x, y and z are each independently the arbitrary integer in 1-3.
7. a kind of preparation method of acrylamide copolymer, the preparation method comprises the following steps, in solution polymerization condition
Under, in the presence of initiator, a kind of monomer mixture is carried out polymerisation in water, it is characterised in that the monomer mixing
It is the monomer with structure shown in formula (8) that thing, which contains monomer E, monomer F and monomer G, the monomer E, and the monomer F is with formula
(9) at least one of monomer of structure shown in-formula (12), the monomer G is the monomer with structure shown in formula (13), and institute
The mass ratio for stating monomer E, the monomer F and the monomer G is 1：0.001-3：0.001-0.5；The solution polymerization bar
Part causes the viscosity average molecular weigh of resulting polymers after polymerisation to be 27,000,000-3,200 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or C1-C4 alkyl, R3' be C1-C14 alkylene
Base；R4’、R5’、R8' and R9' it is each independently C1-C4 alkyl, R12' be C1-C14 alkyl, M3For in H, Na and K extremely
Few one kind, n ' is arbitrary integer in 1-20, and x ', y ' and z ' are each independently the arbitrary integer in 1-5.
8. method according to claim 7, wherein, the monomer E, the monomer F and the monomer G mass ratio are 1：
0.01-1.5：0.01-0.2；The solution polymerization condition make it that the viscosity average molecular weigh of resulting polymers after polymerisation is
29000000-3,100 ten thousand.
9. method according to claim 7, wherein, the monomer F is the monomer with structure shown in formula (9) and formula (11)
At least one of, and R2' and R7' it is each independently hydrogen or methyl；In the monomer G, R12' be C5-C10 alkyl, n '
For the arbitrary integer in 5-20, x ', y ' and z ' are each independently the arbitrary integer in 1-3.
10. method according to claim 7, wherein, when the solution polymerization starts, the weight of the monomer mixture
The ratio of amount and water and the gross weight of monomer mixture is 0.15-0.4：1.
11. method according to claim 7, wherein, when the solution polymerization starts, the weight of the monomer mixture
The ratio of amount and water and the gross weight of monomer mixture is 0.2-0.3：1.
12. method according to claim 7, wherein, the initiator is selected from azo series initiators and redox system draws
Agent is sent out, the consumption of the azo series initiators is the 0.0001-0.1 weight % of the gross weight of monomer mixture, and the oxidation is also
The consumption of former series initiators is the 0.0002-0.3 weight % of the gross weight of monomer mixture；The azo series initiators are water-soluble
Property azo 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.
13. method according to claim 12, wherein, it is different that the water-soluble azo series initiators are selected from 2,2'- azos two
Butyl amidine dihydrochloride, 2,2'- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride and double (the 4- cyano group penta of 4,4'- azos
At least one of acid)；The oxidant is selected from benzoyl peroxide, hydrogen peroxide, TBHP, 2,5- diformazans
At least one of -2,5 pairs, base (hydrogen peroxide) hexane, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate；The inorganic reducing agent
Selected from ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, thio
At least one of sodium sulphate, potassium thiosulfate, rongalite and sodium hydrogensulfite；The organic reducing agent is selected from N, N- dimethyl
Monoethanolamine, N, N- lupetazins, tetramethylurea, N, N-dimethyl-ethylenediamine and N, N, N ', in N '-tetramethylethylenediamine extremely
Few one kind.
14. method according to claim 7, wherein, the solution polymerization is carried out in the presence of an inert gas, described
Polymeric reaction condition includes：Temperature is -10 DEG C to 20 DEG C；Time is 2-12 hours；PH value is 4-12.
15. method according to claim 7, wherein, the polymeric reaction condition includes：Temperature is 5 DEG C to 15 DEG C；Time
For 4-8 hours；PH value is 5-10.
16. the method according to any one in claim 7-15, wherein, methods described also includes to institute after polymerisation
Polymer is obtained to be hydrolyzed and dry.
17. method according to claim 16, wherein, the hydrolysising condition includes：Temperature is 50-110 DEG C；Time is
0.5-6 hours；The hydrolysis causes the degree of hydrolysis of resulting polymers after polymerisation to be 10-30%.
18. method according to claim 16, wherein, the hydrolysising condition includes：Temperature is 70-90 DEG C；Time is 1-4
Hour.
19. method according to claim 16, wherein, the condition of the drying includes：Temperature is 40-120 DEG C；Time is
0.2-4 hours.
20. method according to claim 16, wherein, the condition of the drying includes：Temperature is 70-90 DEG C；Time is
0.5-2 hours.
21. acrylamide copolymer made from the method in claim 7-20 described in any one.
22. acrylamide copolymer in claim 1-6 and 21 described in any one is used as the application of oil displacement agent.
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| CN106317303B (en) * | 2015-06-19 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of polymer and its preparation method and application with surface active function |
| CN106317301B (en) * | 2015-06-19 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of polymer and its preparation method and application with surface active function |
| CN106317305B (en) * | 2015-06-19 | 2018-09-21 | 中国石油化工股份有限公司 | A kind of polymer and its preparation method and application with surface active function |
| CN107226887B (en) * | 2016-03-24 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of polymer and its preparation method and application with surface active function |
| CN107226886B (en) * | 2016-03-24 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of polymer and its preparation method and application with surface active function |
| CN107226885B (en) * | 2016-03-24 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of polymer and its preparation method and application with surface active function |
| CN107226884B (en) * | 2016-03-24 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of polymer and its preparation method and application with surface active function |
| CN107759727B (en) * | 2016-08-16 | 2019-09-27 | 中国石油化工股份有限公司 | A kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active |
| CN108250359A (en) * | 2016-12-29 | 2018-07-06 | 天津博弘化工有限责任公司 | The preparation method of high salt tolerance POLYACRYLAMIDE FLOODING agent |
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