CN104250340B - A kind of polymerizable functional monomer and its preparation method and application - Google Patents
A kind of polymerizable functional monomer and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of temperature-resistant anti-salt displacement of reservoir oil copolymer and preparation method thereof.The copolymer of the present invention is for the oil displacement agent of tertiary oil recovery, it is possible to have the highest aqueous solutions of polymers apparent viscosity at normal temperatures, and under conditions of high temperature, high salinity, aqueous solutions of polymers is maintained to the highest apparent viscosity.
Description
Technical field
The present invention relates to a kind of polymerizable functional monomer and its preparation method and application.
Background technology
Radical polymerization is to prepare one of polyvinyl most efficient method.Currently used ethylene
In based polyalcohol, 70% is above being obtained by radical polymerization.Radical polymerization has many advantages,
As many in suitable monomers, polymerizing condition is gentle, polymerization technique is simple.Owing to many monomers can be carried out certainly
Being polymerized by base, energy water is that medium carries out suspending and emulsion polymerization, and polymerization process is easy, and it is heavy
Existing property is good, thus has become the important skill of commercial production macromolecule product since the fifties in last century
Art.
There is the polymerization monomer of emulsification function, also known as polymerisable emulsifier, except containing in its molecular structure
Have outside the emulsifying agent group of hydrophilic and oleophilic, possibly together with participating in the functional group of Raolical polymerizable,
Becoming a part for polymer, therefore emulsifier molecules will not occur desorbing again, so that polymer beads
Son by electrostatic repulsion and bigger steric restriction effect, makes the stability of latex obtain in coacervation process
A lot of to improve the kind of polymerisable emulsifier, acrylic amide polymerisable emulsifier has reactivity
The particular advantages such as high, polymer molecular weight is high.
Polymer oil-displacing agent has the modified product three of synthetic polymer, biopolymer, natural polymer
Big class.At present, the most frequently used polymer has two classes: one is the biopolymer with Xanthan gun as representative；
Two is the synthetic polymer as representative with partially hydrolyzed polyacrylamide (PHPA) and derivant thereof, with HPAM is
Main.But HPAM temperature-resistant anti-salt performance is undesirable, the ultimate-use (limiting service) temperature under reservoir condition is only 75 DEG C,
In the presence of having salt, viscosity acutely declines, and bivalent metal ion also can make it produce precipitation and lose viscosity.
It addition, HPAM can occur molecular chain rupture under shear action, its tackifying ability is caused to reduce.Grind
Study carefully and show, the poor-performing such as the temperature tolerance of HPAM, salt-resistance and shear resistant so that it is application conditions
It is restricted.Xanthan gun has certain anti-salt resistant to shearing performance, but Xanthan gun meeting in high-temperature stratum
Thermal oxidative degradation occurs, and the formation temperature for tertiary oil recovery typically should not be higher than 60 DEG C.Additionally yellow born of the same parents
The price of glue is five times of HPAM, also limit its popularization.
Polymer molecular chain introduces some high thermal stability monomeric units, the monomer of bigger skeleton
Unit and the group of strong hydration capability, thus strengthen polymer thermostable and molecule chain rigidity, increase
Strength polymer hydration capability so that polymer molecule can keep bigger in high salinity aqueous solution
Hydrodynamics size, this enhances polymer salt resistance ability to a certain extent.It addition, function monomer
Introducing, make polymer hydrolyze under the conditions of high-salinity water quality and be restricted, do not have and calcium and magnesium
There is the phenomenon of precipitation in ion, thus reaches the purpose of anti-salt.
Summary of the invention
The technical problem to be solved in the present invention is:
It is an object of the invention to provide a kind of polymerizable functional monomer and synthetic method thereof, can be used as gathering
Co-emulsifier, and for the synthesis of temperature-resistant anti-salt displacement of reservoir oil copolymer, to improve Polymer Used For Oil Displacement
Performance.
The product technology scheme of the polymerizable functional monomer of the present invention is:
A kind of polymerizable functional monomer, its structure is as shown in (I) formula:
In (I) formula, n is 0 or 1, and m is 4,6 or 8.
For the sake of difference, maleic anhydride is contacted with aromatic diamines and makes anhydride generation open loop by the present invention
And the reaction obtaining amide is referred to as amidation process, carboxylic acid is obtained by sloughing a part water with amine
The reaction of amide is referred to as condensation reaction.
The preparation method technical scheme of the polymerizable functional monomer of the present invention, comprises the following steps:
The first step, under amidation reaction condition, the aromatic diamines making formula be (II) and maleic
Dicarboxylic anhydride reacts, and obtains intermediate M；
(II) in formula, n is 0 or 1, and described intermediate M is as shown in (III) formula:
Second step, under condensationization reaction condition, the binary of fatty acids making formula be (IV) is with described
Intermediate M reacts,
HOOC-(CH2)m-COOH
(IV)
In (IV) formula, m is 4,6 or 8；
Obtain the polymerizable functional monomer as shown in (I) formula；In (I) formula: n is 0 or 1,
M is 4,6 or 8.
Further preferred:
In the first step, described aromatic diamines is selected from: p-phenylenediamine or p dimethylamine；
In order to obtain the intermediate M shown in formula III, the formula used in step (1) is (II)
Aromatic diamines and maleic anhydride carry out the mol ratio of amidation process addition can be in a big way
Interior selection, the mol ratio of aromatic diamines described in preferred steps (1) and maleic anhydride be 1:1～
1.1, more preferably 1:1～1.05.It is that the aromatic diamines of (II) is with suitable by controlling formula
The additional proportion of anhydride maleique carrys out to control as far as possible the fragrance two that formula is (II) within the above range
-NH in amine2With carboxylic acid reaction, obtain intermediate M.
Amidation reaction condition described in the first step can be various aromatic diamines and the maleics two of can making
Anhydride reaction formed amide condition, concrete temperature and time can according to used aromatic diamines with
The character of maleic anhydride selects.In situations where it is preferred, the temperature of amidation process in the first step
Degree is 80 DEG C～110 DEG C, preferably 90 DEG C～100 DEG C；The time of amidation process is 2～6 hours,
It is preferably 3～5 hours.
Aromatic diamines and maleic anhydride in order to make first step formula of be (II) carry out amidatioon
React more easy to control, organic solvent can be added in the first step.The addition of organic solvent can be
Select in relative broad range, it is preferable that described organic solvent is selected from following one or more: acetone,
Ethyl acetate, benzene, dimethylbenzene, dichloromethane and chloroform；Described aromatic diamines has with described
The mol ratio of machine solvent is 1:5～20, preferably 1:10～15.
In order to obtain the polymerizable functional monomer shown in formula I, second step is included in condensation reaction
Under conditions of, the intermediate M that the binary of fatty acids making formula be (IV) and the first step obtain connects
Touch,
This contact can be in second step, formula be (IV) binary of fatty acids with purify after in
Mesosome M directly carries out condensation reaction；
Can also be that, in second step, formula is that the binary of fatty acids of (IV) obtains with the first step
Mixture containing intermediate M can the most directly carry out condensation reaction.
The addition that formula is the binary of fatty acids of (IV) is to obtain the polymerizable merit shown in formula I
Can be as the criterion by property monomer, can be judged by those skilled in the art and choose, in situations where it is preferred, the
The described aromatic diamines added in one step and the binary of fatty acids that formula is (IV) of addition in second step
Mol ratio be, 1:1～1.2, preferably 1:1～1.15.
Condensation reaction condition described in second step can select in relative broad range, specifically can be according to connecing
The degree of the conversion of the polymerizable functional monomer shown in (I) formula touching (i.e. amidation process) is selected
Select.Under preferable case, in second step, the temperature of condensation reaction is 110 DEG C～150 DEG C, is preferably
120 DEG C～130 DEG C；The time of condensation reaction is 4～8 hours, preferably 6～7 hours.
In order to make reaction raw materials be fully utilized with reaction medium, preferably second step formula of is
(IV) binary of fatty acids and the haptoreaction of intermediate M, carried out under conditions of having backflow.
Owing to the binary of fatty acids that formula is (IV) reacts more violent with the amino in intermediate M,
Therefore preferably second step is carried out in the presence of an organic；Described organic solvent in following one
Plant or multiple: acetone, ethyl acetate, benzene, dimethylbenzene, dichloromethane and chloroform；
Second step carries out being not limited to organic solvent in the presence of an organic and adds in second step, only
Want the condensation reaction system of second step exists solvent.Such as, deposit at organic solvent when the first step
Carry out under, and when the product of the first step is directly used in second step without isolation, in second step
Organic solvent can be the organic solvent in first step gained product.The consumption of organic solvent is permissible
Select in relative broad range, it is preferable that formula is the binary of fatty acids of (IV) and rubbing of organic solvent
That ratio is, 1:20～30, preferably 1:20～25；
When the first step and second step are carried out the most in the presence of an organic, respective organic solvent is permissible
Identical or different.
Can also include that the polymerizable functional monomer obtaining second step carries out recrystallization purification, heavily tie
The brilliant solvent used is one of the following or multiple: ethanol, acetone and hexane.
The condition of the re-crystallization step carrying out polymerizable functional monomer uses condition well known in the art.
Preferably, polymerizable functional monomer D1, it is prepared by the following method:
Comprise the following steps:
The first step, under amidation reaction condition, use when in logical formula II, n is 0 to benzene two
Amine and maleic acid anhydride reactant, obtain intermediate as shown in (V) formula；
Second step, under condensationization reaction condition, using m in logical formula IV is adipic acid when 4
With described (V) formula intermediate reaction, obtain the polymerizable functional monomer of structural formula such as (VI) formula
D1；
HOOC-(CH2)m-COOH
(IV)
Amidation process that the preparation method of polymerizable functional monomer provided due to the present invention relates to and
Condensation reaction is and it is known in the art that and reaction that the Direction of Reaction is the clearest and the most definite, therefore the present invention can
The structure of polymerizable functional monomer and the structure of intermediate M can pass through raw material association reaction principle
Confirm.Can also be confirmed by nuclear-magnetism and/or infrared spectrum.
Additionally, present invention also offers the application at polymer oil-displacing agent of the above-mentioned polymerizable functional monomer.
Both included the monomer as polymerization, and formed polymer and use as oil displacement agent, also include being polymerized with other
Thing oil displacement agent mating reaction.
The polymerizable functional monomer product of the present invention, is used for preparing temperature-resistant anti-salt displacement of reservoir oil copolymer.
Described temperature-resistant anti-salt displacement of reservoir oil copolymer, is under the effect of initiator, by least two monomer
Polyreaction complete, as shown in the reaction equation (21):
The temperature-resistant anti-salt displacement of reservoir oil copolymer of the present invention is prepared by the following method:
The first step, is made into aqueous solution by monomer A and polymerizable functional monomer B, regulates pH with alkali
Value is 6～9；Preferably alkali is: sodium hydroxide or sodium carbonate.
Described monomer A is at least one in following free yl polymerizating monomer: acrylamide, third
Olefin(e) acid, 2-acrylamide-2-methylpro panesulfonic acid and NVP；Can be the most independent
A kind of, it is also possible to be multiple mixture.
Described polymerizable functional monomer B be at least one formula be the chemical combination shown in (I)
Thing；In (I) formula, n is 0 or 1, and m is 4,6 or 8；
Described monomer A and described polymerizable functional monomer B total mass concentration in aqueous are
10%～40%, wherein the quality of polymerizable functional monomer B is the 0.8%～16% of monomer A mass；
Second step, at a temperature of 0 DEG C～20 DEG C, under nitrogen protection, adds initiator C, is polymerized 1
Hour～8 hours；
Described initiator C be following in any two kinds: azo initiator, peroxide cause
Agent and redox initiator；The quality of initiator C be above two monomer gross mass 0.01%～
0.1%；
At least one in following of described azo initiator: azo-bis-iso-dimethyl, azo
Two 2,2-Dimethylaziridine hydrochlorates, azodicarbonamide, azo diisopropyl imidazoline hydrochloride, azo isobutyl
Cyano group Methanamide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo diisopropyl imidazoline,
Azodiisobutyronitrile, AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile)；
At least one in following of described peroxide initiator: hydrogen peroxide, Ammonium persulfate.,
Sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester；
At least one in following of described redox initiator: sulfate-sulphite, over cure
Hydrochlorate-thiourea, persulfate-organic salt and Ammonium persulfate .-fatty amine.
Preferably described Ammonium persulfate .-fatty amine be following at least one: Ammonium persulfate .-
N, N, N', N'-tetramethylethylenediamine and Ammonium persulfate .-diethylamine.
3rd step, is warmed up to 40 DEG C～80 DEG C, continues polymerization 1～4 hour；
4th step, takes out the 3rd step gained colloid, pelletize, dry, pulverize, and obtains described resistance to
The anti-salt Polymer Used For Oil Displacement of temperature.
In above method, by a preferred scheme, the long branched chain polymer used for tertiary oil recovery obtained,
Its structural formula such as (22) formula:
In (22) formula: n is 0 or 1；M is 4,6 or 8；X is acrylamide (monomer A)
The degree of polymerization, x=10 ten thousand～500,000；Y is 2-acrylamide-2-methylpro panesulfonic acid (monomer A)
The degree of polymerization, y=5 ten thousand～150,000；Z is the degree of polymerization of polymerizable functional monomer B, z=1 ten thousand～
50000.
The invention has the beneficial effects as follows:
Use the polymer that the polymerizable functional monomer of the present invention prepares, it is possible to gather around at normal temperatures
There is the apparent viscosity of the highest aqueous solutions of polymers, and when it is under conditions of high temperature, high salinity
Aqueous solutions of polymers is maintained to the highest apparent viscosity.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the polymerizable functional monomer prepared by embodiment 1.
Detailed description of the invention
By the following examples the polymerizable functional monomer of the present invention is described in detail.Unless
Special instruction, raw material and reagent that embodiment and experimental example are used all can be commercially available.
Embodiment 1 to 6, the synthesis of polymerizable functional monomer
Embodiment 1
Measure 150 milliliters of dimethylbenzene, take p-phenylenediamine and the 0.1mol maleic anhydride of 0.1mol
Be blended in there-necked flask, be heated to 95 DEG C, reaction 2～6 hours, add 0.1mol oneself two
Acid, at 120 DEG C～130 DEG C, back flow reaction 4～after 8 hours, steam solvent, be dried, refined
After polymerizable functional monomer product, be designated as monomer D1.
Characterizing D1 with infrared spectrometry, result is as it is shown in figure 1, wherein 1321.1cm-1、
1402.6cm-1、1508.8cm-1In-plane bending vibration peak for methylene；1700.6cm-1For C=O
Stretching vibration peak；1625.3cm-1、1544.8cm-1Stretching vibration peak for C=C double bond；3028.5
cm-1For the stretching vibration peak of c h bond on C=C-H, these demonstrate that the existence of double bond；3286.0cm-1
For the stretching vibration peak of O-H on COOH, it was demonstrated that the existence of carboxyl；3078.9cm-1For phenyl ring
The stretching vibration peak of upper c h bond, it was demonstrated that the existence of phenyl ring；3192.8cm-1It is that the flexible of N-H key shakes
Dynamic peak.It is functional that these characteristic absorption peaks demonstrate the polymerizable that product is structure formula VI obtained
Monomer, being n in (I) formula is 0, and m is 4.
Embodiment 2
Measure 150 milliliters of dimethylbenzene, take p-phenylenediamine and the 0.1mol maleic anhydride of 0.1mol
It is blended in there-necked flask, is heated to 90 DEG C, reaction 2～6 hours, add pungent the two of 0.1mol
Acid, at 120 DEG C～130 DEG C, back flow reaction 4～after 8 hours, steam solvent, be dried, refined
After obtain structural formula for the polymerizable functional monomer product of (VII), being n in (I) formula is
0, m is 6, is designated as monomer D2.
Embodiment 3
Measure 150 milliliters of dimethylbenzene, take p-phenylenediamine and the 0.1mol maleic anhydride of 0.1mol
It is blended in there-necked flask, is heated to 100 DEG C, reaction 2～6 hours, add the last of the ten Heavenly stems of 0.1mol
Diacid, at 120 DEG C～130 DEG C, back flow reaction 4～after 8 hours, steam solvent, be dried, essence
Obtain the polymerizable functional monomer product that structural formula is (VIII) after system, be n in (I) formula
Being 0, m is 8, is designated as monomer D3.
Embodiment 4
Measure 150 milliliters of dimethylbenzene, take p dimethylamine and the 0.1mol maleic acid of 0.1mol
Acid anhydride is blended in there-necked flask, is heated to 95 DEG C, reaction 2～6 hours, adds 0.1mol oneself
Diacid, at 120 DEG C～130 DEG C, back flow reaction 4～after 8 hours, steam solvent, be dried, essence
Obtain the polymerizable functional monomer product that structural formula is (Ⅸ) after system, be n in (I) formula
Being 1, m is 4, is designated as monomer D4.
Embodiment 5
Measure 150 milliliters of dimethylbenzene, take p dimethylamine and the 0.1mol maleic acid of 0.1mol
Acid anhydride is blended in there-necked flask, is heated to 90 DEG C, reaction 2～6 hours, adds the pungent of 0.1mol
Diacid, at 120 DEG C～130 DEG C, back flow reaction 4～after 8 hours, steam solvent, be dried, essence
Obtain the polymerizable functional monomer product that structural formula is (Ⅹ) after system, be n in (I) formula
Being 1, m is 6, is designated as monomer D5.
Embodiment 6
Measure 150 milliliters of dimethylbenzene, take p dimethylamine and the 0.1mol maleic acid of 0.1mol
Acid anhydride is blended in there-necked flask, is heated to 100 DEG C, reaction 2～6 hours, adds 0.1mol's
Decanedioic acid, at 120 DEG C～130 DEG C, back flow reaction 4～after 8 hours, steam solvent, be dried,
Obtain the polymerizable functional monomer product that structural formula is (Ⅺ) after Jing Zhi, be in (I) formula
N is 1, and m is 8, is designated as monomer D6.
Embodiment 7-12, the synthesis of temperature-resistant anti-salt displacement of reservoir oil copolymer
Embodiment 7
Weighing acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into aqueous solution,
With sodium hydrate aqueous solution regulation pH value to acid (pH=6), add after adding 0.15 gram of monomer D1
Enter azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams, under nitrogen protection, add Ammonium persulfate. 2.0
Milligram, first selects temperature 20 DEG C, after being polymerized 8 hours, then is warming up to 55 DEG C, continue polymerization 4 hours,
Gained colloid is taken out, pelletize, dry, pulverize, obtain the white granular temperature-resistant anti-salt displacement of reservoir oil with altogether
Copolymer product, its structural formula such as (22) formula, wherein: n is 0, m is 4, x=15 ten thousand～350,000,
Y=5 ten thousand～100,000, z=1 ten thousand～50,000；It is designated as polymer P 1.
Embodiment 8
Weighing acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into aqueous solution,
With sodium hydrate aqueous solution regulation pH value to neutral (pH=7), add after adding 0.15 gram of monomer D2
Enter azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams, under nitrogen protection, add Ammonium persulfate. 2.0
Milligram, first selects temperature 20 DEG C, after being polymerized 8 hours, then is warming up to 55 DEG C, continue polymerization 4 hours,
Gained colloid is taken out, pelletize, dry, pulverize, obtain the white granular temperature-resistant anti-salt displacement of reservoir oil with altogether
Copolymer product, its structural formula such as (22) formula, wherein: n is 0, m is 6, x=20 ten thousand～400,000,
Y=8 ten thousand～120,000, z=1 ten thousand～50,000；It is designated as polymer P 2.
Embodiment 9
Weighing acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into aqueous solution,
With sodium hydrate aqueous solution regulation pH value to alkalescence (pH=8), add after adding 0.15 gram of monomer D3
Enter azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams, under nitrogen protection, add Ammonium persulfate. 2.0
Milligram, first selects temperature 20 DEG C, after being polymerized 8 hours, then is warming up to 55 DEG C, continue polymerization 4 hours,
Gained colloid is taken out, pelletize, dry, pulverize, obtain the white granular temperature-resistant anti-salt displacement of reservoir oil with altogether
Copolymer product, its structural formula such as (22) formula, wherein: n is 0, m is 8, x=30 ten thousand～450,000,
Y=10 ten thousand～150,000, z=1 ten thousand～50,000；It is designated as polymer P 3.
Embodiment 10
Weighing acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into aqueous solution,
With sodium hydrate aqueous solution regulation pH value to alkalescence (pH=9), add after adding 0.15 gram of monomer D4
Enter azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams, under nitrogen protection, add Ammonium persulfate. 2.0
Milligram, first selects temperature 20 DEG C, after being polymerized 8 hours, then is warming up to 55 DEG C, continue polymerization 4 hours,
Gained colloid is taken out, pelletize, dry, pulverize, obtain the white granular temperature-resistant anti-salt displacement of reservoir oil with altogether
Copolymer product, its structural formula such as (22) formula, wherein: n is 1, m is 4, x=25 ten thousand～400,000,
Y=5 ten thousand～100,000, z=1 ten thousand～50,000；It is designated as polymer P 4.
Embodiment 11
Weighing acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into aqueous solution,
With sodium hydrate aqueous solution regulation pH value to alkalescence (pH=8), add after adding 0.15 gram of monomer D5
Enter azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams, under nitrogen protection, add Ammonium persulfate. 2.0
Milligram, first selects temperature 20 DEG C, after being polymerized 8 hours, then is warming up to 55 DEG C, continue polymerization 4 hours,
Gained colloid is taken out, pelletize, dry, pulverize, obtain the white granular temperature-resistant anti-salt displacement of reservoir oil with altogether
Copolymer product, its structural formula such as (22) formula, wherein: n is 1, m is 6, x=30 ten thousand～450,000,
Y=8 ten thousand～150,000, z=1 ten thousand～50,000；It is designated as polymer P 5.
Embodiment 12
Weighing acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into aqueous solution,
With sodium hydrate aqueous solution regulation pH value to alkalescence (pH=8), add after adding 0.15 gram of monomer D6
Enter azo-bis-isobutyrate hydrochloride (V50) 3.0 milligrams, under nitrogen protection, add Ammonium persulfate. 6.0
Milligram, first selects temperature 20 DEG C, after being polymerized 8 hours, then is warming up to 55 DEG C, continue polymerization 4 hours,
Gained colloid is taken out, pelletize, dry, pulverize, obtain the white granular temperature-resistant anti-salt displacement of reservoir oil with altogether
Copolymer product, its structural formula such as (22) formula, wherein: n is 1, m is 8, x=35 ten thousand～500,000,
Y=10 ten thousand～150,000, z=1 ten thousand～50,000；It is designated as polymer P 6.
Embodiment 13 comparative polymer
Weighing acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into aqueous solution,
With sodium hydrate aqueous solution regulation pH value to alkalescence (pH=7.5), add azo two 2,2-Dimethylaziridine hydrochloric acid
Salt (AIBA) 3.0 milligrams, under nitrogen protection, adds Ammonium persulfate. 3.0 milligrams, first selects temperature
Spend 20 DEG C, after being polymerized 8 hours, then be warming up to 55 DEG C, continue polymerization 4 hours, gained colloid is taken
Go out, pelletize, dry, pulverize, obtain white powder acrylamide soluble polymer product, be designated as
Comparative polymer DP.
Test case 1
The intrinsic viscosity of polymer P 1～P6 and DP is according to GB12005.1-89 Intrinsic Viscosity Measurements
Method is measured；Viscosity-average molecular weight is according to formula M η=([η]/K) 1/ α, wherein K=4.5 × 10-3,
α=0.80 calculates；The apparent viscosity of polymer P 1～P6 and DP aqueous solution is passed through
BROOKFIELD DV-III viscosity apparatus is 7.34s in rotating speed perseverance-1, temperature is 25 DEG C and the bar of 85 DEG C
Being measured obtaining under part, wherein, test condition includes: polymer concentration is 1500mg/L, solution
Total salinity is 32868mg/L.Test result is as shown in table 1.
Table 1
| Mη(×104) | η25(mPa·s) | η85(mPa·s) | |
| P1 | 1800 | 34.6 | 18.7 |
| P2 | 1900 | 38.2 | 20.6 |
| P3 | 2000 | 39.8 | 22.3 |
| P4 | 1900 | 37.1 | 20.4 |
| P5 | 2100 | 42.5 | 23.8 |
| P6 | 2200 | 44.9 | 25.5 |
| DP | 1400 | 24.6 | 13.4 |
The viscosity-average molecular weight of M η representation polymer in table 1, η 25 represents aqueous solutions of polymers at 25 DEG C
Apparent viscosity, η 85 represents the apparent viscosity of aqueous solutions of polymers at 85 DEG C.By P1 in table 1 extremely
The data of P6 compare with the data of contrast preparation example DP, it can be seen that the method using the present invention
Polymer P 1 to the P6 prepared can at normal temperatures (25 DEG C) to have the highest polymer water-soluble
The apparent viscosity of liquid, and when it is at high temperature (85 DEG C), the bar of high salinity (32868mg/L)
Under part, aqueous solutions of polymers is maintained to the highest apparent viscosity.
Claims (6)
1. a temperature-resistant anti-salt Polymer Used For Oil Displacement, is characterized in that being prepared by the following method:
The first step, is made into aqueous solution by monomer A and polymerizable functional monomer B, regulates pH with alkali
Value is 6～9；
Described monomer A be following at least one: acrylamide, acrylic acid, 2-acrylamide
Base-2-methyl propane sulfonic acid and NVP；
Described polymerizable functional monomer B be at least one formula be the chemical combination shown in (I)
Thing:
In (I) formula, n is 0 or 1, and m is 4,6 or 8；
Described monomer A and described polymerizable functional monomer B total mass concentration in aqueous are
10%～40%, wherein the quality of polymerizable functional monomer B is the 0.8%～16% of monomer A mass；
Second step, at a temperature of 0 DEG C～20 DEG C, under nitrogen protection, adds initiator C, is polymerized 1
Hour～8 hours；
Described initiator C be following in any two kinds: azo initiator, peroxide initiator
And redox initiator；The quality of initiator C be above two monomer gross mass 0.01%～
0.1%；
3rd step, is warmed up to 40 DEG C～80 DEG C, continues polymerization 1 hour～4 hours；
4th step, takes out the 3rd step gained colloid, pelletize, dry, pulverize, and obtains described resistance to
The anti-salt Polymer Used For Oil Displacement of temperature.
2. the temperature-resistant anti-salt Polymer Used For Oil Displacement described in claim 1, is characterized in that:
In the first step, described alkali is: sodium hydroxide or sodium carbonate.
3. the temperature-resistant anti-salt Polymer Used For Oil Displacement described in claim 1, is characterized in that:
In second step,
At least one in following of described azo initiator: azo-bis-iso-dimethyl, azo
Two 2,2-Dimethylaziridine hydrochlorates, azodicarbonamide, azo diisopropyl imidazoline hydrochloride, azo isobutyl
Cyano group Methanamide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo diisopropyl imidazoline,
Azodiisobutyronitrile, AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile)；
At least one in following of described peroxide initiator: hydrogen peroxide, Ammonium persulfate.,
Sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester；
At least one in following of described redox initiator: sulfate-sulphite, over cure
Hydrochlorate-thiourea and Ammonium persulfate .-fatty amine.
4. the temperature-resistant anti-salt Polymer Used For Oil Displacement described in claim 3, is characterized in that:
Described Ammonium persulfate .-fatty amine be following at least one: Ammonium persulfate .-N, N, N', N'-
Tetramethylethylenediamine and Ammonium persulfate .-diethylamine.
5. a temperature-resistant anti-salt Polymer Used For Oil Displacement, its structure is as shown in (22) formula:
In (22) formula: n is 0 or 1；M is 4,6 or 8；X is the degree of polymerization of acrylamide,
X=10 ten thousand～500,000；Y is the degree of polymerization of 2-acrylamide-2-methylpro panesulfonic acid, y=5 ten thousand～15
Ten thousand；Z is the degree of polymerization of polymerizable functional monomer B, z=1 ten thousand～50,000.
6. a synthetic method for temperature-resistant anti-salt Polymer Used For Oil Displacement, is characterized in that:
The first step, is made into aqueous solution by monomer A and polymerizable functional monomer B, regulates pH with alkali
Value is 6～9；Described alkali is: sodium hydroxide or sodium carbonate；
Described monomer A be following at least one: acrylamide, acrylic acid, 2-acrylamide
Base-2-methyl propane sulfonic acid and NVP；
Described polymerizable functional monomer B be at least one formula be the chemical combination shown in (I)
Thing:
In (I) formula, n is 0 or 1, and m is 4,6 or 8；
Described monomer A and described polymerizable functional monomer B total mass concentration in aqueous are
10%～40%, wherein the quality of polymerizable functional monomer B is the 0.8%～16% of monomer A mass；
Second step, at a temperature of 0 DEG C～20 DEG C, under nitrogen protection, adds initiator C, is polymerized 1
Hour～8 hours；
Described initiator C be following in any two kinds: azo initiator, peroxide initiator
And redox initiator；The quality of initiator C be above two monomer gross mass 0.01%～
0.1%；
At least one in following of described azo initiator: azo-bis-iso-dimethyl, azo
Two 2,2-Dimethylaziridine hydrochlorates, azodicarbonamide, azo diisopropyl imidazoline hydrochloride, azo isobutyl
Cyano group Methanamide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo diisopropyl imidazoline,
Azodiisobutyronitrile, AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile)；
At least one in following of described peroxide initiator: hydrogen peroxide, Ammonium persulfate.,
Sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester；
At least one in following of described redox initiator: sulfate-sulphite, over cure
Hydrochlorate-thiourea and Ammonium persulfate .-fatty amine；
3rd step, is warmed up to 40 DEG C～80 DEG C, continues polymerization 1 hour～4 hours；
4th step, takes out the 3rd step gained colloid, pelletize, dry, pulverize, and obtains described resistance to
The anti-salt Polymer Used For Oil Displacement of temperature.
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| CN101664657A (en) * | 2008-12-11 | 2010-03-10 | 齐齐哈尔大学 | Carboxylate gemini surfactant and preparation method thereof |
| CN102373052A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Binary composite oil displacement agent for tertiary oil recovery and preparation method thereof |
| CN102372820A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101664657A (en) * | 2008-12-11 | 2010-03-10 | 齐齐哈尔大学 | Carboxylate gemini surfactant and preparation method thereof |
| CN102373052A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Binary composite oil displacement agent for tertiary oil recovery and preparation method thereof |
| CN102372820A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof |
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