CN104250340A - Polymerizable functional monomer and preparation method and application thereof - Google Patents
Polymerizable functional monomer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a temperature-resistance salt-tolerance oil-displacement copolymer and a preparation method thereof. The copolymer is used in an oil displacement agent for three-time oil extraction, and can have quite high apparent viscosity of a polymer aqueous solution at room temperature; and moreover, the polymer aqueous solution can still maintain quite high apparent viscosity under conditions of high temperature and high degree of mineralization.
Description
Technical field
The present invention relates to a kind of polymerizable functional monomer and its preparation method and application.
Background technology
One of most effective means of vinyl polymer is prepared in radical polymerization.In the vinyl polymer of current use, more than 70% is obtained by radical polymerization.Radical polymerization has many advantages, as many in suitable monomers, polymerizing condition is gentle, polymerization technique is simple.Because many monomers can carry out radical polymerization, energy water is that medium carries out suspending and letex polymerization, and polymerization process is easy, its favorable reproducibility, since the fifties in last century, thus become the important technology of industrial production macromolecule product.
There is the polymerization single polymerization monomer of emulsification function, also known as polymerisable emulsifier, in its molecular structure except the emulsifying agent group containing hydrophilic and oleophilic, also containing the functional group can participating in Raolical polymerizable, become a part for polymkeric substance, therefore can not there is desorb again in emulsifier molecules, thus make polymer particle in agglomeration process, be subject to electrostatic repulsion and larger steric restriction effect, make the be improved kind of polymerisable emulsifier of the stability of latex a lot, acrylic amide polymerisable emulsifier has the particular advantages such as reactive behavior is high, polymericular weight is high.
Polymer oil-displacing agent has the modified product three major types of synthetic polymer, biopolymer, natural polymer.At present, the most frequently used polymkeric substance has two classes: one is take xanthocyte gum as the biological polymer of representative; Two is the synthetic polymers that are representative with partially hydrolyzed polyacrylamide and derivative thereof, based on HPAM.But HPAM temperature resistant antisalt performance is undesirable, the ultimate-use temperature under reservoir condition is only 75 DEG C, and when having salt to exist, viscosity acutely declines, divalent-metal ion also can make its produce precipitation and loses viscosity.In addition, can there is molecular rupture in HPAM under shearing action, causes its tackifying ability to reduce.Research shows, the temperature tolerance of HPAM, the poor-performing such as salt resistance and shear resistant, make its application conditions be restricted.Xanthocyte gum has certain anti-salt resistant to shearing performance, but xanthocyte gum thermooxidative degradation can occur in high-temperature stratum, and the formation temperature for tertiary oil recovery generally should not higher than 60 DEG C.The price of xanthocyte gum is five times of HPAM in addition, also limit its popularization.
Polymer molecular chain is introduced some high thermal stability monomeric units, the monomeric unit of larger skeleton and the group of strong hydratability, thus strengthen polymer thermostable and molecule chain rigidity, strengthen polymer hydration ability, make the ydrodynamics size that polymer molecule can keep larger in the high salinity aqueous solution, this enhances polymkeric substance salt resistance ability to a certain extent.In addition, the introducing of function monomer, makes polymkeric substance be restricted in high-salinity water quality Water Under solution, there will not be the phenomenon occurring with calcium ions and magnesium ions to precipitate, thus reaches the object of anti-salt.
Summary of the invention
The technical problem to be solved in the present invention is:
The object of this invention is to provide a kind of polymerizable functional monomer and synthetic method thereof, can be used as polymeric emulsifiers, and for the synthesis of temperature resistant antisalt displacement of reservoir oil multipolymer, to improve the performance of Polymer Used For Oil Displacement.
The product technology scheme of 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 be 0 or 1, m be 4,6 or 8.
For the purpose of difference, MALEIC ANHYDRIDE contacts with aromatic diamines and makes acid anhydrides generation open loop and the reaction that obtains acid amides is called amidate action by the present invention, and reaction carboxylic acid and amine being obtained acid amides by sloughing a part water is called condensation reaction.
Preparation method's technical scheme of polymerizable functional monomer of the present invention, comprises the following steps:
The first step, under amidation reaction condition, makes general formula be aromatic diamines and the maleic acid anhydride reactant of (II), obtains intermediate M;
(II) in formula, n is 0 or 1, and described intermediate M is as shown in (III) formula:
Second step, under condensation reaction conditions, makes general formula be that the binary of fatty acids of (IV) and described intermediate M react,
HOOC-(CH
2)
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 be 0 or 1, m be 4,6 or 8.
Further preferably:
In the first step, described aromatic diamines is selected from: Ursol D or p dimethylamine;
In order to obtain the intermediate M shown in formula III, the general formula used in step (1) is that the aromatic diamines of (II) and MALEIC ANHYDRIDE are carried out the mol ratio that amidate action adds and can be selected in a big way, described in preferred steps (1), the mol ratio of aromatic diamines and MALEIC ANHYDRIDE is 1:1 ~ 1.1, more preferably 1:1 ~ 1.05.By control general formula be the aromatic diamines of (II) and the additional proportion of MALEIC ANHYDRIDE control as far as possible in above-mentioned scope general formula be (II) aromatic diamines in-a NH
2with carboxylic acid reaction, obtain intermediate M.
Amidation reaction condition described in the first step can be the various conditions that aromatic diamines and maleic acid anhydride reactant can be made to form acid amides, and concrete temperature and time can be selected according to the character of used aromatic diamines and MALEIC ANHYDRIDE.In the preferred case, in the first step, the temperature of amidate action is 80 DEG C ~ 110 DEG C, is preferably 90 DEG C ~ 100 DEG C; The time of amidate action is 2 ~ 6 hours, is preferably 3 ~ 5 hours.
It is more easy to control in order to make the first step formula of to be that the aromatic diamines of (II) and MALEIC ANHYDRIDE carry out amidate action, can add organic solvent in a first step.The addition of organic solvent can be selected in relative broad range, and preferably, described organic solvent is selected from following one or more: acetone, ethyl acetate, benzene, dimethylbenzene, methylene dichloride and trichloromethane; The mol ratio of described aromatic diamines and described organic solvent is 1:5 ~ 20, is preferably 1:10 ~ 15.
In order to obtain the polymerizable functional monomer shown in formula I, under second step is included in the condition of condensation reaction, general formula is made to be that the binary of fatty acids of (IV) contacts with the intermediate M that the first step obtains,
This contact can be in second step, and general formula is that the binary of fatty acids of (IV) and the intermediate M after purifying directly carry out condensation reaction;
Also can be that, in second step, general formula is that the binary of fatty acids of (IV) directly can carry out condensation reaction without being separated with the mixture containing intermediate M that the first step obtains.
The add-on that general formula is the binary of fatty acids of (IV) is as the criterion to obtain the polymerizable functional monomer shown in formula I, can be judged by those skilled in the art and choose, in the preferred case, the general formula added in the described aromatic diamines added in the first step and second step is the mol ratio of the binary of fatty acids of (IV), 1:1 ~ 1.2, are preferably 1:1 ~ 1.15.
The condition of condensation reaction described in second step can be selected in relative broad range, and the degree that specifically can transform according to the polymerizable functional monomer shown in (I) formula of contact (i.e. amidate action) is selected.Under preferable case, the temperature of condensation reaction in second step is 110 DEG C ~ 150 DEG C, is preferably 120 DEG C ~ 130 DEG C; The time of condensation reaction is 4 ~ 8 hours, is preferably 6 ~ 7 hours.
In order to make reaction raw materials and reaction medium be fully utilized, preferred second step formula of is the binary of fatty acids of (IV) and the contact reacts of intermediate M, carries out under the condition having backflow.
Because general formula is that amino in the binary of fatty acids of (IV) and intermediate M reacts comparatively violent, therefore preferably second step carries out in the presence of an organic; Described organic solvent be selected from following in one or more: acetone, ethyl acetate, benzene, dimethylbenzene, methylene dichloride and trichloromethane;
Second step carries out being not limited to organic solvent in the presence of an organic and adds in second step, as long as there is solvent in the condensation reaction system of second step.Such as, when the first step is carried out in the presence of an organic, and when the reaction product of the first step is directly used in second step without separation, the organic solvent in second step can be the organic solvent in the first step gained reaction product.The consumption of organic solvent can be selected in relative broad range, and preferably, general formula is the binary of fatty acids of (IV) and the mol ratio of organic solvent is that 1:20 ~ 30, are preferably 1:20 ~ 25;
When the first step and second step carry out all in the presence of an organic, respective organic solvent can be identical or different.
The polymerizable functional monomer that can also comprise second step obtains carries out recrystallization purification, the solvent that recrystallization uses be following in one or more: ethanol, acetone and hexane.
The condition of carrying out the re-crystallization step of polymerizable functional monomer adopts condition well known in the art.
Preferably, polymerizable functional monomer D1, prepares by the following method:
Comprise the following steps:
The first step, under amidation reaction condition, uses Ursol D when n is 0 in logical formula II and maleic acid anhydride reactant, obtains intermediate as shown in (V) formula;
Second step, under condensation reaction conditions, uses hexanodioic acid when m is 4 in logical formula IV and described (V) formula intermediate reaction, obtains the polymerizable functional monomer D1 of structural formula as (VI) formula;
HOOC-(CH
2)
m-COOH
（Ⅳ）
The amidate action related to due to the preparation method of polymerizable functional monomer provided by the invention and condensation reaction are known in this field, and the reaction that the Direction of Reaction is very clear and definite, therefore the structure of polymerizable functional monomer of the present invention and the structure of intermediate M can be confirmed by raw material association reaction principle.Also can be confirmed by nuclear-magnetism and/or infrared spectrum.
In addition, present invention also offers the application of above-mentioned polymerizable functional monomer at polymer oil-displacing agent.Both comprised the monomer as polymerization, and formed polymkeric substance and use as oil-displacing agent, also comprise and other polymer oil-displacing agent mating reactions.
Polymerizable functional monomer product of the present invention, for the preparation of temperature resistant antisalt displacement of reservoir oil multipolymer.Described temperature resistant antisalt displacement of reservoir oil multipolymer, is under the effect of initiator, is completed by the polyreaction of at least two kinds of monomers, as shown in reaction formula (21):
Temperature resistant antisalt displacement of reservoir oil multipolymer of the present invention is prepared by the following method:
The first step, monomer A and polymerizable functional monomer B are made into the aqueous solution, are 6 ~ 9 by alkali adjust ph; Preferred bases is: sodium hydroxide or sodium carbonate.
Described monomer A is at least one in following free yl polymerizating monomer: acrylamide, vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid and NVP; Can be wherein a kind of separately, also can be multiple mixture.
Described polymerizable functional monomer B is at least one formula is the compound shown in (I); In (I) formula, n be 0 or 1, m be 4,6 or 8;
Described monomer A and described polymerizable functional monomer B total mass concentration are in aqueous 10% ~ 40%, and wherein the quality of polymerizable functional monomer B is 0.8% ~ 16% of monomer A quality;
Second step, at 0 DEG C ~ 20 DEG C temperature, under nitrogen protection, adds initiator C, is polymerized 1 hour ~ 8 hours;
Described initiator C be following in any two kinds: azo initiator, peroxide type initiators and redox initiator; The quality of initiator C is 0.01% ~ 0.1% of above-mentioned two kinds of monomer total masses;
Described azo initiator be selected from following at least one: azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline hydrochloride, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described peroxide initiator be selected from following at least one: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester;
Described redox initiator be selected from following at least one: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide.
Preferably described ammonium persulphate-aliphatic amide be following at least one: ammonium persulphate-N, N, N', N'-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
3rd step, is warmed up to 40 DEG C ~ 80 DEG C, continues polymerization 1 ~ 4 hour;
4th step, taken out by the 3rd step gained colloid, granulation, dry, pulverize, and obtains described temperature resistant antisalt Polymer Used For Oil Displacement.
In above method, by a preferred scheme, the long branched chain polymer used for tertiary oil recovery obtained, its structural formula is as (22) formula:
In (22) formula: n is 0 or 1; M is 4,6 or 8; X is the polymerization degree of acrylamide (monomer A), x=10 ten thousand ~ 500,000; Y is the polymerization degree of 2-acrylamide-2-methylpro panesulfonic acid (monomer A), y=5 ten thousand ~ 150,000; Z is the polymerization degree of polymerizable functional monomer B, z=1 ten thousand ~ 50,000.
The invention has the beneficial effects as follows:
Adopt the polymkeric substance that polymerizable functional monomer of the present invention prepares, the apparent viscosity of very high aqueous solutions of polymers can be had at normal temperatures, and when its aqueous solutions of polymers under the condition of high temperature, high salinity still can keep very high apparent viscosity.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the polymerizable functional monomer prepared by embodiment 1.
Embodiment
By the following examples polymerizable functional monomer of the present invention is described in detail.Unless stated otherwise, the raw material that uses of embodiment and experimental example and reagent are all by being commercially available.
Embodiment 1 to 6, the synthesis of polymerizable functional monomer
Embodiment 1
Measure 150 milliliters of dimethylbenzene, Ursol D and the 0.1mol MALEIC ANHYDRIDE of getting 0.1mol are blended in there-necked flask, be heated to 95 DEG C, react 2 ~ 6 hours, then add the hexanodioic acid of 0.1mol, at 120 DEG C ~ 130 DEG C, back flow reaction, after 4 ~ 8 hours, steams solvent, dry, obtain polymerizable functional monomer product after refining, be designated as monomer D1.
With infrared spectroscopy, D1 is characterized, result as shown in Figure 1, wherein 1321.1cm
-1, 1402.6cm
-1, 1508.8cm
-1for the in-plane bending vibration peak of methylene radical; 1700.6cm
-1for the stretching vibration peak of C=O; 1625.3cm
-1, 1544.8cm
-1for the stretching vibration peak of C=C double bond; 3028.5cm
-1for the stretching vibration peak of c h bond on C=C-H, these demonstrate that the existence of double bond; 3286.0cm
-1for the stretching vibration peak of O-H on COOH, demonstrate the existence of carboxyl; 3078.9cm
-1for the stretching vibration peak of c h bond on phenyl ring, prove the existence of phenyl ring; 3192.8cm
-1it is the stretching vibration peak of N-H key.These charateristic avsorption bands demonstrate the polymerizable functional monomer that the product obtained is structure formula VI, and being in (I) formula that n is 0, m is 4.
Embodiment 2
Measure 150 milliliters of dimethylbenzene, Ursol D and the 0.1mol MALEIC ANHYDRIDE of getting 0.1mol are blended in there-necked flask, are heated to 90 DEG C, react 2 ~ 6 hours, add the suberic acid of 0.1mol again, at 120 DEG C ~ 130 DEG C, back flow reaction is after 4 ~ 8 hours, steam solvent, drying, obtain the polymerizable functional monomer product of structural formula for (VII) after refining, being n in (I) formula is 0, m is 6, is designated as monomer D2.
Embodiment 3
Measure 150 milliliters of dimethylbenzene, Ursol D and the 0.1mol MALEIC ANHYDRIDE of getting 0.1mol are blended in there-necked flask, are heated to 100 DEG C, react 2 ~ 6 hours, add the sebacic acid of 0.1mol again, at 120 DEG C ~ 130 DEG C, back flow reaction is after 4 ~ 8 hours, steam solvent, drying, obtain the polymerizable functional monomer product of structural formula for (VIII) after refining, being n in (I) formula is 0, m is 8, is designated as monomer D3.
Embodiment 4
Measure 150 milliliters of dimethylbenzene, p dimethylamine and the 0.1mol MALEIC ANHYDRIDE of getting 0.1mol are blended in there-necked flask, are heated to 95 DEG C, react 2 ~ 6 hours, add the hexanodioic acid of 0.1mol again, at 120 DEG C ~ 130 DEG C, back flow reaction is after 4 ~ 8 hours, steam solvent, drying, obtain the polymerizable functional monomer product of structural formula for (Ⅸ) after refining, being n in (I) formula is 1, m is 4, is designated as monomer D4.
Embodiment 5
Measure 150 milliliters of dimethylbenzene, p dimethylamine and the 0.1mol MALEIC ANHYDRIDE of getting 0.1mol are blended in there-necked flask, are heated to 90 DEG C, react 2 ~ 6 hours, add the suberic acid of 0.1mol again, at 120 DEG C ~ 130 DEG C, back flow reaction is after 4 ~ 8 hours, steam solvent, drying, obtain the polymerizable functional monomer product of structural formula for (Ⅹ) after refining, being n in (I) formula is 1, m is 6, is designated as monomer D5.
Embodiment 6
Measure 150 milliliters of dimethylbenzene, p dimethylamine and the 0.1mol MALEIC ANHYDRIDE of getting 0.1mol are blended in there-necked flask, are heated to 100 DEG C, react 2 ~ 6 hours, add the sebacic acid of 0.1mol again, at 120 DEG C ~ 130 DEG C, back flow reaction is after 4 ~ 8 hours, steam solvent, drying, obtain the polymerizable functional monomer product of structural formula for (Ⅺ) after refining, being n in (I) formula is 1, m is 8, is designated as monomer D6.
Embodiment 7-12, the synthesis of temperature resistant antisalt displacement of reservoir oil multipolymer
Embodiment 7
Take acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into the aqueous solution, by aqueous sodium hydroxide solution adjust ph to acid (pH=6), azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams is added after adding 0.15 gram of monomer D1, under nitrogen protection, add ammonium persulphate 2.0 milligrams, first selective temperature 20 DEG C, be polymerized after 8 hours, be warming up to 55 DEG C again, continue polymerization 4 hours, gained colloid is taken out, granulation, dry, pulverize, obtain white granular temperature resistant antisalt displacement of reservoir oil copolymer product, its structural formula is 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, be designated as polymer P 1.
Embodiment 8
Take acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into the aqueous solution, by aqueous sodium hydroxide solution adjust ph to neutral (pH=7), azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams is added after adding 0.15 gram of monomer D2, under nitrogen protection, add ammonium persulphate 2.0 milligrams, first selective temperature 20 DEG C, be polymerized after 8 hours, be warming up to 55 DEG C again, continue polymerization 4 hours, gained colloid is taken out, granulation, dry, pulverize, obtain white granular temperature resistant antisalt displacement of reservoir oil copolymer product, its structural formula is 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, be designated as polymer P 2.
Embodiment 9
Take acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into the aqueous solution, by aqueous sodium hydroxide solution adjust ph to alkalescence (pH=8), azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams is added after adding 0.15 gram of monomer D3, under nitrogen protection, add ammonium persulphate 2.0 milligrams, first selective temperature 20 DEG C, be polymerized after 8 hours, be warming up to 55 DEG C again, continue polymerization 4 hours, gained colloid is taken out, granulation, dry, pulverize, obtain white granular temperature resistant antisalt displacement of reservoir oil copolymer product, its structural formula is 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, be designated as polymer P 3.
Embodiment 10
Take acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into the aqueous solution, by aqueous sodium hydroxide solution adjust ph to alkalescence (pH=9), azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams is added after adding 0.15 gram of monomer D4, under nitrogen protection, add ammonium persulphate 2.0 milligrams, first selective temperature 20 DEG C, be polymerized after 8 hours, be warming up to 55 DEG C again, continue polymerization 4 hours, gained colloid is taken out, granulation, dry, pulverize, obtain white granular temperature resistant antisalt displacement of reservoir oil copolymer product, its structural formula is 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, be designated as polymer P 4.
Embodiment 11
Take acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into the aqueous solution, by aqueous sodium hydroxide solution adjust ph to alkalescence (pH=8), azo-bis-isobutyrate hydrochloride (V50) 1.0 milligrams is added after adding 0.15 gram of monomer D5, under nitrogen protection, add ammonium persulphate 2.0 milligrams, first selective temperature 20 DEG C, be polymerized after 8 hours, be warming up to 55 DEG C again, continue polymerization 4 hours, gained colloid is taken out, granulation, dry, pulverize, obtain white granular temperature resistant antisalt displacement of reservoir oil copolymer product, its structural formula is 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, be designated as polymer P 5.
Embodiment 12
Take acrylamide 4.75 grams, 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into the aqueous solution, by aqueous sodium hydroxide solution adjust ph to alkalescence (pH=8), azo-bis-isobutyrate hydrochloride (V50) 3.0 milligrams is added after adding 0.15 gram of monomer D6, under nitrogen protection, add ammonium persulphate 6.0 milligrams, first selective temperature 20 DEG C, be polymerized after 8 hours, be warming up to 55 DEG C again, continue polymerization 4 hours, gained colloid is taken out, granulation, dry, pulverize, obtain white granular temperature resistant antisalt displacement of reservoir oil copolymer product, its structural formula is 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, be designated as polymer P 6.
Embodiment 13 comparative polymer
Take acrylamide 4.75 grams; 5.25 grams of 2-acrylamide-2-methyl propane sulfonics are made into the aqueous solution; by aqueous sodium hydroxide solution adjust ph to alkalescence (pH=7.5); add azo-bis-isobutyrate hydrochloride (AIBA) 3.0 milligrams; under nitrogen protection; add ammonium persulphate 3.0 milligrams, first selective temperature 20 DEG C, be polymerized after 8 hours; be warming up to 55 DEG C again; continue polymerization 4 hours, gained colloid is taken out, granulation; 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 measures according to GB12005.1-89 For Intrinsic Viscosity Measurements method; 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 the DP aqueous solution is 7.34s by BROOKFIELD DV-III viscosity apparatus in rotating speed perseverance
-1, temperature is carry out mensuration under the condition of 25 DEG C and 85 DEG C to obtain, and wherein, test condition comprises: polymer concentration is 1500mg/L, and solution total mineralization is 32868mg/L.Test result is as shown in table 1.
Table 1
| ? | Mη(×10 4) | 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 the apparent viscosity of aqueous solutions of polymers at 25 DEG C, and η 85 represents the apparent viscosity of aqueous solutions of polymers at 85 DEG C.Compared with the data of contrast preparation example DP by the data of P1 to P6 in table 1, can find out that polymer P 1 to the P6 adopting method of the present invention to prepare (25 DEG C) can have the apparent viscosity of very high aqueous solutions of polymers at normal temperatures, and when its aqueous solutions of polymers under the condition of high temperature (85 DEG C), high salinity (32868mg/L) still can keep very high apparent viscosity.
Claims (7)
1. a temperature resistant antisalt Polymer Used For Oil Displacement, is characterized in that preparing by the following method:
The first step, monomer A and polymerizable functional monomer B are made into the aqueous solution, are 6 ~ 9 by alkali adjust ph; Preferably described alkali is: sodium hydroxide or sodium carbonate.
Described monomer A be following at least one: acrylamide, vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid and NVP;
Described polymerizable functional monomer B is at least one formula is the compound shown in (I):
In (I) formula, n be 0 or 1, m be 4,6 or 8;
Described monomer A and described polymerizable functional monomer B total mass concentration are in aqueous 10% ~ 40%, and wherein the quality of polymerizable functional monomer B is 0.8% ~ 16% of monomer A quality;
Second step, at 0 DEG C ~ 20 DEG C temperature, 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 is 0.01% ~ 0.1% of above-mentioned two kinds of monomer total masses;
3rd step, is warmed up to 40 DEG C ~ 80 DEG C, continues polymerization 1 hour ~ 4 hours;
4th step, taken out by the 3rd step gained colloid, granulation, dry, pulverize, and obtains described temperature resistant antisalt Polymer Used For Oil Displacement.
2. a temperature resistant antisalt Polymer Used For Oil Displacement according to claim 1, is characterized in that:
In a first step, described alkali is: sodium hydroxide or sodium carbonate.
3. a temperature resistant antisalt Polymer Used For Oil Displacement according to claim 1, is characterized in that:
In second step,
Described azo initiator be selected from following at least one: azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline hydrochloride, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described peroxide initiator be selected from following at least one: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester;
Described redox initiator be selected from following at least one: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide.
4. a temperature resistant antisalt Polymer Used For Oil Displacement according to claim 3, is characterized in that:
Described ammonium persulphate-aliphatic amide be following at least one: ammonium persulphate-N, N, N', N'-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
5. a temperature resistant antisalt 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 polymerization degree of acrylamide, x=10 ten thousand ~ 500,000; Y is the polymerization degree of 2-acrylamide-2-methylpro panesulfonic acid, y=5 ten thousand ~ 150,000; Z is the polymerization degree of polymerizable functional monomer B, z=1 ten thousand ~ 50,000.
6. a synthetic method for temperature resistant antisalt Polymer Used For Oil Displacement, is characterized in that:
The first step, monomer A and polymerizable functional monomer B are made into the aqueous solution, are 6 ~ 9 by alkali adjust ph; Preferably described alkali is: sodium hydroxide or sodium carbonate;
Described monomer A be following at least one: acrylamide, vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid and NVP;
Described polymerizable functional monomer B is at least one formula is the compound shown in (I):
In (I) formula, n be 0 or 1, m be 4,6 or 8;
Described monomer A and described polymerizable functional monomer B total mass concentration are in aqueous 10% ~ 40%, and wherein the quality of polymerizable functional monomer B is 0.8% ~ 16% of monomer A quality;
Second step, at 0 DEG C ~ 20 DEG C temperature, 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 is 0.01% ~ 0.1% of above-mentioned two kinds of monomer total masses;
Described azo initiator be selected from following at least one: azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline hydrochloride, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described peroxide initiator be selected from following at least one: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester;
Described redox initiator be selected from following at least one: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide;
3rd step, is warmed up to 40 DEG C ~ 80 DEG C, continues polymerization 1 hour ~ 4 hours.
7. the 4th step, taken out by the 3rd step gained colloid, granulation, dry, pulverize, and obtains described temperature resistant antisalt Polymer Used For Oil Displacement.
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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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| 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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