CN102464798A - Amide macromonomer, thermothickening copolymer, preparation methods and application thereof - Google Patents
Amide macromonomer, thermothickening copolymer, preparation methods and application thereof Download PDFInfo
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Abstract
The invention provides an amide macromonomer, which is characterized by having a structure as shown in formula (1). The invention also provides a thermothickening copolymer, which is characterized in that it is prepared through polymerization of a monomer mixture composed of a monomer (B) and a monomer (A) with a structure shown in formula (4). The monomer (B) is the above amide monomer. And on the basis of the total amount of the monomer mixture, the content of the monomer (A) is 65-90 wt%, and the content of the monomer (B) is 10-35 wt%. In addition, the invention also provides preparation methods of the amide macromonomer and a thermothickening copolymer, as well as application of the thermothickening copolymer as a polymer oil displacement agent and a profile control and water plugging agent. The water-soluble thermothickening copolymer oil displacement agent still has an excellent thermothickening performance under high-temperature and high-salt conditions.
Description
Technical field
The present invention relates to a kind of acid amides and be macromonomer and be the hot thickening copolymer that the macromonomer polymerization obtains, and this acid amides is the preparation method of macromonomer, the preparation method of this hot thickening copolymer and the application of this hot thickening copolymer by this acid amides.
Background technology
As everyone knows, oil is a kind of strategic energy, is global economy development and the indispensable propelling agent of social progress between past more than 100 year.Because its non-renewable and finiteness reserves, for many years, countries in the world are active research and the substitute energy of developing oil all; Although obtain no small progress; Yet at foreseeable future, oil will be the important substance basis that world economy is rely and developed.China is the deficient relatively countries of petroleum resources, and in order to guarantee national economic development and the demand of development to petroleum resources, China just tries to explore, researches and develops the various technology that improve oil recovery since the 1950's.Through effort for many years, obtained the achievement of attracting attention in the world, formed and had world-class raising oil recovery comprehensive technology system.As the polymer displacement of reservoir oil tech that improves one of oil recovery important technology; Its principle is in water filling, to add the water-soluble polymer weight polymers; Take this to improve viscosity in aqueous solution, improve water/oily mobility ratio, increase sweep efficiency; Reduce the oil saturation of swept zone, thereby improve oil recovery.
In the eighties in 20th century, polymer flooding just has been confirmed as one of main direction of China's TOR.Up to now, polymer flooding makes a great contribution for the oil recovery that improves China.With the Daqing oil field is example, and by the end of the year 2007, the polymer flooding year produce oil of Daqing oil field surpassed 1,000 ten thousand tons in continuous 7 years, and the rate of changing oil is more than 150 tons/ton, and waterflood recovery efficiency factor improves more than 10 percentage points.Polymer displacement of reservoir oil tech has become the important leverage of Daqing oil field stable yields.The polymer oil-displacing agent that uses in the industrial production is main with partially hydrolyzed polyacrylamide.The shortcoming of common partially hydrolyzed polyacrylamide is that at high temperature hydrolysis rate is very fast, generates a large amount of carboxyls, divalent cation (Ca in carboxyl and the water
2+, Mg
2+) irreversible fixation make polymkeric substance generation phase-splitting and the deposition, cause solution viscosity significantly to descend.In other words, the performance of common partially hydrolyzed polyacrylamide is difficult to satisfy the request for utilization that oil recovery is improved in the high temperature and high salt oil field.
Have polymer oil-displacing agent of new generation good heat-resistant salt-resistant performance, that can satisfy the request for utilization of high temperature and high salt tertiary oil production in oil field for improving the performance of partially hydrolyzed polyacrylamide, developing, people have carried out number of research projects.For example, US 4644020 discloses the acrylamide copolymer that contains the N-vinyl pyrrolidone, and this multipolymer has excellent anti-hydrolysis ability, and its viscosity in aqueous solution conservation rate is high more a lot of than common partly hydrolysed acrylic amide under hot conditions.But the molecular weight of this polymkeric substance is less, and its solution viscosity does not reach the request for utilization of polymer flooding as yet.CN 1125094C discloses a kind of heat-resistant salt-resistant thickening agent of copolymer; The characteristic of this multipolymer is to contain amphipathic big monomer chain link in the molecule; Demonstrate than the better heat-resistant salt-resistant property of common partially hydrolyzed polyacrylamide; But the amphipathic side chain in this multipolymer links to each other with main chain through ester bond, and at high temperature ester bond is prone to take place hydrolysis, the stability of impact polymer.CN1156497C, CN 1262621C, CN 100386403C etc. have invented the hydrophobic associated polymer oil-displacing agent with different molecular structures; These polymkeric substance common characteristics are the hydrophobic molecule segments that contain some amount in the both sides of its molecular backbone chain; In the aqueous solution; Hydrophobic-hydrophobic interaction between the hydrophobic side chain has formed the physical crosslinking of polymer molecule interchain, improves soltion viscosity and shear-stable purpose thereby reach.Because comonomer deliquescent difference in water, the tensio-active agent that needs usually when synthesizing these multipolymers to add some amount just can obtain the higher product of molecular weight, and polymerization technique is comparatively complicated.On the other hand, hydrophobic monomer content height its decreased solubility then in the hydrophobic associated polymer; Its solvability is better when hydrophobic monomer content in the polymkeric substance is low, but under lower polymer concentration, is difficult to form effective hydrophobic association effect, thereby thickening effectiveness is very unobvious.
More than the main thought of research can be summed up as the synthesizing new heat-resistant salt-resistant polymkeric substance through introducing new heat-resistant salt-resistant monomer, belongs to resist owing to the variation of envrionment conditions the disadvantageous effect that stability caused of polymkeric substance " passive ".In the process of the various water-soluble polymer solution character of research, it is found that have the solution viscosity of some polymkeric substance in certain temperature range, to increase along with the rising of temperature.Wherein the most representative is T 46155 and PNIPAM.For example; EP 0583814 A1 and US 6689856 B2 disclose one type of graft copolymer of being made up of water-soluble main chain (polyacrylic, ionic acrylamide copolymer etc.) and temperature sensitive property side chain (T 46155), and the solution viscosity of this analog copolymer increases with the rising of temperature.The hot thickening polymer of this its invention of patent description is mainly used in personal care product fields such as makeup, does not relate to the application of polymer flooding aspect, thereby does not also have the test of correlated performance.CN 1312830A discloses a kind of polymer compsn with hot thickening character, but its application is the coating baths as paper (plate).CN 101302267A discloses a kind of non-ionic thermal tackifying water-soluble polymers and has explained that it can be applicable to each link of oil-gas mining, but this non-ionic thermal tackifying water-soluble polymers does not prove the tackify effect that can in the mineral reserve water of high salt, still have.
In sum, the hot thickening polymer soltion viscosity variation of temperature that can " initiatively " conform.But the hot thickening polymer of reporting at present; Can not be under high temperature and high salt condition; Be used for polymer oil-displacing agent effectively, therefore, how prepare a kind of hot thickening capabilities that has; Simultaneously under high temperature and high salt condition not the polymer oil-displacing agent of facile hydrolysis be still the important topic of this area, have great importance undoubtedly for development of new heat-resistant salt-resistant polymer oil-displacing agent.
Summary of the invention
The purpose of this invention is to provide a kind ofly under high temperature and high salt condition, still have multipolymer of hot thickening capabilities and preparation method thereof.
It is macromonomer and preparation method thereof that another object of the present invention provides a kind of acid amides.
The invention provides a kind of acid amides is macromonomer, it is characterized in that, this acid amides is that macromonomer has the structure shown in the formula (1),
Wherein, R
1, R
2And R
3Be H or CH independently of one another
3, m is 1-40, n is 1-40.
It is the preparation method of macromonomer that the present invention also provides a kind of acid amides, it is characterized in that, this preparation method comprises that under amidation reaction condition, the compound that will have structure shown in the formula (2) contacts with the compound with structure shown in the formula (3),
Wherein, R
1, R
2And R
3Be H or CH independently of one another
3, X is OH or halogen, and m is 1-40, and n is 1-40.
In addition, the present invention also provides a kind of hot thickening copolymer, it is characterized in that; Said multipolymer is obtained by a kind of monomer mixture polymerization, and said monomer mixture contains monomer (B) and has the monomer (A) of structure shown in the formula (4), and said monomer (B) is monomer for above-mentioned acid amides and is at least a in the monomer by the acid amides that above-mentioned method prepares; And the total amount with monomer mixture is a benchmark; The content of said monomer (A) is 65-90 weight %, and the content of monomer (B) is 10-35 weight %
Wherein, R
4, R
5, R
6And R
7Be the alkyl of hydrophilic radical, H or C1-C4 independently of one another, and R
4, R
5, R
6And R
7In at least one be hydrophilic radical; The weight-average molecular weight of this multipolymer is 500,000-1,200 ten thousand, and according to the measuring method of Q/SH10201572-2006, the dissolution time of multipolymer in water was less than 2 hours.
In addition, the invention provides a kind of preparation method of hot thickening copolymer, said method is included under the solution polymerization condition of alkene; In the presence of initiator, make a kind of monomer mixture in water, carry out polyreaction, it is characterized in that; Said monomer mixture contains monomer (A) and monomer (B), wherein, and the monomer of monomer (A) for having structure shown in the formula (4); Monomer (B) is macromonomer for above-mentioned acid amides and is at least a in the macromonomer by the acid amides that method for preparing obtains; And the total amount with monomer mixture is a benchmark, and the content of said monomer (A) is 65-90 weight %, and the content of monomer (B) is 10-35 weight %.
Adopting acid amides provided by the invention is the of the present invention hot thickening copolymer that macromonomer makes; Under high temperature and high salt condition, still have hot thickening capabilities, and its dissolution rate in water was less than 2 hours; Therefore, can be as polymer oil-displacing agent in oil recovery.
Particularly, can find out from embodiment 1, in the presence of a large amount of divalent salts ionic, along with the rising of temperature, the 72mPas the when 25mPas of the AV of hot thickening copolymer during from 30 ℃ is increased to 90 ℃.This shows that hot thickening copolymer provided by the invention still possesses good hot thickening properties under high temperature and high salt condition.
And the dissolution time of hot thickening copolymer of the present invention in water was less than 2 hours, and according to the company standard Q/SH1020 1572-2006 of Shengli Petroleum Administration Bureau, the polymer dissolution time can be satisfied the requirement of industry spot injection allocation less than 2 hours.This explanation, hot thickening copolymer of the present invention can be used in industry, as the polymer oil-displacing agent and the profile-controlling and plugging agent of TOR.
Embodiment
The invention provides a kind of acid amides is macromonomer, it is characterized in that, this acid amides is that macromonomer has the structure shown in the formula (1),
Wherein, R
1, R
2And R
3Be H or CH independently of one another
3, preferably, R
1, R
2And R
3Be H, m and n are mean polymerisation degree, and wherein, m is 1-40, is preferably 5-38, further is preferably 10-37; N is 1-40, is preferably 5-35, further is preferably 6-31.
The present invention is that the concrete value of m and n does not have special qualification in the macromonomer to said acid amides, and preferably, said acid amides is in the macromonomer, m: n is 1: 0.1-5 further is preferably 1: 0.15-3.5.
According to the present invention, on the basis of the span that satisfies above-mentioned m and n, said acid amides is that the number-average molecular weight of macromonomer is preferably 1500-3000, is preferably 2000-2800.
The invention provides the preparation method that a kind of acid amides is a macromonomer, it is characterized in that, this preparation method comprises that under amidation reaction condition, the compound that will have structure shown in the formula (2) contacts with the compound with structure shown in the formula (3),
Wherein, R
1, R
2, R
3, m and n definition and above-mentioned acid amides be that the definition of macromonomer is identical.X is a halogen, is preferably Br or Cl, further is preferably Cl.
According to the present invention, said number-average molecular weight with compound of structure shown in the formula (3) is preferably 1300-2800, further is preferably 1500-2500.
According to the present invention, the condition of said contact there is not special qualification, can be the amidation reaction condition of routine, preferably, the condition of said contact comprises that the contact temperature is 20-30 ℃.Be 1-6 hour duration of contact, further is preferably 3-5 hour.Said contact temperature refers to and heats up after acrylate chloride joins system, and remains on the temperature that this temperature is carried out amidate action, also refers to the time that finishes to reaction from beginning after acrylate chloride all joins system said duration of contact.Compound with structure shown in the formula (2) is 1 with the mol ratio with compound of structure shown in the formula (3): 0.01-1 further is preferably 1: 0.01-0.5 most preferably is 1: 0.015-0.1.
According to the present invention; The solvent of said amidate action is the conventional solvent in this area, like ether organic solvent, is preferably anhydrous diethyl ether; In order to obtain higher yield; Preferably under stirring condition, the diethyl ether solution that will have the compound of structure shown in the formula (3) is added drop-wise in the diethyl ether solution of the compound of structure shown in (2) that has formula, and the speed of preferred said dropping makes the temperature of reaction system be lower than 4 ℃.When X was halogen, because meeting constantly generates hydrogen halide in the reaction process, a certain amount of triethylamine of therefore preferred adding carried out to forward to impel reaction.Reaction removes solvent through evaporation and obtains paste after finishing, and being acid amides is macromonomer.
Because acid amides of the present invention is that macromonomer obtains through acyl chlorides and amine condensation reaction; And the condensation reaction of acyl chlorides and amine is conventional methodology of organic synthesis; Therefore; According to raw material and reaction conditions, need not special sign is that the polymerisate that provable the present invention obtains is a macromonomer for the target acid amides.
The invention provides a kind of hot thickening copolymer, it is characterized in that, said multipolymer is obtained by a kind of monomer mixture polymerization; Said monomer mixture contains monomer (B) and has the monomer (A) of structure shown in the formula (4), and said monomer (B) is monomer for above-mentioned acid amides and is at least a in the monomer by the acid amides that method for preparing obtains, and is benchmark with the total amount of monomer mixture; The content of said monomer (A) is 65-90 weight %, and the content of monomer (B) is 10-35 weight %, preferably; Total amount with monomer mixture is a benchmark; The content of said monomer (A) is 70-85 weight %, and the content of monomer (B) is 15-30 weight %
Wherein, R
4, R
5, R
6And R
7Be the alkyl of hydrophilic radical, H or C1-C4 independently of one another, and R
4, R
5, R
6And R
7In at least one be hydrophilic radical; The weight-average molecular weight of this hot thickening copolymer is 500,000-1,200 ten thousand, further is preferably 1,000,000-1,100 ten thousand, most preferably is 5,000,000-10,000,000.According to the measuring method of Q/SH1020 1572-2006, the dissolution time of this hot thickening copolymer in water was less than 2 hours.
Said monomer (B) is identical with the preamble description, repeats no more at this.
According to the present invention; Said hydrophilic radical is preferably at least a in the group of structure shown in (5) that has formula, the group with structure shown in the formula (6), the group with structure shown in the formula (7), the group with structure shown in the formula (8), the group with structure shown in the formula (9) and the hydroxylamino aryl
Wherein, R
8, R
9, R
10And R
11Be the alkyl of H or C1-C4 independently of one another, under the preferable case, R
10And/or R
11Be H, M
1, M
2And M
3Be H, Na or K independently of one another, be preferably Na or K.
The compound that meets above-mentioned general formula has a variety of; Preferably; Said monomer (A) is vinyl propanesulfonic acid sodium, N-vinyl pyrrolidone, 2-acrylic amide-2-methyl propane sulfonic acid, acrylic amide, N methacrylamide, N; N-DMAA, N-ethyl acrylamide, N; N-diethylammonium acrylic amide, at least a in hydroxylamino Phenyl Acrylamide, NSC 11448, vinylformic acid and the methylacrylic acid further are preferably at least a in acrylic amide, 2-acrylic amide-2-methyl propane sulfonic acid, vinyl propanesulfonic acid sodium, N-vinyl pyrrolidone, vinylformic acid and the methylacrylic acid.
The invention provides a kind of preparation method of hot thickening copolymer, said method is included under the solution polymerization condition of alkene, in the presence of initiator; Make a kind of monomer mixture in water, carry out polyreaction, it is characterized in that, said monomer mixture contains monomer (A) and monomer (B); Wherein, monomer (A) is monomer with structure shown in the formula (4), and monomer (B) is that acid amides that macromonomer and method for preparing obtain is at least a in the macromonomer for above-mentioned acid amides; And the total amount with monomer mixture is a benchmark, and the content of said monomer (A) is 65-90 weight %, and the content of monomer (B) is 10-35 weight %; Preferably; Total amount with monomer mixture is a benchmark, and the content of said monomer (A) is 70-85 weight %, and the content of monomer (B) is 15-30 weight %.
Said monomer (B) is identical with the preamble description, repeats no more at this.
According to the present invention, when polyreaction began, the weight of monomer mixture was preferably controlled within the specific limits; Particularly; The ratio of the gross weight of the weight of monomer mixture and water and monomer mixture is preferably 0.1-0.5: 1, further be preferably 0.15-0.45: and 1, most preferably be 0.2-0.35: 1.
In order to make hot thickening copolymer have better displacement of reservoir oil performance, the number-average molecular weight of preferred said monomer (B) is 1500-3000, further is preferably 2000-2800.Wherein, in the said monomer (B), m: n is preferably 1: 0.1-5 further is preferably 1: 0.15-3.5.
According to the present invention; Said monomer (A) can be the polymer oil-displacing agent field various monomers that contain ethylene linkage commonly used; Preferably; At least a in the monomer that said monomer (A) is vinyl propanesulfonic acid sodium, N-vinyl pyrrolidone, 2-acrylic amide-2-methyl propane sulfonic acid, have a structure shown in the formula (10) and the monomer with structure shown in the formula (11)
Wherein, R
12, R
13, R
15, R
16, R
17, R
18, R
19Be the alkyl of H or C1-C4 independently of one another, R
14For H, to the alkyl of hydroxyl amino phenyl or C1-C4, M
4Be H, Na or K.
According to the present invention; The mode of initiated polymerization can be the conventional mode in this area, preferably, adopts initiator to cause; Wherein, The consumption of said initiator can further be preferably 0.001-0.8 weight % for the 0.0001-1 weight % of the gross weight of monomer (A) and monomer (B), most preferably is 0.01-0.6 weight %.
Wherein, the kind of said initiator is the conventional various initiators in this area, for example inorganic peroxide series initiators, redox series initiators and azo series initiators.
Particularly; Said initiator is the two methylpent hydrochlorates of ammonium persulphate, Sodium Persulfate, Potassium Persulphate, ammonium persulphate-S-WAT, Sodium Persulfate-sodium sulfite anhy 96, Sodium Persulfate-rongalite, Sodium Persulfate-oxalic acid, Sodium Persulfate-urea, Potassium Persulphate-rongalite, Potassium Persulphate-urea, Potassium Persulphate-oxalic acid, potassium hydrogen persulfate-potassium sulfite, trolamine-Sulfothiorine, trolamine-potassium sulfite, trolamine-S-WAT, Diisopropyl azodicarboxylate, azo, azo two isobutyl imidazoline salt hydrochlorates, 2, at least a in 2-azo two (the 2-methyl-propyl miaow) dihydrochloride.
According to the present invention, the condition of said polyreaction can be the normal condition of this area, as long as make the hot thickening copolymer that obtains meet above-mentioned requirements; Preferably, the condition of said polyreaction comprises, protection of inert gas; Polymeric reaction temperature is 5 ℃-80 ℃; Further be preferably 20 ℃-60 ℃, most preferably be 30 ℃-60 ℃, after the temperature of said polyreaction refers to the initiator adding; Polymerization reaction system is warmed up to a constant temp, and remains on the temperature when carrying out polyreaction under this steady temperature; Polymerization reaction time is 0.25-24 hour, further is preferably 4-8 hour, and polymerization reaction time is for keeping the time of above-mentioned temperature of reaction.The original ph of said polyreaction is 8-12, further is preferably 11-12.
Said rare gas element comprises in the nitrogen that this area is conventional or the periodic table of elements and at least a in the neutral element gas to be preferably nitrogen.Said protection of inert gas feeds in the middle of carrying out rare gas element protects except being included in polyreaction; In reaction system, feed rare gas element before also being included in the adding initiator; To remove the dissolved oxygen in the aqueous solution; The method that the method that this step feeds rare gas element is known for those skilled in the art altogether, among the present invention, the time that feeds rare gas element is preferably 30-60 minute.
The present invention also provides the hot thickening copolymer by above-mentioned polymerization method preparation.
Hot thickening copolymer provided by the invention and can be used as polymer oil-displacing agent and profile-controlling and plugging agent according to the hot thickening copolymer that method provided by the invention prepares.
Below, through embodiment content of the present invention is done further explanation.
The number average of macromonomer and multipolymer and weight-average molecular weight are measured through gel permeation chromatography (GPC, available from Waters, model Waters 515) appearance in the embodiment of the invention.
PH in the embodiment of the invention measures through PHS-3B type pH meter.
The dissolution time of multipolymer is measured according to the method for the company standard Q/SH1020 1572-2006 of Shengli Petroleum Administration Bureau in the embodiment of the invention.
The AV of aqueous copolymers solution uses the DV-III ULTRA type rotational viscosimeter of BROOKFIELD company to measure in the embodiment of the invention.
Preparation embodiment 1
It is macromonomer that this preparation embodiment is used to prepare acid amides, i.e. monomer in the polyreaction (B).
200 weight part acrylate chlorides are dissolved in 100 weight part anhydrous diethyl ethers, and stirring makes acrylate chloride solution; Compound shown in the 100 weight part formulas (12) (m=37, n=7, molecular weight are 2600, available from Huntsman company) and 5 weight part triethylamines are dissolved in 100 parts of anhydrous diethyl ethers make solution A; Under stirring the acrylate chloride drips of solution is added in the solution A, controlled temperature is no more than 4 ℃ in the dropping process, after dropwising, reacts 5 hours down for 25 ℃ in room temperature, and evaporation obtained paste except that desolvating after reaction finished, and was macromonomer B1.
Preparation Comparative Examples 1
Preparing acid amides according to the method for preparing embodiment 1 is macromonomer, and different is, adds the compound that 100 weight parts have a structure shown in the formula (13) and replaces the compound shown in the 100 weight part formulas (12).Obtain macromonomer DB1.
Preparation embodiment 2
It is macromonomer that this preparation embodiment is used to prepare acid amides, i.e. monomer in the polyreaction (B).
200 weight part acrylate chlorides are dissolved in 100 weight part anhydrous diethyl ethers, and stirring makes acrylate chloride solution; Compound shown in the 200 weight part formulas (14) (m=10, n=31, molecular weight are 2100, available from Huntsman company) and 5 weight part triethylamines are dissolved in 100 parts of anhydrous diethyl ethers make solution B; Under stirring the acrylate chloride drips of solution is added in the solution B, controlled temperature is no more than 4 ℃ in the dropping process, after dropwising, reacts 3 hours down at 20 ℃, and evaporation obtained paste except that desolvating after reaction finished, and was macromonomer B2.
Preparation embodiment 3
It is macromonomer that this preparation embodiment is used to prepare acid amides, i.e. monomer in the polyreaction (B).
200 weight part acrylate chlorides are dissolved in 100 weight part anhydrous diethyl ethers, and stirring makes acrylate chloride solution; Compound shown in the 400 weight part formulas (15) (m=29, n=6, molecular weight are 2100, available from Huntsman company) and 5 weight part triethylamines are dissolved in 100 parts of anhydrous diethyl ethers make solution C; Under stirring the acrylate chloride drips of solution is added in the solution C, controlled temperature is no more than 4 ℃ in the dropping process, after dropwising, reacts 4 hours down at 30 ℃, and evaporation obtained paste except that desolvating after reaction finished, and was macromonomer B3.
Embodiment 1
Present embodiment is used to prepare hot thickening copolymer of the present invention.
To containing 15 weight % acrylic amides, 10 weight % vinylformic acid are among the aqueous solution X of 10 weight % monomers B 1; It is 11-12 that the sodium hydroxide solution that adds 30 weight % is adjusted to pH, feeds nitrogen and removes dissolved oxygen in 60 minutes, and attemperation is 10 ℃; Total amount with aqueous solution X is a benchmark, adds content and be the Potassium Persulphate of 0.05 weight % and oxalic acid that content is 0.03 weight % as initiator, is warming up to 35 ℃ and keep this temperature; Reacted 4 hours; Obtain hot thickening copolymer P1, the weight-average molecular weight of hot thickening copolymer P1 is 8,200,000, and the dissolution time of hot thickening copolymer P1 was less than 2 hours.
Comparative Examples 1
Prepare multipolymer according to embodiment 1 described method, different is, does not add monomers B 1, obtains multipolymer DP1, and the weight-average molecular weight of multipolymer DP1 is 9,900,000.
Comparative Examples 2
Prepare multipolymer according to embodiment 1 described method, different is, with containing 20 weight % acrylic amides, and 10 weight % vinylformic acid, the aqueous solution of 0.1 weight % monomers B 1 replaces aqueous solution X, obtains multipolymer DP2, and the weight-average molecular weight of multipolymer DP2 is 9,200,000.
Comparative Examples 3
Prepare multipolymer according to embodiment 1 described method, different is, replaces the monomers B 1 of 10 weight % with the monomer DB1 of 10 weight %, obtains multipolymer DP3, and the weight-average molecular weight of multipolymer DP3 is 3,800,000.
Embodiment 2
Present embodiment is used to prepare hot thickening copolymer of the present invention.
To containing 19 weight % acrylic amides, 6 weight %2-acrylic amide-2-methyl propane sulfonic acids (available from Shandong chemical company of alliance) are among the aqueous solution Y of 5 weight % monomers B 1; It is 11-12 that the sodium hydroxide solution that adds 30 weight % is adjusted to pH, feeds nitrogen and removes dissolved oxygen in 40 minutes, and attemperation is 10 ℃; Total amount with aqueous solution Y is a benchmark, and the V50 that adds content and be 0.005 weight % is as initiator, is warming up to 60 ℃ and keep this temperature; Reacted 8 hours; Obtain hot thickening copolymer P2, the weight-average molecular weight of hot thickening copolymer P2 is 9,850,000, and the dissolution time of hot thickening copolymer P2 was less than 2 hours.
Embodiment 3
Present embodiment is used to prepare hot thickening copolymer of the present invention.
To containing 15 weight % acrylic amides, 3 weight % vinylbenzenesulfonic acid sodium are among the aqueous solution Z of 5 weight % monomers B 3; It is 11-12 that the sodium hydroxide solution that adds 30 weight % is adjusted to pH, feeds nitrogen and removes dissolved oxygen in 45 minutes, and attemperation is 15 ℃; Total amount with aqueous solution Z is a benchmark, adds content and be the Potassium Persulphate of 0.08 weight % and urea that content is 0.04 weight % as initiator, is warming up to 30 ℃ and keep this temperature; Reacted 5 hours; Obtain hot thickening copolymer P3, the weight-average molecular weight of hot thickening copolymer P3 is 7,700,000, and the dissolution time of hot thickening copolymer P3 was less than 2 hours.
Embodiment 4
Present embodiment is used to prepare hot thickening copolymer of the present invention.
To containing 10 weight % acrylic amides, 4 weight %N-vinyl pyrrolidones are in the water solution A of 6 weight % monomers B 3; It is 11-12 that the sodium hydroxide solution that adds 30 weight % is adjusted to pH, feeds nitrogen and removes dissolved oxygen in 30 minutes, and attemperation is 5 ℃; Adding is a benchmark with the total amount of water solution A, content be the Potassium Persulphate of 0.06 weight % as initiator, be warming up to 60 ℃ and keep this temperature; Reacted 5 hours; Obtain hot thickening copolymer P4, the weight-average molecular weight of hot thickening copolymer P4 is 7,950,000, and the dissolution time of hot thickening copolymer P4 was less than 2 hours.
Embodiment 5
Present embodiment is used to prepare hot thickening copolymer of the present invention.
Method according to embodiment 1 prepares hot thickening copolymer, and different is, the pH that regulates the aqueous solution is 7, obtains hot thickening copolymer P5, and the weight-average molecular weight of hot thickening copolymer P5 is 6,200,000, and the dissolution time of hot thickening copolymer P5 was less than 2 hours.
Test case 1
Method preparation total mineralization according to the company standard Q/SH1020 1572-2006 of Shengli Petroleum Administration Bureau is the simulation mineral reserve water of 19334mg/L (wherein calcium ion and mg ion total concn are 514mg/L); With this simulation mineral reserve water is that the solvent compound concentration is the copolymer solution of 3000mg/L, stirs 24 hours under the room temperature; Measure the AV of copolymer solution under differing temps, investigate the copolymer solution AV with the variation of temperature situation.
Record on the DV-III ULTRA type rotational viscosimeter of AV through BROOKFIELD company, during measurement shearing rate constant be 7.34s
-1, measuring temperature range is 30 ℃-90 ℃, temperature rise rate is 2 ℃/minute.
Copolymer p 1-P5 and DP1-DP3 through cutting, freeze-drying and pulverising step, are processed behind the powdery copolymer AV of measuring copolymer p 1-P5 and DP1-DP3 according to aforesaid method, and the result lists in the table 1.
Table 1
Can find out that by table 1 hot thickening copolymer of the present invention still possesses extremely excellent hot thickening properties in the mineral reserve water of high salt concentration, can be used in oil-displacing agent and profile-controlling and plugging agent.
The multipolymer DP1 of preparation is multipolymer oil-displacing agent commonly used in the present industry in the Comparative Examples 1, and multipolymer DP1 does not possess hot thickening properties.
Two kinds of monomeric ratios in the Comparative Examples 2 are 300: 1, and the AV of the multipolymer DP2 that obtains descends along with the rising of temperature, but fall is littler than DP1.
Monomer DB1 in the Comparative Examples 3 has only polyoxyethylated segment, and the be far from hot thickening effectiveness of embodiments of the invention 1 of the hot thickening effectiveness that obtains multipolymer DP3 in the Comparative Examples 3 is good.Explain that the present invention uses T 46155 and polyoxypropylene double focusing compound segment, and make its limited proportion within the specific limits, can access multipolymer with excellent heat thickening properties.
The pH value of copolymerized solution is 7 among the embodiment 5, compares with the embodiment 1-3 of meta-alkalescence, and the hot thickening effectiveness of the hot thickening copolymer that obtains among the embodiment 5 is slightly poor, explains that it is preferred implementation of the present invention that the pH value that makes copolyreaction is controlled at 11-12.
Claims (26)
1. an acid amides is a macromonomer, it is characterized in that, this acid amides is that macromonomer has the structure shown in the formula (1),
Wherein, R
1, R
2And R
3Be H or CH independently of one another
3, m is 1-40, n is 1-40.
2. acid amides according to claim 1 is a macromonomer, and wherein, said acid amides is in the macromonomer, m: n is 1: 0.1-5.
3. acid amides according to claim 1 and 2 is a macromonomer, and wherein, said acid amides is that the number-average molecular weight of macromonomer is 1500-3000.
4. the preparation method that acid amides is a macromonomer is characterized in that, this preparation method comprises that under amidation reaction condition, the compound that will have structure shown in the formula (2) contacts with the compound with structure shown in the formula (3),
Wherein, R
1, R
2And R
3Be H or CH independently of one another
3, X is a halogen, and m is 1-40, and n is 1-40.
5. method according to claim 4, wherein, the condition of said contact comprises that the contact temperature is 20-30 ℃, and be 1-6 hour duration of contact, and the compound with structure shown in the formula (2) is 1 with the mol ratio with compound of structure shown in the formula (3): 0.01-1.
6. according to claim 4 or 5 described methods, wherein, said number-average molecular weight with compound of structure shown in the formula (3) is 1300-2800.
7. according to claim 4 or 5 described methods, wherein, in the said compound with structure shown in the formula (3), m: n is 1: 0.1-5.
8. hot thickening copolymer; It is characterized in that; Said multipolymer is obtained by a kind of monomer mixture polymerization, and said monomer mixture contains monomer (B) and has the monomer (A) of structure shown in the formula (4), and said monomer (B) is monomer for any described acid amides among the claim 1-3 and is at least a in the monomer by the acid amides that any described method among the claim 4-7 prepares; And the total amount with monomer mixture is a benchmark; The content of said monomer (A) is 65-90 weight %, and the content of monomer (B) is 10-35 weight %
Wherein, R
4, R
5, R
6And R
7Be the alkyl of hydrophilic radical, H or C1-C4 independently of one another, and R
4, R
5, R
6And R
7In at least one be hydrophilic radical;
The weight-average molecular weight of this hot thickening copolymer is 500,000-1,200 ten thousand, and according to the measuring method of Q/SH10201572-2006, the dissolution time of this hot thickening copolymer in water was less than 2 hours.
9. hot thickening copolymer according to claim 8 wherein, is a benchmark with the total amount of monomer mixture, and the content of said monomer (A) is 70-85 weight %, and the content of monomer (B) is 15-30 weight %.
10. hot thickening copolymer according to claim 8; Wherein, Said hydrophilic radical is for having at least a in the group of structure shown in the formula (5), the group with structure shown in the formula (6), the group with structure shown in the formula (7), the group with structure shown in the formula (8), the group with structure shown in the formula (9) and the hydroxylamino aryl
Wherein, R
8, R
9, R
10And R
11Be the alkyl of H or C1-C4 independently of one another, M
1, M
2And M
3Be H, Na or K independently of one another.
11. hot thickening copolymer according to claim 10; Wherein, Said monomer (A) is vinyl propanesulfonic acid sodium, N-vinyl pyrrolidone, 2-acrylic amide-2-methyl propane sulfonic acid, acrylic amide, N methacrylamide, N; N-DMAA, N-ethyl acrylamide, N, N-diethylammonium acrylic amide, at least a in hydroxylamino Phenyl Acrylamide, NSC 11448, vinylformic acid and the methylacrylic acid.
12. the preparation method of a hot thickening copolymer; Said method is included under the solution polymerization condition of alkene, in the presence of initiator, makes a kind of monomer mixture in water, carry out polyreaction; It is characterized in that; Said monomer mixture contains monomer (A) and monomer (B), wherein, and the monomer of monomer (A) for having structure shown in the formula (4); Monomer (B) is macromonomer for any described acid amides among the claim 1-3 and is at least a in the macromonomer by the acid amides that any described method among the claim 4-7 prepares; And the total amount with monomer mixture is a benchmark, and the content of said monomer (A) is 65-90 weight %, and the content of monomer (B) is 10-35 weight %.
13. method according to claim 12, wherein, when said polyreaction began, the ratio of the gross weight of the weight of monomer mixture and water and monomer mixture was 0.1-0.5: 1.
14. method according to claim 13, wherein, when said polyreaction began, the ratio of the gross weight of the weight of monomer mixture and water and monomer mixture was 0.15-0.45: 1.
15. method according to claim 12 wherein, is a benchmark with the total amount of monomer mixture, the content of said monomer (A) is 70-85 weight %, and the content of monomer (B) is 15-30 weight %.
16. method according to claim 12; Wherein, At least a in the monomer that said monomer (A) is vinyl propanesulfonic acid sodium, N-vinyl pyrrolidone, 2-acrylic amide-2-methyl propane sulfonic acid, have a structure shown in the formula (10) and the monomer with structure shown in the formula (11)
Wherein, R
12, R
13, R
15, R
16, R
17, R
18, R
19Be the alkyl of H or C1-C4 independently of one another, R
14For H, to the alkyl of hydroxyl amino phenyl or C1-C4, M
4Be H, Na or K.
17. method according to claim 16; Wherein, Said monomer (A) is vinyl propanesulfonic acid sodium, N-vinyl pyrrolidone, 2-acrylic amide-2-methyl propane sulfonic acid, acrylic amide, N methacrylamide, N; N-DMAA, N-ethyl acrylamide, N, N-diethylammonium acrylic amide, at least a in hydroxylamino Phenyl Acrylamide, NSC 11448, vinylformic acid and the methylacrylic acid.
18. according to any described method among the claim 12-17, wherein, the consumption of said initiator is the 0.0001-1 weight % of the gross weight of monomer mixture.
19. method according to claim 18, wherein, the consumption of said initiator is the 0.001-0.8 weight % of the gross weight of monomer mixture.
20. method according to claim 18, wherein, said initiator is at least a in inorganic peroxide series initiators, redox series initiators and the azo series initiators.
21. method according to claim 20; Wherein, Said initiator is the two methylpent hydrochlorates of ammonium persulphate, Sodium Persulfate, Potassium Persulphate, ammonium persulphate-S-WAT, Sodium Persulfate-sodium sulfite anhy 96, Sodium Persulfate-rongalite, Sodium Persulfate-oxalic acid, Sodium Persulfate-urea, Potassium Persulphate-rongalite, Potassium Persulphate-urea, Potassium Persulphate-oxalic acid, potassium hydrogen persulfate-potassium sulfite, trolamine-Sulfothiorine, trolamine-potassium sulfite, trolamine-S-WAT, Diisopropyl azodicarboxylate, azo, azo two isobutyl imidazoline salt hydrochlorates, 2, at least a in 2-azo two (the 2-methyl-propyl miaow) dihydrochloride.
22. according to any described method among the claim 12-17, wherein, the condition of said polyreaction comprises; Protection of inert gas; Polymeric reaction temperature is 5 ℃-80 ℃, and polymerization reaction time is 0.25-24 hour, and the original ph of said polyreaction is 8-12.
23. method according to claim 22, wherein, the condition of said polyreaction comprises that polymeric reaction temperature is 20 ℃-60 ℃, and polymerization reaction time is 4-8 hour, and the pH value of the initial soln of said polyreaction is 11-12.
24. hot thickening copolymer by any described method preparation among the claim 12-23.
25. any described hot thickening copolymer is as the application of polymer oil-displacing agent in claim 8-11 and 24.
26. any described hot thickening copolymer is as the application of profile-controlling and plugging agent in claim 8-11 and 24.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153363A (en) * | 2015-08-07 | 2015-12-16 | 中国石油化工股份有限公司胜利油田分公司勘探开发研究院 | Partially-crosslinked and partially-branched copolymer oil displacement agent and preparation method thereof |
| CN106554067A (en) * | 2016-11-17 | 2017-04-05 | 烟台智本知识产权运营管理有限公司 | Ter-polymers are used for the degreaser that heavy crude heat extraction sewage is processed |
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| CN1398905A (en) * | 2001-05-16 | 2003-02-26 | 莱雅公司 | Water soluble polymers with water soluble main chain and side unit and its prepn process, composition containing them and its beautifying use |
| CN101302267A (en) * | 2007-05-11 | 2008-11-12 | 中国科学院成都有机化学有限公司 | Non-ionic thermal tackifying water-soluble polymers |
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| EP0583814A1 (en) * | 1992-08-20 | 1994-02-23 | Sofitech N.V. | Thermoviscosifying polymers, their synthesis and their uses in particular in the oil industry |
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| CN106554067A (en) * | 2016-11-17 | 2017-04-05 | 烟台智本知识产权运营管理有限公司 | Ter-polymers are used for the degreaser that heavy crude heat extraction sewage is processed |
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