CN102050917A - Macromolecular compound containing aliphatic tertiary amine group as well as preparation method thereof and application in oil displacement agent - Google Patents
Macromolecular compound containing aliphatic tertiary amine group as well as preparation method thereof and application in oil displacement agent Download PDFInfo
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Abstract
The invention relates to a macromolecular compound containing aliphatic tertiary amine groups, as well as a preparation method thereof and the application in oil displacement agents, in particular to a preparation method of high-molecular-weight long-chain branched polyacrylamide with temperature resistance and salt resistance. In the invention, a synthesized macromolecular compound containing aliphatic tertiary amine groups and a persulfate compound form an oxidation-reduction initiator system, and the oxidation-reduction initiator system initiates the polymerization of acrylamide and temperature-resistant salt-resistant monomers to form the high-molecular-weight long-chain branched polyacrylamide with temperature resistance and salt resistance. The temperature resistance and the salt resistance of the product are higher than those of the product in the prior art. The invention is applied in the field of tertiary oil recovery.
Description
Technical field
The present invention relates to the tertiary oil recovery field, be specifically related to a kind of synthetic and application in preparation long branched chain structure high molecular weight temperature-tolerant anti-salt polyacrylamide of macromole of fatty tertiary amine group.
Background technology
Polyacrylamide is the multiduty water-soluble polymer of a class, has a wide range of applications in paper industry, textile industry, metallurgy, ore dressing and sewage disposal.In recent years, along with the increasing of oilfield exploitation difficulty, be that the polymer oil-displacing agent of representative has excellent performance with the polyacrylamide solution in tertiary oil recovery, for vital role has been brought into play in oilfield stable production, volume increase.Industrial application has also driven the research and development upsurge of polyacrylamide, is example with the tertiary oil recovery, and based on economic benefit with satisfy the reservoir geology environment, preparation high molecular and temperature-resistant and anti-salt type polyacrylamide are present main directions.The importance of molecular weight is to prepare the aqueous solutions of polymers of identical viscosity, molecular weight is high more, required polymer loading is just few more, and practical effect has shown that also high molecular weight polyacrylamide all will obviously be better than common polyacrylamide on salt tolerance, shear resistant and raising recovery ratio.The synthesizing new function monomer, comprise the temperature resistant antisalt monomer, zwitterionic monomer and hydrophobic monomer are again with the acrylamide copolymerization, improving solution viscosity by the ratio of raising function monomer or from increasing the Intermolecular Forces angle, is the synthetic thinking of temperature-resistant and anti-salt type polyacrylamide.If want this type of polyacrylamide that better temperature resistant antisalt effect is arranged, still will be to improve molecular weight as the basis, but the purity of function monomer, solubility property and space steric effect, make the multicomponent system polymerizing condition more complicated, molecular weight of product is not easy to do greatly, from chemical terms and physical angle, the experiment conception that improves the multipolymer over-all properties often can not fully realize, therefore farthest improves the research basis that molecular weight is a temperature-resistant and anti-salt type polyacrylamide.An effective way that increases molecular weight is to select suitable initiator system by experiment, and good initiator system can be controlled inductive phase when ensureing high conversion, reduce automatic hastening phenomenon, and reacting balance is carried out.
In recent years, around the polyacrylamide initiator system, researcher is at synthesizing formula, does a lot of work in aspects such as triggering mechanism and synthesis technique.Wherein being oxygenant with the persulphate, is that the oxidation-reduction trigger system of reductive agent becomes a new research focus with the small molecules tertiary amine.Qiu Kunyuan etc. have carried out systematic study to persulphate and aliphatic amide system, measure through radical-scavenging and spectrum wave spectrum (ESR), find when used aliphatic amide is primary, during secondary amine, generation be nitrogen free radical, if tertiary amine then forms carbon radicals.They are to persulphate and N, N, and N ', N '-Tetramethyl Ethylene Diamine, systematic study has been carried out at room temperature acrylamide triggered polymerization, and proposed may triggering mechanism.Functional initiator system not only can improve the molecular weight of polymkeric substance, also can determine the molecular structure of product simultaneously, for synthetic special construction polyacrylamide provides method.Open loyal the bath and synthesized serial water miscible fat tertiary amine base monomer, polymerizing acrylamide triggered used as reductive agent and persulphate composition oxidation-reduction system, obtain having branched structure, molecular weight is up to up to ten million polyacrylamides.Tertiary amine groups monomer in this initiator system has dual-use function, both can participate in causing, and can participate in polymerization again, so the system initiating activity is very high.On this basis, they have also studied and will contain the ternary oxidation-reduction trigger system that the tertiary amine groups monomer is formed as second reductive agent and ammonium persulphate and sodium bisulfite, when polymerizing acrylamide triggered, induction period in polymerization is controlled, molecular weight of product height and gel content are low, are very potential and practical initiator systems.
In the oxidation-reduction trigger system of persulphate and fat tertiary amine (monomer) composition, the structure of reductive agent tertiary amine will directly influence the initiator system activity, the molecular structure of decision polymer molecular weight and product.For the research of this type of initiator system, reductive agent also only is limited to the small molecules tertiary amine at present, and for multi-functional macromole tertiary amine the research report is not arranged as yet.In the present invention, we have prepared the macromole of fatty tertiary amine group, used as reductive agent, form novel oxidation-reduction trigger system with the oxygenant persulphate, polymerizing acrylamide triggered, the high molecular weight temperature-tolerant anti-salt type polyacrylamide of synthetic long branched chain structure.
Summary of the invention
The technical problem to be solved in the present invention is:
At conventional polypropylene acid amides temperature resistant antisalt poor performance, and adopt the synthetic Molecular Weight for Polyacrylamide of the temperature resistant antisalt monomer copolymerization method big shortcoming that is not easy to do, the invention provides macromole of a kind of fatty tertiary amine group and preparation method thereof, itself and persulphate are formed oxidation-reduction trigger system, acrylamide triggered and temperature resistant antisalt monomer polymerization in the aqueous solution, obtain the long branched chain structure high molecular weight temperature-tolerant anti-salt polyacrylamide, the temperature resistant antisalt performance of product improves a lot than currently available products.
Product technology scheme of the present invention is:
A kind of macromole of fatty tertiary amine group, the macromolecular structural formula of described fatty tertiary amine group is shown in (1) formula:
(1) in the formula: R
1Be H or CH
3R
2Be ester group or amide group; R
3Be C
1～C
6Alkyl;
M is the polymerization degree of fatty tertiary amine groups monomeric repeating unit;
N is the polymerization degree of N,N-DMAA repeating unit;
m∶n＝1∶1～1000；
The macromolecular molecular-weight average of described fatty tertiary amine group is 2000～1000000.
Preferably in (1) formula: R
2Be amide group; R
3Be ethylidene or propylidene.
Preferred m: n=1: 9～100;
The macromolecular molecular-weight average of preferred described fatty tertiary amine group is 10000～200000.
Preparation method's technical scheme of the present invention is:
Press mass fraction, raw material comprises: 1 part of fat tertiary amine base monomer; 1～2000 part of N,N-DMAA, preferred 20～1000; 1～10000 part of solvent, preferred 60～4000; 0.01～20 part of initiator; 0～20 part of chain-transfer agent, described chain-transfer agent can add, also can not add;
Described fat tertiary amine base monomer structure is suc as formula (2):
(2) in the formula: R
1Be H or CH
3R
2Be ester group or amide group; R
3Be C
1～C
6Alkyl;
Described initiator is: the fine or azo diisobutyl amidine hydrochloride of azo two isobutyls;
Described solvent is at least a in following: methyl alcohol, second alcohol and water.
Described preparation method may further comprise the steps:
The 1st step added reaction vessel with described fat tertiary amine base monomer, N,N-DMAA, was dissolved in the described solvent, pressed mass ratio,
Fat tertiary amine base monomer: N,N-DMAA: solvent=1: 1～2000: 1～10000
The 2nd step fed nitrogen in reaction vessel, deoxygenation is more than 20 minutes;
The 3rd goes on foot, and adds 0.01～20 part described initiator in reaction vessel, under 60～70 ℃, reacts 4～12 hours;
In the 4th step, 40%～70% of the total mass of desolvating is taken out in decompression in reaction vessel, with the residuum solid-liquid separation, removes solid phase;
The 5th step, liquid phase is precipitated in ether 2～4 times, dry under 30 ℃～45 ℃, obtain the macromole product of structural formula for the fatty tertiary amine group of (1) formula.
The macromolecular molecular weight of fatty tertiary amine group is measured by gel permeation chromatography (GPC), and fat tertiary amine base monomer and N,N-DMAA monomer molar ratio are by nucleus magnetic hydrogen spectrum in the multipolymer
1H-NMR determines.
Further preferred:
In (2) formula, R
3Be ethylidene or propylidene.
In the 1st step, fat tertiary amine base monomer: N,N-DMAA: solvent=1: 20～1000: 60～4000,
In the 3rd step, press mass fraction, also add 0.01～20 part described chain-transfer agent.
Described chain-transfer agent is at least a in following: Thiovanic acid, mercaptoethylamine, mercaptoethanol and iodoacetic acid.
In the 3rd step, the reaction times is 6～8 hours;
Take into full account the influence of polyacrylamide amine molecule visco-elasticity and temperature resistant antisalt performance to oil displacement efficiency, the macromole and the persulphate of the fatty tertiary amine group that obtains are formed oxidation-reduction trigger system, acrylamide triggered and temperature resistant antisalt monomer copolymerization obtains target product in the aqueous solution.
Utilisation technology scheme of the present invention is the agent of preparation temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING.
Press mass fraction, the composition of raw materials of described oil-displacing agent is:
0.01～10 part of the macromole of described fatty tertiary amine group, 100 parts of acrylamides, 10～300 parts of temperature resistant antisalt monomers, 0.001～0.1 part of sodium bisulfite, 0.001～0.2 part of persulphate, 0.001～0.2 part of azo diisobutyl amidine hydrochloride, 0.005～1 part of disodium ethylene diamine tetraacetate, 0.005～1 part in urea, 10～200 parts in alkali, 100～10000 parts of deionized waters.
Described temperature resistant antisalt monomer is at least a in following: 2-acrylamido-2-methyl propane sulfonic acid, N-vinyl pyrrolidone and N,N-DMAA;
Described persulphate is at least a in following: ammonium persulphate and Potassium Persulphate; Initiator system of ammonium persulfate.
Described alkali is at least a in following: sodium hydroxide, potassium hydroxide and yellow soda ash; Preferred sodium hydroxide.
The preparation method of described oil-displacing agent may further comprise the steps:
The 1st step joined 100 parts of acrylamides, 10～300 parts of temperature resistant antisalt monomers in the reaction vessel, was dissolved in water;
The 2nd step fed nitrogen in reaction vessel, deoxygenation is more than 20 minutes;
In the 3rd step, add 0.001～0.2 part of azo diisobutyl amidine hydrochloride, 0.001～0.2 part of persulphate, 0.01 the macromole of～10 parts of fatty tertiary amine groups, 0.005～1 part of disodium ethylene diamine tetraacetate, 0.005～1 part of urea, 10～200 parts of alkali, regulating the pH value is 5～14;
The 4th step, carry out the one-step polymerization reaction, temperature is 0 ℃～30 ℃, the reaction times is 4～12 hours, preferred 2～6 hours;
The 5th step was warming up to 35 ℃～50 ℃, carried out two sections polyreactions, and the reaction times is 4～12 hours, preferred 2～6 hours; Obtain the gum polymers product;
The 6th step, above-mentioned product granulation, drying is pulverized; Obtain described oil-displacing agent.
Granulation, drying is pulverized and is adopted routine techniques well known in the art.
Further preferred:
After above-mentioned the 3rd step, increase by the 3.1st step, in reaction vessel, feed nitrogen, deoxygenation is more than 20 minutes; Add aqueous solution of sodium bisulfite, wherein the add-on of sodium bisulfite is 0.001～0.1 part.
Above-mentioned polyreaction goes on foot stage feeding polymerization by the aqueous solution two under the effect of oxidation-reduction composite initiator: first section oxidation-reduction trigger system, second section is used water-soluble azo initiator.Under the low temperature, the macromole of fatty tertiary amine group is as reductive agent and persulphate and sodium bisulfite composition binary or ternary oxidation-reduction trigger system, temperature resistant antisalt monomer polymerization acrylamide triggered and commonly used.A plurality of fat tertiary amine groups are connected on the same macromolecular main chain, and during with persulphate generation single electron transfer, the methyl that is connected with tertiary amine produces carbon radicals, produce a plurality of free radicals on the same macromole and cause the common initiated polymerization of point, form long branched chain structure.In polymerization system, the ratio of the macromole reductive agent of fatty tertiary amine group can be regulated the ratio of long branched chain structure in product.The sodium bisulfite activity is higher, can be used as second reductive agent and participates in initiated polymerization, controls its add-on further controlled polymerization inductive phase, also can not add according to actual needs.The second step elevated temperature main purpose is to improve transformation efficiency, and azo diisobutyl amidine hydrochloride thermolysis at high temperature produces free radical, causes the small portion of residual monomer polymerization, further improves molecular weight of product.
The macromolecular molecular weight of fatty tertiary amine group can be controlled by the chain-transfer agent consumption among the present invention; Change fat tertiary amine base monomer and N,N-DMAA monomer ratio, can regulate and control active point, the both number of fat tertiary amine group of causing on the macromole of fatty tertiary amine group.Cause more and a little not only help to improve Molecular Weight for Polyacrylamide, structurally can produce long branched chain structure simultaneously.Long branched chain structure has strengthened intermolecular chain entanglement ability, improves the relaxation time of molecular motion, closely improves the visco-elasticity of polymer molecule, helps improving oil displacement efficiency.From the rheology angle, poly-drive solution and cross in the layer in underground migration, the long branched chain structure molecule has better shearing sensibility than the linear structure molecule, helps the expeling of oil in the aperture rock.In addition, the macromole of fatty tertiary amine group is a solid, and no volatilization gas and peculiar smell produce, than the more environmental protection of small molecules tertiary amine.The monomeric selections of temperature resistant antisalt such as comonomer 2-acrylamido-2-methyl propane sulfonic acid, N-vinyl pyrrolidone, N,N-DMAA have guaranteed the temperature resistant antisalt performance of polymkeric substance.
The invention has the beneficial effects as follows:
The present invention uses the macromole of fatty tertiary amine group and persulphate composition oxidation-reduction trigger system to prepare long branched chain structure high molecular weight temperature-tolerant anti-salt type polyacrylamide, existing polyacrylamide, better heatproof, anti-salt and anti-shear performance are arranged, can be used as the tertiary oil recovery oil-displacing agent and use.
Description of drawings
Fig. 1 is the gel permeation chromatography graphic representation of the macromole A of fatty tertiary amine group.
Fig. 2 is the hydrogen spectrogram of the macromole A of fatty tertiary amine group.
Fig. 3 is concentration 1500mg/L, salinity 30000mg/L, the curve comparison diagram of embodiment 3, embodiment 4, embodiment 5 and conventional polypropylene amide solution apparent viscosity and temperature.
Embodiment
The macromolecular molecular weight of fatty tertiary amine group adopts gel permeation chromatography (GPC) test, and eluent is N, dinethylformamide, and flow rate 1.0mL/min, 35 ℃ of column temperatures, the standard polyoxyethylene is proofreaied and correct; Molecular composition is passed through
1H-NMR determines.
This performance of polyacrylamide base index determining is as follows: intrinsic viscosity [η] is according to GB12005.1-89 polyacrylamide intrinsic viscosity measuring method; Molecular weight is measured according to GB12005.10-92 Molecular Weight for Polyacrylamide mensuration-viscosimetry, by formula M=([η]/K)
1/ α, K=4.75 * 10 wherein
-3, α=0.80; Solid content is according to GB12005.2-89 polyacrylamide determination of solid content method; Degree of hydrolysis is according to GB12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method; The polyacrylamide solution apparent viscosity is measured with the Brookfield viscosmeter under the nominative testing temperature.
Embodiment 1
The macromole A for preparing fatty tertiary amine group: the poly-N,N-DMAA of poly-N-(3-dimethylamino-propyl) acrylamide-co-, structure are as (3) formula:
With 3.12 gram N-(3-dimethylamino-propyl) acrylamides and 17.84 gram N, the N-DMAA is dissolved in the 80.0 gram dehydrated alcohols, logical high pure nitrogen deoxygenation 20～30 minutes, sulfydryl b ammonium salt hydrochlorate and 166 milligrams of azo two isobutyls of adding 1.16 grams are fine, under 60 ℃～70 ℃, to react 6 hours, 60% of the total mass of desolvating is taken out in decompression, with the residuum centrifugation, remove solid phase; Liquid phase is precipitated in ether 3 times, obtain white solid, be the product of structural formula (3) 40 ℃ of following dryings.Molecular weight of product Mn=16500, described two monomeric repeating units are than m: n=1: 9.The gel permeation chromatography graphic representation is seen Fig. 1, and the hydrogen spectrogram is seen Fig. 2.
Embodiment 2
The macromole B for preparing fatty tertiary amine group: the poly-N,N-DMAA of poly-N-(3-dimethylamino-propyl) acrylamide-co-, structure is as (3) formula;
With 312 milligrams of N-(3-dimethylamino-propyl) acrylamide and 19.6 gram N, the N-DMAA is dissolved in the 80.0 gram dehydrated alcohols, logical high pure nitrogen deoxygenation 20～30 minutes, it is fine to add 166 milligrams of azo two isobutyls, under 60 ℃～70 ℃, to react 6 hours, 60% of the total mass of desolvating is taken out in decompression, with the residuum centrifugation, remove solid phase; Liquid phase is precipitated in ether 3 times, obtain white solid 40 ℃ of following dryings.Molecular weight of product Mn=138000, described two monomeric repeating units are than m: n=1: 100.
The preparation of embodiment 3 temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING agent
Under the room temperature, with 5.10 gram acrylamides, 4.90 gram 2-acrylamido-2-methyl propane sulfonic acid joins in the polyreaction bottle, add 19 gram water dissolution, logical nitrogen deoxygenation is after 20 minutes, the adding mass concentration is 0.1% the azo diisobutyl amidine hydrochloride aqueous solution 1.0 grams, mass concentration is 0.1% ammonium persulfate aqueous solution 2.0 grams, the macromole A of 100 milligrams of fatty tertiary amine groups, mass concentration is 0.3% disodium ethylene diamine tetra-acetic acid aqueous solution 1.5 grams, mass concentration is 0.6% aqueous solution of urea 1.0 grams, mass concentration is 25% sodium hydroxide solution 3.7 grams, transfers pH=7.5, continues letting nitrogen in and deoxidizing after 20 minutes, the adding mass concentration is 0.05% sodium sulfite solution 3.0 grams, after 6 hours, be warmed up to 50 ℃ of reactions 4 hours 8 ℃ of reactions, obtain the gum polymers product.Obtain temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING agent product through granulation, drying, pulverizing.Survey intrinsic viscosity 23.33dl/g.
The preparation of embodiment 4 temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING agent
Under the room temperature, with 8.0 gram acrylamides, 2.0 gram 2-acrylamido-2-methyl propane sulfonic acid joins in the polyreaction bottle, add 19 gram water dissolution, logical nitrogen deoxygenation is after 20 minutes, add mass concentration successively and be 0.025% the azo diisobutyl amidine hydrochloride aqueous solution 1.0 grams, mass concentration is 0.1% ammonium persulfate aqueous solution 1.0 grams, the macromole A of 50 milligrams of fatty tertiary amine groups, mass concentration is 0.3% disodium ethylene diamine tetra-acetic acid aqueous solution 1.5 grams, mass concentration is 0.6% aqueous solution of urea 1.0 grams, mass concentration is 25% sodium hydroxide solution 3.8 grams, transfer pH=9, after 6 hours, be warmed up to 50 ℃ of reactions 4 hours 8 ℃ of reactions, obtain the gum polymers product.Obtain temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING agent product through granulation, drying, pulverizing.Survey intrinsic viscosity 20.13dl/g.
The preparation of embodiment 5 temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING agent
Under the room temperature, with 5.10 gram acrylamides, 3.00 gram 2-acrylamido-2-methyl propane sulfonic acid and 1.9 gram N, the N-DMAA joins in the polyreaction bottle, add 19 gram water dissolution, logical nitrogen deoxygenation is after 20 minutes, add mass concentration successively and be 0.025% the azo diisobutyl amidine hydrochloride aqueous solution 1.0 grams, mass concentration is 0.1% ammonium persulfate aqueous solution 1.0 grams, the macromole B of 10 milligrams of fatty tertiary amine groups, mass concentration is 0.3% disodium ethylene diamine tetra-acetic acid aqueous solution 1.5 grams, and mass concentration is 0.6% aqueous solution of urea, 1.0 grams, and mass concentration is 25% sodium hydroxide solution 3.7 grams, transfer pH=11, continue letting nitrogen in and deoxidizing after 20 minutes, add mass concentration and be 0.05% sodium sulfite solution 2.3 grams, 8 ℃ of reactions after 6 hours, be warmed up to 50 ℃ of reactions 4 hours, obtain the gum polymers product.Obtain temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING agent product through granulation, drying, pulverizing.Survey intrinsic viscosity 21.53dl/g.
Test case
The macromole of fatty tertiary amine group has been carried out gel permeation chromatography and the hydrogen stave is levied.Fig. 1 is the gel permeation chromatography curve of the macromole A of fatty tertiary amine group, and as can be seen from the figure the gel permeation chromatography curve of macromole A is a unimodal distribution, number-average molecular weight Mn=16500.Fig. 2 is the hydrogen spectrum of the macromole A of fatty tertiary amine group, the feature hydrogen in two monomeric repeating units in the macromole A molecular structural formula is belonged to, and the area by feature hydrogen is than calculating two monomeric repeating units than m: n=1: 9.
Under the same conditions, the product of embodiment 3, embodiment 4, embodiment 5 gained and conventional polypropylene acid amides are carried out performance relatively, gained the results are shown in Table 1 and Fig. 3.
It is 1500mg/L that table 1 has provided solid content, molecular weight, degree of hydrolysis and polymer solution concentration, under different salinities, and the apparent viscosity data in the time of 25 ℃.As can be seen from the table, when low ore deposit is spent, conventional polypropylene acid amides viscosity is bigger, but raising along with salinity, viscosity degradation is remarkable, and embodiment 3, embodiment 4, embodiment 5 products still keep than high viscosity when salinity 30000mg/L, and product of this explanation this patent embodiment gained has excellent anti-salt property.
Fig. 3 has provided the product and the conventional polypropylene acid amides of embodiment 3, embodiment 4, embodiment 5 gained, is 1500mg/L in concentration, and salinity is under the 30000mg/L, the temperature variant curve of solution apparent viscosity.In 25～90 ℃ of Range of measuring temp, embodiment 3, embodiment 4, embodiment 5 apparent viscosities are higher than the plain polypropylene acid amides all the time, illustrate through the above-mentioned three kinds of products of this patent method synthetic to have good heat resistance.
The contrast of this performance of table 1 polyacrylamide base
Claims (11)
1. the macromole of a fatty tertiary amine group is characterized in that:
The macromolecular structural formula of described fatty tertiary amine group is shown in (1) formula:
(1) in the formula: R
1Be H or CH
3R
2Be ester group or amide group; R
3Be C
1～C
6Alkyl;
M is the polymerization degree of fatty tertiary amine groups monomeric repeating unit;
N is the polymerization degree of N,N-DMAA repeating unit;
m∶n＝1∶1～1000；
The macromolecular molecular-weight average of described fatty tertiary amine group is 2000～1000000.
2. the macromole of fatty tertiary amine group according to claim 1 is characterized in that:
(1) in the formula: R
2Be amide group; R
3Be ethylidene or propylidene.
3. according to the macromole of the described fatty tertiary amine group of one of claim 1 to 2, it is characterized in that:
(1) in the formula: m: n=1: 10～100;
The macromolecular molecular-weight average of described fatty tertiary amine group is 10000～200000.
4. the macromolecular preparation method of the described fatty tertiary amine group of one of claim 1 to 3,
It is characterized in that:
Press mass fraction, raw material comprises: 1 part of fat tertiary amine base monomer; 1～2000 part of N,N-DMAA; 1～10000 part of solvent; 0.01～20 part of initiator;
Described fat tertiary amine base monomer structure is suc as formula (2):
(2) in the formula: R
1Be H or CH
3R
2Be ester group or amide group; R
3Be C
1～C
6Alkyl;
Described initiator is: the fine or azo diisobutyl amidine hydrochloride of azo two isobutyls;
Described solvent is at least a in following: methyl alcohol, second alcohol and water;
Described preparation method may further comprise the steps:
The 1st step added reaction vessel with described fat tertiary amine base monomer, N,N-DMAA, was dissolved in the described solvent, pressed mass ratio,
Fat tertiary amine base monomer: N,N-DMAA: solvent=1: 1～2000: 1～10000;
The 2nd step fed nitrogen in reaction vessel, deoxygenation is more than 20 minutes;
The 3rd goes on foot, and adds 0.01～20 part described initiator in reaction vessel, under 60～70 ℃, reacts 4～12 hours;
In the 4th step, 40%～70% of the total mass of desolvating is taken out in decompression in reaction vessel, with the residuum solid-liquid separation, removes solid phase;
The 5th step, liquid phase is precipitated in ether 2～4 times, dry under 30 ℃～45 ℃, obtain the macromole product of structural formula for the fatty tertiary amine group of (1) formula.
5. preparation method according to claim 4 is characterized in that:
In (2) formula: R
3Be ethylidene or propylidene;
In the 1st step, fat tertiary amine base monomer: N,N-DMAA: solvent=1: 20～1000: 60～4000.
6. according to the described preparation method of one of claim 4 to 5, it is characterized in that:
In the 3rd step, press mass fraction, also add 0.01～20 part chain-transfer agent;
Described chain-transfer agent is at least a in following: Thiovanic acid, mercaptoethylamine, mercaptoethanol and iodoacetic acid.
7. preparation method according to claim 6 is characterized in that:
In the 3rd step, the reaction times is 6～8 hours.
8. the preparation method of an oil-displacing agent is characterized in that:
Press mass fraction, the composition of raw materials of described oil-displacing agent is:
0.01 the product of the described method preparation of one of the macromole of one of～10 parts of claims 1 to 3 described fatty tertiary amine group or claim 4 to 7,100 parts of acrylamides, 10～300 parts of temperature resistant antisalt monomers, 0.001～0.1 part of sodium bisulfite, 0.001～0.2 part of persulphate, 0.001～0.2 part of azo diisobutyl amidine hydrochloride, 0.005～1 part of disodium ethylene diamine tetraacetate, 0.005～1 part in urea, 10～200 parts in alkali, 100～10000 parts of deionized waters;
Described temperature resistant antisalt monomer is at least a in following: 2-acrylamido-2-methyl propane sulfonic acid, N-vinyl pyrrolidone and N,N-DMAA;
Described persulphate is at least a in following: ammonium persulphate and Potassium Persulphate;
Described alkali is at least a in following: sodium hydroxide, potassium hydroxide and yellow soda ash;
The preparation method of described oil-displacing agent may further comprise the steps:
The 1st step joined 100 parts of acrylamides, 10～300 parts of temperature resistant antisalt monomers in the reaction vessel, was dissolved in water;
The 2nd step fed nitrogen in reaction vessel, deoxygenation is more than 20 minutes;
In the 3rd step, add 0.001～0.2 part of azo diisobutyl amidine hydrochloride, 0.001～0.2 part of persulphate, 0.01 the macromole of～10 parts of described fatty tertiary amine groups, 0.005～1 part of disodium ethylene diamine tetraacetate, 0.005～1 part of urea, 10～200 parts of alkali, regulating the pH value is 5～14;
The 4th step, carry out the one-step polymerization reaction, temperature is 0 ℃～30 ℃, the reaction times is 4～12 hours, preferred 2～6 hours;
The 5th step was warming up to 35 ℃～50 ℃, carried out two sections polyreactions, and the reaction times is 4～12 hours, obtains the gum polymers product;
The 6th step, above-mentioned product granulation, drying is pulverized; Obtain the agent of temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING.
9. preparation method according to claim 8 is characterized in that:
After the 3rd step, increase by the 3.1st step: feed nitrogen in reaction vessel, deoxygenation is more than 20 minutes; Add aqueous solution of sodium bisulfite, wherein the add-on of sodium bisulfite is 0.001～0.1 part.
10. according to Claim 8 to one of 9 described preparation methods, it is characterized in that:
Described persulphate is an ammonium persulphate;
Described alkali is sodium hydroxide;
Preferably, in the 4th step, the one-step polymerization reaction times is 2～6 hours;
In the 5th step, two sections polymerization reaction times are 2～6 hours.
11. one kind according to Claim 8 to the temperature resistant antisalt long-chain branch POLYACRYLAMIDE FLOODING agent of one of 10 described method preparations.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102887970A (en) * | 2011-07-18 | 2013-01-23 | 中国石油化工股份有限公司 | Solution polymerization method |
| CN103864986A (en) * | 2012-12-07 | 2014-06-18 | 中国石油化工股份有限公司 | Acrylamide polymer, its preparation method and its application |
| CN104558407A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant water-soluble polymer, and preparation and application method thereof |
| CN105440203A (en) * | 2014-08-13 | 2016-03-30 | 中国石油化工股份有限公司 | Polymer with surface active function and preparation method thereof |
| CN105566540A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Polymer and use thereof |
| CN105566529A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Polymer and use thereof |
| CN105566541A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Polymer and use thereof |
| CN105566515A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Structure-oriented composite initiator system and acrylamide polymer and preparation method and application thereof |
| CN110591020A (en) * | 2019-09-06 | 2019-12-20 | 重庆云天化瀚恩新材料开发有限公司 | ASA high-rubber powder with excellent weather resistance, preparation method and application thereof |
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| CN102887970B (en) * | 2011-07-18 | 2014-03-12 | 中国石油化工股份有限公司 | Solution polymerization method |
| CN102887970A (en) * | 2011-07-18 | 2013-01-23 | 中国石油化工股份有限公司 | Solution polymerization method |
| CN103864986B (en) * | 2012-12-07 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of acrylamide polymer and its preparation method and application |
| CN103864986A (en) * | 2012-12-07 | 2014-06-18 | 中国石油化工股份有限公司 | Acrylamide polymer, its preparation method and its application |
| CN104558407A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant water-soluble polymer, and preparation and application method thereof |
| CN104558407B (en) * | 2013-10-24 | 2017-02-15 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant water-soluble polymer, and preparation and application method thereof |
| CN105440203A (en) * | 2014-08-13 | 2016-03-30 | 中国石油化工股份有限公司 | Polymer with surface active function and preparation method thereof |
| CN105440203B (en) * | 2014-08-13 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of polymer with surface active function and preparation method thereof |
| CN105566540A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Polymer and use thereof |
| CN105566529A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Polymer and use thereof |
| CN105566541A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Polymer and use thereof |
| CN105566515A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Structure-oriented composite initiator system and acrylamide polymer and preparation method and application thereof |
| CN105566515B (en) * | 2014-10-15 | 2018-09-21 | 中国石油化工股份有限公司 | A kind of structure directing type composite initiator agent system and acrylamide polymer and its preparation method and application |
| CN110591020A (en) * | 2019-09-06 | 2019-12-20 | 重庆云天化瀚恩新材料开发有限公司 | ASA high-rubber powder with excellent weather resistance, preparation method and application thereof |
| CN110591020B (en) * | 2019-09-06 | 2022-05-20 | 重庆云天化瀚恩新材料开发有限公司 | ASA high-rubber powder with excellent weather resistance, preparation method and application thereof |
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