CN105566515A - Structure-oriented composite initiator system and acrylamide polymer and preparation method and application thereof - Google Patents
Structure-oriented composite initiator system and acrylamide polymer and preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses a structure-oriented composite initiator system and an acrylamide polymer and a preparation method and application thereof. The structure-oriented composite initiator system contains a redox system initiator, the redox system initiator comprises oxidizing and reducing agents, wherein the structure-oriented composite initiator system further comprises a polyamide-amine dendritic macromolecule. The acrylamide polymer has a higher molecular weight, higher shear resistance, better anti-aging properties, and good water-soluble and other advantages, and the acrylamide polymer has high apparent viscosity in high temperature and high salinity water, and can be used as a high temperature and high salinity oil reservoir tertiary oil recovery oil displacement agent.
Description
Technical field
The present invention relates to a kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application.More specifically, the present invention relates to the application of a kind of structure directing type composite initiator system, the preparation method using the acrylamide polymer of this structure directing type composite initiator system, the acrylamide polymer prepared by the method and described acrylamide polymer.
Background technology
High molecular weight moieties hydro-polyacrylamide, just can realize the winding state between molecular chain under low concentration, and increasing glutinous Be very effective, is therefore a widely used class Polymer Used For Oil Displacement in tertiary oil production in oil field.But this type of aqueous solutions of polymers is as the result of use of oil-displacing agent, the impact by oil reservoir resource environment is very large.For a class and the two class oil reservoirs of low temperature, less salt, the polyacrylamide of high molecular is in actual oil reservoir oil displacement process, and chemical stability is better, viscosity retention rate is high, can reduce water-oil mobility ratio constantly, improves swept volume, reduce the oil saturation involving oil reservoir, thus improve recovery ratio.But under the high temperature conditions, the hydrolysis of polyacrylamide amine molecule and degraded serious; Under high salt condition, the easy Precipitation of polyacrylamide, it is very low that solution retains viscosity, finally causes oil displacement efficiency poor, do not have obvious economic benefit.
In order to improve the temperature resistant antisalt performance of polyacrylamide, carry out a large amount of tackling key problem research both at home and abroad, the main chain yardstick around polymkeric substance, chain size distribution, construction unit composition, micro-sequential structure carry out large quantity research related work, as temperature resistant antisalt monomer-polymer, hydrophobic associated polymer, amphiphilic polymers, composite polymer, comb shaped polymer, template polymer etc.Its feature of each tool of these type polymers, polyacrylamide more traditional in some performance index increases.Polymer viscoelastic oil-displacement mechanism is thought, why polymers soln significantly can improve oil recovery factor, mainly improves sweep efficiency by viscosity and improves oil displacement efficiency by elasticity.
From molecular topology angle, the initiation of long chain branched not only can improve resistant polymers self resistance to mechanical shear ability, can also increase chain entanglement ability between molecular chain simultaneously, improves the time of relaxation of molecular motion, and then improve solution visco-elasticity, be conducive to improving oil displacement efficiency.But the correlative study work of starting with from polymer molecule topological framework is less, and CN102675535A discloses a kind of branched polyacrylamide and preparation method thereof.This branched polyacrylamide is by dimethylsulfoxide solvent, diethylenetriamine and methyl acrylate generation addition reaction, then add excessive quadrol, removes methyl-sulphoxide and unnecessary quadrol after reacting by heating, add maleic anhydride again, generate branching function monomer; This branching function monomer and acrylamide monomer polymerization reaction take place, thus prepare branched polyacrylamide.CN102321221A discloses the preparation method that a kind of polymine is the star polyacrylamide polymer of core.The method adopts aqueous solution photopolymerization mode, utilizes the acrylamide triggered monomer copolymerization that waits of thioxanthone modified polyethyleneimine to synthesize Star Polyacrylamide.The polymkeric substance resistance to mechanical cutting performance that above-mentioned two kinds of methods obtain strengthens to some extent, but technological operation is relatively loaded down with trivial details, and the polymerization utilizing above-mentioned two kinds of methods to carry out acrylamide is difficult to obtain the acrylamide polymer with more high molecular, the more important thing is, the polymerization using existing initiator system to carry out acrylamide can not obtain has higher anti-shear performance and higher ageing resistance and at high temperature and still have the acrylamide polymer of high apparent viscosity in the water of high salinity.
Therefore, more high molecular, higher anti-shear performance, higher ageing resistance at high temperature and the acrylamide polymer still in the water of high salinity with high apparent viscosity is a technical problem urgently to be resolved hurrily is obtained.
Summary of the invention
The object of the invention is to overcome the polymerization using existing initiator system to carry out acrylamide be difficult to obtain there is higher molecular weight, higher anti-shear performance, higher ageing resistance and at high temperature and still have the deficiency of the acrylamide polymer of high apparent viscosity in the water of high salinity, a kind of structure directing type composite initiator system and acrylamide polymer and preparation method thereof and the application of described acrylamide polymer in polymer oil-displacing agent are provided.Acrylamide polymer provided by the invention has the feature of higher molecular weight, higher anti-shear performance, higher ageing resistance and good water solubility, and this acrylamide polymer at high temperature, have high apparent viscosity in the water of high salinity.
The invention provides a kind of structure directing type composite initiator system, this structure directing type composite initiator system contains redox series initiators, described redox series initiators comprises Oxidizing and Reducing Agents, wherein, described structure directing type composite initiator system is also containing Polyamidoamine Dendrimers.
The present inventor is found by research, the structure directing type composite initiator containing Polyamidoamine Dendrimers is adopted to carry out the polymerization of acrylamide, the acrylamide polymer prepared is made to have the feature of higher molecular weight, higher anti-shear performance, higher ageing resistance and good water solubility, and this acrylamide polymer at high temperature, have high apparent viscosity in the water of high salinity, can be used as high temperature and high salt oil deposit Flooding Agent for EOR.This may be because: the amine groups according to the reductibility had in the Polyamidoamine Dendrimers in structure directing type composite initiator system of the present invention is oxidized to living radical, trigger monomer is polymerized, generate star-type polymer, thus form the topological framework of polymkeric substance.
Another object of the present invention is to the preparation method that a kind of acrylamide polymer is provided, under the method is included in the existence of initiator and inorganic base substance, acrylamide and temperature resistant antisalt monomer are polymerized in water, wherein, described initiator contains structure directing type composite initiator system provided by the invention.
Present invention also offers a kind of acrylamide polymer prepared by aforesaid method.
The present invention still further provides the application of aforesaid propylene amide polymer in polymer oil-displacing agent.
Acrylamide polymer according to the present invention has the ageing resistance of higher molecular weight, higher anti-shear performance and Geng Gao, and this acrylamide polymer good water solubility, at high temperature, there is high apparent viscosity in the water of high salinity, can be used as high temperature and high salt oil deposit Flooding Agent for EOR.
Preparation method's step of acrylamide polymer provided by the invention is simple, obtained acrylamide polymer have low, the higher molecular weight of residual monomer content, higher anti-shear performance, higher ageing resistance, good water solubility and at high temperature, there is in the water of high salinity the feature of high apparent viscosity.
Particularly, for embodiment 1, the acrylamide polymer adopting the preparation method of the acrylamide polymer of structure directing type composite initiator system provided by the invention to obtain is 1500mg/L and salinity is can reach 28.8mPas the apparent viscosity of 95 DEG C in the water of 32000mg/L in concentration, above-mentioned solution is carried out in the environment of the basic anaerobic of 95 DEG C the weathering test of 3 months, aged viscosity retention rate is 94.3%, this acrylamide polymer is 99.5% according to the shear viscosity retention rate that Shengli Oil Field company standard Q/SH10201572-2006 tests, and the polyacrylamide of commercially available high molecular is 1500mg/L and salinity is be only 8.9mPas the apparent viscosity of 95 DEG C in the water of 32000mg/L in concentration, under similarity condition, aged viscosity retention rate is only 65.2%, this acrylamide polymer is 90.0% according to the shear viscosity retention rate that Shengli Oil Field company standard Q/SH10201572-2006 tests.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of structure directing type composite initiator system, this structure directing type composite initiator system contains redox series initiators, described redox series initiators comprises Oxidizing and Reducing Agents, wherein, described structure directing type composite initiator system is also containing Polyamidoamine Dendrimers.
Structure directing type composite initiator system according to the present invention contains formula Polyamidoamine Dendrimers, this Polyamidoamine Dendrimers not only plays the effect of reductive agent and participates in initiated polymerization in structure directing type composite initiator system, and makes this polymer formation hub-and-spoke configuration.
Polyamidoamine Dendrimers is the macromolecular material of a class dissaving structure, is structurally different from traditional branched polymer, its size, controlled shape, and there is cavity inside, and surface has abundant functional group.Polyamidoamine Dendrimers is made up of three parts usually: first part is active centre, is the start-up portion of dendrimer, namely initial initiated core; The internal layer that second section is made up of multiple repetition branching unit, is positioned at the middle part of dendrimer; Part III has the skin enriching surface functional group, is the end part of dendrimer, and these three parts influence each other formation one independently molecular system.
Inventive point of the present invention is that described structure directing type composite initiator system contains Polyamidoamine Dendrimers, described Polyamidoamine Dendrimers can be the various Polyamidoamine Dendrimers containing amine groups of this area, under preferable case, it is 1 generation of core that described Polyamidoamine Dendrimers is selected from quadrol, 2 generations, 3 generations, 4 generations, 5 generations, 6 generations, 7 generations, 8 generations, 9 generations, the Polyamidoamine Dendrimers in 10 generations, with 1, 4-butanediamine is 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, the Polyamidoamine Dendrimers in 6 generations, with 1, 6-hexanediamine is 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, the Polyamidoamine Dendrimers in 6 generations, take cystamine as 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, one or more in the Polyamidoamine Dendrimers in 6 generations.
In the present invention, take quadrol as 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, 6 generations, 7 generations, 8 generations, 9 generations, 10 generations Polyamidoamine Dendrimers refer to quadrol to be the Polyamidoamine Dendrimers in active centre; Take Putriscine as 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, 6 generations Polyamidoamine Dendrimers refer to Putriscine to be the Polyamidoamine Dendrimers in active centre; With 1,6-hexanediamine be 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, 6 generations Polyamidoamine Dendrimers refer to that with 1,6-hexanediamine be the Polyamidoamine Dendrimers in active centre; Take cystamine as 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, 6 generations Polyamidoamine Dendrimers refer to cystamine to be the Polyamidoamine Dendrimers in active centre.
In the present invention, above-mentioned Polyamidoamine Dendrimers can be commercially available, and also can adopt the known method synthesis in organic synthesis field.Such as, be prepared according to the synthetic method of dispersing in document " synthesis of Polyamidoamine Dendrimers and application " (synthesis of Polyamidoamine Dendrimers and application, Chinese Plastics, 2011,25 (10): 28-33).Such as, Polyamidoamine Dendrimers synthesis mechanism is (as quadrol, 1 from the initiation core of multifunctional groups, 4-butanediamine, 1,6-hexanediamine, cystamine) set out, carry out Michael addition reaction completely with methyl acrylate and obtain 0.5 generation (0.5G) Polyamidoamine Dendrimers, then carry out the amidate action of ester with excessive quadrol (EDA) and 0.5 PAMAM dendrimer, obtain 1.0 generations (1.0G) Polyamidoamine Dendrimers.Continuous repetition above-mentioned steps, can obtain the Polyamidoamine Dendrimers of different algebraically.For quadrol and methyl acrylate, following formula (1) and formula (2) are shown in concrete reaction:
In above-mentioned reaction process, general formula also can be adopted to be the α of H2C=CHCOOR, and beta-unsaturated carboxylic acid ester replaces methyl acrylate, and wherein R is the alkyl of C2-C4.
The present invention be by use Polyamidoamine Dendrimers to obtain in structure directing type composite initiator system have low, the higher molecular weight of residual monomer content, higher anti-shear performance, higher ageing resistance, good water solubility and at high temperature, there is the acrylamide polymer of the feature of high apparent viscosity, therefore according to the conventional various redox series initiators that the redox series initiators in structure directing type composite initiator system of the present invention can be in this area in the water of high salinity.
According to the present invention, described redox series initiators comprises Oxidizing and Reducing Agents, described oxygenant can be selected from peroxidation two acyl compounds, alkyl peroxide compounds, hydroperoxide and persulphate one or more; Preferably, described oxygenant is selected from one or more in dibenzoyl peroxide, lauroyl peroxide, tertbutyl peroxide, 2,5-dimethyl-hexyl-2,5-two hydrogen peroxide, hydrogen peroxide, ammonium persulphate, Sodium Persulfate and Potassium Persulphate; Further preferably, described oxygenant is ammonium persulphate and/or Potassium Persulphate.
According to the present invention, described reductive agent be selected from vitriol, sulphite, hydrosulphite, thiosulphate, amine and cuprous chloride one or more; Preferably, described reductive agent is selected from ferrous sulfate, ferrous ammonium sulphate, cuprous chloride, potassium sulfite, S-WAT, bisulfite amine, Potassium hydrogen sulfite, Sulfothiorine, Potassium Thiosulphate, sodium bisulfite, N, N-dimethylethanolamine, N, N-lupetazin, N, N, N ', N '-tetramethyl-urea element, rongalite, N, N, N ', one or more in N '-Tetramethyl Ethylene Diamine; Further preferably, described reductive agent is ferrous ammonium sulphate, sodium bisulfite and N, N, N ', one or more in N '-Tetramethyl Ethylene Diamine.
According to structure directing type composite initiator system of the present invention, the content of described redox series initiators and Polyamidoamine Dendrimers can carry out appropriate selection according to concrete service requirements, usually, with the total amount of described structure directing type composite initiator system for benchmark, the content of described oxygenant can be 4-85 % by weight; The weight ratio of described oxygenant, reductive agent and Polyamidoamine Dendrimers can be 1:0.1-10:0.1-10; Be preferably 1:0.5-1:0.5-1.
According to the present invention, in order to make described structure directing type composite initiator system have higher initiating activity, under preferable case, described structure directing type composite initiator system is also containing water-soluble azo series initiators.Described water-soluble azo series initiators can be the various water-soluble azo based compound being suitable for use as radical polymerization initiator.Preferably, described water-soluble azo series initiators is 2, two (2-amidine propane) dihydrochloride, 2 of 2 '-azo, two (the 2-tetrahydroglyoxaline propane) dihydrochloride and 4 of 2 '-azo, one or more in 4 '-azo two (4-cyanopentanoic acid), more preferably 2, two (2-amidine propane) dihydrochloride of 2 '-azo.
According to the present invention, the consumption of described water-soluble azo series initiators can change in wider scope, usually, with the total amount of described structure directing type composite initiator system for benchmark, the content of described water-soluble azo series initiators is 20-40 % by weight, is preferably 25-35 % by weight.
The present inventor finds in research process, when described structure directing type composite initiator system contains redox series initiators, when Polyamidoamine Dendrimers and water-soluble azo series initiators, when the oxygenant in described redox series initiators is ammonium persulphate and/or Potassium Persulphate, reductive agent is ferrous ammonium sulphate, sodium bisulfite and N, N, N ', one or more in N '-Tetramethyl Ethylene Diamine, and described Polyamidoamine Dendrimers to be selected from quadrol be 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, 6 generations, 7 generations, 8 generations, 9 generations, the Polyamidoamine Dendrimers in 10 generations, take Putriscine as 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, the Polyamidoamine Dendrimers in 6 generations, with 1 generation that 1,6-hexanediamine is core, 2 generations, 3 generations, 4 generations, 5 generations, the Polyamidoamine Dendrimers in 6 generations, take cystamine as 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, during one or more in the Polyamidoamine Dendrimers in 6 generations, the viscosity-average molecular weight of the acrylamide polymer obtained can reach more than 2,500 ten thousand (being between 2,920 ten thousand-3,650 ten thousand), concentration is 1500mg/L and the aqueous solution that salinity is the acrylamide polymer of 32000mg/L can reach 15.8-29mPas the apparent viscosity of 95 DEG C, and by the weathering test of 3 months of carrying out in the environment of this solution basic anaerobic at 95 DEG C, aged viscosity retention rate is 90.8-95%, and this acrylamide polymer is 95.2-100% according to the shear viscosity retention rate that Shengli Oil Field company standard Q/SH10201572-2006 tests.
Separately deposit before use according to each component in structure directing type composite initiator system of the present invention, add in reaction system separately or jointly in use.
The present invention also provides a kind of preparation method of acrylamide polymer, under the method is included in the existence of initiator and inorganic base substance, acrylamide and temperature resistant antisalt monomer are polymerized in water, wherein, described initiator contains structure directing type composite initiator system provided by the invention.
Acrylamide polymer in the present invention refers to the polymkeric substance by acrylamide and temperature resistant antisalt monomer are reacted and obtained under condition of copolymer, comprises the structural unit formed by acrylamide and the structural unit formed by temperature resistant antisalt monomer.
According to the preparation method of acrylamide polymer of the present invention, under the existence of initiator and inorganic base substance, the method for acrylamide and temperature resistant antisalt monomer being carried out being polymerized in water can be the ordinary method of this area.Under preferable case, under the existence of initiator and inorganic base substance, the mode that acrylamide and temperature resistant antisalt monomer carry out being polymerized in water is comprised: by inorganic base substance and the aqueous solution containing described acrylamide and temperature resistant antisalt monomer, under protection of inert gas, be polymerized after Polyamidoamine Dendrimers, reductive agent and oxygenant and optional water-soluble azo series initiators are mixed with the mixture of gained; Under further preferable case; under the existence of initiator and inorganic base substance; the mode that acrylamide and temperature resistant antisalt monomer carry out being polymerized in water is comprised: by inorganic base substance and the aqueous solution containing described acrylamide and temperature resistant antisalt monomer; under protection of inert gas, be polymerized after Polyamidoamine Dendrimers, reductive agent and oxygenant and water-soluble azo series initiators are mixed with the mixture of gained.
Due to method of the present invention be by Polyamidoamine Dendrimers make acrylamide and temperature resistant antisalt monomer be aggregated in lower initial polymerization reaction temperature under carry out realizing object of the present invention, therefore, according to the preparation method of acrylamide polymer of the present invention, for the consumption of the oxygenant in described redox series initiators, there is no particular limitation, can be consumption conventional in this area.Under preferable case, with the described acrylamide of 100 weight parts for benchmark, the consumption of the oxygenant in described redox series initiators is 0.001-0.1 weight part, is more preferably 0.005-0.05 weight part.
According to the present invention, the consumption of described reductive agent and Polyamidoamine Dendrimers can carry out appropriate selection according to concrete service requirements, usually, the weight ratio of described oxygenant, reductive agent and Polyamidoamine Dendrimers can be 1:0.1-10:0.1-10; Preferably, the weight ratio of described oxygenant, reductive agent and described Polyamidoamine Dendrimers is 1:0.5-1:0.5-1.
Adopt structure directing type composite initiator system of the present invention, according to aforesaid method, acrylamide and temperature resistant antisalt monomer are polymerized in water, the feature of structure directing type composite initiator system of the present invention can be given full play to, so obtain have higher molecular weight, higher anti-shear performance, higher ageing resistance, good water solubility and at high temperature, there is in the water of high salinity the acrylamide polymer of high apparent viscosity.
Usually, the decomposition temperature of azo series initiators is generally 35-90 DEG C, according to the research of the present inventor, with regard to structure directing type composite initiator system provided by the invention, the temperature of acrylamide polymers system generally can reach about 60 DEG C, therefore water-soluble azo series initiators is combined with Redox initiator systems of the present invention and Polyamidoamine Dendrimers, the feature that the initial kick off temperature of Redox initiator systems of the present invention is low can be played on the one hand, initiated polymerization is carried out with lesser temps, azo series initiators system can the phase produces the polymerization that free radical causes unreacted monomer after polymerization on the other hand, thus improve the transformation efficiency of monomer further.
According to the present invention, described water-soluble azo series initiators can be the various water-soluble azo based compound being suitable for use as radical polymerization initiator.Preferably, described water-soluble azo series initiators is 2, two (2-amidine propane) dihydrochloride, 2 of 2 '-azo, two (the 2-tetrahydroglyoxaline propane) dihydrochloride and 4 of 2 '-azo, one or more in 4 '-azo two (4-cyanopentanoic acid), be more preferably 2, two (2-amidine propane) dihydrochloride of 2 '-azo.
When containing water-soluble azo series initiators in described structure directing type composite initiator system, described water-soluble azo series initiators suitably can be selected according to concrete application scenario, as long as monomer conversion can be made to meet the demands.Usually, with the acrylamide of 100 weight parts for benchmark, the amount of described water-soluble azo series initiators is preferably 0.001-0.1 weight part, is preferably 0.005-0.05 weight part.When the amount of described water-soluble azo series initiators is within above-mentioned scope, gratifying transformation efficiency can be obtained.
According to the preparation method of acrylamide polymer of the present invention, acrylamide and temperature resistant antisalt monomer are carried out being polymerized the heat and salt resistance that can significantly improve the acrylamide polymer obtained.Described temperature resistant antisalt monomer can for various acrylamide polymer of can giving be with the monomer of heat and salt resistance, and described temperature resistant antisalt monomer also should have good Copolymerization activity in addition.
The present inventor finds in research process, when described temperature resistant antisalt monomer is vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid, N, N-DMAA, N, during one or more in N-acrylamide, N-vinyl pyrrolidone, 2-acrylamido-dodecane sulfonic acid, 2-acrylamido-tetradecane sulfonic acid and 2-acrylamido-n-Hexadecane sulfonic acid, the acrylamide polymer that temperature resistant antisalt performance significantly improves can be obtained.More preferably, described temperature resistant antisalt monomer is one or more in 2-acrylamide-2-methylpro panesulfonic acid, N-vinyl pyrrolidone and 2-acrylamido-tetradecane sulfonic acid.
According to the present invention, the amount of described heatproof antioxygen monomer can carry out appropriate selection according to the kind of selected temperature resistant antisalt monomer.Under preferable case, with 100 parts by weight propylene acid amides for benchmark, the consumption of described temperature resistant antisalt monomer is 0.1-250 weight part.When the amount of described temperature resistant antisalt monomer is within above-mentioned scope, the acrylamide polymer with good temperature resistant antisalt performance can be obtained.Under the prerequisite guaranteeing temperature resistant antisalt performance, from the consumption reducing temperature resistant antisalt monomer further, and then the further angle reducing the cost of the preparation method of acrylamide polymer of the present invention is set out, with 100 parts by weight propylene amide monomers for benchmark, the consumption more preferably 0.2-200 weight part of described temperature resistant antisalt monomer.
Be included in the existence of initiator and inorganic base substance according to the preparation method of acrylamide polymer of the present invention under, acrylamide is polymerized with temperature resistant antisalt monomer.Described inorganic base substance is for regulating the pH value of polymerization system.The various basic cpds that can realize above-mentioned purpose that described inorganic base substance can be commonly used for this area.Under preferable case, described inorganic base substance is one or more in sodium hydroxide, potassium hydroxide and sodium carbonate.The consumption of described inorganic base substance can carry out appropriate selection according to the composition of polymerization system, meets service requirements be as the criterion to make the pH value of polymerization system.
The present inventor finds in research process, and the pH value of polymerization system is in the scope of 4-10, and polyreaction can be made to carry out more stably.From the angle of the stability of further polyreaction, the pH value of polymerization system is preferably in the scope of 5-9.
According to the preparation method of acrylamide polymer of the present invention, described acrylamide and being aggregated in water of temperature resistant antisalt monomer are carried out, and the amount for water is not particularly limited, and can be the conventional amount used of this area.Under preferable case, with 100 parts by weight propylene acid amides for benchmark, the consumption of water is 100-3000 weight part.When the amount of water is within above-mentioned scope, local superheating can be avoided further, thus it is too fast to be easier to prevent polymerization system from heating up.More preferably, with 100 parts by weight propylene acid amides for benchmark, the amount of water is 200-2000 weight part.
According to the preparation method of acrylamide polymer of the present invention, owing to have employed according to structure directing type composite initiator system of the present invention, thus can be polymerized by trigger monomer at lower temperatures.Usually, it can be-10 DEG C to 20 DEG C according to the polymerization initiation temperature of the preparation method of acrylamide polymer of the present invention.More preferably, be 5-15 DEG C according to the polymerization initiation temperature of the preparation method of acrylamide polymer of the present invention.
According to the preparation method of acrylamide polymer of the present invention, the time of described polymerization can carry out appropriate selection according to the monomer conversion of the kind of the temperature resistant antisalt monomer of described use and consumption and expection.Under preferable case, the time of described polymerization is 2-12 hour.More preferably, the time of described polymerization is 4-8 hour.
In preparation method according to acrylamide polymer of the present invention, acrylamide and temperature resistant antisalt monomer be aggregated in protection of inert gas under carry out.In the present invention, described rare gas element refers to the gas that can not participate in polyreaction, such as: one or more in nitrogen and the periodic table of elements in neutral element gas, and neutral element gas such as argon gas in the described periodic table of elements.
Can also comprise according to the preparation method of acrylamide polymer of the present invention and resulting polymers after polyreaction is hydrolyzed and drying.What those skilled in the art can know is, hydrolytic process comprises hydrolytic reagent and polymer reaction, by hydrolysis, some acrylamide structural unit is transformed into acrylate structural unit, is so more conducive to improving the apparent viscosity of the polymers soln under the molecular weight of polymkeric substance and hot conditions.
In the present invention, the condition of described hydrolysis is not particularly limited, and under preferable case, the condition of described hydrolysis comprises: temperature is 50-110 DEG C, is preferably 70-90 DEG C; Time is 0.5-6 hour, is preferably 1-4 hour; After described hydrolysis makes polyreaction, the degree of hydrolysis of resulting polymers can be 10-30%.
In the present invention, described degree of hydrolysis refers to that the mole number of acrylate structural unit accounts for the per-cent of the total mole number of the structural unit of acrylamide polymer of the present invention.Described degree of hydrolysis is determined by the consumption of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic alkaline compounds that can realize above-mentioned purpose that this area is commonly used, and can be selected from one or more in sodium hydroxide, potassium hydroxide and sodium carbonate.The consumption of described hydrolytic reagent can carry out appropriate selection according to the degree of hydrolysis of acrylamide polymer, meet service requirements to make the degree of hydrolysis of acrylamide polymer to be as the criterion, the consumption of preferred inorganic alkaline compound makes the degree of hydrolysis of acrylamide polymer be 10-30%.
Those skilled in the art can know, and by regulating the consumption of inorganic alkaline compound, can obtain the acrylamide polymer of different degree of hydrolysis.
In the present invention, the mole number of described inorganic alkaline compound equals the mole number of acrylate structural unit.
According to the present invention, the present invention is to drying conditions without particular requirement, and described drying means can adopt hot air seasoning, and described warm air drying temperature can be 40-120 DEG C, is preferably 70-90 DEG C; Time is 0.2-4 hour, is preferably 0.5-2 hour.
In addition; preparation method of the present invention also comprises product drying obtained and carries out pulverizing and sieving; the condition of described pulverizing and screening is conventionally known to one of skill in the art; such as the product obtained after warm air drying is put into tablets press and carry out granulation; and be the screen cloth of 15-100 micron by sieve diameter by the pellet obtained, thus obtain the acrylamide polymer product of powdery.
One of the present invention preferred embodiment in, the preparation method of described acrylamide polymer comprises the following steps of carrying out successively:
(1) acrylamide, temperature resistant antisalt monomer and water are mixed to form the comonomer aqueous solution, regulate the pH value of the aqueous solution to 4-10 with mineral alkali, the starting temperature controlling solution polymerization is-10 DEG C to 20 DEG C;
(2) pass into nitrogen in the aqueous solution obtained to step (1) and carry out deoxygenation, deoxygenation more than 30 minutes;
(3) under the condition of logical nitrogen, in the aqueous solution that step (2) obtains, add Polyamidoamine Dendrimers, water-soluble azo series initiators and redox series initiators, carry out adiabatic polymerisation, obtain copolymer gel;
(4) copolymer gel is carried out the acrylamide polymer product that granulation, hydrolysis, secondary granulation, drying, pulverizing and a screening obtain temperature resistant antisalt.
Present invention also offers the acrylamide polymer obtained according to aforesaid method.
In addition, present invention also offers the application of described acrylamide polymer in oil-displacing agent.Acrylamide polymer provided by the invention is particularly useful for high temperature and high salt oil deposit and adopts oil-displacing agent three times.
Below will be described the present invention by embodiment.
The performance measurement that following examples and comparative example relate to is as follows:
1, AM residual monomer content, dissolution time, filtration ratio and shear viscosity retention rate are tested according to Shengli Oil Field company standard Q/SH10201572-2006;
2, viscosity-average molecular weight (M
η) according to People's Republic of China (PRC) oil and gas industry standard SY/T5862-2008, adopt By Dilution, wherein, M
η=([η]/0.000373)
1.515, [η] is intrinsic viscosity;
3, the apparent viscosity of polymers soln is the solution with the salt solution of salinity 32000mg/L, polymkeric substance being made into 1500mg/L, with Brookfield viscometer at 95 DEG C, measures under 7.34s-1 condition;
4, the testing method of the aged viscosity retention rate of the acrylamide polymer aqueous solution comprises: be dissolved in the salt solution of salinity 32000mg/L by acrylamide polymer with the concentration of 1500mg/L, solution deoxygenation is less than 1mg/L to oxygen level, by the aqueous solution that obtains at 95 DEG C of temperature, after aging 3 months, with 25 DEG C of the above-mentioned aqueous solution of Brookfield viscometer determining at 7.34s
-1apparent viscosity under condition, with following formulae discovery apparent viscosity retention rate:
Apparent viscosity × 100% of the apparent viscosity/aging front acrylamide polymer aqueous solution of the acrylamide polymer aqueous solution after apparent viscosity retention rate=aging.
In following examples and comparative example; be purchased from Beijing victory the triumphant model reaching bulk material equipment company limited be SLG (J)-120 tablets press on carry out granulation; pulverizing on the pulverizer that Beijing triumphant model reaching bulk material equipment company limited of victory is DGF being purchased, by the acrylamide polymer product after pulverizing is the screen cloth of 15-100 micron by sieve diameter.
In following examples and comparative example, acrylamide is purchased from Bao Mo biochemical industry limited-liability company, 2-acrylamide-2-methylpro panesulfonic acid is purchased from Xiamen Changtian Enterprise Co., Ltd., NVP is purchased from Jiaozhuo Zhong Wei Chemical Co., Ltd., and 2-acrylamido-tetradecane sulfonic acid is according to literature method (oil field chemical, Chemical Industry Press, Zhang Guanghua edits, 2005, chapter 2,54 pages) preparation; 2,2 '-azo (2-amidine propane) dihydrochloride, quadrol are core (1 generation) polyamide-amide dendrimer, quadrol is core (3 generation) polyamide-amide dendrimer, quadrol is core (5 generation) polyamide-amide dendrimer, quadrol is core (8 generation) polyamide-amide dendrimer, quadrol is core (10 generation) polyamide-amide dendrimer, Putriscine is core (5 generation) polyamide-amide dendrimer available from Aldrich Co.
Embodiment 1
The present embodiment is used for illustrating according to structure directing type composite initiator of the present invention and acrylamide polymer and preparation method thereof.
200 kilograms of deionized waters are added in batching kettle, under whipped state, add double centner acrylamide, 0.2 kilogram of 2-acrylamide-2-methylpro panesulfonic acid, add the sodium hydroxide solution that concentration is 20 % by weight, regulate the pH value to 5 of gained solution, solution temperature 5 DEG C is controlled with chilled brine, monomer solution is pumped in polymeric kettle, logical high pure nitrogen deoxygenation 0.5 hour, adding 2.5 grams of quadrols is core (1 generation) polyamide-amide dendrimer, 5 grams of water-soluble azo initiators 2, two (2-amidine propane) dihydrochloride of 2 '-azo, add 2.5 grams of sodium bisulfites and 5 grams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, 8 hours reaction times.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.2MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 10%, mediated by the multipolymer micelle obtained contact with sodium hydroxide grain alkali, under temperature 70 C, be hydrolyzed 4 hours, after secondary granulation, drying 0.5 hour under 90 DEG C of hot blast conditions, by crushing and screening and be packaged to be 20-80 object product.The acrylamide polymer product performance obtained are listed in table 1.
Embodiment 2
The present embodiment is used for illustrating according to structure directing type composite initiator of the present invention and acrylamide polymer and preparation method thereof.
2000 kilograms of deionized waters are added in batching kettle, under whipped state, add double centner acrylamide, 200 kilograms of 2-acrylamide-2-methylpro panesulfonic acids, add the sodium hydroxide solution that concentration is 20 % by weight, regulate the pH value to 9 of gained solution, solution temperature 15 DEG C is controlled with chilled brine, monomer solution is pumped in polymeric kettle, logical high pure nitrogen deoxygenation 0.5 hour, adding 40 grams of quadrols is core (3 generation) polyamide-amide dendrimer, 50 grams of water-soluble azo initiators 2, two (2-amidine propane) dihydrochloride of 2 '-azo, add 40 grams of sodium bisulfites and 50 grams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, 4 hours reaction times.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.2MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 30%, mediated by the multipolymer micelle obtained contact with sodium hydroxide grain alkali, at temperature 90 DEG C, be hydrolyzed 1 hour, after secondary granulation, drying 2 hours under 70 DEG C of hot blast conditions, by crushing and screening and be packaged to be 20-80 object product.The acrylamide polymer product performance obtained are listed in table 1.
Embodiment 3
The present embodiment is used for illustrating according to structure directing type composite initiator of the present invention and acrylamide polymer and preparation method thereof.
1000 kilograms of deionized waters are added in batching kettle, under whipped state, add double centner acrylamide, double centner 2-acrylamide-2-methylpro panesulfonic acid, add the sodium hydroxide solution that concentration is 20 % by weight, regulate the pH value to 7 of gained solution, solution temperature 10 DEG C is controlled with chilled brine, monomer solution is pumped in polymeric kettle, logical high pure nitrogen deoxygenation 0.5 hour, adding 25 grams of quadrols is core (5 generation) polyamide-amide dendrimer, 25 grams of water-soluble azo initiators 2, two (2-amidine propane) dihydrochloride of 2 '-azo, add 25 grams of sodium bisulfites and 25 grams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, 6 hours reaction times.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.2MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, mediated by the multipolymer micelle obtained contact with sodium hydroxide grain alkali, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, drying 1.5 hours under 80 DEG C of hot blast conditions, by crushing and screening and be packaged to be 20-80 object product.The acrylamide polymer product performance obtained are listed in table 1.
Comparative example 1
The method identical with embodiment 3 is adopted to prepare acrylamide polymer, unlike, not adding quadrol is core (5 generation) polyamide-amide dendrimer.
Embodiment 4
The present embodiment is used for illustrating according to structure directing type composite initiator of the present invention and acrylamide polymer and preparation method thereof.
1000 kilograms of deionized waters are added in batching kettle, under whipped state, add double centner acrylamide, 50 kilograms of 2-acrylamide-2-methylpro panesulfonic acids, 50 kilograms of NVPs, add the sodium hydroxide solution that concentration is 20 % by weight, regulate the pH value to 7 of gained solution, solution temperature 10 DEG C is controlled with chilled brine, monomer solution is pumped in polymeric kettle, logical high pure nitrogen deoxygenation 0.5 hour, adding 25 grams of quadrols is core (8 generation) polyamide-amide dendrimer, 25 grams of water-soluble azo initiators 2, two (2-amidine propane) dihydrochloride of 2 '-azo, add 25 grams of sodium bisulfites and 25 grams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, 4 hours reaction times.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.2MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, mediated by the multipolymer micelle obtained contact with sodium hydroxide grain alkali, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, drying 1.5 hours under 80 DEG C of hot blast conditions, by crushing and screening and be packaged to be 20-80 object product.The acrylamide polymer product performance obtained are listed in table 1.
Embodiment 5
The present embodiment is used for illustrating according to structure directing type composite initiator of the present invention and acrylamide polymer and preparation method thereof.
1000 kilograms of deionized waters are added in batching kettle, under whipped state, add double centner acrylamide, 95 kilograms of 2-acrylamide-2-methylpro panesulfonic acids, 5 kilograms of 2-acrylamido-tetradecane sulfonic acid, add the sodium hydroxide solution that concentration is 20 % by weight, regulate the pH value to 7 of gained solution, solution temperature 10 DEG C is controlled with chilled brine, monomer solution is pumped in polymeric kettle, logical high pure nitrogen deoxygenation 0.5 hour, adding 25 grams of quadrols is core (10 generation) polyamide-amide dendrimer, 25 grams of water-soluble azo initiators 2, two (2-amidine propane) dihydrochloride of 2 '-azo, add 25 grams of sodium bisulfites and 25 grams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, 4 hours reaction times.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.2MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, mediated by the multipolymer micelle obtained contact with sodium hydroxide grain alkali, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, drying 1.5 hours under 80 DEG C of hot blast conditions, by crushing and screening and be packaged to be 20-80 object product.The acrylamide polymer product performance obtained are listed in table 1.
Embodiment 6
The present embodiment is used for illustrating according to structure directing type composite initiator of the present invention and acrylamide polymer and preparation method thereof.
3000 kilograms of deionized waters are added in batching kettle, under whipped state, add double centner acrylamide, 0.1 kilogram of 2-acrylamide-2-methylpro panesulfonic acid, add the sodium hydroxide solution that concentration is 20 % by weight, regulate the pH value to 4 of gained solution, solution temperature 20 DEG C is controlled with chilled brine, monomer solution is pumped in polymeric kettle, logical high pure nitrogen deoxygenation 0.5 hour, add 100 gram 1, 4-butanediamine is core (5 generation) polyamide-amide dendrimer, 100 grams of water-soluble azo initiators 2, two (2-amidine propane) dihydrochloride of 2 '-azo, add 100 grams of sodium bisulfites and 100 grams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, 8 hours reaction times.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.2MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 10%, mediated by the multipolymer micelle obtained contact with sodium hydroxide grain alkali, under temperature 70 C, be hydrolyzed 4 hours, after secondary granulation, drying 0.5 hour under 90 DEG C of hot blast conditions, by crushing and screening and be packaged to be 20-80 object product.The acrylamide polymer product performance obtained are listed in table 1.
Embodiment 7
The present embodiment is used for illustrating according to structure directing type composite initiator of the present invention and acrylamide polymer and preparation method thereof.
Identical method is adopted to prepare acrylamide polymer with embodiment 2, unlike, without hydrolysis, namely do not carry out being mediated with sodium hydroxide grain alkali by the multipolymer micelle obtained in embodiment 2 and contact, at 90 DEG C, be hydrolyzed the step of 1 hour.The acrylamide polymer product performance obtained are listed in table 1.
Table 1
The data of associative list 1 are known, the polymericular weight that embodiment 3 obtains can reach 3,650 ten thousand, and comparative example 1 obtains polymericular weight is only 2,700 ten thousand, the polymericular weight that embodiment 3 obtains than comparative example 1 improves nearly 9,500,000, the apparent viscosity of corresponding 95 DEG C improves 15mPas, aged viscosity retention rate improves 24.8%, shear viscosity retention rate improves 9.2%, illustrate that quadrol in the present invention is the apparent viscosity that the introducing of core (5 generation) polyamide-amide dendrimer is more conducive to improving the molecular weight of polymkeric substance and the polymers soln under the condition of high temperature and high salinity, ageing resistance and anti-shear performance.
By embodiment 2 compared with embodiment 7, the molecular weight obtaining polymkeric substance in embodiment 7 is 2,920 ten thousand, and the apparent viscosity of 95 DEG C is 15.8mPas, and aged viscosity retention rate is 90.8%, and shear viscosity retention rate is 95.2%, all lower than the index result of embodiment 2.To illustrate that in polymer architecture suitably introducing sodium acrylate structural unit is more conducive to improving the apparent viscosity of the molecular weight of polymkeric substance and the polymers soln under the condition of high temperature and high salinity, ageing resistance and anti-shear performance.
For embodiment 1, the acrylamide polymer that the present invention obtains is under the condition of high salinity 32000mg/L, high temperature 95 DEG C, solution apparent viscosity can reach 28.8mPas, aged viscosity retention rate is 94.3%, shear viscosity retention rate 99.5%, and commercially available high molecular weight polyacrylamide solution apparent viscosity is only 8.9mPas, aged viscosity retention rate is 65.2%, shear viscosity retention rate is 90.0%, compared with commercially available prod, temperature resistant antisalt acrylamide polymer of the present invention has larger thickening, anti-aging and anti-shearing advantage.Therefore, acrylamide polymer provided by the invention has good temperature resistant antisalt performance, ageing resistance and anti-shear performance.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (16)
1. a structure directing type composite initiator system, this structure directing type composite initiator system contains redox series initiators, described redox series initiators comprises Oxidizing and Reducing Agents, it is characterized in that, described structure directing type composite initiator system is also containing Polyamidoamine Dendrimers.
2. structure directing type composite initiator system according to claim 1, wherein, it is 1 generation of core that described Polyamidoamine Dendrimers is selected from quadrol, 2 generations, 3 generations, 4 generations, 5 generations, 6 generations, 7 generations, 8 generations, 9 generations, the Polyamidoamine Dendrimers in 10 generations, with 1, 4-butanediamine is 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, the Polyamidoamine Dendrimers in 6 generations, with 1, 6-hexanediamine is 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, the Polyamidoamine Dendrimers in 6 generations, take cystamine as 1 generation of core, 2 generations, 3 generations, 4 generations, 5 generations, one or more in the Polyamidoamine Dendrimers in 6 generations.
3. structure directing type composite initiator system according to claim 1, wherein, with the total amount of described structure directing type composite initiator system for benchmark, the content of described oxygenant is 4-85 % by weight, the weight ratio of described oxygenant, reductive agent and Polyamidoamine Dendrimers is 1:0.1-10:0.1-10, is preferably 1:0.5-1:0.5-1.
4. the structure directing type composite initiator system according to claim 1 or 3, wherein, described oxygenant be selected from peroxidation two acyl compounds, alkyl peroxide compounds, hydroperoxide and persulphate one or more; Described reductive agent be selected from vitriol, sulphite, hydrosulphite, thiosulphate, formaldehyde sulfoxylate salt, amine and cuprous chloride one or more.
5. structure directing type composite initiator system according to claim 4, wherein, described oxygenant is selected from dibenzoyl peroxide, lauroyl peroxide, tertbutyl peroxide, 2, one or more in 5-dimethyl-hexyl-2,5-two hydrogen peroxide, hydrogen peroxide, ammonium persulphate, Sodium Persulfate and Potassium Persulphates; Described reductive agent is selected from ferrous sulfate, ferrous ammonium sulphate, cuprous chloride, potassium sulfite, S-WAT, bisulfite amine, sodium bisulfite, Potassium hydrogen sulfite, Sulfothiorine, Potassium Thiosulphate, rongalite, N, N-dimethylethanolamine, N, N-lupetazin, N, N, N ', N '-tetramethyl-urea element and N, N, N ', N ' one or more in-Tetramethyl Ethylene Diamine.
6. according to the structure directing type composite initiator system in claim 1-5 described in any one, wherein, described structure directing type composite initiator system is also containing water-soluble azo series initiators, with the total amount of described structure directing type composite initiator system for benchmark, the content of described water-soluble azo series initiators is 20-40 % by weight; Described water-soluble azo series initiators is selected from 2, two (2-amidine propane) dihydrochloride, 2 of 2 '-azo, two (the 2-tetrahydroglyoxaline propane) dihydrochloride and 4 of 2 '-azo, one or more in 4 '-azo two (4-cyanopentanoic acid).
7. the preparation method of an acrylamide polymer, under the method is included in the existence of initiator and inorganic base substance, acrylamide and temperature resistant antisalt monomer are polymerized in water, it is characterized in that, described initiator contains the structure directing type composite initiator system in claim 1-6 described in any one.
8. method according to claim 7; wherein; under the existence of initiator and inorganic base substance; the mode that acrylamide and temperature resistant antisalt monomer carry out being polymerized in water is comprised: by inorganic base substance and the aqueous solution containing acrylamide and temperature resistant antisalt monomer; under protection of inert gas, be polymerized after Polyamidoamine Dendrimers, reductive agent and oxygenant and optional water-soluble azo series initiators are mixed with the mixture of gained.
9. the method according to claim 7 or 8, wherein, with the described acrylamide of 100 weight parts for benchmark, the consumption of described temperature resistant antisalt monomer is 0.1-250 weight part, the consumption of described oxygenant is 0.001-0.1 weight part, and the consumption of described water is 100-3000 weight part.
10. the method according to claim 7 or 8, wherein, described temperature resistant antisalt monomer is vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid, N, one or more in N-DMAA, N, N-acrylamide, N-vinyl pyrrolidone, 2-acrylamido-dodecane sulfonic acid, 2-acrylamido-tetradecane sulfonic acid and 2-acrylamido-n-Hexadecane sulfonic acid; Described inorganic base substance is one or more in sodium hydroxide, potassium hydroxide and sodium carbonate.
11. methods according to claim 7 or 8, wherein, the starting temperature of described polymerization is-10 DEG C to 20 DEG C, and the time of described polymerization is 2-12 hour.
12. methods according to claim 7 or 8, wherein, the method also comprises and to be hydrolyzed by the polymkeric substance obtained after polyreaction and dry.
13. methods according to claim 12, wherein, described hydrolysising condition comprises: temperature is 50-110 DEG C, and the time is 0.5-6 hour, and the degree of hydrolysis of the polymkeric substance that described hydrolysis obtains after making polyreaction is 10-30%.
14. 1 kinds of acrylamide polymers prepared by the method in claim 7-13 described in any one.
15. acrylamide polymers according to claim 14, wherein, concentration is 1500mg/L and the aqueous solution that salinity is the acrylamide polymer of 32000mg/L is 15.8-29mPas the apparent viscosity of 95 DEG C.
The application of acrylamide polymer described in 16. claims 14 or 15 in polymer oil-displacing agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317299A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
| CN107510849A (en) * | 2017-08-16 | 2017-12-26 | 暨南大学 | A kind of glutathione response type dual drug carrier and its preparation method and application |
| CN110818858A (en) * | 2019-11-22 | 2020-02-21 | 西南石油大学 | Viscosity-reducing oil-displacing polymer for conventional heavy oil reservoir and preparation method thereof |
| CN117264141A (en) * | 2023-11-16 | 2023-12-22 | 克拉玛依市新聚工贸有限责任公司 | Temperature-resistant salt-resistant acrylamide polymer for fracturing and preparation process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050917A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Macromolecular compound containing aliphatic tertiary amine group as well as preparation method thereof and application in oil displacement agent |
| WO2011123591A1 (en) * | 2010-03-31 | 2011-10-06 | Wayne State University | Injectable dendrimer hydrogel nanoparticles |
| CN103849367A (en) * | 2014-03-20 | 2014-06-11 | 西南石油大学 | Branched hydrophobic associated polymer oil-displacing agent and preparation method thereof |
-
2014
- 2014-10-15 CN CN201410544980.1A patent/CN105566515B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050917A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Macromolecular compound containing aliphatic tertiary amine group as well as preparation method thereof and application in oil displacement agent |
| WO2011123591A1 (en) * | 2010-03-31 | 2011-10-06 | Wayne State University | Injectable dendrimer hydrogel nanoparticles |
| CN103849367A (en) * | 2014-03-20 | 2014-06-11 | 西南石油大学 | Branched hydrophobic associated polymer oil-displacing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 方申文等: ""树核星形聚丙烯酰胺的制备及其稀溶液性质"", 《石油化工》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317299A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
| CN106317299B (en) * | 2015-06-18 | 2018-08-17 | 中国石油化工股份有限公司 | Acrylamide copolymer and its preparation method and application |
| CN107510849A (en) * | 2017-08-16 | 2017-12-26 | 暨南大学 | A kind of glutathione response type dual drug carrier and its preparation method and application |
| CN107510849B (en) * | 2017-08-16 | 2020-02-07 | 暨南大学 | Glutathione response type dual drug carrier and preparation method and application thereof |
| CN110818858A (en) * | 2019-11-22 | 2020-02-21 | 西南石油大学 | Viscosity-reducing oil-displacing polymer for conventional heavy oil reservoir and preparation method thereof |
| CN110818858B (en) * | 2019-11-22 | 2022-01-28 | 西南石油大学 | Viscosity-reducing oil-displacing polymer for conventional heavy oil reservoir and preparation method thereof |
| CN117264141A (en) * | 2023-11-16 | 2023-12-22 | 克拉玛依市新聚工贸有限责任公司 | Temperature-resistant salt-resistant acrylamide polymer for fracturing and preparation process thereof |
| CN117264141B (en) * | 2023-11-16 | 2024-02-09 | 克拉玛依市新聚工贸有限责任公司 | Temperature-resistant salt-resistant acrylamide polymer for fracturing and preparation process thereof |
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