CN105461855A - Hydrophobic associated polymer and preparing method thereof - Google Patents
Hydrophobic associated polymer and preparing method thereof Download PDFInfo
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- CN105461855A CN105461855A CN201511018165.2A CN201511018165A CN105461855A CN 105461855 A CN105461855 A CN 105461855A CN 201511018165 A CN201511018165 A CN 201511018165A CN 105461855 A CN105461855 A CN 105461855A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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Abstract
The invention provides a hydrophobic associated polymer. The hydrophobic associated polymer comprises four repetitive units (please see the specification), wherein y=0.001-0.2, z=0.005-0.3, m=0.03-0.2 and x+y+z+m=1; A is a monomeric unit of a hydrophobic monomer, and the hydrophobic monomer is selected from one or more of allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid, acrylamide alkyl sulfonic acid salt, alkyl phenol polyoxyethylene acrylic ester and acrylic acid polyoxyethylene alkyl ester; D is a monomeric unit of a functional monomer; the viscosity average molecular weight of the hydrophobic associated polymer ranges from 500 thousands to 15 millions. Compared with the prior art, hydrophilic base groups can be provided through the monomeric unit of acrylamide in the hydrophobic associated polymer; hydrophobic lateral groups can be provided through the monomeric unit of the hydrophobic monomer, and the necessary viscoelasticity of a solution is provided; the solubleness of the hydrophobic associated polymer can be improved through a sodium acrylate unit; the temperature resistance and the salt tolerance of the hydrophobic associated polymer can be improved through the monomeric unit of the functional monomer.
Description
Technical field
The invention belongs to technical field of polymer, particularly relate to a kind of hydrophobic associated polymer and preparation method thereof.
Background technology
In oil-field development utilisation technology, usually formation environment is needed to carry out rebuilding construction etc., the fluid using certain performance is needed to carry out mass transfer, conveying, by injecting these fluids to stratum, Cucumber is brought into stratum and produce work in order to transform ground environment, reach the object of oil-gas field development and volume increase.Meanwhile, relevant utilisation technology also requires that these fluids itself also possess some specific performance, such as thickening property, visco-elasticity, drag reduction, perviousness, improves mobility ratio etc.Wherein, the most frequently used fluid is exactly the aqueous solution, and the advantages such as source is wide, economy, constructability that it has, by adding natural or synthesizing water-solubility polymer in water, can obtain and have the above high performance aqueous solution.This kind of water-soluble polymer has the strong and good visco-elasticity of thickening property, and molecular chain has a lot of active group, so that carry out physics and chemical improvement to fluid property, possesses easy construction simultaneously, the plurality of advantages such as consumption is few, and cost is low, can bring higher economic interests for oil field.Therefore, this kind of water-soluble polymer is widely used in oilfield technology.
In prior art, the water-soluble polymer of use mainly comprises water-soluble polymer that is natural or synthesis.The yield and quality of natural polymer is owing to being subject to the restriction in season, area, stability can not be protected, and relative to synthesis polymer, its consumption is large, readily biodegradable, higher residue also can grievous injury stratum environment, brings many new problems to later development.At present, synthesizing polymer most popular is polyacrylamide, although its various aspects of performance all can reach construction requirement, but be easy to cause mechano-degradation in pumping procedure, soltion viscosity declines fast, simultaneously under some high temperature and high salinity reservoir media, polyacrylamide is salt tolerant not, and at high temperature very easily degrade, thus cause properties significantly to decline, and be difficult to further overcome on the basis of its existing molecular structure, therefore, to its modification from polymer molecular structure, anti-shearing to improve it, heat-resistant salt-resistant performance has been extremely urgent.
For above-mentioned Problems existing, investigators propose hydrophobically associating polymers on this basis.Hydrophobically associating polymers (HAWSP) refers to the water-soluble polymers with a small amount of hydrophobic grouping on polymer hydrophilicity macromolecular chain.In aqueous, HAWSP concentration is higher than after critical association concentration, and macromolecular chain is assembled by hydrophobic association polymer effect, namely forms Interpolymer Association dynamic physical cross-linked network, soltion viscosity is increased substantially without the need to chemically crosslinked.Simultaneously, some tensio-active agent add the hydrophobic interaction that also can strengthen polymer molecule interchain, Interpolymer Association dynamic physical cross-linked network intensity is increased, the supramolecule physical cross-linked network existed in HAWSP and surfactant soln also makes this solution have the characteristic of frozen glue, thus provides good visco-elasticity.In addition, this supramolecule dynamic physical cross-linked network has and destroys and the feature of reversible recovery at low shear rates at high shear rates, makes its stable performance, and possesses excellent heatproof, salt tolerance, good shear thinning behavior, visco-elasticity etc.The performance of these excellences all shows that hydrophobic associated polymer has the potentiality of existing common oil field water-soluble polymer as an alternative.
The present invention considers to provide a kind of new hydrophobic association polymer polymkeric substance.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide good hydrophobic association polymer polymkeric substance of a kind of new salt resistant character and preparation method thereof.
The invention provides a kind of hydrophobic associated polymer, comprise following four repeating units:
Wherein, described y=0.001 ~ 0.2, z=0.005 ~ 0.3, m=0.03 ~ 0.2, x+y+z+m=1; Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer be selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid one or more; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another; Described D is the monomeric unit of function monomer; Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with contain hold in the Hete rocyclic derivatives of thiazolinyl one or more;
The viscosity-average molecular weight of described hydrophobic associated polymer is 50 ~ 1,500 ten thousand.
Preferably, described y=0.001 ~ 0.1.
Preferably, described m=0.05 ~ 0.16.
Preferably, in described allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid, the carbonatoms of alkyl is 4 ~ 20 independently of one another.
Preferably, in described alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid, the polyoxyethylated polymerization degree is 7 ~ 20 independently of one another.
Preferably, described hydrophobic monomer is hexadecyl allyl group dibrominated Tetramethyl Ethylene Diamine, 2-acrylamido tetradecane sodium sulfonate, 2-acrylamido-2-methyl dodecane sulfonic acid sodium, octyl phenol polyoxyethylene acrylate, Nonyl pheno acrylate, dodecyl polyoxyethylene acrylate, vinylformic acid polyoxyethylene cetyl base ester, vinylformic acid polyoxyethylene stearyl base ester, hexadecyl phenol polyethenoxy acrylate, heptadecyl phenol polyethenoxy acrylate, sodium dodecyl allyl base dibrominated Tetramethyl Ethylene Diamine, one or more in octadecyl allyl group dibrominated Tetramethyl Ethylene Diamine and 2-acrylamido Sodium sterylsulfonate.
Preferably, the carbonatoms of described function monomer is 2 ~ 20.
Preferably, described function monomer is one or more in 2-acrylamide-2-methylpro panesulfonic acid and sulfonate, vinyl sulfonic acid and sulfonate thereof, styrene sulfonic acid and sulfonate thereof and NVP.
Present invention also offers a kind of preparation method of hydrophobic associated polymer, comprising:
Under initiator effect, acrylamide monomer, function monomer and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer after hydrolysis;
Or: under hydrolytic reagent existent condition, add the acrylamide triggered monomer of initiator, hydrophobic monomer and function monomer and carry out copolyreaction, obtain hydrophobic associated polymer; ; Or: under initiator effect, acrylamide monomer, sodium acrylate monomers, function monomer and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer;
Described hydrophobic monomer be selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid one or more; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another;
Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with contain hold in the Hete rocyclic derivatives of thiazolinyl one or more;
The mole number of described hydrophobic monomer and the ratio of total moles monomer are (0.001 ~ 0.2): 1;
The mole number of described function monomer and the ratio of total moles monomer are (0.005 ~ 0.3): 1.
Present invention also offers the application of hydrophobic associated polymer in oilfield chemistry, water treatment, papermaking or mineral floating field.
The invention provides a kind of hydrophobic associated polymer, comprise following four repeating units, wherein, described y=0.001 ~ 0.2, z=0.005 ~ 0.3, m=0.03 ~ 0.2, x+y+z+m=1; Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer be selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid one or more; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another; Described D is the monomeric unit of function monomer; Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with contain hold in the Hete rocyclic derivatives of thiazolinyl one or more; The viscosity-average molecular weight of described hydrophobic associated polymer is 50 ~ 1,500 ten thousand.Compared with prior art, hydrophobic associated polymer of the present invention is made up of four kinds of unit, and hydrophilic unit is that acrylamide participates in copolymerization and forms, and it can be hydrophobic association polymer and provides hydrophilic group, ensures that polymkeric substance has good water-soluble; Hydrophobic units is that hydrophobic monomer participates in copolymerization formation, it can be hydrophobic associated polymer and provides hydrophobic side base, ensures that polymer chain has certain hydrophobic property, in water, produce heat resistance and salt tolerance between each hydrophobic side base, form spacial framework, thus provide necessary visco-elasticity for solution; Sodium acrylate can improve the solvability of hydrophobic associated polymer; Functional unit is that function monomer participates in copolymerization formation, and it can improve the heat-resistant salt-resistant performance of polymkeric substance; Above-mentioned four kinds of unit actings in conjunction, improve the temperature tolerance of hydrophobic associated polymer, salt tolerance and anti-shear performance.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the hydrophobic associated polymer obtained in the embodiment of the present invention 3;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the hydrophobic associated polymer obtained in the embodiment of the present invention 3.
Embodiment
Below in conjunction with the accompanying drawing of the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of hydrophobic associated polymer, comprise following four repeating units:
Wherein, described y=0.001 ~ 0.2, is preferably 0.001 ~ 0.15, is more preferably 0.001 ~ 0.1, then is preferably 0.001 ~ 0.05, most preferably is 0.001 ~ 0.01; Described z=0.005 ~ 0.3, is preferably 0.05 ~ 0.2, most preferably is 0.08 ~ 0.16; Described m=0.03 ~ 0.2, is preferably 0.05 ~ 0.16, most preferably is 0.1 ~ 0.16; X+y+z+m=1; Described m/ (x+m) is preferably 0.04 ~ 0.2, is more preferably 0.1 ~ 0.16.
Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer be selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid one or more, be preferably the one in allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another, is preferably 4 ~ 20, is more preferably 6 ~ 20, then be preferably 10 ~ 20; In alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid, the carbonatoms of alkyl is preferably less than or equal to 20 independently of one another, is more preferably 4 ~ 20, then is preferably 6 ~ 20, most preferably is 10 ~ 20; In described alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid, the polyoxyethylated polymerization degree is preferably 7 ~ 20 independently of one another, is more preferably 10 ~ 20.In the present invention, described hydrophobic monomer most preferably is hexadecyl allyl group dibrominated Tetramethyl Ethylene Diamine, 2-acrylamido tetradecane sodium sulfonate, 2-acrylamido-2-methyl dodecane sulfonic acid sodium, octyl phenol polyoxyethylene acrylate, Nonyl pheno acrylate, dodecyl polyoxyethylene acrylate, vinylformic acid polyoxyethylene cetyl base ester, vinylformic acid polyoxyethylene stearyl base ester, hexadecyl phenol polyethenoxy acrylate, heptadecyl phenol polyethenoxy acrylate, sodium dodecyl allyl base dibrominated Tetramethyl Ethylene Diamine, one or more in octadecyl allyl group dibrominated Tetramethyl Ethylene Diamine and 2-acrylamido Sodium sterylsulfonate.Described D is the monomeric unit of function monomer; Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with containing hold in the Hete rocyclic derivatives of thiazolinyl one or more, the carbonatoms of described function monomer is preferably 2 ~ 20, is more preferably 2 ~ 15, more preferably 2 ~ 10; In the present invention, described function monomer most preferably be in 2-acrylamide-2-methylpro panesulfonic acid and sulfonate, vinyl sulfonic acid and sulfonate thereof, styrene sulfonic acid and sulfonate thereof and NVP one or more.
The viscosity-average molecular weight of described hydrophobic associated polymer is 50 ~ 1,500 ten thousand, is preferably 200 ~ 1,500 ten thousand, is more preferably 500 ~ 1,500 ten thousand, then is preferably 800 ~ 1,500 ten thousand, most preferably is 900 ~ 1,300 ten thousand.
Hydrophobic associated polymer of the present invention is made up of four kinds of unit, and hydrophilic unit is that acrylamide participates in copolymerization and forms, and it can be hydrophobic association polymer and provides hydrophilic group, ensures that polymkeric substance has good water-soluble; Hydrophobic units is that hydrophobic monomer participates in copolymerization formation, it can be hydrophobic associated polymer and provides hydrophobic side base, ensures that polymer chain has certain hydrophobic property, in water, produce heat resistance and salt tolerance between each hydrophobic side base, form spacial framework, thus provide necessary visco-elasticity for solution; Sodium acrylate can improve the solvability of hydrophobic associated polymer; Functional unit is that function monomer participates in copolymerization formation, and the introducing of these monomeric units can improve the heat-resistant salt-resistant performance of polymkeric substance; Above-mentioned four kinds of unit actings in conjunction, improve the temperature tolerance of hydrophobic associated polymer, salt tolerance and anti-shear performance.
Present invention also offers a kind of preparation method of above-mentioned hydrophobic associated polymer, the mode that this method is hydrolyzed after being introduces sodium acrylate, comprise: under initiator effect, acrylamide monomer, hydrophobic monomer and function monomer are carried out copolyreaction, after hydrolysis, obtains hydrophobic associated polymer; Described hydrophobic monomer be selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid one or more; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another; Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with contain hold in the Hete rocyclic derivatives of thiazolinyl one or more; The mole number of described hydrophobic monomer and the ratio of total moles monomer are (0.001 ~ 0.2): 1; The mole number of described function monomer and the ratio of total moles monomer are (0.005 ~ 0.3): 1.
Wherein, described hydrophobic monomer and function monomer are all same as above, do not repeat them here; The integral molar quantity of described acrylamide monomer, hydrophobic monomer and function monomer and the mol ratio of hydrophobic monomer are 1:(0.001 ~ 0.2), be preferably 1:(0.001 ~ 0.15), be more preferably 1:(0.001 ~ 0.1), be preferably 1:(0.001 ~ 0.05 again), most preferably be 1:(0.001 ~ 0.01); The mole number of described function monomer and the total mol ratio of monomer are (0.005 ~ 0.3): 1, are preferably (0.05 ~ 0.2): 1, most preferably are (0.08 ~ 0.16): 1.Described initiator is initiator well known to those skilled in the art, there is no special restriction, is preferably persulphate and sulfite oxidation and reduces initiator system in the present invention; It is Redox initiator systems well known to those skilled in the art that described persulphate and sulfite oxidation reduce initiator system, there is no special restriction, the mass ratio of persulphate described in the present invention and sulphite is preferably (1 ~ 3): 1; In described initiator, the quality optimization of oxygenant is 0.05% ~ 1% of total monomer quality.
In the present invention, copolymerization can be undertaken by water solution polymerization process, micell polymerization method or antiphase emulsifiable method again.
When carrying out copolymerization by water solution polymerization process, preferably acrylamide monomer, hydrophobic monomer being mixed with function monomer, being heated to kick off temperature, then adding initiator, carry out copolyreaction.Wherein, copolyreaction is preferably carried out in water, and the total in aqueous mass concentration of acrylamide monomer, hydrophobic monomer and function monomer is preferably 15% ~ 30%, is more preferably 20% ~ 30%; The pH value of mixing rear solution is preferably 5 ~ 13; In described initiator, the quality optimization of oxygenant is 0.05% ~ 1% of acrylamide monomer, hydrophobic monomer and function monomer total mass, is more preferably 0.05% ~ 0.6%, then is preferably 0.09% ~ 0.4%; In described initiator, the mass ratio of persulphate and sulphite is preferably (1.7 ~ 1): 1, is more preferably (1 ~ 1.5): 1; Described kick off temperature is preferably 20 DEG C ~ 45 DEG C, is more preferably 20 DEG C ~ 40 DEG C, then is preferably 20 DEG C ~ 30 DEG C; Described copolyreaction is preferably carried out under the condition of thermal insulation; The time of described polyreaction is preferably 5 ~ 7h.
When copolymerization process is micell polymerization method, preferably acrylamide monomer, hydrophobic monomer is mixed with function monomer, preferably also add tensio-active agent, be heated to kick off temperature, then add initiator, carry out copolyreaction.Wherein, described copolyreaction is preferably carried out in water; The total in aqueous mass concentration of described acrylamide monomer, hydrophobic monomer and function monomer is preferably 12% ~ 35%, is more preferably 20% ~ 35%, then is preferably 20% ~ 30%; The pH value of mixing rear solution is preferably 4 ~ 10; Described tensio-active agent is preferably anion surfactant, is more preferably one or more in sodium laurylsulfonate, sodium lauryl sulphate and Sodium dodecylbenzene sulfonate; The mol ratio of described tensio-active agent and hydrophobic monomer is preferably (2 ~ 20): 1, is more preferably (5 ~ 20): 1, most preferably is (8 ~ 15): 1; The quality optimization of described initiator is 0.05% ~ 1% of acrylamide monomer, hydrophobic monomer and function monomer total mass, is more preferably 0.05% ~ 0.6%, most preferably is 0.09% ~ 0.4%; In described initiator, the mass ratio of persulphate and sulphite is (5:3) ~ (1:1), is more preferably (4:3) ~ (1:1); Described kick off temperature is preferably 20 DEG C ~ 65 DEG C, is more preferably 20 DEG C ~ 50 DEG C, then is preferably 20 DEG C ~ 40 DEG C; Described copolyreaction is preferably carried out under the condition of thermal insulation; The time of described copolyreaction is preferably 5 ~ 7h, more preferably in the temperature 30min of reaction system, rises above 1 DEG C, and reaction terminates.
When carrying out copolymerization by antiphase emulsifiable method, preferably carry out in accordance with the following methods: propionic acid amide monomer, hydrophobic monomer and function monomer will be gathered soluble in water, as aqueous phase; Preferably also add emulsifying agent, emulsifying agent is dissolved in Oil solvent, as oil phase; Aqueous phase is mixed with oil phase, is heated to kick off temperature, then add initiator, carry out copolyreaction.Wherein, described Oil solvent is Oil solvent well known to those skilled in the art, there is no special restriction, is preferably one or more in kerosene, white oil and whiteruss, is more preferably kerosene in the present invention; The water oil ratio of described Oil solvent and water is preferably (1 ~ 2): 1; After mixing, in mixing solutions, total monomer concentration is preferably 20 ~ 35wt%, is more preferably 25 ~ 30wt%; Described emulsifying agent is emulsifying agent well known to those skilled in the art, there is no special restriction, being preferably HLB value in the present invention is the nonionogenic tenside of 6 ~ 8, be more preferably the compound emulsifying agent of Span class nonionogenic tenside and/or Tween class nonionogenic tenside composition, most preferably be Span-80/Tween-20 compound emulsifying agent; The quality optimization of described emulsifying agent is 10% ~ 20% of monomer total mass, is more preferably 12% ~ 18%, then is preferably 14% ~ 18%; In described initiator, the quality optimization of oxygenant is 0.1% ~ 0.5% of monomer total mass, is more preferably 0.1% ~ 0.3%, then is preferably 0.1% ~ 0.2%; Described kick off temperature is preferably 20 DEG C ~ 40 DEG C, is more preferably 20 DEG C ~ 30 DEG C; The time of described copolyreaction is preferably 5 ~ 7h, is more preferably 4 ~ 6h; Preferably also breakdown of emulsion process is carried out after adopting antiphase emulsifiable method copolymerization.
After copolyreaction completes, preferably carry out granulation, be then hydrolyzed; The method of described granulation is method well known to those skilled in the art, there is no special restriction; Described hydrolysis hydrolytic reagent used is hydrolytic reagent well known to those skilled in the art, and there is no special restriction, the present invention is preferably alkali metal hydroxide, is more preferably potassium hydroxide and/or sodium hydroxide, then is preferably sodium hydroxide; The temperature of described hydrolysis is preferably 70 DEG C ~ 100 DEG C, is more preferably 80 DEG C ~ 100 DEG C, then is preferably 90 DEG C ~ 100 DEG C; The time of described hydrolysis is preferably 1 ~ 3h; The degree of hydrolysis of described hydrolysis is preferably 4% ~ 20%, is more preferably 5% ~ 20%, then is preferably 10% ~ 20%.
After hydrolysis, preferably carry out drying and obtain hydrophobic associated polymer; The temperature of described drying is preferably 80 DEG C ~ 95 DEG C; The time of described drying is preferably 0.5 ~ 4h, is more preferably 0.5 ~ 3h, then is preferably 1 ~ 2h.
Present invention also offers a kind of method that front hydrolysis method prepares above-mentioned hydrophobic associated polymer, comprise: under hydrolytic reagent existent condition, add the acrylamide triggered monomer of initiator, hydrophobic monomer and function monomer and carry out copolyreaction, obtain hydrophobic associated polymer; Preferably after copolyreaction completely, continue slaking certain hour, obtain hydrophobic associated polymer.Described hydrophobic monomer be selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid one or more; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another; Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with contain hold in the Hete rocyclic derivatives of thiazolinyl one or more; The mole number of described hydrophobic monomer and the ratio of total moles monomer are (0.001 ~ 0.2): 1; The mole number of described function monomer and the ratio of total moles monomer are (0.005 ~ 0.3): 1.
Wherein, described acrylamide monomer, hydrophobic monomer, function monomer and initiator are all same as above, do not repeat them here; Described hydrolytic reagent is hydrolytic reagent well known to those skilled in the art, there is no special restriction, is preferably alkali metal hydroxide, is more preferably potassium hydroxide and/or sodium hydroxide in the present invention, then is preferably sodium hydroxide; The amount that described hydrolytic reagent adds is 0.4% ~ 20% of monomer total mass, is more preferably 1% ~ 15%, then is preferably 2% ~ 10%.
Copolymerization in front method for hydrolysis preparation can be undertaken by water solution polymerization process, micell polymerization method or antiphase emulsifiable method again.Wherein, described water solution polymerization process, micell polymerization method and antiphase emulsifiable method are all same as above, just while adding acrylamide monomer and hydrophobic monomer, add hydrolytic reagent, do not repeat them here.
Preferably carry out slaking after copolyreaction, then carry out granulation, dry, obtain hydrophobic associated polymer; The method of described granulation is method well known to those skilled in the art, there is no special restriction; The temperature of described drying is preferably 80 DEG C ~ 95 DEG C; The time of described drying is preferably 0.5 ~ 4h, is more preferably 0.5 ~ 3h, then is preferably 1 ~ 2h.
Present invention also offers a kind of method adopting cohydrolysis to prepare above-mentioned hydrophobic associated polymer, comprising: under initiator effect, acrylamide monomer, sodium acrylate monomers, function monomer and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer; One or more in described allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another; Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with contain hold in the Hete rocyclic derivatives of thiazolinyl one or more; The mole number of described hydrophobic monomer and the ratio of total moles monomer are (0.001 ~ 0.2): 1; The mole number of described function monomer and the ratio of total moles monomer are (0.005 ~ 0.3): 1.
Wherein, described hydrophobic monomer, function monomer and initiator are all same as above, do not repeat them here; Preparing hydrophobic associated polymer at co-hydrolysis is some acrylamide monomer sodium acrylate monomers substituted, therefore the integral molar quantity of described acrylamide monomer, sodium acrylate monomers, function monomer and hydrophobic monomer and the mol ratio of hydrophobic monomer are 1:(0.001 ~ 0.2), be preferably 1:(0.001 ~ 0.15), be more preferably 1:(0.001 ~ 0.1), be preferably 1:(0.001 ~ 0.05 again), most preferably be 0.001 ~ 0.01; The ratio of the mole number that described sodium acrylate monomers is total with monomer is (0.03 ~ 0.2): 1, is preferably (0.05 ~ 0.16): 1, then is preferably (0.1 ~ 0.16): 1; The mole ratio of described acrylamide monomer and sodium acrylate monomers total mole number and sodium acrylate monomers is preferably 1:(0.04 ~ 0.2), be more preferably 1:(0.1 ~ 0.16).
Copolymerization in cohydrolysis method preparation is also undertaken by water solution polymerization process, micell polymerization method or antiphase emulsifiable method.Wherein, described water solution polymerization process, micell polymerization method and antiphase emulsifiable method are all same as above, just replace acrylamide monomer with part acrylic acid sodium monomer, do not repeat them here.
Preferably carry out slaking after copolyreaction, more preferably carry out granulation, dry, obtain hydrophobic associated polymer; The method of described granulation is method well known to those skilled in the art, there is no special restriction; The temperature of described drying is preferably 80 DEG C ~ 95 DEG C; The time of described drying is preferably 0.5 ~ 4h, is more preferably 0.5 ~ 3h, then is preferably 1 ~ 2h.
The present invention adopts initiator to prepare hydrophobic associated polymer, and composite initiator is decomposed to form monomer radical in water, and monomer radical and vinyl monomer carry out addition, forms monomer radical, i.e. spike; Then monomer radical opens the π key of other vinyl monomer molecules, adds and is shaped as new free radical.The new free radical reaction activity of such formation can not decay, and continues the addition carrying out interlock type with vinyl monomer, and carries out transfer reaction in this manner.Active collision occurs between two chain free radicals, and double-basis termination reaction occurs, and polyreaction terminates, and forms polymeric colloid.
Present invention also offers a kind of above-mentioned hydrophobic associated polymer oilfield chemistry, water treatment, papermaking with or mineral floating field in application.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of hydrophobic associated polymer provided by the invention and preparation method thereof is described in detail.
Reagent used in following examples is commercially available.
Embodiment 1
By acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium feed intake by the mol ratio of 85:14.2:0.8, add in 5000mL beaker to dissolve with pure water and be mixed with the mixing solutions that monomer total mass concentration is 25%, add Sodium dodecylbenzene sulfonate according to the ratio of hydrophobic monomer volumetric molar concentration 10 times and stir, then beaker is put into 30 DEG C of water-baths be incubated to solution temperature be 30 DEG C, add ammonium persulphate and sodium bisulfite composite initiator initiated polymerization, wherein ammonium persulphate and sodium bisulfite mass ratio are 5:4, ammonium persulphate addition is 0.1% of monomer mass, polyreaction is carried out under adiabatic conditions, inserts thermometer monitors polyreaction and carries out degree, think that polyreaction completes substantially when temperature in 30min rises above 1 DEG C at reaction system center, 1h after polyreaction completes, take out colloid, colloid is cut into 3 ~ 5mm size particles, hydrolytic reagent NaOH adds according to the amount of 2.4g/100g colloid, mix, transferred in plastics bag and seal, then constant temperature 95 DEG C hydrolysis 2h (excluding air of trying one's best when should be noted that sealing in constant temperature oven, and the ammonia produced when retaining enough space hydrolysis, when noting being hydrolyzed, sealing bag does not break), after being hydrolyzed, colloid being spread out and paves on 500 eye mesh screens, put into baking oven constant temperature 90 DEG C of dry 40min ~ 90min, take out the acquisition hydrophobic associated polymer that sieves.
The hydrophobic associated polymer obtained in embodiment 1 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of massfraction 0.2%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 132mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 1 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,278 ten thousand.
Embodiment 2
Acrylamide monomer, sodium acrylate monomers, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium are joined in deionized water in the mol ratio (ratios of four) of 69:16:14.2:0.8, abundant dissolving, this solution is as aqueous phase; Add in kerosene mass ratio be Span-80:Tween-20=8:2 composition compound emulsifying agent and be stirred to abundant dissolving, as oil phase, compound emulsifying agent additive capacity is 15%18% of total system quality.Under high velocity agitation, added by aqueous phase solution in oil phase, emulsification 20min, be transferred in 5000mL beaker, the total mass concentration of monomer is 25%.Add ammonium persulphate and sodium bisulfite composite initiator initiated polymerization during emulsion constant temperature to 30 DEG C, wherein ammonium persulphate and sodium bisulfite mass ratio are 5:4, and ammonium persulphate dosage is 0.1% of monomer mass; Reaction is carried out in 30 DEG C of water-baths, after reaction 4 ~ 6h, obtains white emulsion.
The emulsion obtained is put into-20 DEG C and carries out freezing breakdown of emulsion, precipitation, centrifugation, by gained throw out dehydrated alcohol repetitive scrubbing 3 times, 90 DEG C of dry 1h, through pulverizing, sieving, obtain certain particle diameter dry powder sample and are hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 2 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 96mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 2 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,163 ten thousand.
Embodiment 3
Acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium are fed intake by the mol ratio of 85:14.2:0.8, join in 5000mL beaker to dissolve with pure water and be mixed with the mixing solutions that monomer total mass concentration is 25%, beaker is put in 30 DEG C of water-baths and be incubated until solution temperature is after 30 DEG C, add ammonium persulphate and sodium bisulfite composite initiator initiated polymerization, wherein ammonium persulphate and sodium bisulfite mass ratio are 5:4, and ammonium persulphate is 0.1% of monomer total mass; Polyreaction is carried out under the condition of thermal insulation, inserts thermometer monitors polyreaction and carries out degree, think that polyreaction completes substantially when temperature in 30min rises above 1 DEG C at reaction system center; 1h after polyreaction completes, take out colloid, colloid is cut into 3 ~ 5mm size particles, hydrolytic reagent NaOH is added according to the amount of 2.4g/100g colloid, mix, transfer in plastics bag and seal, then constant temperature 95 DEG C hydrolysis 2h (excluding air of trying one's best when should be noted that sealing in constant temperature oven, and the ammonia produced when retaining enough space hydrolysis, when noting being hydrolyzed, sealing bag does not break).After being hydrolyzed, colloid being spread out and paves on 500 eye mesh screens, put into baking oven constant temperature 90 DEG C of drying 40 ~ 90min, take out the acquisition hydrophobic associated polymer that sieves.
Utilize infrared spectra to analyze the hydrophobic associated polymer obtained in embodiment 3, obtain its infrared spectrogram, as shown in Figure 1.As shown in Figure 1, in FTIR spectrum figure, 3568cm-
1and 3183cm-
1place belongs to unsymmetrically and the symmetrical stretching vibration peak of N-H key; 2946cm-
1and 1458cm-
1belonging to stretching vibration peak and the flexural vibration peak of c h bond respectively, is the charateristic avsorption band of long-chain methylene radical, 1667cm-
1belong to the stretching vibration peak of amide I band C=O; 1607cm-
1belong to the flexural vibration peak that acid amides II is with N-H; 1410cm-
1belong to the stretching vibration peak of C-O key, 1315cm-
1belong to the stretching vibration peak of C-N key, wave number is 1194cm-
1, 1119cm-
1near have sulfonic charateristic avsorption band, comprehensive above data products contains the groups such as amide group, chain alkyl, sulfonic group.
Utilize nucleus magnetic resonance to analyze the hydrophobic associated polymer obtained in embodiment 3, obtain its hydrogen nuclear magnetic resonance spectrogram, as shown in Figure 2.As shown in Figure 2, δ=0.91 ~ 0.93 (h) is the chemical shift of hydrophobic monomer terminal methyl hydrogen, and δ=1.08 ~ 1.18 (a) is-CH a series of on chain alkyl
2the chemical shift of hydrogen, δ=1.23 ~ 1.61 (b) is methylene radical (-CH on main chain
2) chemical shift of hydrogen, δ=2.11 (c) for the chemical shift of methyne hydrogen (-CH-) hydrogen in main chain, δ=2.61 (d) is and N
+-the CH be connected
3the chemical shift of hydrogen, δ=3.08 ~ 3.30 (e) is-CH be connected with sulfonic group
2the chemical shift of hydrogen, δ=3.52 (i) is for hydrophobic grouping connects N
+-CH
2(two-CH
2be connected) chemical shift of hydrogen, δ=4.7 are solvent D
2o peak, the amide group (-CONH that δ=6.87 ~ 7.68 (f, g) is acrylamide and AMPS
2,-CONH-) and the chemical shift of upper hydrogen.
The hydrophobic associated polymer obtained in embodiment 3 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 132mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 3 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,427 ten thousand.
Embodiment 4
According to the polymerization process in embodiment 1 and step, change the mol ratio of acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium into 85.7:14.2:0.1, obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 4 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 73mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 4 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,404 ten thousand.
Embodiment 5
According to the polymerization process in embodiment 1 and step, change the mol ratio of acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium into 80.8:14.2:5, obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 5 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 64mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 5 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 6,090,000.
Embodiment 6
According to the polymerization process in embodiment 1 and step, change the mol ratio of acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium into 73.8:14.2:12, obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 6 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 25mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 6 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 4,300,000.
Embodiment 7
According to the polymerization process in embodiment 1 and step, change the mol ratio of acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium into 65.8:14.2:20, obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 7 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 6.6mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 7 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,210,000.
Embodiment 8
According to the polymerization process in embodiment 1 and step, hydrophobic monomer is changed into vinylformic acid polyoxyethylene cetyl base ester (polyoxyethylene number of repeat unit is 12), obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 8 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2w%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 98mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 8 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,107 ten thousand.
Embodiment 9
According to the polymerization process in embodiment 1 and step, hydrophobic monomer is changed into vinylformic acid polyoxyethylene stearyl base ester (polyoxyethylene number of repeat unit is 12), obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 9 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-
1under shearing rate, viscosity reaches 87mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 9 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,016 ten thousand.
Embodiment 10
According to the polymerization process in embodiment 1 and step, hydrophobic monomer is changed into hexadecyl phenol polyethenoxy butyl acrylate (polyoxyethylene number of repeat unit is 12), obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 10 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s
-1under shearing rate, viscosity reaches 92mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 10 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 9,030,000.
Embodiment 11
According to the polymerization process in embodiment 1 and step, hydrophobic monomer is changed into 2-acrylamido dodecane sulfonic acid sodium, obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 11 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s
-1under shearing rate, viscosity reaches 135mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 11 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,293 ten thousand.
Embodiment 12
According to the polymerization process in embodiment 1 and step, change function monomer into NVP, obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 12 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s
-1under shearing rate, viscosity reaches 91mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 12 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,032 ten thousand.
Embodiment 13
According to the polymerization process in embodiment 1 and step, just the mol ratio of acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium changes 94.2:5:0.8 into, obtains hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 13 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s
-1under shearing rate, viscosity reaches 122mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 13 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 1,405 ten thousand.
Embodiment 14
According to the polymerization process in embodiment 1 and step, just the mol ratio of acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer octadecyl allyl group dibrominated tetramethyl-second two ammonium changes 71.2:28:0.8 into, obtains hydrophobic associated polymer.
The hydrophobic associated polymer obtained in embodiment 14 is dissolved in 20,000 salinities, in the salt solution of calcium ions and magnesium ions concentration 1000mg/L, is mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s
-1under shearing rate, viscosity reaches 20mPas.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 14 according to GB/T12005.10-92, obtaining its viscosity-average molecular weight is 4,160,000.
Claims (10)
1. a hydrophobic associated polymer, comprises following four repeating units:
Wherein, described y=0.001 ~ 0.2, z=0.005 ~ 0.3, m=0.03 ~ 0.2, x+y+z+m=1; Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer be selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid one or more; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another; Described D is the monomeric unit of function monomer; Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with contain hold in the Hete rocyclic derivatives of thiazolinyl one or more;
The viscosity-average molecular weight of described hydrophobic associated polymer is 50 ~ 1,500 ten thousand.
2. hydrophobic associated polymer according to claim 1, is characterized in that, described y=0.001 ~ 0.1.
3. hydrophobic associated polymer according to claim 1, is characterized in that, described m=0.05 ~ 0.16.
4. hydrophobic associated polymer according to claim 1, it is characterized in that, in described allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid, the carbonatoms of alkyl is 4 ~ 20 independently of one another.
5. hydrophobic associated polymer according to claim 1, is characterized in that, in described alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid, the polyoxyethylated polymerization degree is 7 ~ 20 independently of one another.
6. hydrophobic associated polymer according to claim 1, it is characterized in that, described hydrophobic monomer is hexadecyl allyl group dibrominated Tetramethyl Ethylene Diamine, 2-acrylamido tetradecane sodium sulfonate, 2-acrylamido-2-methyl dodecane sulfonic acid sodium, octyl phenol polyoxyethylene acrylate, Nonyl pheno acrylate, dodecyl polyoxyethylene acrylate, vinylformic acid polyoxyethylene cetyl base ester, vinylformic acid polyoxyethylene stearyl base ester, hexadecyl phenol polyethenoxy acrylate, heptadecyl phenol polyethenoxy acrylate, sodium dodecyl allyl base dibrominated Tetramethyl Ethylene Diamine, one or more in octadecyl allyl group dibrominated Tetramethyl Ethylene Diamine and 2-acrylamido Sodium sterylsulfonate.
7. hydrophobic associated polymer according to claim 1, is characterized in that, the carbonatoms of described function monomer is 2 ~ 20.
8. hydrophobic associated polymer according to claim 1, it is characterized in that, described function monomer is one or more in 2-acrylamide-2-methylpro panesulfonic acid and sulfonate, vinyl sulfonic acid and sulfonate thereof, styrene sulfonic acid and sulfonate thereof and NVP.
9. a preparation method for hydrophobic associated polymer, is characterized in that, comprising:
Under initiator effect, acrylamide monomer, function monomer and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer after hydrolysis;
Or: under hydrolytic reagent existent condition, add the acrylamide triggered monomer of initiator, hydrophobic monomer and function monomer and carry out copolyreaction, obtain hydrophobic associated polymer;
Or: under initiator effect, acrylamide monomer, sodium acrylate monomers, function monomer and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer; Described hydrophobic monomer be selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of vinylformic acid one or more; In described allyl alkyl quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbonatoms of alkyl is less than or equal to 20 independently of one another;
Described function monomer be selected from containing the end sulfonic acid of thiazolinyl and sulfonate derivatives thereof with contain hold in the Hete rocyclic derivatives of thiazolinyl one or more;
The mole number of described hydrophobic monomer and the ratio of total moles monomer are (0.001 ~ 0.2): 1;
The mole number of described function monomer and the ratio of total moles monomer are (0.005 ~ 0.3): 1.
10. the hydrophobic associated polymer described in any line of claim 1 ~ 8 or the application of hydrophobic associated polymer in oilfield chemistry, water treatment, papermaking or mineral floating field prepared by claim 9.
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| WO2017113773A1 (en) * | 2015-12-29 | 2017-07-06 | 四川光亚聚合物化工有限公司 | Hydrophobic associated polymer and preparation method therefor |
| CN106947453A (en) * | 2017-03-28 | 2017-07-14 | 四川光亚聚合物化工有限公司 | A kind of polymer flooding fluid composition and preparation method thereof |
| CN107033293A (en) * | 2017-05-16 | 2017-08-11 | 西南石油大学 | A kind of double tail hydrophobic associated polymers with surface-active and preparation method thereof |
| CN108485632A (en) * | 2018-05-29 | 2018-09-04 | 华东理工大学 | A kind of alkali-free binary oil displacement system and its application |
| CN109265591A (en) * | 2018-09-13 | 2019-01-25 | 西南石油大学 | One kind having the polymer and preparation method of upper critical consolute temperature (UCST) and salt responsiveness |
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| CN104403054A (en) * | 2014-11-27 | 2015-03-11 | 胜利油田胜利化工有限责任公司 | Hydrophobic associated anionic polyacrylamide water-in-water emulsion and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017113773A1 (en) * | 2015-12-29 | 2017-07-06 | 四川光亚聚合物化工有限公司 | Hydrophobic associated polymer and preparation method therefor |
| CN106947453A (en) * | 2017-03-28 | 2017-07-14 | 四川光亚聚合物化工有限公司 | A kind of polymer flooding fluid composition and preparation method thereof |
| CN107033293A (en) * | 2017-05-16 | 2017-08-11 | 西南石油大学 | A kind of double tail hydrophobic associated polymers with surface-active and preparation method thereof |
| CN108485632A (en) * | 2018-05-29 | 2018-09-04 | 华东理工大学 | A kind of alkali-free binary oil displacement system and its application |
| CN109265591A (en) * | 2018-09-13 | 2019-01-25 | 西南石油大学 | One kind having the polymer and preparation method of upper critical consolute temperature (UCST) and salt responsiveness |
| CN109265591B (en) * | 2018-09-13 | 2021-02-23 | 西南石油大学 | Polymer with upper critical eutectic temperature (UCST) and salt responsiveness and preparation method thereof |
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