CN105418862A - Hydrophobic associated polymer and preparation method thereof - Google Patents
Hydrophobic associated polymer and preparation method thereof Download PDFInfo
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- CN105418862A CN105418862A CN201511022812.7A CN201511022812A CN105418862A CN 105418862 A CN105418862 A CN 105418862A CN 201511022812 A CN201511022812 A CN 201511022812A CN 105418862 A CN105418862 A CN 105418862A
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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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Abstract
The invention provides a hydrophobic associated polymer, which comprises the following four repetitive units represented in the description. In the formula, y=0.001 to 0.02, z=0.01 to 0.12, m=0.08-0.3, and x+y+z+m=1; the A represents a monomer unit of hydrophobic monomer, which can be one or more of allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid, acrylamide alkyl sulfonate, alkyl phenol polyoxyethylene acrylate, and polyoxyethylene alkyl acrylate; the D represents a monomer unit of functional monomer, and the viscosity average molecular weight of the hydrophobic associated polymer is in a range of 30 million to 45 million. Compared with the prior art, the provided acrylamide monomer unit of the hydrophobic associated polymer can provide hydrophilic groups; the monomer unit of hydrophobic monomer can provide hydrophobic side groups, the provided polymer can construct spatial network in water and provides viscosity for the solution; monomer unit of acrylic acid ions can improve the solubility of polymer; and the introduction of monomer unit of functional monomer can improve the temperature resistant and salt resistant performance of the polymer.
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, chemical transformation to fluid property, possesses easy construction simultaneously, consumption is few, the plurality of advantages such as 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 ~ 0.02, z=0.01 ~ 0.12, m=0.08 ~ 0.3, 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 3000 ~ 4,500 ten thousand.
Preferably, described y=0.001 ~ 0.01.
Preferably, described m=0.1 ~ 0.25.
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 in alkyl alkyl carbonatoms in the carbonatoms of alkyl be 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 one or more of hexadecyl allyl group dibrominated Tetramethyl Ethylene Diamine, 2-acrylamido tetradecane sodium sulfonate, Nonyl pheno acrylate, dodecyl polyoxyethylene acrylate, vinylformic acid polyoxyethylene cetyl base ester, vinylformic acid polyoxyethylene stearyl base ester, hexadecyl phenol polyethenoxy acrylate, vinylformic acid polyoxyethylene cetyl base ester, heptadecyl phenol polyethenoxy butyl acrylate and 4-dodecylphenol polyoxyethylene acrylate.
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 and hydrophobic monomer carries out copolyreaction, obtain hydrophobic associated polymer;
Or: under initiator effect, acrylamide monomer, Acrylic Acid Monomer and/or 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 ~ 0.02): 1;
The mole number of described function monomer and the ratio of total moles monomer are (0.01 ~ 0.12): 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 ~ 0.02, z=0.01 ~ 0.12, m=0.08 ~ 0.3, 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 3000 ~ 4,500 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 the monomeric unit of acrylamide, and it can be hydrophobic association polymer and provides hydrophilic group, ensures that polymkeric substance has good water-soluble; Hydrophobic units is the monomeric unit of hydrophobic monomer, 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; The monomeric unit of acrylate ionomer can improve the solvability of hydrophobic associated polymer, improves the rheological property of polymkeric substance; Functional unit is the monomeric unit of function monomer, 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.
Accompanying drawing explanation
Fig. 1 is the infrared 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 ~ 0.02, is preferably 0.001 ~ 0.01, is more preferably 0.001 ~ 0.006, then is preferably 0.002 ~ 0.006, most preferably is 0.003 ~ 0.005; Described z=0.01 ~ 0.12, is preferably 0.01 ~ 0.1, is more preferably 0.02 ~ 0.08, most preferably is 0.03 ~ 0.05; Described m=0.08 ~ 0.3, is preferably 0.1 ~ 0.25, is more preferably 0.15 ~ 0.25, then is preferably 0.2 ~ 0.25; X+y+z+m=1; Described m/ (x+m) is preferably 0.08 ~ 0.2, is more preferably 0.1 ~ 0.15.
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 be in hexadecyl allyl group dibrominated Tetramethyl Ethylene Diamine, 2-acrylamido tetradecane sodium sulfonate, Nonyl pheno acrylate, dodecyl polyoxyethylene acrylate, octadecyl allyl group dibrominated Tetramethyl Ethylene Diamine, hexadecyl polyoxyethylene acrylate, vinylformic acid polyoxyethylene cetyl base ester, heptadecyl phenol polyethenoxy acrylate and 4-dodecylphenol polyoxyethylene acrylate one or more.
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 3000 ~ 4,500 ten thousand, is preferably 3200 ~ 4,300 ten thousand, is more preferably 3200 ~ forty-two million, then is preferably 3400 ~ forty-two million, most preferably is 3500 ~ 41,000,000.
Hydrophobic associated polymer of the present invention is made up of four kinds of unit, and hydrophilic unit is the monomeric unit of acrylamide, and it can be hydrophobic association polymer and provides hydrophilic group, ensures that polymkeric substance has good water-soluble; Hydrophobic units is the monomeric unit of hydrophobic monomer, 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; The monomeric unit of acrylate ionomer can improve the solvability of hydrophobic associated polymer, improves the rheological property of polymkeric substance; Functional unit is the monomeric unit of function monomer, and the introducing of these monomers can improve the heat-resistant salt-resistant performance of polymkeric substance; Above-mentioned four kinds of unit interact, and 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 acrylate ionomer, 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 and derivative, 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 ~ 0.02): 1; The mole number of described function monomer and the ratio of total moles monomer are (0.01 ~ 0.12): 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 ~ 0.02), be preferably 1:(0.001 ~ 0.01), be more preferably 1:(0.001 ~ 0.006), be preferably 1:(0.002 ~ 0.006 again), most preferably be 1:(0.003 ~ 0.005); The mole number of described function monomer and the total mol ratio of monomer are (0.01 ~ 0.12): 1, be preferably (0.02 ~ 0.1): 1, be more preferably (0.02 ~ 0.08): 1, most preferably be (0.03 ~ 0.05): 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 0.002% ~ 0.09% of total monomer quality.
In the present invention, copolymerization can be undertaken by water solution polymerization process, micell polymerization method or reverse microemulsion process again.
When carrying out copolymerization by water solution polymerization process, preferably acrylamide monomer, hydrophobic monomer are mixed with function monomer, temperature is adjusted to kick off temperature, then adds initiator, carries 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 ~ 7; In described initiator, the quality optimization of oxygenant is 0.002% ~ 0.09% of acrylamide monomer and hydrophobic monomer total mass, is more preferably 0.002% ~ 0.05%, then is preferably 0.002% ~ 0.03%, most preferably is 0.002% ~ 0.008%; 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-7 DEG C ~ 10 DEG C, is more preferably-7 DEG C ~ 5 DEG C, then is preferably-5 DEG C ~ 0 DEG C; Described copolyreaction is preferably carried out under the condition of thermal insulation; The time of described copolyreaction is preferably 5 ~ 7h.
When copolymerization process is micell polymerization method, preferably acrylamide monomer, hydrophobic monomer are mixed with function monomer, preferably also add tensio-active agent, temperature is adjusted to kick off temperature, then adds initiator, carries 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 5 ~ 7; 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 ~ 30): 1, is more preferably (5 ~ 25): 1, then is preferably (8 ~ 25): 1, most preferably be (10 ~ 25): 1; The quality optimization of described initiator is 0.002% ~ 0.08% of acrylamide monomer, hydrophobic monomer and function monomer total mass, be more preferably 0.002% ~ 0.06%, be more preferably 0.002% ~ 0.04%, then be preferably 0.002% ~ 0.03%, most preferably be 0.002% ~ 0.01%; 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-10 DEG C ~ 10 DEG C, is more preferably-5 DEG C ~ 5 DEG C, then is preferably-5 DEG C ~ 3 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 reverse microemulsion process, 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 (1.5 ~ 2): 1; After mixing, in mixing solutions, total monomer concentration is preferably 20 ~ 35wt%, is more preferably 20 ~ 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 Span class nonionogenic tenside and/or Tween class nonionogenic tenside, be preferably Span class nonionogenic tenside again, most preferably be Span-80; ; 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 0.005% ~ 0.05% of monomer total mass, is more preferably 0.005% ~ 0.03%, then is preferably 0.005% ~ 0.01%; Described kick off temperature is preferably-5 DEG C ~ 15 DEG C, is more preferably-5 DEG C ~ 15 DEG C, then is preferably as-5 DEG C ~ 10 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 reverse microemulsion process copolymerization.
After employing aqueous solution polymerization and micell polymerization method copolyreaction complete, preferably carry out granulating from colloid, be then hydrolyzed; Polymkeric substance after breakdown of emulsion without the need to granulation process, but is hydrolyzed by conversed phase micro emulsion copolymerization after precipitation, dissolving again, dry and pulverizing; The method of described granulation is method well known to those skilled in the art, there is no special restriction; Hydrolytic reagent used in described hydrolytic process is hydrolytic reagent well known to those skilled in the art, there is no special restriction, the present invention is preferably alkali metal hydroxide or alkaline carbonate, 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% ~ 30%, is more preferably 5% ~ 25%, then is preferably 15% ~ 20%.
The object of hydrolysis is to make the acrylamide unit hydrolysis of part copolymerization to form the unit of acrylate ionomer copolymerization formation, therefore the present invention also when reacting beginning with acrylate monomer Substitute For Partial acrylamide monomer, can form the unit that acrylate ionomer copolymerization is formed after hydrolysis.
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, comprising: under hydrolytic reagent existent condition, add the acrylamide triggered monomer of initiator and hydrophobic monomer carries 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 ~ 0.02): 1; The mole number of described function monomer and the ratio of total moles monomer are (0.01 ~ 0.12): 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% ~ 11%.
Copolymerization in the preparation of front method for hydrolysis micro-or reverse microemulsion process can be carried out by water solution polymerization process, micell polymerization method again.Wherein, described water solution polymerization process, micell polymerization method and reverse microemulsion process are all same as above, just while adding acrylamide monomer and hydrophobic monomer, add hydrolytic reagent, do not repeat them here.
After adopting aqueous solution polymerization and micell polymerization method copolyreaction, preferably carry out granulating from colloid, dry, obtain hydrophobic associated polymer; Conversed phase micro emulsion copolymerization without the need to granulation process, but by the polymkeric substance after breakdown of emulsion through precipitation, obtains 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, comprise: under initiator effect, acrylamide monomer, Acrylic Acid Monomer and/or 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 ~ 0.02): 1; The mole number of described function monomer and the ratio of total moles monomer are (0.01 ~ 0.12): 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 described acrylamide monomer, Acrylic Acid Monomer and/or acrylate monomers, function monomer and the integral molar quantity of hydrophobic monomer and the mol ratio of hydrophobic monomer are 1:(0.001 ~ 0.02), be preferably 1:(0.001 ~ 0.01), be more preferably 1:(0.001 ~ 0.006), be preferably 1:(0.002 ~ 0.006 again), most preferably be 1:(0.003 ~ 0.005); The ratio of described Acrylic Acid Monomer and/or the acrylate monomers mole number total with monomer is (0.08 ~ 0.3): 1, be preferably (0.1 ~ 0.25): 1, be more preferably (0.15 ~ 0.25): 1, then be preferably (0.2 ~ 0.25): 1; The mol ratio of described acrylamide monomer and Acrylic Acid Monomer and/or the total molar weight of acrylate monomers and Acrylic Acid Monomer and/or acrylate monomers is preferably 1:(0.04 ~ 0.3), be more preferably 1:(0.1 ~ 0.25).
Copolymerization in cohydrolysis method preparation is also undertaken by water solution polymerization process, micell polymerization method or reverse microemulsion process.Wherein, described water solution polymerization process, micell polymerization method and reverse microemulsion process are all same as above, just replace acrylamide monomer by part propylene acid mono and/or acrylate monomers, do not repeat them here.
Preferably granulating from colloid is carried out again after adopting aqueous solution polymerization and micell polymerization method copolyreaction, dry, obtain hydrophobic associated polymer; Conversed phase micro emulsion copolymerization is without the need to granulation process, but by the polymkeric substance precipitation after breakdown of emulsion, drying, obtains 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 the application of a kind of above-mentioned hydrophobic associated polymer in oilfield chemistry, water treatment, papermaking or mineral floating field.
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 micell polymerization method
By acrylamide monomer, function monomer AMPS and hydrophobic monomer hexadecyl phenol polyethenoxy acrylate (polyoxyethylene repeating unit is 15) feed intake by the mol ratio of 96.7:3:0.3, add in 5000mL beaker to dissolve with pure water and be mixed with the mixing solutions that total monomer is 23wt%, add Sodium dodecylbenzene sulfonate in the ratio of hydrophobic monomer volumetric molar concentration 24 times and stir, beaker is put into-20 DEG C of water-baths insulation until solution temperature is for after-5 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 dosage is the 0.002wt% 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 2.81g/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.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 1, preparation 5000mg/L polymers soln, dissolution time 2.7h, insolubles content is 0.13%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 71mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 84%.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 1 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 3,989 ten thousand.
Embodiment 2 conversed phase micro emulsion copolymerization
Sodium acrylate monomers, acrylamide monomer, function monomer AMPS and hydrophobic monomer hexadecyl phenol polyethenoxy acrylate (polyoxyethylene repeating unit is 15) are joined in deionized water according to mol ratio 15:81.7:3:0.3, abundant dissolving, this solution is as aqueous phase; Add emulsifying agent span-80 to kerosene and be stirred to abundant dissolving, as oil phase.Under high velocity agitation, added by aqueous phase solution in oil phase and make emulsifying agent mass concentration be 15% of monomer mass, emulsification 20min, be transferred in 5000mL beaker, total monomer is 23wt%.Emulsion constant temperature adds ammonium persulphate and sodium bisulfite composite initiator initiated polymerization to when-5 DEG C, and wherein, the quality of ammonium persulphate is 0.005% of monomer mass, ammonium persulphate and sodium bisulfite mass ratio are 5:4, reaction is carried out in-5 DEG C of water-baths, after 4 ~ 6h, obtains white emulsion.
The white emulsion obtained is put into-20 DEG C and carry out freezing broken glue, then shred with dehydrated alcohol repetitive scrubbing, 90 DEG C of dryings, sieve, obtain certain particle diameter dry powder sample and hydrophobic associated polymer.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 2, preparation 5000mg/L polymers soln, dissolution time 2.9h, insolubles content is 0.14%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 72mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 80.6%.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 2 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 4,019 ten thousand.
Embodiment 3 water solution polymerization process
Acrylamide monomer, function monomer AMPS are mixed in 5000mL beaker with hydrophobic monomer tetradecyl allyl group dichloride tetramethyl-second two ammonium, the ratio of three is 96.9:3:0.1, and total monomer is 23wt%.Constant temperature is to after-5 DEG C in a water bath, add initiator initiated polymerization, in initiator, the concentration of oxygenant is 0.002% of monomer mass, wherein ammonium persulphate and sodium bisulfite mass ratio are 5:4, polyreaction is carried out under adiabatic conditions, insert thermometer monitors polyreaction at reaction system center and carry out degree, think that polyreaction completes substantially when temperature in 30min rises above 1 DEG C.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 2.81g/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.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 3, preparation 5000mg/L polymers soln, dissolution time 3.5h, insolubles content is 0.16%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 46mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 88%.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 3 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 4,523 ten thousand.
Embodiment 4
According to the polymerization process in embodiment 3 and step, change the mol ratio of acrylamide monomer, function monomer AMPS and hydrophobic monomer hexadecyl phenol polyethenoxy acrylate (polyoxyethylene repeating unit is 15) into 96.5:3:0.5, obtain hydrophobic associated polymer.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 4, preparation 5000mg/L polymers soln, dissolution time 2.6h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 67mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 87%.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 4 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 3,758 ten thousand.
Embodiment 5
According to the polymerization process in embodiment 3 and step, change the mol ratio of acrylamide monomer, function monomer AMPS and hydrophobic monomer hexadecyl phenol polyethenoxy acrylate (polyoxyethylene repeating unit is 15) into 96:3:1, obtain hydrophobic associated polymer.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 5, preparation 5000mg/L polymers soln, dissolution time 2.3h, insolubles content is 0.1%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 43mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 83%.
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 3,002 ten thousand.
Embodiment 6
According to the polymerization process in embodiment 3 and step, change acrylamide monomer, function monomer NVP (NVP) into 94.9:5:0.1 with the mol ratio of hydrophobic monomer hexadecyl phenol polyethenoxy acrylate (polyoxyethylene repeating unit is 15), obtain hydrophobic associated polymer.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 6, preparation 5000mg/L polymers soln, dissolution time 2.6h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 69mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 86%.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 6 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 3,851 ten thousand.
Embodiment 7
According to the polymerization process in embodiment 3 and step, change the mol ratio of acrylamide monomer, function monomer Sodium styrene sulfonate and hydrophobic monomer hexadecyl phenol polyethenoxy acrylate (polyoxyethylene repeating unit is 15) into 89.9:10:0.1, obtain hydrophobic associated polymer.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 7, preparation 5000mg/L polymers soln, dissolution time 2.3h, insolubles content is 0.1%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 43mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 82%.
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 3,017 ten thousand.
Embodiment 8
According to the polymerization process in embodiment 3 and step, hydrophobic monomer is changed into 2-acrylamido dodecane sulfonic acid sodium, obtain hydrophobic associated polymer.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 8, preparation 5000mg/L polymers soln, dissolution time 2.6h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 45mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 87%.
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 3,712 ten thousand.
Embodiment 9
According to the polymerization process in embodiment 1 and step, hydrophobic monomer is changed into pentadecyl allyl group dichloride Tetramethyl Ethylene Diamine, obtain hydrophobic associated polymer.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 9, preparation 5000mg/L polymers soln, dissolution time 2.5h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 68mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 85%.
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 3,363 ten thousand.
Embodiment 10
According to the polymerization process in embodiment 3 and step, hydrophobic monomer is changed into vinylformic acid polyoxyethylene tetradecyl ester (polyoxyethylene repeating unit is 16), obtain hydrophobic associated polymer.
Total mineralization is adopted to be 80,000 water, Ca
2+, Mg
2+total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in the simulation salt solution of 3000mg/L and embodiment 10, preparation 5000mg/L polymers soln, dissolution time 2.5h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 95 DEG C, and shearing rate is 7.34s
-1lower test polymer viscosity number is 56mPas; Stir 20s through waring agitator speed 3000r/min, viscosity retention ratio is 86%.
Use Ubbelohde viscometer (0.55mm caliber) to test the hydrophobic associated polymer obtained in embodiment 10 by GB/T12005.10-92, obtaining its viscosity-average molecular weight is 3,243 ten thousand.
Claims (10)
1. a hydrophobic associated polymer, comprises following four repeating units:
Wherein, described y=0.001 ~ 0.02, z=0.01 ~ 0.12, m=0.08 ~ 0.3, 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 3000 ~ 4,500 ten thousand.
2. hydrophobic associated polymer according to claim 1, is characterized in that, described y=0.001 ~ 0.01.
3. hydrophobic associated polymer according to claim 1, is characterized in that, described m=0.1 ~ 0.25.
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 in alkyl alkyl carbonatoms in the carbonatoms of alkyl be 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 one or more of hexadecyl allyl group dibrominated tetramethyl-second two ammonium, 2-acrylamido tetradecane sodium sulfonate, Nonyl pheno acrylate, dodecyl polyoxyethylene acrylate, vinylformic acid polyoxyethylene cetyl base ester, vinylformic acid polyoxyethylene stearyl base ester, hexadecyl phenol polyethenoxy acrylate, vinylformic acid polyoxyethylene cetyl base ester, heptadecyl phenol polyethenoxy acrylate and 4-dodecylphenol polyoxyethylene acrylate.
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 and hydrophobic monomer carries out copolyreaction, obtain hydrophobic associated polymer;
Or: under initiator effect, acrylamide monomer, Acrylic Acid Monomer and/or 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 ~ 0.02): 1;
The mole number of described function monomer and the ratio of total moles monomer are (0.01 ~ 0.12): 1.
10. the hydrophobic associated polymer described in claim 1 ~ 8 any one or the application of the hydrophobic associated polymer prepared by claim 9 in oilfield chemistry, water treatment, papermaking or mineral floating field.
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