CN105601806A - Hydrophobic associated polymer and preparation method thereof - Google Patents
Hydrophobic associated polymer and preparation method thereof Download PDFInfo
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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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F2/32—Polymerisation in water-in-oil emulsions
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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Abstract
The invention provides a hydrophobic associated polymer, shown as a formula (I), wherein y is equal to 0.001-0.2, z is equal to 0.03-0.2, and x plus y plus z is equal to 1; A is a monomeric unit of a hydrophobic monomer; the hydrophobic monomer is selected from one or more of allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfoacid and sulfonate thereof, alkylphenol polyoxyethylene acrylate and polyoxyethylene alkyl acrylate. Compared with the prior art, the monomer unit of acrylamide in the hydrophobic associated polymer can provide hydrophilic groups for a hydrophobic association material; the monomeric unit of the hydrophobic monomer can provide hydrophobic lateral groups for the hydrophobic associated polymer and generate a hydrophobic association effect among the hydrophobic lateral groups in water, and thus can provide necessary viscoelasticity for a solution; a sodium acrylate unit can improve the solubleness of the hydrophobic associated polymer; the three units act together, thus improving the salt resistance and the shear-resistant property of the hydrophobic associated polymer. The formula (I) is shown in the description.
Description
Technical field
The invention belongs to technical field of polymer, relate in particular to a kind of hydrophobic associated polymer and preparation side thereofMethod.
Background technology
In oil field development application technology, conventionally need to carry out rebuilding construction etc. to ground environment, need to makeCarry out mass transfer, conveying with the fluid of certain performance, by inject these fluids to stratum, by CucumberBring stratum into and produce work in order to transform ground environment, reach the object of oil-gas field development and volume increase. Meanwhile,Relevant application technology also requires these fluids itself also to possess some specific performance, for example thickening property,Viscoplasticity, drag reduction, permeability, the mobility ratio etc. of improving. Wherein, the most frequently used fluid is exactly the aqueous solution,It has the advantages such as source is wide, economy, constructability, natural or synthetic water-soluble by adding in waterProperty macromolecule, can obtain and have the above high performance aqueous solution. This class water soluble polymer has thickeningThe viscoplasticity that property is strong and good, and on strand, there are a lot of active groups, so that convection cell performance is enteredThe plurality of advantages such as row physics and chemical improvement possess easy construction simultaneously, and consumption is few, and cost is low, canFor bringing higher economic interests in oil field. Therefore, this class water soluble polymer is widely used in oil field skillIn art.
In prior art, the water soluble polymer of use mainly comprises natural or synthetic water-soluble high scoreSon. The yield and quality of natural polymer is owing to being subject to the restriction in season, area, and stability can notBe protected, and with respect to synthetic macromolecule, its consumption is large, easily biological-degradable, higher residue alsoEnvironment in meeting grievous injury stratum, brings many new problems to later development. At present, synthetic macromoleculeMost popular is polyacrylamide, although its various aspects of performance all can reach construction requirement,In pumping procedure, be easy to cause mechanical degradation, solution viscosity declines fast, simultaneously in some high temperature high mineralizationUnder degree reservoir media, polyacrylamide is salt tolerant not, and at high temperature very easily degraded, thereby causes every propertyCan significantly decline, and on the basis of its existing molecular structure, be difficult to further overcome, therefore,From polymer molecular structure, to its modification, to improve, it is anti-shearing, heat-resistant salt-resistant performance has been to compel at eyebrowEyelash.
For the problem of above-mentioned existence, researchers have proposed water-soluble hydrophobic associated polymerization on this basisThing. Water-soluble hydrophobic associated polymer (HAWSP) refer on polymer hydrophilicity macromolecular chain withThe water-soluble polymer of a small amount of hydrophobic grouping. In the aqueous solution, HAWSP concentration is higher than critical association concentrationAfter, macromolecular chain is assembled by hydrophobic association polymer effect, forms Interpolymer Association moving without chemical crosslinkingState physical cross-linked network, increases substantially solution viscosity. Meanwhile, adding also of some surfactantThe hydrophobic effect that can strengthen polymer molecule interchain, makes Interpolymer Association dynamic physical cross-linked network intensityIncrease, the supermolecule physical cross-linked network existing in HAWSP and surfactant solution also makes this moltenLiquid has the characteristic of frozen glue, thereby good viscoplasticity is provided. In addition, this supermolecule dynamic physical is crosslinkedNetwork have under high-rate of shear destroy and under low shear rate the feature of reversible recovery, make itStable performance, and possess excellent heatproof, salt tolerance, good shear thinning behavior, viscoplasticity etc. ThisSome excellent performances all show that hydrophobic associated polymer has that existing common oil field water dissolubility is high as an alternativeThe potentiality of molecule.
The present invention considers to provide a kind of new hydrophobic association polymer polymer.
Summary of the invention
In view of this it is good that, the technical problem to be solved in the present invention is to provide a kind of new salt resistant characterHydrophobic association polymer polymer and preparation method thereof.
The invention provides a kind of hydrophobic associated polymer, shown in (I):
Wherein, described y=0.001～0.2, z=0.03～0.2, x+y+z=1; Described A is the list of hydrophobic monomerBody unit; Described hydrophobic monomer is selected from pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and sulfonic acid thereofOne or more in salt, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid; InstituteState the carbon number of alkyl in pi-allyl alkyl quaternary ammonium salts and acrylamide alkyl sulfonic acid and sulfonate thereof separatelyBe less than or equal to independently 20;
The viscosity average molecular weigh of described hydrophobic associated polymer is 50～1,500 ten thousand.
Preferably, described y=0.005～0.1.
Preferably, described z=0.05～0.16.
Preferably, alkyl in described pi-allyl alkyl quaternary ammonium salts and acrylamide alkyl sulfonic acid and sulfonate thereofCarbon number be 4～20 independently of one another.
Preferably, alkyl in described alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acidCarbon number be 4～20 independently of one another.
Preferably, polyoxy in described alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acidThe degree of polymerization of ethene is 7～20 independently of one another.
Preferably, described hydrophobic monomer is cetyl pi-allyl dibrominated tetramethylethylenediamine, 2-acryloylAmido tetradecane sodium sulfonate, 2-acrylamido-2-methyl dodecane sulfonic acid sodium, octyl phenol polyoxy ethylene propyleneOlefin(e) acid ester, Nonyl pheno acrylate, dodecyl polyoxyethylene acrylate, octadecylPi-allyl dibrominated tetramethylethylenediamine, acrylic acid polyoxyethylene cetyl ester, acrylic acid polyoxyethyleneStearyl, heptadecyl phenol polyethenoxy acrylate, dodecyl pi-allyl dibrominated tetramethylEthylenediamine, 2-acrylamido Sodium sterylsulfonate, with cetyl phenol polyethenoxy acrylate in oneKind or multiple. Preferably, the viscosity average molecular weigh of described hydrophobic associated polymer is 400～1,500 ten thousand.
The present invention also provides a kind of preparation method of hydrophobic associated polymer, comprising:
Under initator effect, acrylamide monomer and hydrophobic monomer carry out copolyreaction, after hydrolysis, obtainHydrophobic associated polymer;
Or: under the condition existing at hydrolytic reagent, add the acrylamide triggered monomer of initator and hydrophobic listBody carries out copolyreaction, obtains hydrophobic associated polymer;
Or: under initator effect, acrylamide monomer, sodium acrylate monomers and hydrophobic monomer carry outCopolyreaction, obtains hydrophobic associated polymer;
Described hydrophobic monomer be selected from pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and sulfonate thereof,One or more in the polyxyethylated ester of alkylphenol-polyethenoxy acrylate and acrylic acid; Described alkeneIn propyl group alkyl quaternary ammonium salts and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbon number of alkyl is less than or equal to20；
The molal quantity of described hydrophobic monomer is (0.001～0.2) with the ratio of total moles monomer: 1.
The present invention also provides hydrophobic associated polymer at oilfield chemistry, water treatment, papermaking or mineral floatingApplication in field.
The invention provides a kind of hydrophobic associated polymer, shown in (I), described y=0.001～0.2,Z=0.03～0.2, x+y+z=1; Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer is selected from alkenePropyl group alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylateWith one or more in the polyxyethylated ester of acrylic acid; Described pi-allyl alkyl quaternary ammonium salts and acryloylIn amine alkyl sulfonic acid and sulfonate thereof, the carbon number of alkyl is less than or equal to 20; Described hydrophobic associated polymerViscosity average molecular weigh be 50～1,500 ten thousand. Compared with prior art, hydrophobic associated polymer of the present invention is by threePlant unit composition, hydrophilic unit participates in copolymerization by acrylamide and forms, and it can be hydrophobic association polymer parent is providedThe group of water-based, ensures that polymer has good water-soluble; Hydrophobic units is that hydrophobic monomer participates in copolymerizationForm, it can be hydrophobic associated polymer hydrophobic side group is provided, and ensures that polymer chain has certain hydrophobicCharacteristic produces hydrophobic association effect between each hydrophobic side group in water, forms spacial framework, fromAnd provide necessary viscoplasticity for solution; PAA can improve the dissolubility of hydrophobic associated polymer; OnState three kinds of unit actings in conjunction, improved salt tolerance and the anti-shear performance of hydrophobic associated polymer.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the product of polymerisation in the embodiment of the present invention 1;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the product of polymerisation in the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with the accompanying drawing of the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clearlyChu, intactly description, obviously, described embodiment is only the present invention's part embodiment, and notWhole embodiment. Based on the embodiment in the present invention, those of ordinary skill in the art are not makingThe every other embodiment obtaining under creative work prerequisite, belongs to the scope of protection of the invention.
The invention provides a kind of hydrophobic associated polymer, shown in (I):
Wherein, described y=0.001～0.2, is preferably 0.005～0.15, and more preferably 0.005～0.1, optimumElect 0.005～0.05 as; Described z=0.03～0.2, is preferably 0.03～0.16, and more preferably 0.05～0.16,Most preferably be 0.1～0.16; X+y+z=1; Described z/ (x+z) is preferably 0.04～0.2, more preferably0.08～0.16。
Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer be selected from pi-allyl alkyl quaternary ammonium salts,Acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and acrylic acid polyoxyethyleneOne or more in Arrcostab, be preferably pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid andOne in sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid; DescribedIn pi-allyl alkyl quaternary ammonium salts and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbon number of alkyl is only separatelyOn the spot be less than or equal to 20, be preferably 4～20, more preferably 6～20, then be preferably 10～20; Alkyl phenol is poly-In the polyxyethylated ester of oxygen ethylene-acrylate and acrylic acid, the carbon number of alkyl is preferred independently of one anotherFor being less than or equal to 20, more preferably 4～20, then be preferably 6～20, most preferably be 10～20; Described alkylIn the polyxyethylated ester of phenol polyethenoxy acrylate and acrylic acid, the polyoxyethylated degree of polymerization is independent separatelyBe preferably 7～20, more preferably 10～20. In the present invention, described hydrophobic monomer most preferably is hexadecaneBase pi-allyl dibrominated tetramethylethylenediamine, 2-acrylamido tetradecane sodium sulfonate, 2-acrylamido-2-Methyl dodecane sulfonic acid sodium, octyl phenol polyoxy ethylene-acrylate, Nonyl pheno acrylate,Dodecyl polyoxyethylene acrylate, octadecyl pi-allyl dibrominated tetramethylethylenediamine, acrylic acidPolyoxyethylene cetyl ester, acrylic acid polyoxyethylene stearyl, heptadecyl phenol polyethenoxy thirdOlefin(e) acid ester, dodecyl pi-allyl dibrominated tetramethylethylenediamine, 2-acrylamido Sodium sterylsulfonate,With one or more in cetyl phenol polyethenoxy acrylate. Gluing of described hydrophobic associated polymerAverage molecular weight is 50～1,500 ten thousand, is preferably 100～1,500 ten thousand, more preferably 300～1,500 ten thousand, more excellentElect 500～1,500 ten thousand as, most preferably be 700～1,300 ten thousand.
Hydrophobic associated polymer of the present invention is made up of three kinds of unit, and hydrophilic unit participates in copolymerization by acrylamideForm, it can be hydrophobic association polymer hydrophilic group is provided, and ensures that polymer has good water-soluble;Hydrophobic units is that hydrophobic monomer participates in copolymerization formation, and it can be hydrophobic associated polymer hydrophobic side group is provided,Ensure that polymer chain has certain hydrophobic property, in water, between each hydrophobic side group, produce hydrophobic associationEffect, forms spacial framework, thereby provides necessary viscoplasticity for solution; PAA can improveThe dissolubility of hydrophobic associated polymer; Above-mentioned three kinds of unit actings in conjunction, have improved hydrophobic associated polymerSalt tolerance and anti-shear performance.
The present invention also provides a kind of preparation method of above-mentioned hydrophobic associated polymer, and the method is later waterThe mode of separating is introduced PAA, comprising: under initator effect, by acrylamide monomer and hydrophobic listBody carries out copolyreaction, obtains hydrophobic associated polymer after hydrolysis; Described hydrophobic monomer is selected from pi-allyl alkaneBased quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and propyleneOne or more in the polyxyethylated ester of acid; Described pi-allyl alkyl quaternary ammonium salts and acrylamide alkylIn sulfonic acid and sulfonate thereof, the carbon number of alkyl is less than or equal to 20; The molal quantity of described hydrophobic monomer and listThe ratio of body total mole number is (0.001～0.2): 1.
Wherein, described hydrophobic monomer is same as above, does not repeat them here; Described acrylamide monomer, thirdThe total mole number of olefin(e) acid sodium monomer and hydrophobic monomer and the mole ratio of hydrophobic monomer are 1:(0.001～0.2),Be preferably 1:(0.005～0.15), more preferably 1:(0.005～0.1), most preferably be 1:(0.005～0.05).Described initator is initator well known to those skilled in the art, there is no special restriction, the present inventionIn be preferably persulfate and sulfite oxidation reduction initiator system; Described persulfate and sulfurous acidSalt redox initiator system is redox initiator system well known to those skilled in the art,There is no special restriction, the mass ratio of persulfate described in the present invention and sulphite is preferably (1～3):1; In described initator, the quality of oxidant is total monomer quality 0.05%～1%.
In the present invention, copolymerization can be entered by water solution polymerization process, micell polymerization method or antiphase emulsifiable method againOK.
In the time carrying out copolymerization by water solution polymerization process, preferably acrylamide monomer is mixed with hydrophobic monomer,Be heated to initiation temperature, then add initator, carry out copolyreaction. Wherein, copolyreaction is preferably at waterIn carry out, acrylamide monomer and hydrophobic monomer total mass concentration in the aqueous solution is preferably 15%～30%,More preferably 20%～30%; The pH value of mixing rear solution is preferably 5～13; In described initator, be oxidizedThe quality optimization of agent is 0.1%～1% of acrylamide monomer and hydrophobic monomer gross mass, more preferably0.1%～0.6%, then be preferably 0.1%～0.4%; The quality of persulfate and sulphite in described initatorThan being preferably (1.7～1): 1, more preferably (1～1.5): 1; Described initiation temperature is preferably 30 DEG C～45 DEG C,More preferably 35 DEG C～45 DEG C; Described copolyreaction is preferably carried out under adiabatic condition; Described copolyreactionTime be preferably 5～7h.
In the time that copolymerization is micell polymerization method, preferably acrylamide monomer is mixed with hydrophobic monomer, preferably alsoAdd surfactant, be heated to initiation temperature, then add initator, carry out copolyreaction. Wherein,Described copolyreaction is preferably carried out in water; Described acrylamide monomer and hydrophobic monomer are total in the aqueous solutionMass concentration be preferably 12%～35%, more preferably 20%～35%, then be preferably 20%～30%; MixedThe pH value of closing rear solution is preferably 4～10; Described surfactant is preferably anion surfactant,More preferably a kind of in dodecyl sodium sulfate, lauryl sodium sulfate and neopelex orMultiple; The mol ratio of described surfactant and hydrophobic monomer is preferably (2～30): 1, more preferably(5～25): 1, then be preferably (5～20): 1, most preferably be (5～15): 1; Described initatorQuality optimization is 0.05%～1% of monomer gross mass, more preferably 0.08%～0.8%, more preferably0.1%～0.5%, most preferably be 0.1%～0.3%; The quality of persulfate and sulphite in described initatorThan being (5:3)～(1:1), more preferably (4:3)～(1:1); Described initiation temperature is preferredBe 30 DEG C～60 DEG C, more preferably 30 DEG C～50 DEG C, then be preferably 35 DEG C～45 DEG C; Described copolyreaction is excellentBe selected under adiabatic condition and carry out; The time of described copolyreaction is preferably 5～7h, more preferably when reaction bodyIn the temperature 30min of system, rise and be no more than 1 DEG C, reaction finishes.
In the time carrying out copolymerization by antiphase emulsifiable method, preferably carry out in accordance with the following methods: will gather propionamide listBody is soluble in water, as water; Hydrophobic monomer is dissolved in oil solvent, preferably also adds emulsifying agent, doFor oil phase; Water is mixed with oil phase, be heated to initiation temperature, then add initator, carry out copolymerization anti-Should. Wherein, described oil solvent is oil solvent well known to those skilled in the art, there is no special limitSystem, is preferably one or more in kerosene, white oil and atoleine, more preferably kerosene in the present invention;The oil-water ratio of described oil solvent and water is preferably (1～1.5): 1; Total monomer concentration in mixed solution after mixingBe preferably 20～35wt%, more preferably 25～30wt%; Described emulsifying agent is known for those skilled in the artEmulsifying agent, there is no special restriction, in the present invention, be preferably HLB value and be 6～8 nonionic tableSurface-active agent, more preferably Span class non-ionic surface active agent and/or Tween class non-ionic surface are livedProperty agent, then be preferably Span class non-ionic surface active agent and Tween class non-ionic surface active agent,Be preferably Span-80 and Tween-20; Described Span class non-ionic surface active agent and Tween class are non-The mass ratio of ionic surface active agent is preferably (5～15): 2, and more preferably (6～10): 2, optimumElect 8:2 as; The quality optimization of described emulsifying agent is 10%～20% of monomer gross mass, more preferably12%～18%, then be preferably 14%～18%; In described initator, the quality optimization of oxidant is the total matter of monomer0.1%～0.5%, more preferably 0.1%～0.3% of amount, then be preferably 0.1%～0.2%; Described initiation temperatureBe preferably 30 DEG C～45 DEG C, more preferably 35 DEG C～45 DEG C; The time of described copolyreaction is preferably 5～7h,More preferably 4～6h; After adopting antiphase emulsifiable method copolymerization, preferably also carry out breakdown of emulsion processing.
After copolyreaction completes, preferably carry out granulation, be then hydrolyzed; The method of described granulation isMethod well known to those skilled in the art, there is no special restriction; The hydrolytic reagent that described hydrolysis is usedFor hydrolytic reagent well known to those skilled in the art, there is no special restriction, the present invention is preferably alkali goldBelong to hydroxide, more preferably potassium hydroxide and/or NaOH, then be preferably NaOH; Described waterThe temperature of separating is preferably 70 DEG C～100 DEG C, and more preferably 80 DEG C～100 DEG C, then be 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%, more preferably5%～20%, then be preferably 10%～20%.
After hydrolysis, be preferably dried and obtain hydrophobic associated polymer; Described dry temperature is preferably 80 DEG C～95 DEG C; The described dry time is preferably 0.5～4h, more preferably 0.5～3h, then be preferably 1～2h.
The present invention also provides a kind of front Hydrolyze method to prepare the method for above-mentioned hydrophobic associated polymer, comprising:Under the condition existing at hydrolytic reagent, add the acrylamide triggered monomer of initator and hydrophobic monomer to carry out copolymerizationReaction, obtains hydrophobic associated polymer; Preferably after copolyreaction completely, continue slaking certain hour,To hydrophobic associated polymer. Described hydrophobic monomer is selected from pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulphurOne in acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acidOr multiple; The carbon of alkyl in described pi-allyl alkyl quaternary ammonium salts and acrylamide alkyl sulfonic acid and sulfonate thereofAtomicity is less than or equal to 20; The molal quantity of described hydrophobic monomer with the ratio of total moles monomer is(0.001～0.2)：1。
Wherein, described acrylamide monomer, hydrophobic monomer and initator are all same as above, no longer superfluous at thisState; Described hydrolytic reagent is hydrolytic reagent well known to those skilled in the art, there is no special restriction, thisIn invention, be preferably alkali metal hydroxide, more preferably potassium hydroxide and/or NaOH, then be preferablyNaOH; The amount that described hydrolytic reagent adds is 0.4%～20% of monomer gross mass, more preferably1%～15%, then be preferably 2%～10%.
Copolymerization in front method for hydrolysis preparation can be passed through again water solution polymerization process, micell polymerization method or anti-phaseEmulsion method carries out. Wherein, all the same institutes of described water solution polymerization process, micell polymerization method and antiphase emulsifiable methodState, just in adding acrylamide monomer and hydrophobic monomer, add hydrolytic reagent, at this no longerRepeat.
After copolyreaction, preferably carry out granulation, dry, obtain hydrophobic associated polymer; Described granulationMethod is method well known to those skilled in the art, there is no special restriction; Described dry temperatureBe preferably 80 DEG C～95 DEG C; The described dry time is preferably 0.5～4h, more preferably 0.5～3h, more excellentElect 1～2h as.
The present invention also provides a kind of method that adopts cohydrolysis to prepare above-mentioned hydrophobic associated polymer, comprising:Under initator effect, acrylamide monomer, sodium acrylate monomers and hydrophobic monomer carry out copolyreaction,Obtain hydrophobic associated polymer; Described hydrophobic monomer is selected from pi-allyl alkyl quaternary ammonium salts, acrylamide alkylIn sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid oneKind or multiple; Alkyl in described pi-allyl alkyl quaternary ammonium salts and acrylamide alkyl sulfonic acid and sulfonate thereofCarbon number is less than or equal to 20; The molal quantity of described hydrophobic monomer with the ratio of total moles monomer is(0.001～0.2)：1。
Wherein, described hydrophobic monomer and initator are all same as above, do not repeat them here; At co-hydrolysisPrepare hydrophobic associated polymer and be that part propylene amide monomer sodium acrylate monomers is substituted, therefore described inThe total mole number of acrylamide monomer, sodium acrylate monomers and hydrophobic monomer and the mole ratio of hydrophobic monomerFor 1:(0.001～0.2), be preferably 1:(0.005～0.15), more preferably 1:(0.005～0.1),Most preferably be 1:(0.005～0.05); The ratio of the total molal quantity of described sodium acrylate monomers and monomer is(0.03～0.2): 1, be preferably (0.03～0.16): 1, more preferably (0.05～0.16): 1, thenBe preferably (0.1～0.16): 1; The mole that described acrylamide monomer and sodium acrylate monomers are total and thirdThe mol ratio of olefin(e) acid sodium monomer is preferably 1:(0.04～0.2), more preferably 1:(0.08～0.16).
Copolymerization in cohydrolysis method preparation also can be passed through water solution polymerization process, micell polymerization method or anti-phase breastLiquid method is carried out. Wherein, described water solution polymerization process, micell polymerization method antiphase emulsifiable method are all same as above,Just replace part propylene amide monomer by sodium acrylate monomers, do not repeat them here.
After copolyreaction, preferably carry out slaking, more preferably carry out granulation, dry, obtain hydrophobic association poly-Compound; The method of described granulation is method well known to those skilled in the art, there is no special restriction;Described dry temperature is preferably 80 DEG C～95 DEG C; The described dry time is preferably 0.5～4h, more preferablyBe 0.5～3h, then be preferably 1～2h.
The present invention adopts initator to prepare hydrophobic associated polymer, and composite initiator is decomposed to form list in waterBody free radical, monomer free radical and vinyl monomer carry out addition, form monomer free radical, i.e. spike;Then monomer free radical is opened the π key of other vinyl monomer molecules, adds and is shaped as new free radical. Like thisThe new radical reaction activity forming can not decay, and continues to carry out adding of interlock type with vinyl monomerBecome, and carry out in this manner chain propagation reaction. Between two chain free radicals, there is active collision,Double-basis cessation reaction occurs, and polymerisation finishes, and forms polymeric colloid.
The present invention also provide a kind of above-mentioned hydrophobic associated polymer oilfield chemistry, water treatment, papermaking withOr application in mineral floating field.
In order to further illustrate the present invention, below in conjunction with embodiment to a kind of hydrophobic association provided by the inventionPolymer and preparation method thereof is described in detail.
In following examples, reagent used is commercially available.
Embodiment 1
Acrylamide and cetyl pi-allyl dibrominated tetramethyl second two ammoniums are entered by the mol ratio of 99:1.0Row feeds intake, and joins in 5000mL beaker to dissolve with pure water that to be mixed with monomer total mass concentration be 25%Mixed solution, puts into 45 DEG C of water-baths insulation by beaker until after solution temperature is 45 DEG C, add persulfuric acidPotassium and sodium hydrogensulfite composite initiator initiated polymerization, wherein potassium peroxydisulfate and sodium hydrogensulfite mass ratio are1:1, potassium peroxydisulfate dosage is 0.10% of monomer gross mass. Polymerisation is carried out under adiabatic environment,Reaction system center is inserted thermometer monitoring polymerisation and is carried out degree, when temperature rise in 30 minutes does not surpassWhile crossing 1 DEG C, think that polymerisation completes substantially. 1h after polymerisation completes, takes out colloid, and colloid is cutBe slit into 3～5mm size particles, add the hydrolytic reagent NaOH that accounts for colloid gross mass 2.4%, mix,Then be transferred in polybag and seal, in constant temperature oven, 95 DEG C of hydrolysis 2h of constant temperature are (while should be noted that sealingDeaeration as far as possible, and retain the ammonia producing when enough spaces hold hydrolysis, sealing while noting hydrolysisBag does not break). After being hydrolyzed, colloid is spread out and paved on 500 eye mesh screens, put into baking oven perseverance95 DEG C of dry 1h of temperature, take out the acquisition hydrophobic associated polymer that sieves.
Utilize infrared spectrum to analyze the product of polymerisation in embodiment 1, obtain its infrared spectrum,As shown in Figure 1. As shown in Figure 1, in Fourier's infrared spectrogram, 3571cm-1And 3184cm-1Place is returnedBelong to antisymmetry and the symmetrical stretching vibration peak of N-H key; 2942cm-1And 1454cm-1Belong to respectivelyThe stretching vibration peak of c h bond and flexural vibrations peak, 1673cm-1Belonging to acid amides I shakes with the flexible of C=OMoving peak, 1611cm-1Belong to the flexural vibrations peak of acid amides II with N-H; Comprehensive above data product containsThe group such as amide groups, alkyl.
Utilize nuclear magnetic resonance to analyze the product of polymerisation in embodiment 1, obtain its nuclear magnetic resonanceHydrogen spectrogram, as shown in Figure 2. As shown in Figure 2, at δ=2.1ppm, there are two strong peaks at 1.55ppm place,Area Ratio is 2:1, can illustrate and in product, have a large amount of-CH2-and-CH-structure, and this polymerization justThe chemical shift of hydrogen on methylene and methine on the main chain of thing; Alkane in hydrophobic monomer at δ=1.07ppmSerial methylene (CH on base chain2) chemical shift of hydrogen; δ=3.5ppm place occurs that peak is hydrophobic monomerN+-CH3And N+-CH2The chemical shift of upper hydrogen; The weak peak occurring at δ=0.91ppm place is hydrophobic monomerTerminal methyl-CH3The displacement of hydrogen; δ=6.7ppm is acrylamide amide groups (CONH2) the above change of hydrogenDisplacement study; δ=4.70ppm is the peak of solvent heavy water.
Utilize Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 1To hydrophobic associated polymer test, calculating its viscosity average molecular weigh is 1,350 ten thousand.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution of preparation in embodiment 1, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 127mPas.
Embodiment 2 adds monomer and neopelex surfactant in 5000mL beaker,Wherein acrylamide monomer and hydrophobic monomer cetyl pi-allyl dibrominated tetramethyl second two ammoniums are pressed 99:1.0Mol ratio feed intake, add quantitative pure water, stir and be mixed with monomer total mass concentration and be25% mixed solution, adds neopelex and fully stirs by 5 times of hydrophobic monomer molar concentrationMix evenly, beaker is put into 45 DEG C of water-baths insulations until after solution temperature is 45 DEG C, add potassium peroxydisulfateWith sodium hydrogensulfite composite initiator initiated polymerization, wherein potassium peroxydisulfate and sodium hydrogensulfite mass ratio are 1:1, potassium peroxydisulfate addition is monomer mass 0.10%; Polymerisation is carried out under adiabatic environment, insteadAnswer system center to insert thermometer monitoring polymerisation and carry out degree, when temperature rise in 30 minutes is no more than1 DEG C time, think that polymerisation completes substantially. 1h after polymerisation completes, takes out colloid, and colloid is cutBecome 3～5mm size particles, add the hydrolytic reagent NaOH that accounts for colloid gross mass 2.4%, mix,Then transfer in polybag and seal, then in constant temperature oven, 95 DEG C of hydrolysis 2h of constant temperature (should be noted that closeThe deaeration of trying one's best when envelope, and retain the ammonia producing when enough spaces hold hydrolysis, while noting hydrolysisSealing bag does not break). After being hydrolyzed, colloid is spread out and paved on 500 eye mesh screens, put into baking95 DEG C of dry 1h of case constant temperature, take out the acquisition hydrophobic associated polymer that sieves.
Utilize Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 2The hydrophobic associated polymer obtaining is tested, and calculating its viscosity average molecular weigh is 8,900,000.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution obtaining in embodiment 2, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 102mPas.
Embodiment 3
By sodium acrylate monomers, acrylamide monomer and hydrophobic monomer cetyl pi-allyl dibrominated tetramethylBase second two ammoniums join in deionized water, fully dissolve, and this solution is as water; In kerosene, add matterAmount is than the compound emulsifying agent for Span-80:Tween-20=8:2 composition and be stirred to abundant dissolving, asOil phase. Under high-speed stirred, aqueous phase solution is added in oil phase and carries out emulsification 20min, be then transferred toIn 5000mL beaker, wherein monomer total mass concentration is 25%, acrylamide monomer, PAA listBody, with hydrophobic monomer cetyl pi-allyl dibrominated tetramethyl second two ammonium three mol ratios be 83:16:1,Compound emulsifying agent additive capacity is 18% of total system quality. When 45 DEG C of emulsion constant temperature, add and account for monomer matterPotassium peroxydisulfate and sodium hydrogensulfite composite initiator initiated polymerization, wherein potassium peroxydisulfate and the sulfurous of amount 0.10%Acid hydrogen sodium mass ratio is 1:1, and reaction is carried out in 45 DEG C of water-baths, after reaction 4～6h, react and substantially complete,Obtain white emulsion.
Add absolute ethyl alcohol to carry out breakdown of emulsion the white emulsion obtaining, precipitation, centrifugation, gained is heavyAbsolute ethanol washing 3 times of shallow lake thing, put into 95 DEG C of dry 1h of baking oven constant temperature, through pulverizing, sieving, obtainCertain particle diameter dry powder sample is hydrophobic associated polymer.
Utilize Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 3The hydrophobic associated polymer obtaining is tested, and calculating its viscosity average molecular weigh is 8,640,000.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution obtaining in embodiment 3, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 95mPas.
Embodiment 4
According to the polymerization in embodiment 1 and step, by acrylamide monomer and hydrophobic monomer hexadecaneA mole proportioning for base pi-allyl dibrominated tetramethyl second two ammoniums changes 99.5:0.5 into, obtains hydrophobic association polymerizationThing.
Use Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 5To hydrophobic associated polymer test, calculating its viscosity average molecular weigh is 1,510 ten thousand.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution obtaining in embodiment 4, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 90mPas. .
Embodiment 5
According to the polymerization in embodiment 1 and step, by acrylamide monomer and hydrophobic monomer hexadecaneA mole proportioning for base pi-allyl dibrominated tetramethyl second two ammoniums changes 95:5 into, obtains hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 5The hydrophobic associated polymer obtaining is tested, and calculating its polymer viscosity average molecular weigh is 6,900,000.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution obtaining in embodiment 5, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 42mPas.
Embodiment 6
According to the polymerization in embodiment 1 and step, by acrylamide monomer and hydrophobic monomer hexadecaneA mole proportioning for base pi-allyl dibrominated tetramethyl second two ammoniums changes 88:12 into, obtains hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 6The hydrophobic associated polymer obtaining is tested, and calculating its viscosity average molecular weigh is 3,050,000.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution obtaining in embodiment 6, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 25mPas.
Embodiment 7
According to the polymerization in embodiment 1 and step, by hydrophobic monomer cetyl pi-allyl dibrominatedTetramethyl second two ammoniums replace with 2-acrylamido tetradecane sodium sulfonate, obtain hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 7To hydrophobic associated polymer test, calculating its viscosity average molecular weigh is 1,480 ten thousand.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution obtaining in embodiment 7, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 113mPa·s。
Embodiment 8
According to the polymerization in embodiment 1 and step, by hydrophobic monomer cetyl pi-allyl dibrominatedTetramethyl second two ammoniums replace with Nonyl pheno (10) acrylate, obtain hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 8To hydrophobic associated polymer test, calculating its viscosity average molecular weigh is 7,800,000.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution obtaining in embodiment 8, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 89mPas.
Embodiment 9
According to the polymerization in embodiment 1 and step, by hydrophobic monomer cetyl pi-allyl dibrominatedTetramethyl second two ammoniums replace with dodecyl polyoxyethylene (20) acrylate, obtain hydrophobic association polymerizationThing.
Use Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 9To hydrophobic associated polymer test, calculating its viscosity average molecular weigh is 1,052 ten thousand.
Adopting total salinity is 20,000 water, Ca2+、Mg2+Total ion concentration is the simulation salt solution of 1000mg/LWith the hydrophobic associated polymer prepared polymer solution obtaining in embodiment 9, when polymer solution concentration is2000mg/L, temperature is 80 DEG C, shear rate is 7.34s-1Lower test polymer viscosity number is 104mPa·s。
Claims (10)
1. a hydrophobic associated polymer, shown in (I):
Wherein, described y=0.001～0.2, z=0.03～0.2, x+y+z=1; Described A is the list of hydrophobic monomerBody unit; Described hydrophobic monomer is selected from pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and sulfonic acid thereofOne or more in salt, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid; InstituteState the carbon number of alkyl in pi-allyl alkyl quaternary ammonium salts and acrylamide alkyl sulfonic acid and sulfonate thereof separatelyBe less than or equal to independently 20;
The viscosity average molecular weigh of described hydrophobic associated polymer is 50～1,500 ten thousand.
2. hydrophobic associated polymer according to claim 1, is characterized in that, described iny＝0.005～0.1。
3. hydrophobic associated polymer according to claim 1, is characterized in that, described inz＝0.05～0.16。
4. hydrophobic associated polymer according to claim 1, is characterized in that, described pi-allyl alkaneIn based quaternary ammonium salt and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbon number of alkyl is independently of one another4～20。
5. hydrophobic associated polymer according to claim 1, is characterized in that, described alkyl phenol is poly-In the polyxyethylated ester of oxygen ethylene-acrylate and acrylic acid, the carbon number of alkyl is independently of one another4～20。
6. hydrophobic associated polymer according to claim 1, is characterized in that, described alkyl phenol is poly-In the polyxyethylated ester of oxygen ethylene-acrylate and acrylic acid, the polyoxyethylated degree of polymerization is independently of one another7～20。
7. hydrophobic associated polymer according to claim 1, is characterized in that, described hydrophobic monomerFor cetyl pi-allyl dibrominated tetramethylethylenediamine, 2-acrylamido tetradecane sodium sulfonate, 2-propyleneAmide groups-2-methyl dodecane sulfonic acid sodium, octyl phenol polyoxy ethylene-acrylate, Nonyl pheno thirdOlefin(e) acid ester, dodecyl polyoxyethylene acrylate, octadecyl pi-allyl dibrominated tetramethylethylenediamine,Acrylic acid polyoxyethylene cetyl ester, acrylic acid polyoxyethylene stearyl, heptadecyl phenol polyoxyEthylene-acrylate, dodecyl pi-allyl dibrominated tetramethylethylenediamine, 2-acrylamido octadecane sulphurAcid sodium, with cetyl phenol polyethenoxy acrylate in one or more.
8. hydrophobic associated polymer according to claim 1, is characterized in that, described hydrophobic associationThe viscosity average molecular weigh of polymer is 400～1,500 ten thousand.
9. a preparation method for hydrophobic associated polymer, is characterized in that, comprising:
Under initator effect, acrylamide monomer and hydrophobic monomer carry out copolyreaction, after hydrolysis, obtainHydrophobic associated polymer;
Or: under the condition existing at hydrolytic reagent, add the acrylamide triggered monomer of initator and hydrophobic listBody carries out copolyreaction, obtains hydrophobic associated polymer;
Or: under initator effect, acrylamide monomer, sodium acrylate monomers and hydrophobic monomer carry outCopolyreaction, obtains hydrophobic associated polymer;
Described hydrophobic monomer be selected from pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and sulfonate thereof,One or more in the polyxyethylated ester of alkylphenol-polyethenoxy acrylate and acrylic acid; Described alkeneIn propyl group alkyl quaternary ammonium salts and acrylamide alkyl sulfonic acid and sulfonate thereof, the carbon number of alkyl is less than or equal to20；
The molal quantity of described hydrophobic monomer is (0.001～0.2) with the ratio of total moles monomer: 1.
10. hydrophobic associated polymer or the claim 9 described in claim 1～8 any one is preparedThe application of hydrophobic associated polymer in oilfield chemistry, water treatment, papermaking or mineral floating field.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109713157A (en) * | 2018-12-10 | 2019-05-03 | 云谷（固安）科技有限公司 | Display panel and preparation method thereof and display device |
| CN114190385A (en) * | 2021-12-23 | 2022-03-18 | 山东贵合生物科技有限公司 | Benzyl-kresoxim-methyl powder and preparation method thereof |
| CN114539465A (en) * | 2022-03-30 | 2022-05-27 | 成都工业学院 | Associative acrylate grouting material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317501A (en) * | 2001-04-19 | 2001-10-17 | 石油勘探开发科学研究院油田化学研究所 | High-molecular hydrophobic associated polymer, its preparing process and its application in petroleum recovery |
| CN104140507A (en) * | 2014-07-24 | 2014-11-12 | 山东大学 | Modified acrylamide water-soluble polymer containing super-long hydrophobic long chain and preparation method of modified acrylamide water-soluble polymer |
| 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 |
| CN104448130A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant copolymer for oilfield, and preparation method and application thereof |
| CN104448125A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
-
2015
- 2015-12-29 CN CN201511022852.1A patent/CN105601806A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317501A (en) * | 2001-04-19 | 2001-10-17 | 石油勘探开发科学研究院油田化学研究所 | High-molecular hydrophobic associated polymer, its preparing process and its application in petroleum recovery |
| CN104448130A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant copolymer for oilfield, and preparation method and application thereof |
| CN104448125A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
| CN104140507A (en) * | 2014-07-24 | 2014-11-12 | 山东大学 | Modified acrylamide water-soluble polymer containing super-long hydrophobic long chain and preparation method of modified acrylamide water-soluble polymer |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 冯茹森等: "不同疏水缔合聚合物之间协同效应的研究", 《精细化工》 * |
| 张洁辉等: "烷基酚聚氧乙烯醚丙烯酸酯共聚物表面活性剂的合成与性质", 《精细石油化工》 * |
| 王玉鹏等: "AM/AA/AMPS/AMC14S共聚物的制备与表征", 《青岛科技大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109713157A (en) * | 2018-12-10 | 2019-05-03 | 云谷（固安）科技有限公司 | Display panel and preparation method thereof and display device |
| CN114190385A (en) * | 2021-12-23 | 2022-03-18 | 山东贵合生物科技有限公司 | Benzyl-kresoxim-methyl powder and preparation method thereof |
| CN114539465A (en) * | 2022-03-30 | 2022-05-27 | 成都工业学院 | Associative acrylate grouting material and preparation method and application thereof |
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