CN105646771A - Hydrophobic associated polymer and preparation method thereof - Google Patents
Hydrophobic associated polymer and preparation method thereof Download PDFInfo
- Publication number
- CN105646771A CN105646771A CN201511018833.1A CN201511018833A CN105646771A CN 105646771 A CN105646771 A CN 105646771A CN 201511018833 A CN201511018833 A CN 201511018833A CN 105646771 A CN105646771 A CN 105646771A
- Authority
- CN
- China
- Prior art keywords
- hydrophobic
- associated polymer
- monomer
- acrylate
- hydrophobic associated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- 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
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a hydrophobic associated polymer, as shown in formula (I), y = 0.001 to 0.02, z = 0.08 to 0.3, and x + y + z = 1; A is a monomeric unit of a hydrophobic monomer; the hydrophobic monomer is selected from one or more of allylic alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol ethoxylate acrylate, polyoxyethylene alkyl acrylate and fluoro substituted alkyl acrylate. Compared with the prior art, the monomeric unit of acrylamide in the hydrophobic associated polymer can provide a hydrophilic group; the monomeric unit of the hydrophobic monomer can provide a hydrophobic side group for the hydrophobic associated polymer, and provide necessary viscoelasticity for a solution; the solubility of the hydrophobic associated polymer can be improved by the monomeric unit of sodium acrylate; under the combined action of three units, the salt tolerance and shear resistance of the hydrophobic associated polymer can be improved.
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 application technology, typically require and ground environment is carried 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 stratum generation effect into transform ground environment, reach the purpose of oil-gas field development and volume increase. Meanwhile, relevant application technology also requires that these fluids itself also possess some specific performance, for instance thickening property, viscoelasticity, drag reduction, permeability, improve mobility ratio etc. Wherein, the most frequently used fluid is exactly aqueous solution, and it has, and source is wide, economical, be easy to the advantages such as construction, by adding natural or synthesizing water-solubility macromolecule in water, can obtain and have above high performance aqueous solution. This kind of water soluble polymer has the viscoelasticity that thickening property is strong and good, and strand has a lot of active group, so that convection cell performance carries out transformation physics, chemistry, it is provided simultaneously with easy construction, consumption is few, the plurality of advantages such as cost is low, it is possible to 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 natural or synthesis water soluble polymer. 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 macromolecule, its consumption is big, easily biological-degradable, higher exhibition also can grievous injury stratum environment, bring many new problems to later development. at present, synthesizing macromolecule most popular is polyacrylamide, although its various aspects of performance all can reach construction requirement, but in pumping procedure, easily cause mechanical degradation, solution 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 causing that properties significantly declines, and be difficult to further overcome on the basis of its existing molecular structure, therefore, from polymer molecular structure, it is modifiied, anti-shearing to improve it, heat-resistant salt-resistant performance has been extremely urgent.
For above-mentioned Problems existing, researcheres propose hydrophobically associating polymers on this basis. Hydrophobically associating polymers (HAWSP) refers to the water-soluble polymer on polymer hydrophilicity macromolecular chain with a small amount of hydrophobic group. In aqueous, HAWSP concentration is higher than after critical association concentration, and macromolecular chain is assembled by hydrophobic association polymer effect, it is not necessary to namely chemical crosslinking forms Interpolymer Association dynamic physical cross-linked network, makes solution viscosity increase substantially. Simultaneously, the addition of some surfactant also can strengthen the hydrophobic interaction of polymer molecule interchain, Interpolymer Association dynamic physical cross-linked network intensity is increased, HAWSP also makes this solution have the characteristic of frozen glue with the supermolecule physical cross-linked network of existence in surfactant solution, thus providing good viscoelasticity. Destroy and the feature of reversible recovery at low shear rates at high shear rates additionally, this supermolecule dynamic physical cross-linked network has so that its stable performance, and possess the heatproof of excellence, salt tolerance, good shear thinning behavior, viscoelasticity 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 polymer.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is in that to provide good hydrophobic association polymer polymer of a kind of new salt resistant character and preparation method thereof.
The invention provides a kind of hydrophobic associated polymer, as shown in formula (I):
Wherein, described y=0.001��0.02, z=0.08��0.3, x+y+z=1; Described A is the group that hydrophobic monomer copolymerization is formed; One or more in the alkyl acrylate that allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace of described hydrophobic monomer.
Preferably, the viscosity-average molecular weight of described hydrophobic associated polymer is 3000��45,000,000.
Preferably, described y=0.001��0.01.
Preferably, described hydrophobic monomer is selected from one or more in allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid.
Preferably, in described allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid, the carbon number of alkyl is each independently 4��20.
Preferably, alkylphenol-polyethenoxy acrylate described in described alkane is each independently 7��20 with the polyoxyethylated degree of polymerization in the polyxyethylated ester of acrylic acid.
Preferably, the number that in the alkyl acrylate that described fluorine replaces, fluorine replaces is 4��10.
Preferably, described hydrophobic monomer is one or more in cetyl pi-allyl dibrominated tetramethylethylenediamine, 2-acrylamido tetradecane sodium sulfonate, 2-acrylamido-2-methyl dodecane sulfonic acid sodium, Nonyl pheno acrylate, octyl phenol polyoxyethylene acrylate, dodecyl polyoxyethylene acrylate, octadecyl pi-allyl dibrominated tetramethylethylenediamine, cetyl polyoxyethylene acrylate.
The preparation method that present invention also offers a kind of hydrophobic associated polymer, including:
Under initiator effect, acrylamide monomer and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer after hydrolysis;
Or: deposit in case at hydrolytic reagent, add the acrylamide triggered monomer of initiator and carry out copolyreaction with hydrophobic monomer, obtain hydrophobic associated polymer;
Or: under initiator effect, acrylamide monomer, sodium acrylate monomers and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer;
Described hydrophobic monomer is selected from one or more in allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, the alkyl acrylate of fluorine replacement, N-alkyl-substituted acrylamide, alkyl acrylate and alkyl methacrylate
The molal quantity of described hydrophobic monomer and the ratio of total moles monomer are (0.001��0.02): 1.
Present invention also offers hydrophobic associated polymer application in oilfield chemistry, water process, papermaking or mineral floating field.
The invention provides a kind of hydrophobic associated polymer, as shown in formula (I), described y=0.001��0.02, z=0.08��0.3, x+y+z=1; Described A is the group that hydrophobic monomer copolymerization is formed; Alkyl acrylate, N-alkyl-substituted acrylamide, alkyl acrylate and alkyl methacrylate that described hydrophobic monomer replaces selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine one or more. Compared with prior art, hydrophobic associated polymer of the present invention is made up of three kinds of unit, and hydrophilic unit is the monomeric unit of acrylamide, and it can provide hydrophilic group for hydrophobic association polymer, it is ensured that polymer has good water solublity; Hydrophobic units is the monomeric unit of hydrophobic monomer, it can provide hydrophobic side base for hydrophobic associated polymer, it is ensured that polymer chain has certain hydrophobic property, produces heat resistance and salt tolerance in water between each hydrophobic side base, form spacial framework, thus providing necessary viscoelasticity for solution; The monomeric unit of sodium acrylate can improve the dissolubility of hydrophobic associated polymer, improves the rheological property of polymer; Above-mentioned three kinds of unit combineds effect, improve salt tolerance and the anti-shear performance of hydrophobic associated polymer.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the hydrophobic associated polymer obtained 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 clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments. Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
The invention provides a kind of hydrophobic associated polymer, as shown in formula (I):
Wherein, described y=0.001��0.02, it is preferred to 0.001��0.01, more preferably 0.001��0.006, is further preferably 0.002��0.005; Described z=0.08��0.3, it is preferred to 0.1��0.3, more preferably 0.15��0.3, is further preferably 0.15��0.25, it is most preferred that it is 0.2��0.25; X+y+z=1; Described z/ (x+z) is preferably 0.1��0.32, more preferably 0.2��0.3.
Described A is the group that hydrophobic monomer copolymerization is formed, described hydrophobic monomer is selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace alkyl acrylate in one or more, it is preferably selected from allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, one or more in the alkyl acrylate that the polyxyethylated ester of acrylic acid and fluorine replace, it is more preferably allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, one in the alkyl acrylate that the polyxyethylated ester of acrylic acid and fluorine replace, in the alkyl acrylate that described allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid and fluorine replace, the carbon number of alkyl is preferably less than equal to 20 independently of one another, it is more preferably 4��20, it is further preferably 6��18, it is most preferred that be 10��18,; Described alkylphenol-polyethenoxy acrylate is preferably 7��20 independently of one another with the polyoxyethylated degree of polymerization in the polyxyethylated ester of acrylic acid, more preferably 10��20; The number that in the alkyl acrylate that described fluorine replaces, fluorine replaces is preferably 4��8, more preferably 6��8, and the alkyl acrylate that heretofore described fluorine replaces most preferably is Hexafluorobutyl mathacrylate. In the present invention, described hydrophobic monomer most preferably is one or more in cetyl pi-allyl dibrominated tetramethylethylenediamine, 2-acrylamido tetradecane sodium sulfonate, 2-acrylamido-2-methyl dodecane sulfonic acid sodium, Nonyl pheno acrylate, octyl phenol polyoxyethylene acrylate, dodecyl polyoxyethylene acrylate, octadecyl pi-allyl dibrominated tetramethylethylenediamine and cetyl polyoxyethylene acrylate.
The viscosity-average molecular weight of described hydrophobic associated polymer is preferably 3000��45,000,000, more preferably 3050��forty-two million, is further preferably 3050��40,000,000, is further preferably 3100��38,000,000, it is most preferred that be 3100��37,000,000.
Hydrophobic associated polymer of the present invention is made up of three kinds of unit, and hydrophilic unit is the monomeric unit of acrylamide, and it can provide hydrophilic group for hydrophobic association polymer, it is ensured that polymer has good water solublity; Hydrophobic units is the monomeric unit of hydrophobic monomer, it can provide hydrophobic side base for hydrophobic associated polymer, it is ensured that polymer chain has certain hydrophobic property, produces heat resistance and salt tolerance in water between each hydrophobic side base, form spacial framework, thus providing necessary viscoelasticity for solution; The monomeric unit of sodium acrylate can improve the dissolubility of hydrophobic associated polymer, improves the rheological property of polymer; Above-mentioned three kinds of unit combineds effect, improve salt tolerance and the anti-shear performance of hydrophobic associated polymer.
The preparation method that present invention also offers a kind of above-mentioned hydrophobic associated polymer, the mode that the method is hydrolyzed after being introduces sodium acrylate, including: under initiator effect, acrylamide monomer and hydrophobic monomer are carried out copolyreaction, after hydrolysis, obtains hydrophobic associated polymer; One or more in the alkyl acrylate that allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace of described hydrophobic monomer; The molal quantity of described hydrophobic monomer and the ratio of total moles monomer are (0.001��0.02): 1.
Wherein, described hydrophobic monomer is same as above, does not repeat them here; Described acrylamide monomer and the integral molar quantity of hydrophobic monomer are 1:(0.001��0.02 with the mol ratio of hydrophobic monomer), it is preferably 1:(0.001��0.01), it is more preferably 1:(0.001��0.006), it is further preferably 1:(0.002��0.006), it is most preferred that for 1:(0.003��0.005). Described initiator is initiator well known to those skilled in the art, there is no special restriction, is preferably persulfate and sulfite oxidation reduction initiator system in the present invention; Described persulfate is Redox initiator systems well known to those skilled in the art with sulfite oxidation reduction initiator system, there is no the mass ratio of special restriction, heretofore described persulfate and sulphite and be preferably (1��3): 1; In described initiator, the Functionality, quality and appealing design of oxidant elects the 0.005%��0.09% of total monomer quality as.
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, it is preferable that mixed with hydrophobic monomer by acrylamide monomer, heating, to initiation temperature, adds initiator, carries out copolyreaction. Wherein, copolyreaction carries out preferably in water, and the total in aqueous mass concentration of acrylamide monomer and hydrophobic monomer is preferably 15%��30%, more preferably 20%��30%; The pH value of mixing rear solution is preferably 5��7; In described initiator, the Functionality, quality and appealing design of oxidant elects the 0.006%��0.09% of monomer gross mass as, more preferably 0.006%��0.05%, is further preferably 0.006%��0.03%, it is most preferred that be 0.006%��0.01%; In described initiator, persulfate is preferably (1��1.7) with the mass ratio of sulphite: 1, more preferably (1��1.5): 1; Described initiation temperature is preferably-7 DEG C��10 DEG C, more preferably-7 DEG C��5 DEG C, be further preferably-5 DEG C��0 DEG C; Described copolyreaction carries out preferably in when adiabatic; The time of described copolyreaction is preferably 5��7h.
When copolymerization process is micell polymerization method, it is preferable that acrylamide monomer is mixed with hydrophobic monomer, it is preferable that be additionally added surfactant, regulates to initiation temperature, add initiator, carry out copolyreaction. Wherein, described copolyreaction carries out preferably in water; The total in aqueous mass concentration of described acrylamide monomer and hydrophobic monomer is preferably 12%��35%, more preferably 20%��35%, is further preferably 20%��30%; The pH value of mixing rear solution is preferably 5��7; Described surfactant is preferably anion surfactant, more preferably one or more in dodecyl sodium sulfate, sodium lauryl sulphate and dodecylbenzene sodium sulfonate; The mol ratio of described surfactant and hydrophobic monomer is preferably (2��20): 1, more preferably (3��15): 1, is further preferably (5��15): 1, it is most preferred that for (5��12): 1; The Functionality, quality and appealing design of described initiator elects the 0.005%��0.09% of monomer gross mass as, more preferably 0.005%��0.05%, more preferably 0.005%��0.03%, is further preferably 0.005%��0.01%; In described initiator, persulfate is (5:3)��(1:1) with the mass ratio of sulphite, more preferably (4:3)��(1:1); Described initiation temperature is preferably-10 DEG C��10 DEG C, more preferably-5 DEG C��5 DEG C, be further preferably-5 DEG C��0 DEG C; Described copolyreaction carries out preferably in when adiabatic; The time of described copolyreaction is preferably 5��7h, and more preferably when rising above 1 DEG C in the temperature 30min of reaction system, reaction terminates.
When carrying out copolymerization by reverse microemulsion process, it is preferable that carry out in accordance with the following methods: by soluble in water for poly-propionic acid amide. monomer, as aqueous phase; Hydrophobic monomer is dissolved in oil solvent, it is preferable that be additionally added emulsifying agent, as oil phase; Aqueous phase is mixed with oil phase, regulates to initiation temperature, 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 liquid paraffin, more preferably kerosene in the present invention; The oil-water ratio of described oil solvent and water is preferably (1��1.5): 1; After mixing, in mixed solution, total monomer concentration is preferably 25��40wt%, more preferably 25��30wt%;Described emulsifying agent is emulsifying agent well known to those skilled in the art, there is no special restriction, being preferably HLB value in the present invention is the nonionic surfactant of 6��8, it is more preferably Span class nonionic surfactant and/or Tween class nonionic surfactant, it is further preferably Span class nonionic surfactant and Tween class nonionic surfactant, it is most preferred that for Span-60 and Tween-80; The mass ratio of described Span class nonionic surfactant and Tween class nonionic surfactant is preferably (3��12): 3, more preferably (4��10): 3, it is most preferred that for (6��8): 3; The Functionality, quality and appealing design of described emulsifying agent elects the 10%��25% of monomer gross mass as, more preferably 12%��18%, is further preferably 14%��18%; In described initiator, the Functionality, quality and appealing design of oxidant elects the 0.005%��0.09% of monomer gross mass as, more preferably 0.005%��0.05%, is further preferably 0.005%��0.03%, it is most preferred that be 0.005%��0.01%; Described initiation temperature is preferably-5 DEG C��15 DEG C, more preferably-5 DEG C��10 DEG C, be further preferably-5 DEG C��8 DEG C, it is most preferred that for-5 DEG C��3 DEG C; Described copolyreaction carries out preferably in when adiabatic; The time of described copolyreaction is preferably 5��7h, more preferably 4��6h; Preferably breakdown of emulsion process is also carried out after adopting reverse microemulsion process copolymerization.
Adopting polymerisation in solution, micell polymerization method, after being polymerized, it is preferable that carry out granulating from colloid, be then hydrolyzed, conversed phase micro emulsion copolymerization is without granulation process, but the polymer after breakdown of emulsion is hydrolyzed after precipitation, dissolving again, precipitates, is dried; The method of described pelletize is method well known to those skilled in the art, there is no special restriction; Hydrolytic reagent used by described hydrolysis is hydrolytic reagent well known to those skilled in the art, there is no special restriction, and the present invention is preferably alkali metal hydroxide, more preferably potassium hydroxide and/or sodium hydroxide, is further preferably sodium hydroxide; The temperature of described hydrolysis is preferably 70 DEG C��100 DEG C, more preferably 80 DEG C��100 DEG C, is further 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 8%��30%, more preferably 10%��25%, is further preferably 15%��23%.
After hydrolysis, it is preferable that be 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, is further preferably 1��2h.
Present invention also offers a kind of method that front Hydrolyze method prepares above-mentioned hydrophobic associated polymer, including: deposit in case at hydrolytic reagent, add the acrylamide triggered monomer of initiator and carry out copolyreaction with hydrophobic monomer, obtain hydrophobic associated polymer. One or more in the alkyl acrylate that allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace of described hydrophobic monomer; The molal quantity of described hydrophobic monomer and the ratio of total moles monomer are (0.001��0.02): 1.
Wherein, described acrylamide monomer, hydrophobic 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, more preferably potassium hydroxide and/or sodium hydroxide, be further preferably sodium hydroxide in the present invention;What described hydrolytic reagent added measures 0.4%��20% for monomer gross mass, more preferably 0.4%��15%, is further preferably 0.4%��12%.
Copolymerization in the preparation of front method for hydrolysis can be undertaken by water solution polymerization process, micell polymerization method or reverse microemulsion process again. Wherein, described water solution polymerization process, micell polymerization method and reverse microemulsion process are all same as above, are simply simultaneously introduced hydrolytic reagent what add acrylamide monomer and hydrophobic monomer, do not repeat them here.
Adopt polymerisation in solution, micell polymerization method, after being polymerized, it is preferable that carry out granulating from colloid, dry, obtain hydrophobic associated polymer; Conversed phase micro emulsion copolymerization is without granulation process, but is precipitated by the polymer after breakdown of emulsion, dry obtains hydrophobic associated polymer; The method of described pelletize 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 preferably 0.5��3h, is further preferably 1��2h.
Present invention also offers a kind of method adopting cohydrolysis to prepare above-mentioned hydrophobic associated polymer, including: under initiator effect, acrylamide monomer, sodium acrylate monomers and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer; One or more in the alkyl acrylate that allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace of described hydrophobic monomer; The molal quantity of described hydrophobic monomer and the ratio of total moles monomer are (0.001��0.02): 1.
Wherein, described hydrophobic monomer is all same as above with initiator, does not repeat them here; Preparing hydrophobic associated polymer at co-hydrolysis is some acrylamide monomer sodium acrylate monomers substituted, therefore the integral molar quantity of described acrylamide monomer, sodium acrylate monomers and hydrophobic monomer is 1:(0.001��0.02 with the mol ratio of hydrophobic monomer), it is preferably 1:(0.001��0.01), it is more preferably 1:(0.001��0.006), be further preferably 1:(0.002��0.005); The ratio of the molal quantity that described sodium acrylate monomers is total with monomer is (0.08��0.3): 1, it is preferably (0.1��0.25): 1, it is more preferably (0.15��0.25): 1, it is further preferably (0.2��0.28): 1,, it is most preferred that for (0.2��0.25): 1; Mole and the mol ratio of sodium acrylate monomers that described acrylamide monomer is total with sodium acrylate monomers are preferably 1:(0.1��0.35), more preferably 1:(0.22��0.27).
Copolymerization in cohydrolysis method preparation carries out also by water solution polymerization process, micell polymerization method or reverse microemulsion process. Wherein, described water solution polymerization process, micell polymerization method reverse microemulsion process are all same as above, simply replace some acrylamide monomer by sodium acrylate monomers, do not repeat them here.
Adopt polymerisation in solution, micell polymerization method, after being polymerized, it is preferable that carry out granulating from colloid, dry, obtain hydrophobic associated polymer; Conversed phase micro emulsion copolymerization is without granulation process, but through precipitating to dry, the polymer after breakdown of emulsion is obtained hydrophobic associated polymer; The method of described pelletize 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 preferably 0.5��3h, is further 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 �� key of other vinyl monomer molecules, adds and is shaped as new free radical. The new radical reaction activity so formed will not decay, and continuation and vinyl monomer carry out the addition of interlock type, and carry out chain propagation reaction in this manner. Activity collision occurring between two chain free radicals, occurs double-basis to terminate reaction, polyreaction terminates.
Present invention also offers a kind of above-mentioned hydrophobic associated polymer oilfield chemistry, water process, papermaking with or mineral floating field in application.
In order to further illustrate the present invention, below in conjunction with embodiment to a kind of hydrophobic associated polymer provided by the invention and preparation method thereof detailed description.
Reagent used in following example is commercially available.
Embodiment 1 water solution polymerization process
Acrylamide monomer and hydrophobic monomer 2-acrylamido tetradecane sodium sulfonate are fed intake by the mol ratio of 99.7:0.3, join 5000mL beaker dissolves with pure water and be configured to the mixed solution that monomer total mass concentration is 25%, after system is down to-5 DEG C, add potassium peroxydisulfate and sodium sulfite composite initiator causes polymerization, wherein potassium peroxydisulfate and sodium sulfite mass ratio are 1:1, and potassium peroxydisulfate dosage is the 0.005% of monomer gross mass. Polyreaction carries out under adiabatic environment, inserts thermometer monitors polyreaction at reaction system center and carries out degree, when in 30 minutes, temperature thinks that polyreaction is basically completed when rising above 1 DEG C. Polyreaction complete after 1h, take out colloid, colloid is cut into 3��5mm size particles, add the hydrolytic reagent NaOH accounting for colloid gross mass 2.81%, mix homogeneously, is then transferred in plastic bag and seals, and in constant temperature oven, constant temperature 95 DEG C hydrolysis 2h (gets rid of air when should be noted that sealing as far as possible, and the ammonia produced when retaining enough space hydrolysis, seal bag when noting being hydrolyzed and do not break). After being hydrolyzed, colloid is spread out and paves on 500 eye mesh screens, put into 95 DEG C of dry 1h of baking oven constant temperature, take out the acquisition hydrophobic associated polymer that sieves.
Utilize nuclear magnetic resonance, NMR that the hydrophobic associated polymer obtained in embodiment 1 is analyzed, obtain its hydrogen nuclear magnetic resonance spectrogram, as shown in Figure 1. As shown in Figure 1, ��=6.87��7.68ppm is-NH on acrylamide2Upper HhChemical shift, ��=4.70ppm is solvent D2The chemical shift of the H of O solvent, ��=3.35��3.53ppm is hydrophobic monomer HgChemical shift, and ��=2.50��2.67ppm is hydrophobic monomer HlChemical shift, ��=2.11, the strong peak of 2.21ppm are three kinds of monomeric building blocks-CH of main chain2Methine hydrogen and H in-CH-b��Hd��HfChemical shift, ��=1.54, the strong peak of 1.63ppm are three kinds of construction unit-CH of main chain2-CH-methylene hydrogen and Ha��Hc��HeChemical shift, and both area ratio 1:2, meet both molar ratios. ��=1.17ppm is H in hydrophobic monomeriChemical shift, ��=1.05��1.09ppm is long-chain methylene H in hydrophobic monomerjChemical shift, ��=0.74, the weak peak of 0.75ppm are then hydrophobic monomer end group-CH3Middle HkAbsworption peak.
Utilizing Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 1 to be tested, it is 36,580,000 that calculating obtains its viscosity-average molecular weight.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is simulation saline and the hydrophobic associated polymer prepared polymer solution of preparation in embodiment 1 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 2.5h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 65mPa s; Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 90.5%.
Embodiment 2 micell polymerization method
Monomer and surfactant is added in 5000mL beaker, wherein acrylamide monomer and hydrophobic monomer 2-propionamido-tetradecane sodium sulfonate feed intake by the mol ratio of 99.7:0.3, dodecylbenzene sodium sulfonate is added by the 12 of hydrophobic monomer molar concentration times, add quantitative pure water, stir and be configured to the mixed solution that monomer total mass concentration is 25%, after system is down to-5 DEG C, add potassium peroxydisulfate and sodium sulfite composite initiator causes polymerization, wherein potassium peroxydisulfate and sodium sulfite mass ratio are 1:1, potassium peroxydisulfate addition is the 0.008% of monomer mass, polyreaction carries out under adiabatic environment, inserts thermometer monitors polyreaction at reaction system center and carries out degree, when in 30 minutes, temperature thinks that polyreaction is basically completed when rising above 1 DEG C. polyreaction complete after 1h, take out colloid, colloid is cut into 3��5mm size particles, add the hydrolytic reagent NaOH accounting for colloid gross mass 2.81%, mix homogeneously, is then transferred in plastic bag and seals, and in constant temperature oven, constant temperature 95 DEG C hydrolysis 2h (gets rid of air when should be noted that sealing as far as possible, and the ammonia produced when retaining enough space hydrolysis, seal bag when noting being hydrolyzed and do not break). after being hydrolyzed, colloid is spread out and paves on 500 eye mesh screens, put into 95 DEG C of dry 1h of baking oven constant temperature, take out the acquisition hydrophobic associated polymer that sieves.
Utilizing Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 2 to be tested, calculating its viscosity-average molecular weight is 34,950,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 2 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 2.4h, insolubles content is 0.11%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 78mPa s; Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 87%.
Embodiment 3 conversed phase micro emulsion copolymerization
Joining in deionized water by sodium acrylate monomers, acrylamide monomer and hydrophobic monomer 2-acrylamide tetradecane sodium sulfonate, fully dissolve, this solution is as aqueous phase; In kerosene, add mass ratio be the Span-60:Tween-80=7:3 compound emulsifying agent formed and stir to fully dissolving, as oil phase. Under high velocity agitation, aqueous phase solution is added oil phase carries out emulsifying 20min, it is then transferred in 5000mL beaker, wherein monomer total mass concentration is 25%, sodium acrylate monomers, acrylamide monomer and hydrophobic monomer 2-acrylamide tetradecane sodium sulfonate three's mol ratio are 93.7:6:0.3, and compound emulsifying agent additive capacity is the 19% of total system quality. Add the potassium peroxydisulfate accounting for monomer mass 0.008% when emulsion is reduced to-5 DEG C and sodium sulfite composite initiator causes polymerization, wherein potassium peroxydisulfate and sodium sulfite mass ratio are 1:1, react and carry out adiabatic when, react after reaction 4��6h and be basically completed, obtain product.
The product obtained is added ethanol and carries out breakdown of emulsion, precipitation, centrifugation, by gained precipitate absolute ethanol washing 3 times, put into 95 DEG C of dry 1h of baking oven constant temperature, size-reduced, sieve, obtain certain particle diameter dry powder sample and hydrophobic associated polymer.
Utilizing Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 3 to be tested, calculating its viscosity-average molecular weight is 32,500,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 3 of 3000mg/L, and when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 64mPa s; Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 89.5%.
Embodiment 4
According to the polymerization in embodiment 3 and step, compound emulsifying agent additive capacity is changed into the 25% of total system quality, obtains hydrophobic associated polymer.
Using Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 4 to be tested, calculating its viscosity-average molecular weight is 34,550,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 4 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 2.4h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 85mPa s; Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 89.6%.
Embodiment 5
According to the polymerization in embodiment 1 and step, change the mol ratio of acrylamide monomer, sodium acrylate monomers and hydrophobic monomer 2-acrylamido tetradecane sodium sulfonate into 93.9:6:0.1, obtain hydrophobic associated polymer.
Using Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 5 to be tested, calculating its polymer viscosity-average molecular weight is 45,060,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 5 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 3h, insolubles content is 0.15%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 52mPa s; Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 91.2%.
Embodiment 6
According to the polymerization in embodiment 1 and step, change the mol ratio of acrylamide monomer, sodium acrylate monomers and hydrophobic monomer 2-acrylamido tetradecane sodium sulfonate into 93.5:6:0.5, obtain hydrophobic associated polymer.
Using Ubbelohde viscometer (0.55mm caliber) according to the GB/T12005.10-92 hydrophobic associated polymer prosperous test of gold to obtaining in embodiment 6, calculating its viscosity-average molecular weight is 33,120,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 6 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 2.8h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 89mPa s;Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 94.4%.
Embodiment 7
According to the polymerization in embodiment 1 and step, hydrophobic monomer 2-acrylamido tetradecane sodium sulfonate is replaced with octadecyl pi-allyl dibrominated tetramethylethylenediamine, obtains hydrophobic associated polymer.
Using Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 7 to be tested, calculating its viscosity-average molecular weight is 35,760,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 7 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 2.5h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 55mPa s; Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 90%.
Embodiment 8
According to the polymerization in embodiment 1 and step, hydrophobic monomer 2-acrylamido tetradecane sodium sulfonate is replaced with Nonyl pheno (8) acrylate, obtains hydrophobic associated polymer.
Using Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 8 to be tested, calculating its viscosity-average molecular weight is 38,610,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 8 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 2.7h, insolubles content is 0.13%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 67.2mPa s; Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 89.9%.
Embodiment 9
According to the polymerization in embodiment 1 and step, hydrophobic monomer 2-acrylamido tetradecane sodium sulfonate is replaced with cetyl polyoxyethylene (16) acrylate, obtains hydrophobic associated polymer.
Using Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 9 to be tested, calculating its viscosity-average molecular weight is 36,090,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 9 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 2.6h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 58mPa s; Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 90.2%.
Embodiment 10
According to the polymerization in embodiment 1 and step, hydrophobic monomer 2-acrylamido tetradecane sodium sulfonate is replaced with hexafluorobutyl acrylate, obtains hydrophobic associated polymer.
Using Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92, the hydrophobic associated polymer obtained in embodiment 10 to be tested, calculating its viscosity-average molecular weight is 36,540,000.
Adopting total salinity is 80,000 water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 10 of 3000mg/L, preparation 5000mg/L polymer solution, dissolution time 2.5h, insolubles content is 0.12%, when polymer solution concentration is 2000mg/L, temperature is 85 DEG C, and shear rate is 7.34s-1Lower test polymer viscosity number is 61mPa s;Stirring 20s through waring agitator speed 3000r/min, viscosity retention ratio is 86%.
Claims (10)
1. a hydrophobic associated polymer, as shown in formula (I):
Wherein, described y=0.001��0.02, z=0.08��0.3, x+y+z=1; Described A is the monomeric unit of hydrophobic monomer; One or more in the alkyl acrylate that allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace of described hydrophobic monomer.
2. hydrophobic associated polymer according to claim 1, it is characterised in that the viscosity-average molecular weight of described hydrophobic associated polymer is 3000��45,000,000.
3. hydrophobic associated polymer according to claim 1, it is characterised in that described y=0.001��0.01.
4. hydrophobic associated polymer according to claim 1, it is characterized in that, described hydrophobic monomer is selected from one or more in allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid.
5. 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, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid, the carbon number of alkyl is each independently 4��20.
6. hydrophobic associated polymer according to claim 1, it is characterised in that described alkylphenol-polyethenoxy acrylate is each independently 7��20 with the polyoxyethylated degree of polymerization in the polyxyethylated ester of acrylic acid.
7. hydrophobic associated polymer according to claim 1, it is characterised in that the number that in the alkyl acrylate that described fluorine replaces, fluorine replaces is 4��10.
8. hydrophobic associated polymer according to claim 1, it is characterized in that, described hydrophobic monomer is one or more in cetyl pi-allyl dibrominated tetramethylethylenediamine, 2-acrylamido tetradecane sodium sulfonate, 2-acrylamido-2-methyl dodecane sulfonic acid sodium, Nonyl pheno acrylate, octyl phenol polyoxyethylene acrylate, dodecyl polyoxyethylene acrylate, octadecyl pi-allyl dibrominated tetramethylethylenediamine, cetyl polyoxyethylene acrylate.
9. the preparation method of a hydrophobic associated polymer, it is characterised in that including:
Under initiator effect, acrylamide monomer and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer after hydrolysis;
Or: deposit in case at hydrolytic reagent, add the acrylamide triggered monomer of initiator and carry out copolyreaction with hydrophobic monomer, obtain hydrophobic associated polymer;
Or: under initiator effect, acrylamide monomer, sodium acrylate monomers and hydrophobic monomer carry out copolyreaction, obtain hydrophobic associated polymer;
Described hydrophobic monomer is selected from one or more in allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, the alkyl acrylate of fluorine replacement, N-alkyl-substituted acrylamide, alkyl acrylate and alkyl methacrylate
The molal quantity of described hydrophobic monomer and the ratio of total moles monomer are (0.001��0.02): 1.
10. the hydrophobic associated polymer described in claim 1��8 any one or the application in oilfield chemistry, water process, papermaking or mineral floating field of the hydrophobic associated polymer prepared by claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511018833.1A CN105646771A (en) | 2015-12-29 | 2015-12-29 | Hydrophobic associated polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511018833.1A CN105646771A (en) | 2015-12-29 | 2015-12-29 | Hydrophobic associated polymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105646771A true CN105646771A (en) | 2016-06-08 |
Family
ID=56478446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511018833.1A Pending CN105646771A (en) | 2015-12-29 | 2015-12-29 | Hydrophobic associated polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105646771A (en) |
Cited By (3)
| 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 |
| CN107814871A (en) * | 2016-09-12 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of polymer for having surface active function and its preparation method and application |
| CN108658491A (en) * | 2018-05-29 | 2018-10-16 | 江苏苏博特新材料股份有限公司 | A kind of amphipathic multi-functional hybrid particle and preparation method thereof based on aluminum oxide |
Citations (3)
| 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 |
| CN1513890A (en) * | 2003-07-28 | 2004-07-21 | 西南石油学院 | AM/NaAA/AHAC trielement hylrophobic association polymer and its synthesis method |
| CN1793189A (en) * | 2005-12-08 | 2006-06-28 | 西南石油学院 | Water-solubility molecule associatad three-construction units hydrophobic associated polymer and synthesizing process thereof |
-
2015
- 2015-12-29 CN CN201511018833.1A patent/CN105646771A/en active Pending
Patent Citations (3)
| 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 |
| CN1513890A (en) * | 2003-07-28 | 2004-07-21 | 西南石油学院 | AM/NaAA/AHAC trielement hylrophobic association polymer and its synthesis method |
| CN1793189A (en) * | 2005-12-08 | 2006-06-28 | 西南石油学院 | Water-solubility molecule associatad three-construction units hydrophobic associated polymer and synthesizing process thereof |
Non-Patent Citations (2)
| 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》 * |
| 江立鼎，等: "表面活性单体NaAMC14S丙烯酰胺共聚物的分子链微结构与疏水缔合性", 《高分子学报》 * |
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 |
| CN107814871A (en) * | 2016-09-12 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of polymer for having surface active function and its preparation method and application |
| CN108658491A (en) * | 2018-05-29 | 2018-10-16 | 江苏苏博特新材料股份有限公司 | A kind of amphipathic multi-functional hybrid particle and preparation method thereof based on aluminum oxide |
| CN108658491B (en) * | 2018-05-29 | 2020-11-17 | 江苏苏博特新材料股份有限公司 | Amphiphilic multifunctional hybrid particle based on aluminum oxide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105646772B (en) | A kind of hydrophobic associated polymer and preparation method thereof | |
| CN105646776B (en) | A kind of hydrophobic associated polymer and preparation method thereof | |
| CN105646777A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN101649024B (en) | Preparation method of water-in-water cationic polyacylamide emulsion | |
| CN105418862A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN102770505A (en) | Enhanced oil recovery process using water soluble polymers having improved shear resistance | |
| CN102051165B (en) | Xanthan gum graft copolymer oil displacement agent as well as preparation method and application thereof | |
| CN105542070A (en) | Hydrophobic association polymer and preparation method thereof | |
| CN102977877A (en) | Drag reducer for shale gas fracture and preparation method of drag reducer | |
| CN103320112B (en) | A kind of anti-shearing dendritic polymers oil-displacing agent and synthetic method thereof | |
| CN105601805A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN105461855B (en) | A kind of hydrophobic associated polymer and preparation method thereof | |
| CN102372807B (en) | Preparation method of heat-resistance and salt-tolerance anionic polyacrylamide for oil displacement | |
| CN105601804A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN104560002A (en) | Drag reducer for fracturing shale gas and preparation method of drag reducer | |
| CN105646771A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN105504155A (en) | Hydrophobically associating polymer and preparation method thereof | |
| CN106833590A (en) | A kind of Water-In-Oil association type displacement of reservoir oil concentration thickener and preparation method thereof | |
| CN104892823A (en) | Medium-low molecular weight rigid tackifying polymer and preparation method and application thereof | |
| CN105646775A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN105601806A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN102850487A (en) | Water-soluble hydrophobic associated polymer oil displacement agent and synthesis method thereof | |
| CN104974298A (en) | Resistance reducing agent for fracture and preparation method thereof | |
| CN104558404A (en) | Hydrophobically associating polymer for shale gas exploitation | |
| CN105504154B (en) | A kind of hydrophobic associated polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160608 |