CN105646774A - Hydrophobic associated polymer and preparation method thereof - Google Patents
Hydrophobic associated polymer and preparation method thereof Download PDFInfo
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- CN105646774A CN105646774A CN201511019779.2A CN201511019779A CN105646774A CN 105646774 A CN105646774 A CN 105646774A CN 201511019779 A CN201511019779 A CN 201511019779A CN 105646774 A CN105646774 A CN 105646774A
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Abstract
The invention provides a hydrophobic associated polymer and a preparation method thereof. Under the action of an initiator, an acrylamide monomer and a hydrophobic monomer are subjected to a polymerization reaction in a supercritical carbon dioxide environment to obtain a hydrophobic associated polymer; the molar ratio of the acrylamide monomer to the hydrophobic monomer is 1: (0.001 to 0.2). Compared with the prior art, the hydrophobic associated polymer comprises a monomeric unit of acrylamide and a monomeric unit of a hydrophobic monomer, the monomeric unit of acrylamide can provide a hydrophilic group for the hydrophobic associated polymer and ensures that the polymer has good water solubility; the monomeric unit of the hydrophobic monomer can provide a hydrophobic side group for the hydrophobic associated polymer and ensures that a polymer chain has a certain hydrophobic character, and hydrophobic groups gather in water due to a hydrophobic interaction to form a spatial network structure, thereby providing necessary viscoelasticity for a solution; the method for preparing the hydrophobic associated polymer using supercritical carbon dioxide is simple, the reaction conditions are mild and the yield is relatively high.
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 residue 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 heat resistance and salt tolerance, 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. But the method that the preparation method of existing hydrophobic associated polymer adopts polymerization is prepared, complicated condition and wayward.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is in that to provide a kind of hydrophobic association polymer polymer and preparation method thereof, and this preparation method is easier.
The invention provides a kind of hydrophobic associated polymer, including formula (I) and the repetitive shown in formula (II):
Wherein, described x:y=1:(0.001��0.2); Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer is selected from one or more in N-alkyl-substituted acrylamide and derivant, alkyl acrylate, alkyl methacrylate, the alkyl acrylate of fluorine replacement, the alkyl methacrylate of fluorine replacement, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid.
Preferably, in the alkyl methacrylate that the alkyl acrylate that described N-alkyl-substituted acrylamide and derivant thereof, alkyl acrylate, alkyl methacrylate, allyl alkyl quaternary ammonium salt, acrylic acid alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace and fluorine replace, the carbon number of alkyl is each independently 4��40.
Preferably, the repetitive shown in formula (III) is also included:
Wherein, described x:z=1:(0.001��0.3); Described D is the monomeric unit of function monomer; Described function monomer is selected from containing the sulfonic acid and sulfonate derivatives thereof of holding thiazolinyl and containing one or more in the Hete rocyclic derivatives holding thiazolinyl.
Preferably, the repetitive shown in formula (IV) is also included:
Wherein, x:m=1:(0.03��0.3).
Preferably, the viscosity-average molecular weight of described hydrophobic associated polymer is 50��8,000,000.
The preparation method that present invention also offers a kind of hydrophobic associated polymer, including:
Under the effect of initiator, acrylamide monomer and hydrophobic monomer are carried out polyreaction in supercritical carbon dioxide environment, obtains hydrophobic associated polymer; The mol ratio of described acrylamide monomer and hydrophobic monomer is 1:(0.001��0.2); Described hydrophobic monomer is selected from one or more in N-alkyl-substituted acrylamide and derivant, alkyl acrylate, alkyl methacrylate, the alkyl acrylate of fluorine replacement, the alkyl methacrylate of fluorine replacement, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid.
Preferably, the temperature of described polyreaction is 40 DEG C��80 DEG C; The time of described polyreaction is 3��5h.
Preferably, the pressure of described polyreaction is 8��16MPa.
Preferably, the quality of described initiator is the 0.1%��2% of all monomer gross masses.
Present invention also offers the application in oilfield chemistry, water process, papermaking or mineral floating field of a kind of hydrophobic associated polymer.
The invention provides a kind of hydrophobic associated polymer and preparation method thereof, under the effect of initiator, acrylamide monomer and hydrophobic monomer are carried out polyreaction in supercritical carbon dioxide environment, obtains hydrophobic associated polymer; The mol ratio of described acrylamide monomer and hydrophobic monomer is 1:(0.001��0.2); Described hydrophobic monomer is selected from one or more in N-alkyl-substituted acrylamide and derivant, alkyl acrylate, alkyl methacrylate, the alkyl acrylate of fluorine replacement, the alkyl methacrylate of fluorine replacement, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid. Compared with prior art, hydrophobic associated polymer of the present invention includes the monomeric unit of acrylamide and the monomeric unit of hydrophobic monomer, 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, and in water, hydrophobic group is assembled due to hydrophobic interaction, form spacial framework, thus providing necessary viscoelasticity for solution; Two kinds of unit combineds effect improve the temperature tolerance of hydrophobic associated polymer, salt tolerance and anti-shear performance; Further, adopting supercritical carbon dioxide to prepare hydrophobic associated polymer preparation method simple, reaction condition is gentle, and productivity is higher.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the hydrophobic associated polymer obtained in the embodiment of the present invention 1;
Fig. 2 is the hydrophobic associated polymer obtained in the embodiment of the present invention 11H-NMR spectrum.
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, including formula (I) and the repetitive shown in formula (II):
Wherein, described x:y=1:(0.001��0.2), it is preferred to 1:(0.003��0.15), it is further preferably 1:(0.003��0.1), it is more preferably 1:(0.003��0.05), it is most preferred that for 1:(0.003��0.02), described A is the monomeric unit of hydrophobic monomer, described hydrophobic monomer is selected from N-alkyl-substituted acrylamide and derivant thereof, alkyl acrylate, alkyl methacrylate, the alkyl acrylate that fluorine replaces, the alkyl methacrylate that fluorine replaces, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, one or more in alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid, it is preferably N-alkyl-substituted acrylamide and derivant thereof, alkyl acrylate, alkyl methacrylate, the alkyl acrylate that fluorine replaces, the alkyl methacrylate that fluorine replaces, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate and the one in the polyxyethylated ester of acrylic acid,In the alkyl methacrylate that the alkyl acrylate that described N-alkyl-substituted acrylamide and derivant thereof, alkyl acrylate, alkyl methacrylate, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace and fluorine replace, the carbon number of alkyl is preferably 4��40 independently of one another, it is more preferably 4��30, is further preferably 6��20, described N-alkyl-substituted acrylamide derivant preferably comprises the derivant of benzene ring structure, 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 7��16, in the alkyl methacrylate that the alkyl acrylate that described fluorine replaces and fluorine replace, the number of fluorine atom is preferably 4��10 independently of one another, it is more preferably 6��8, it is most preferred that for 2-(N-ethylperfluoro sulfanilic acid) ethyl methacrylate or 2-(N-ethylperfluoro octane) butyl methacrylate, heretofore described hydrophobic monomer most preferably is 2-(N-ethylperfluoro sulfanilic acid) ethyl methacrylate, 2-(N-ethylperfluoro octane) butyl methacrylate, dodecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate, lauryl methacrylate, hexadecyl metrhacrylate, octadecyl methacrylate, N-dodecylacrylamide, N-cetyl acrylamide, N-phenethyl acrylamides, 2-acrylamido-2-methyl pentacosane base sodium sulfonate, N-octyl group propionic acid amide., 2-acrylamido-2-methyl docosyl sodium sulfonate, N-myristyl acrylamide, N, N-dioctyl acrylamide, Hexafluorobutyl mathacrylate, tetradecyl methylacrylate, [(1-naphthyl) methyl] acrylamide, 2-(1-acetamide naphthalene) ethyl acrylate, N-[(1-pyrenyl sulfonamide) ethyl] acrylamide, 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, one or more in octadecyl pi-allyl dibrominated tetramethylethylenediamine and cetyl polyoxyethylene acrylate.
According to the present invention, described hydrophobic associated polymer preferably also includes the repetitive shown in formula (III):
Wherein, described x:z=1:(0.001��0.3), it is preferred to 1:(0.005��0.25), more preferably 1:(0.008��0.2), be further preferably (0.01��0.15); Described D is the monomeric unit of function monomer; Described function monomer is selected from containing the sulfonic acid and sulfonate derivatives thereof of holding thiazolinyl and containing one or more in the Hete rocyclic derivatives holding thiazolinyl; The carbon number of described function monomer is preferably 2��20, more preferably 2��15, is further preferably 2��10; In the present invention, described function monomer most preferably is one or more in 2-acrylamide-2-methylpro panesulfonic acid and sulfonate, vinyl sulfonic acid and sulfonate, styrene sulfonic acid and sulfonate thereof and NVP.
According to the present invention, described hydrophobic associated polymer preferably also includes the repetitive shown in formula (IV):
Wherein, x:m=1:(0.03��0.3), it is preferred to 1:(0.03��0.25), more preferably 1:(0.05��0.20), be further preferably (0.1��0.20).
In the present invention, the viscosity-average molecular weight of described hydrophobic associated polymer is preferably 50��8,000,000, more preferably 150��8,000,000, is further preferably 250��8,000,000, it is most preferred that be 300��8,000,000.
Hydrophobic associated polymer of the present invention includes four kinds of repetitives, and hydrophilic unit is the monomeric unit of acrylamide, and it can provide hydrophilic group for hydrophobic associated polymer, it is ensured that polymer has good water solublity; Hydrophobic units is the group of the monomeric unit of hydrophobic monomer, it can provide hydrophobic side base for hydrophobic associated polymer, ensure that polymer chain has certain hydrophobic property, in water, hydrophobic group is assembled due to hydrophobic interaction, form spacial framework, thus providing necessary viscoelasticity for solution; The monomeric unit of acrylate ionomer can provide the dissolubility of hydrophobic associated polymer, polymer-modified rheological property; Functional unit is that function monomer copolymerization is formed, and the introducing of these monomers can improve the heat-resistant salt-resistant performance of polymer; Above-mentioned four kinds of unit combineds effect, improve the temperature tolerance of hydrophobic associated polymer, salt tolerance and anti-shear performance.
The preparation method that present invention also offers a kind of above-mentioned hydrophobic associated polymer, including: under the effect of initiator, acrylamide monomer and hydrophobic monomer are carried out polyreaction in supercritical carbon dioxide environment, obtains hydrophobic associated polymer; The mol ratio of described acrylamide monomer and hydrophobic monomer is 1:(0.001��0.2); Described hydrophobic monomer is selected from one or more in N-alkyl-substituted acrylamide and derivant, alkyl acrylate, alkyl methacrylate, the alkyl acrylate of fluorine replacement, the alkyl methacrylate of fluorine replacement, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid.
Wherein, described acrylamide monomer is all same as above with hydrophobic monomer, does not repeat them here; The mol ratio of described acrylamide monomer and hydrophobic monomer is 1:(0.001��0.2), it is preferably 1:(0.003��0.15), it is further preferably 1:(0.003��0.1), it is more preferably 1:(0.003��0.05), it is most preferred that for 1:(0.003��0.02); Described initiator is initiator well known to those skilled in the art, there is no special restriction, the present invention is preferably azo-initiator, be more preferably in azodiisobutyronitrile (AIBN), AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group Methanamide, azo dicyclohexyl formonitrile HCN and azo-bis-iso-dimethyl one or more, be further preferably one or more in azodiisobutyronitrile (AIBN), AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile); The Functionality, quality and appealing design of described initiator elects the 0.1%��2% of all monomer gross masses as, more preferably 0.3%��1.5%, is further preferably 0.4%��1%, it is most preferred that be 0.4%��0.8%.
Under the effect of initiator, acrylamide monomer and hydrophobic monomer are carried out polyreaction in supercritical carbon dioxide environment, preferably it is additionally added function monomer, the mol ratio of described acrylamide monomer and function monomer is 1:(0.001��0.3), it is preferably 1:(0.005��0.25), it is more preferably 1:(0.008��0.2), be further preferably (0.1��0.15); The temperature of described polyreaction is preferably 40 DEG C��80 DEG C, more preferably 45 DEG C��75 DEG C; The time of described polyreaction is preferably 3��5h;The pressure of described polyreaction is preferably 8��16MPa, more preferably 10��14MPa.
In the present invention, preferably the heating in the environment that airtight, carbon dioxide exist of initiator, acrylamide monomer and hydrophobic monomer is carried out polyreaction, after temperature rises, supplementary pressure, it is further continued for heating and carries out polyreaction, more preferably when temperature rises to lower than polymeric reaction temperature 2 DEG C��3 DEG C, the pressure that supplementary pressure needs to polyreaction, it is further continued for heating and carries out polyreaction; Course of reaction controls pressure in scope.
Hydrophobic associated polymer of the present invention includes the monomeric unit of acrylamide and the monomeric unit of hydrophobic monomer, 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, and in water, hydrophobic group is assembled due to hydrophobic interaction, form spacial framework, thus providing necessary viscoelasticity for solution; Two kinds of unit combineds effect improve the temperature tolerance of hydrophobic associated polymer, salt tolerance and anti-shear performance; Further, adopting supercritical carbon dioxide to prepare hydrophobic associated polymer preparation method simple, reaction condition is gentle, and productivity is higher.
Carbon dioxide has relatively low critical parameters (TcIt is 31.18 DEG C, PcFor 7.38MPa), supercritical carbon dioxide has the high density of similar liquids and close to the low viscosity of gas, thus easy expanding as gas, there is again the dissolubility as liquid, utilize supercritical carbon dioxide as polymerization reaction medium, its mass transfer and heat transfer rate are fast, and reaction temperature and pressure controllable are good. By controlling reaction pressure and temperature so that monomer is dissolved in supercritical carbon dioxide, and when uniform temperature, initiator is decomposed into formation monomer radical in supercritical carbon dioxide; Monomer radical and vinyl monomer carry out addition, form 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, and by reducing temperature and pressure, is released by carbon dioxide, it is thus achieved that polymer.
Present invention also offers the application in the fields such as oilfield chemistry, water process, papermaking and mineral floating of a kind of above-mentioned hydrophobic associated polymer.
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��5
The synthesis conditions such as the kind of each monomer and initiator and rate of charge, reaction temperature, pressure are in Table 1. In table 1, initiator is AIBN, and concentration is account for the mass fraction of total monomer, and function monomer is 2-acrylamide-2-methyl propane sulfonic sodium, and hydrophobic monomer is Hexafluorobutyl mathacrylate.
Various monomers in table 1 and initiator are put in 1L stainless steel cauldron, seals, pass into CO2About 10min drains air in still, it is then shut off terminal valve, starts magnetic agitation, heat temperature raising, when temperature rises to lower than design temperature 2 DEG C��3 DEG C, open high-pressure pump, be supplemented to reaction pressure, along with the rising of temperature, the pressure of reactor will constantly rise, when temperature reaches required temperature, control the pressure of reactor so that it is maintain within required pressure limit, the change of temperature and pressure during record reaction, reaction 3��5h, closes heating power supply, and natural cooling reactor is to room temperature, open air outlet valve, slowly release CO2, open reaction kettle cover, obtain white solid product and hydrophobic associated polymer.
Utilize infrared spectrum that the hydrophobic associated polymer obtained in embodiment 1 is analyzed, obtain its infrared spectrogram, as shown in Figure 1. As shown in Figure 1, in FTIR spectrum figure, wave number is 3581cm-1And 3162cm-1Place belongs to antisymmetric stretching vibration and the symmetrical stretching vibration peak of N-H key; 2937cm-1And 1449cm-1Place is respectively belonging to stretching vibration peak and the bending vibration peak of C-H; 1681cm-1Belong to the stretching vibration of amide �� C=O; 1412cm-1Place belongs to COO-Stretching vibration peak; 1349cm-1And 1317cm-1For C-N stretching vibration peak; 1187cm-1For SO3Stretching vibration peak; 1125cm-1For the stretching vibration peak of C-O-C key, 1043cm-1Stretching vibration peak for C-F key.
Utilize proton nmr spectra that the hydrophobic associated polymer obtained in embodiment 1 is analyzed, obtain it1H-NMR spectrum, as shown in Figure 2. As shown in Figure 2, �� 1.15 (e) is hydrophobic monomer side chain-CH3The chemical shift of hydrogen, �� 1.46���� 1.50 (a) is-CH on acrylamide, AMPS and hydrophobic monomer2The chemical shift of hydrogen, �� 1.52 (c) is-CH in AMPS3The chemical shift of hydrogen; �� 2.11���� 2.35 (b) is the chemical shift of-CH hydrogen on acrylamide, AMPS and hydrophobic monomer, �� 3.55 (d) is for connecting the chemical shift of sulfonic-CH2 hydrogen in AMPS, on �� 4.28 (f), �� 4.67 (g) respectively hydrophobic group, ester group is connected on the chemical shift of-CH2 hydrogen and hydrophobic chain-CF2With-CF3Between the chemical shift of-CH (F) hydrogen. Wherein, �� 3.22 is the chemical shift of solvent DMSO
Use Ubbelohde viscometer (0.55mm caliber) to test and calculate polymer viscosity-average molecular weight by GB/T12005.10-92 to the hydrophobic associated polymer obtained in embodiment 1��5, obtain result in Table 1.
Adopting total salinity is 2.0 ten thousand water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 1��5 of 1000mg/L, is 85 DEG C in temperature, and shear rate is 7.34s-1Lower test polymer solution concentration is 2000mg/L viscosity number. Obtain result in Table 1.
Utilizing the gas chromatography hydrophobic associated polymer to obtaining in embodiment 1��5 to carry out test analysis, obtain residual monomer content and product purity, result is in Table 1.
The raw material of table 1 embodiment 1��5, reaction condition and test result
Embodiment 6��10
The synthesis conditions such as the kind of each monomer and initiator and rate of charge, reaction temperature, pressure are in Table 2. In table 2, initiator is AIBN, and concentration is account for the mass fraction of total monomer, and function monomer is 2-acrylamide-2-methyl propane sulfonic sodium, and hydrophobic monomer is Hexafluorobutyl mathacrylate.
Various monomers in table 2 and initiator are put in 1L stainless steel cauldron, seals, pass into CO2About 10min drains air in still, it is then shut off terminal valve, starts magnetic agitation, heat temperature raising, when temperature rises to lower than design temperature 2 DEG C��3 DEG C, open high-pressure pump, be supplemented to reaction pressure, along with the rising of temperature, the pressure of reactor will constantly rise, when temperature reaches required temperature, control the pressure of reactor so that it is maintain within required pressure limit, the change of temperature and pressure during record reaction, reaction 3��5h, closes heating power supply, and natural cooling reactor is to room temperature, open air outlet valve, slowly release CO2, open reaction kettle cover, obtain white solid product and hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) to test and calculate polymer viscosity-average molecular weight by GB/T12005.10-92 to the hydrophobic associated polymer obtained in embodiment 6��10, obtain result in Table 2.
Adopting total salinity is 2.0 ten thousand water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 6��10 of 1000mg/L, it is 85 DEG C in temperature, shear rate is 7.34s-1Lower test polymer solution concentration is 2000mg/L viscosity number. Obtain result in Table 2.
Utilizing the gas chromatography hydrophobic associated polymer to obtaining in embodiment 6��10 to carry out test analysis, obtain residual monomer content and product purity, result is in Table 2.
The raw material of table 2 embodiment 6��10, reaction condition and test result
Embodiment 11��15
The synthesis conditions such as the kind of each monomer and initiator and rate of charge, reaction temperature, pressure are in Table 3. In table 3, initiator is AIBN, and concentration is account for the mass fraction of total monomer, and function monomer is 2-acrylamide-2-methyl propane sulfonic sodium, and hydrophobic monomer is Hexafluorobutyl mathacrylate.
Various monomers in table 3 and initiator are put in 1L stainless steel cauldron, seals, pass into CO2About 10min drains air in still, it is then shut off terminal valve, starts magnetic agitation, heat temperature raising, when temperature rises to lower than design temperature 2 DEG C��3 DEG C, open high-pressure pump, be supplemented to reaction pressure, along with the rising of temperature, the pressure of reactor will constantly rise, when temperature reaches required temperature, control the pressure of reactor so that it is maintain within required pressure limit, the change of temperature and pressure during record reaction, reaction 3��5h, closes heating power supply, and natural cooling reactor is to room temperature, open air outlet valve, slowly release CO2, open reaction kettle cover, obtain white solid product and hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) to test and calculate polymer viscosity-average molecular weight by GB/T12005.10-92 to the hydrophobic associated polymer obtained in embodiment 11��15, obtain result in Table 3.
Adopting total salinity is 2.0 ten thousand water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 11��15 of 1000mg/L, is 85 DEG C in temperature, and shear rate is 7.34s-1Lower test polymer solution concentration is 2000mg/L viscosity number. Obtain result in Table 3.
Utilizing the gas chromatography hydrophobic associated polymer to obtaining in embodiment 11��15 to carry out test analysis, obtain residual monomer content and product purity, result is in Table 3.
The raw material of table 3 embodiment 11��15, reaction condition and test result
Embodiment 16��20
The synthesis conditions such as the kind of each monomer and initiator and rate of charge, reaction temperature, pressure are in Table 4. In table 4, initiator is AIBN, and concentration is account for the mass fraction of total monomer, and function monomer is 2-acrylamide-2-methyl propane sulfonic sodium, and hydrophobic monomer is Hexafluorobutyl mathacrylate.
Various monomers in table 4 and initiator are put in 1L stainless steel cauldron, seals, pass into CO2About 10min drains air in still, it is then shut off terminal valve, starts magnetic agitation, heat temperature raising, when temperature rises to lower than design temperature 2 DEG C��3 DEG C, open high-pressure pump, be supplemented to reaction pressure, along with the rising of temperature, the pressure of reactor will constantly rise, when temperature reaches required temperature, control the pressure of reactor so that it is maintain within required pressure limit, the change of temperature and pressure during record reaction, reaction 3��5h, closes heating power supply, and natural cooling reactor is to room temperature, open air outlet valve, slowly release CO2, open reaction kettle cover, obtain white solid product and hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) to test and calculate polymer viscosity-average molecular weight by GB/T12005.10-92 to the hydrophobic associated polymer obtained in embodiment 16��20, obtain result in Table 4.
Adopting total salinity is 2.0 ten thousand water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 16��20 of 1000mg/L, is 85 DEG C in temperature, and shear rate is 7.34s-1Lower test polymer solution concentration is 2000mg/L viscosity number. Obtain result in Table 4.
Utilizing the gas chromatography hydrophobic associated polymer to obtaining in embodiment 16��20 to carry out test analysis, obtain residual monomer content and product purity, result is in Table 4.
The raw material of table 4 embodiment 16��20, reaction condition and test result
Embodiment 21��25
The synthesis conditions such as the kind of each monomer and initiator and rate of charge, reaction temperature, pressure are in Table 5. In table 5, initiator is AIBN, and concentration is account for the mass fraction of total monomer, and function monomer is 2-acrylamide-2-methyl propane sulfonic sodium, and hydrophobic monomer is Hexafluorobutyl mathacrylate.
Various monomers in table 5 and initiator are put in 1L stainless steel cauldron, seals, pass into CO2About 10min drains air in still, it is then shut off terminal valve, starts magnetic agitation, heat temperature raising, when temperature rises to lower than design temperature 2 DEG C��3 DEG C, open high-pressure pump, be supplemented to reaction pressure, along with the rising of temperature, the pressure of reactor will constantly rise, when temperature reaches required temperature, control the pressure of reactor so that it is maintain within required pressure limit, the change of temperature and pressure during record reaction, reaction 3��5h, closes heating power supply, and natural cooling reactor is to room temperature, open air outlet valve, slowly release CO2, open reaction kettle cover, obtain white solid product and hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) to test and calculate polymer viscosity-average molecular weight by GB/T12005.10-92 to the hydrophobic associated polymer obtained in embodiment 21��25, obtain result in Table 5.
Adopting total salinity is 2.0 ten thousand water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 21��25 of 1000mg/L, is 85 DEG C in temperature, and shear rate is 7.34s-1Lower test polymer solution concentration is that 2000mg/L viscosity number obtains result in Table 5.
Utilizing the gas chromatography hydrophobic associated polymer to obtaining in embodiment 21��25 to carry out test analysis, obtain residual monomer content and product purity, result is in Table 5.
The raw material of table 5 embodiment 21��25, reaction condition and test result
Embodiment 26��32
The synthesis conditions such as the kind of each monomer and initiator and rate of charge, reaction temperature, pressure are in Table 6. In table 6, initiator is AIBN, and concentration is account for the mass fraction of total monomer, and acrylamide, function monomer and hydrophobic monomer mol ratio are 89.2:10:0.8, and function monomer is 2-acrylamide-2-methyl propane sulfonic sodium.
Various monomers in table 6 and initiator are put in 1L stainless steel cauldron, seals, pass into CO2About 10min drains air in still, it is then shut off terminal valve, starts magnetic agitation, heat temperature raising, when temperature rises to lower than design temperature 2 DEG C��3 DEG C, open high-pressure pump, be supplemented to reaction pressure, along with the rising of temperature, the pressure of reactor will constantly rise, when temperature reaches required temperature, control the pressure of reactor so that it is maintain within required pressure limit, the change of temperature and pressure during record reaction, reaction 3��5h, closes heating power supply, and natural cooling reactor is to room temperature, open air outlet valve, slowly release CO2, open reaction kettle cover, obtain white solid product and hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) to test and calculate polymer viscosity-average molecular weight by GB/T12005.10-92 to the hydrophobic associated polymer obtained in embodiment 26��32, obtain result in Table 6.
Adopting total salinity is 2.0 ten thousand water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 26��30 of 1000mg/L, is 85 DEG C in temperature, and shear rate is 7.34s-1Lower test polymer solution concentration is that 2000mg/L viscosity number obtains result in Table 6.
Utilizing the gas chromatography hydrophobic associated polymer to obtaining in embodiment 26��32 to carry out test analysis, obtain residual monomer content and product purity, result is in Table 6.
The raw material of table 6 embodiment 26��32, reaction condition and test result
Embodiment 33��35
The synthesis conditions such as the kind of each monomer and initiator and rate of charge, reaction temperature, pressure are in Table 6. In table 7, initiator is AIBN, and concentration is account for the mass fraction of total monomer, and acrylamide, function monomer and hydrophobic monomer mol ratio are 89.2:10:0.8, and hydrophobic monomer is Hexafluorobutyl mathacrylate.
Various monomers in table 7 and initiator are put in 1L stainless steel cauldron, seals, pass into CO2About 10min drains air in still, it is then shut off terminal valve, starts magnetic agitation, heat temperature raising, when temperature rises to lower than design temperature 2 DEG C��3 DEG C, open high-pressure pump, be supplemented to reaction pressure, along with the rising of temperature, the pressure of reactor will constantly rise, when temperature reaches required temperature, control the pressure of reactor so that it is maintain within required pressure limit, the change of temperature and pressure during record reaction, reaction 3��5h, closes heating power supply, and natural cooling reactor is to room temperature, open air outlet valve, slowly release CO2, open reaction kettle cover, obtain white solid product and hydrophobic associated polymer.
Use Ubbelohde viscometer (0.55mm caliber) to test and calculate polymer viscosity-average molecular weight by GB/T12005.10-92 to the hydrophobic associated polymer obtained in embodiment 33��35, obtain result in Table 7.
Adopting total salinity is 2.0 ten thousand water, Ca2+��Mg2+Total ion concentration is the hydrophobic associated polymer prepared polymer solution obtained in simulation saline and the embodiment 33��35 of 1000mg/L, is 85 DEG C in temperature, and shear rate is 7.34s-1Lower test polymer solution concentration is that 2000mg/L viscosity number obtains result in Table 6.
Utilizing the gas chromatography hydrophobic associated polymer to obtaining in embodiment 33��35 to carry out test analysis, obtain residual monomer content and product purity, result is in Table 7.
The raw material of table 7 embodiment 33��35, reaction condition and test result
Claims (10)
1. a hydrophobic associated polymer, including formula (I) and the repetitive shown in formula (II):
Wherein, described x:y=1:(0.001��0.2); Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer is selected from one or more in N-alkyl-substituted acrylamide and derivant, alkyl acrylate, alkyl methacrylate, the alkyl acrylate of fluorine replacement, the alkyl methacrylate of fluorine replacement, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid.
2. hydrophobic associated polymer according to claim 1, it is characterized in that, in the alkyl methacrylate that the alkyl acrylate that described N-alkyl-substituted acrylamide and derivant thereof, alkyl acrylate, alkyl methacrylate, allyl alkyl quaternary ammonium salt, acrylic acid alkyl sulfonic acid and sulfonate thereof, alkylphenol-polyethenoxy acrylate, the polyxyethylated ester of acrylic acid, fluorine replace and fluorine replace, the carbon number of alkyl is each independently 4��40.
3. hydrophobic associated polymer according to claim 1, it is characterised in that also include the repetitive shown in formula (III):
Wherein, described x:z=1:(0.001��0.3); Described D is the monomeric unit of function monomer; Described function monomer is selected from containing the sulfonic acid and sulfonate derivatives thereof of holding thiazolinyl and containing one or more in the Hete rocyclic derivatives holding thiazolinyl.
4. hydrophobic associated polymer according to claim 1, it is characterised in that also include the repetitive shown in formula (IV):
Wherein, x:mm=1:(0.03��0.3).
5. hydrophobic associated polymer according to claim 1, it is characterised in that the viscosity-average molecular weight of described hydrophobic associated polymer is 50��8,000,000.
6. the preparation method of a hydrophobic associated polymer, it is characterised in that including:
Under the effect of initiator, acrylamide monomer and hydrophobic monomer are carried out polyreaction in supercritical carbon dioxide environment, obtains hydrophobic associated polymer; The mol ratio of described acrylamide monomer and hydrophobic monomer is 1:(0.001��0.2); Described hydrophobic monomer is selected from one or more in N-alkyl-substituted acrylamide and derivant, alkyl acrylate, alkyl methacrylate, the alkyl acrylate of fluorine replacement, the alkyl methacrylate of fluorine replacement, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and sulfonate, alkylphenol-polyethenoxy acrylate and the polyxyethylated ester of acrylic acid.
7. preparation method according to claim 6, it is characterised in that the temperature of described polyreaction is 40 DEG C��80 DEG C; The time of described polyreaction is 3��5h.
8. preparation method according to claim 6, it is characterised in that the pressure of described polyreaction is 8��16MPa.
9. preparation method according to claim 6, it is characterised in that the quality of described initiator is the 0.1%��2% of all monomer gross masses.
10. the hydrophobic associated polymer described in Claims 1 to 5 any one or the application in oilfield chemistry, water process, papermaking or mineral floating field of the hydrophobic associated polymer prepared by claim 6��9 any one.
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