CN106608971A - Anti-calcium tackifier copolymerization complex and preparation method thereof - Google Patents
Anti-calcium tackifier copolymerization complex and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anti-calcium tackifier copolymerization complex and a preparation method thereof. The anti-calcium tackifier copolymerization complex comprises a structural unit A, a structural unit B and a structural unit C. The structural unit A is acrylamide, the structural unit B is a zwitterionic monomer methacryloyloxyethyl-N, N-dimethylpropanesulfonate (DMAPS), and the structural unit C is an ionic complex of the structural unit B and cationic polyamine. The copolymerization complex comprises, by weight, 10 to 75% of the structural unit A, 8 to 55% of the zwitterionic monomer and 1 to 50% of the cationic polyamine, and preferably, comprises 30 to 65% of the structural unit A, 20 to 60% of the zwitterionic monomer and 3 to 40% of the cationic polyamine. The tackifier obtained by the preparation method can resist a temperature of 150 DEG C, has a saturated anti-NaCl concentration and an anti-CaCl2 concentration of 20% and has excellent shale inhibition performances and de-filtration performances.
Description
Technical field
The present invention relates to polymer for drilling fluid and preparation method thereof in Process of Oil Well Drilling, more particularly to a kind of drilling fluid high temperature resistant anticalcium viscosifier and preparation method thereof.
Background technology
In drilling process, in order to ensure low solid phase under drilling fluid there is higher viscosity and good rheological characteristic, it usually needs addition viscosifier are improving the viscosity of drilling fluid.Drilling fluid tackifier is the very long high molecular weight water soluble polymer of strand, and viscosifier also tend to also serve as shale control agent except playing viscosifying action（Coating agent）, fluid loss additive and flow pattern modifier etc..Therefore, be often conducive to improving the rheological characteristic of drilling fluid using viscosifier, be also beneficial to wellbore stability.
Drilling fluid tackifier is of paramount importance one kind in drilling well auxiliary agent, is broadly divided into natural plant and the synthesis big class of macromolecule two, is ensureing drilling fluid safe construction, taking the aspects such as abrasive band bits have important function.But existing drilling fluid tackifier such as xanthan gum, 80A51
Deng, construction at high temperature needs are not well positioned to meet, most of viscosifier Efficient Adhesive Promotion under the conditions of higher than 150 DEG C declines rapidly, even disappears completely.In terms of salt resistance, anti- high calcium chloride concentration also drilling fluid field problem demanding prompt solution, current almost polymer of the not anti-calcium chloride concentration more than 15% in conventional viscosifier, thus tackifier for drilling fluid heat resistance conventional at present and anti-calcium and anti-salt performance tend not to take into account.
CN102372818A
With anticalcium polymeric viscosifiers disclosed in CN102464761A, mainly obtained by introducing sulfonation group or hydrophobic group in acrylamide copolymer, can only meet calcium ion concentration and be not higher than 2000mg/L
Cryogenic conditions under（Less than 100 DEG C）Use demand.High temperature resistant viscosifier disclosed in CN101955564A, CN103113518A and CN102127401A, the resistance to elevated temperatures of viscosifier is obviously improved, and heatproof reaches more than 200 DEG C；Anti-calcium and anti-salt performance is not referred to, but speculates that anti-calcium and anti-salt performance is not improved from monomer used and preparation method.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of anticalcium viscosifier copolymerization associated complex and preparation method thereof.Up to 150 DEG C, anti-NaCl concentration reaches saturation, anti-CaCl to the viscosifier heatproof that the inventive method is obtained2Concentration is up to 20%.Higher apparent viscosity is maintained after high temperature ageing, while also having preferable yield value.
The invention provides a kind of anticalcium viscosifier copolymerization associated complex, the copolymerization associated complex contains construction unit A, construction unit B and construction unit C, the construction unit A be acrylamide, the construction unit B be zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate（DMAPS）, the construction unit C is the ion association body of construction unit B and cationic polyamine, and on the basis of the total amount of the copolymerization associated complex, the content of the construction unit A is 10-75 weight %, preferably 30-65 weight %；The total content of the zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 8-55 weight %, preferably 20-60 weight %；The content of the cationic polyamine is 1-50 weight %, preferably 3-40 weight %；The copolymerization associated complex is 40-70mPas in 150 DEG C of apparent viscosities after aging 16 hours.
According to the viscosifier copolymerization associated complex that the present invention is provided, the structural formula of the construction unit A acrylamides is：
Formula（I）, the construction unit B zwitterionic monomers methylacryoyloxyethyl-N, the structural formula of N- dimethyl propylene sulfonate (DMAPS) is：Formula（II）, the construction unit C has the structure shown in following formula：
Formula（III）
Wherein, dotted line ... represents ion association, X-For inorganic anion；R、R9、R9’、R10、R10' it is respectively following formula（IV）Shown structure：Formula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, t is the integer of 1-5, and z is the integer of 0-5；
N, p are respectively the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10；L, l ' and l " value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree is 0.5-2mmol/g.Further preferably the kinematic viscosity of the cationic polyamine is 150-450mm2/ s, cationic degree is 0.5-1.5mmol/g.
Above-mentioned cationic polyamine can balance anion with multiple nitrogen cations for various with corresponding, and under preferable case, the cationic polyamine is by formula（V）Shown end amine and formula（VI）Shown cyclic ethers and formula（VII）Shown haloalkylene oxide is obtained by condensation reaction
T, n, p are respectively the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10.When x is 0, formula（V）End diamidogen is represented, y is preferably the integer of 1-7；When x is not equal to 0, and during y=2, formula（V）Polyethylene polyamine is represented, x is the integer of 1-10.
Wherein the definition of substituent group and subscript with it is identical above.
Specifically, the cationic polyamine can be obtained by following methods：Mol ratio to Deca cyclic ethers in the amine of end, cyclic ethers and end amine at stirring condition and 50-120 DEG C is 2-4：1,1-4 hours are reacted after completion of dropwise addition, 80-150 DEG C is then heated to, Deca haloalkylene oxide under stirring condition, haloalkylene oxide is 0.2-0.7 with the mol ratio of end amine：1,1-4 hours are reacted after completion of dropwise addition, then terminating reaction.
It should be noted that although temperature range 50-120 DEG C before heating up overlaps with temperature range 80-150 DEG C after intensification, the temperature of the latter must be higher than the former temperature.
Can be by adding hydrochloric acid come terminating reaction.The addition of hydrochloric acid is preferably hydrochloric acid：End amine=1-3：1（Mol ratio）.
Under preferable case, the end amine is one or more in ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, TEPA.
Under preferable case, the cyclic ethers is one or more in oxirane, expoxy propane, tetrahydrofuran.
Under preferable case, the haloalkylene oxide is one or more in epoxychloropropane, epoxy bromopropane, epoxy chlorobutane.
According to the copolymerization associated complex that the present invention is provided, under preferable case, the weight average molecular weight of the copolymerization associated complex is 500,000-500 ten thousand, more preferably 1,000,000-300 ten thousand.
In the present invention, copolymerization associated complex refers to the structure for both having included being formed in polymer by copolymerization, also the structure formed by ion association is included, wherein construction unit A, construction unit B are formed by copolymerization, construction unit B and cationic polyamine are combined together by ion association, form construction unit C.Dotted line ... in each structural formula represents ion association.
In the present invention, the content of copolymerization associated complex cationic polyamine refers to the total content of the various versions provided by cationic polyamine in copolymerization associated complex, including the amount of the cationic polyamine for forming copolymerization associated complex, also including the amount of the cationic polyamine for not forming copolymerization associated complex.
The means of testing grasped due to inventor is limited and/or limitation based on existing means of testing, the present invention each construction unit of copolymerization associated complex content be only capable of testing be construction unit corresponding with monomer content, and the content of construction unit C can not be measured, the amount of the zwitterionic structural elements for participating in associating and have neither part nor lot in association can not be measured, the content of i.e. above-mentioned zwitterionic structural elements includes associating to form the zwitterionic structural elements i.e. content of construction unit B of construction unit C with cationic polyamine, also include not with the content of the zwitterionic structural elements to form construction unit C that associate with cationic polyamine.
In the present invention, the content of each construction unit can determine by way of content of monomer calculating or nuclear magnetic resonance, NMR before and after reaction are with reference to infrared spectrum analysiss.
In the present invention, the alkyl of the C1-C5 can be one or more in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl.The substituent group of the alkyl of the C1-C5 for example can be halogen or hydroxyl.
According to the copolymerization associated complex that the present invention is provided, it is conventional covalent polymerization methodses between wherein construction unit A, construction unit B, pass through Covalent bonding together between i.e., and construction unit C then by its anion and cation respectively with construction unit B on cation and anion become the construction unit of copolymerization associated complex with ion association, so as to its network structure is introduced in copolymerization associated complex so that copolymerization associated complex has higher shear force and heat-resistant salt-resistant.Above-mentioned ion association can by by its with obtained by carrying out being simply mixed the mixture for obtaining by the copolymerization associated complex and cationic polyamine between construction unit A, construction unit B and measure the greatest differences of its shear force and heat-resistant salt-resistant under the same conditions and speculate with reference to the principles of chemistry.
In the present invention, the content of each construction unit can determine by way of content of monomer calculating or nuclear magnetic resonance, NMR before and after reaction are with reference to infrared spectrum analysiss.
The present invention also provides a kind of preparation method of above-mentioned viscosifier copolymerization associated complex, the method comprising the steps of：
（1）Inorganic salt is mixed with water, the inorganic salt solution of 2wt%～30wt% is prepared；
（2）Cationic polyamine and water are hybridly prepared into into cationic polyamine aqueous solution, the mass concentration of the cationic polyamine aqueous solution is 0.5%～3%；
（3）Methylacryoyloxyethyl-N is weighed,
N- dimethyl propylenes sulfonate and acrylamide and step（1）In inorganic salt solution mixing, methylacryoyloxyethyl-N,
N- dimethyl propylenes sulfonate and acrylamide monomer total mass concentration are 5%～20%, and according to acrylamide, methylacryoyloxyethyl-N,
On the basis of the total amount of N- dimethyl propylenes sulfonate and cationic polyamine, the consumption of acrylamide is 10-75 weight %, preferably 30-65 weight %；The consumption of methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 15-65 weight %, preferably 20-60 weight %；N is passed through after fully dissolving20.5～1h of deoxygenation, while being warming up to 40～60 DEG C, adds 0.5～2h of initiator for reaction after 5～10min of constant temperature；
（4）By step（2）The cationic polyamine aqueous solution of preparation is added to step（3）In the product for obtaining, mix homogeneously is warming up to 50～70 DEG C simultaneously, continues to react 3～5；With acrylamide, methylacryoyloxyethyl-N, on the basis of the total amount of N- dimethyl propylenes sulfonate and cationic polyamine, the consumption of cationic polyamine is 1-50 weight %, preferably 3-40 weight %；
（5）By step（4）The product for obtaining is washed with acetone soln, and the solid sediment obtained after washing is viscosifier through drying and after crushing.
The preparation method of the copolymerization associated complex provided according to the present invention, the environment that the anion and cation that one Main Function of the inorganic salt is to provide on zwitterionic structural elements is exchanged/associated with cation and anion on cationic polyamine, as long as therefore can provide above-mentioned environment inorganic salt may be used as the present invention inorganic salt.Under preferable case, the inorganic salt is one or more in ammonium salt, calcium salt, magnesium salt, mantoquita, zinc salt, aluminium salt, zirconates.The inorganic salt is preferably used in the form of a solution.
The present inventor is by research it has furthermore been found that different types of inorganic salt, and the solution concentration for reaching optimum efficiency is different, and for example, when the inorganic salt is ammonium salt, the inorganic salt solution concentration is preferably 10wt%～30wt%；When the inorganic salt is calcium salt, magnesium salt, mantoquita, zinc salt, the inorganic salt solution concentration is preferably 5%～15%, more preferably 10%～15%；When the inorganic salt is aluminium salt, the inorganic salt solution concentration is preferably 2wt%～10wt%；When the inorganic salt is zirconates, described inorganic salt solution concentration is preferably 2wt%～5wt%.The concentration of above-mentioned inorganic salt solution only considers the amount of inorganic salt and its solvent, does not consider the amount of other materials such as monomer.
When the inorganic salt be ammonium salt when, be specifically as follows ammonium chloride, ammonium bromide, one or more of ammonium nitrate；When the inorganic salt is calcium salt, calcium chloride, calcium bromide are specifically as follows；When the inorganic salt be magnesium salt when, be specifically as follows magnesium chloride, magnesium bromide, magnesium sulfate, one or more of magnesium nitrate；When the inorganic salt be aluminium salt when, be specifically as follows aluminum chloride, aluminium bromide, aluminum sulfate, one or more of aluminum nitrate；When the inorganic salt be mantoquita when, be specifically as follows copper chloride, copper bromide, copper sulfate, one or more of copper nitrate；When the inorganic salt be zinc salt when, be specifically as follows zinc chloride, zinc bromide, one or more of zinc nitrate；When the inorganic salt be zirconates when, be specifically as follows zirconium chloride, zirconium bromide, zirconium oxychloride, one or more of zirconium nitrate.
The preparation method of the copolymerization associated complex provided according to the present invention, step（3）Carry out in the presence of initiator, the species and consumption of the initiator are referred to prior art to be carried out.Under preferable case, the initiator can be one or more in sodium peroxydisulfate, potassium peroxydisulfate, Ammonium persulfate..The consumption of the initiator is preferably the 0.3-0.7wt% of monomer total amount.
In the inventive method, the monomer gross mass concentration is the ratio of monomer mass and water gross mass.
The preparation method of the copolymerization associated complex provided according to the present invention, the cationic polyamine has following formula（i）Shown structure：
Formula（i）
Wherein, X-For inorganic anion；R、R9、R9’、R10、R10' it is respectively following formula（IV）Shown structureFormula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, t is the integer of 1-5, and z is the integer of 0-5；N, p are respectively the integer of 1-5, and x is the integer of 0-10, and y is the integer of 1-10；L, l ' and l ' ' value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree is 0.5-2mmol/g.
Above-mentioned cationic polyamine is referred to the preparation method of cationic polyamine polymer disclosed in CN103773332A and is prepared：By carrying out polyreaction and obtaining end amine, cyclic ethers and epoxy alkyl halide.The end amine can be the alkyl diamine that alkyl diamine such as carbon number is 1-6, concrete such as ethylenediamine, propane diamine, butanediamine, pentanediamine or hexamethylene diamine；Can also be polyamines polyene such as NH2-(CH2-CH2-NH)nH wherein n are the integer of 1-5, such as diethylenetriamine, triethylene tetramine or TEPA.The cyclic ethers can be cyclic ethers such as oxirane, expoxy propane, the epoxy butane that carbon number is 2-6.The epoxy alkyl halides such as can be epoxychloropropane, epoxy bromopropane or epoxy chlorobutane.But in order to ensure association and more preferable property of drilling fluid is obtained, the kinematic viscosity of the cationic polyamine should be controlled to 100-500mm2/ s, cationic degree should be controlled to 0.5-2mmol/g.Kinematic viscosity and cationic degree can be controlled by controlling the addition of cyclic ethers and epoxy alkyl halide within the above range.Usually control end amine and the mol ratio of cyclic ethers are 1：（2-4）.End amine is 1 with the mol ratio of epoxy alkyl halide：（0.2-0.7）.Other reaction conditions and operation are referred to above-mentioned prior art to be carried out.
The cationic polyamine is preferably used as an aqueous solution, and the concentration of cationic polyamine aqueous solution is preferably 0.5-3wt%, and the wherein amount of water is the total Water in reaction system.
According to the method that the present invention is provided, step（6）The purpose of products therefrom washing with acetone is to remove unreacted component, and dry temperature can be 100-120 DEG C, and the dry time can be 16-24 hours.
Compared with prior art, the viscosifier copolymerization associated complex that the present invention is provided and preparation method thereof advantage is as follows：
（1）The copolymerization associated complex that the present invention is provided, by containing acrylamide construction unit, zwitterionic structural elements and cationic polyamine construction unit simultaneously with certain proportion, and cationic polyamine construction unit has specific kinematic viscosity and cationic degree, during so that the copolymerization associated complex being used as drilling fluid tackifier, gained drilling fluid not only has good apparent viscosity after high temperature ageing, but also with preferable shear force, and heatproof, at least up to more than 150 DEG C, anti-NaCl concentration reaches saturation, anti-CaCl2Concentration is up to 20%.
（2）In the preparation method of viscosifier copolymerization associated complex of the present invention, before the reaction the phase is by using high concentration inorganic salt solution, sulfonic group zwitterionic monomer can be made to combine to form special construction with inorganic salt, because the presence of metal ion in inorganic salt causes the structure of sulfonic group zwitterionic monomer more to stretch, substantially reduce during polymerization intermolecular sterically hindered, make monomer molecule arrangement even closer, considerably increase the molecular weight of polymer.After the reaction the phase is by adding low molecular weight cationic polyamine, further had an effect with the sulfonic group in zwitterionic monomer by the ammonium cation on low molecular weight cationic polyamine structure, form more stable network structure, strengthen the structural viscosity of polymer, while ensureing that viscosifier have good apparent viscosity, preferable shear force is provided with again.
（3）Viscosifier copolymerization associated complex prepared by the inventive method has long-chain branch and rigid annular group.In aqueous due to the presence of long-chain branch and rigid annular group, increased the sterically hindered of polymer, increase the hydrodynamic volume of polymer, the trend for causing the fracture hydrolysis of polymer temperature influence is reduced, so as to improve the performance of its heatproof, at least up to 150 DEG C, what is had reaches 180 DEG C to heatproof.
Description of the drawings
Fig. 1 and Fig. 2 be respectively the infrared of DMAPS and1HNMR spectrograms.
Specific embodiment
The effect and effect of the inventive method are illustrated with reference to embodiment, but following examples do not constitute the restriction to the present invention program.The present invention is described further for the following examples.In following examples, kinematic viscosity adopts GB GB/T
265 oil product kinematic viscosity algoscopys and dynamic viscosity calculating method are measured；Cationic degree is measured using colloid titration method；Apparent viscosity and yield value are determined by six fast rotating cylinder viscometer methods.Wherein, shear force represents the structural viscosity that system has, and shear force is bigger, illustrates that the performance of the suspension landwaste of drilling fluid is better.
DMAPS monomers used in the embodiment of the present invention and comparative example can be prepared as follows：
Weigh 785g dimethylaminoethyl methacrylates to pour in reactor, in being then placed in thermostat water bath, heat and start stirring.The PS of 122g is weighed again, and in being added directly into dimethylaminoethyl methacrylate, reaction temperature is 55 DEG C, and the crude product of DMAPS is obtained after stirring reaction 2h.DMAPS crude products are transferred in large stretch of filter paper and are wrapped, the use of ethanol is solvent extraction 2.5h in being positioned over Soxhlet extraction device, extracting is placed on filter paper bag in drying baker after finishing, and is dried at 35 DEG C, finally gives pure DMAPS monomers.The infrared spectrum of the DMAPS and hydrogen nuclear magnetic spectrogram are respectively as depicted in figs. 1 and 2.
Cationic polyamine used is prepared as follows in the embodiment of the present invention and comparative example：
In 1000mL four round flask, add 60g ethylenediamines, 70 DEG C are warming up under agitation, then gradually Deca 116g expoxy propane, controlling reaction temperature 60-100 DEG C, 95 DEG C are warming up to after reaction 1h, gradually Deca 185g epoxychloropropane, controlling reaction temperature is 90-150 DEG C, when thickening behavior occurs in question response system, hydrochloric acid is added after at least maintaining half an hour, hydrochloric acid is 2 with the mol ratio of ethylenediamine:1, reaction 4h obtains cationic polyamine 1.The kinematic viscosity of cationic polyamine 1 is 330mm2/ s, cationic degree is 1.8mmol/g.
Wherein, R9、R9’、R10、R10' it is respectively following formula（IV-1）Shown structureFormula（IV-1）
In 1000mL four round flask, add 60g hexamethylene diamines, 70 DEG C are warming up under agitation, then gradually Deca 116g oxirane, controlling reaction temperature 60-100 DEG C, 95 DEG C are warming up to after reaction 1h, gradually Deca 185g epoxy bromopropane, controlling reaction temperature is 90-150 DEG C, when thickening behavior occurs in question response system, hydrochloric acid is added after at least maintaining half an hour, hydrochloric acid is 2 with the mol ratio of hexamethylene diamine:1, reaction 4h obtains cationic polyamine 2.The kinematic viscosity of cationic polyamine 2 is 460mm2/ s, cationic degree is 1.9 mmol/g.
In 1000mL four round flask, add 60g triolefin tetramines, 70 DEG C are warming up under agitation, then gradually Deca 116g epoxy butane, controlling reaction temperature 60-100 DEG C, 95 DEG C are warming up to after reaction 1h, gradually Deca 185g epoxy chlorobutane, controlling reaction temperature is 90-150, when thickening behavior occurs in question response system, hydrochloric acid is added after at least maintaining half an hour, hydrochloric acid is 2 with the mol ratio of triolefin tetramine:1, reaction 4h obtains cationic polyamine 3.The kinematic viscosity of cationic polyamine 3 is 410 mm2/ s, cationic degree is 1.5 mmol/g.
Embodiment 1
Weigh 440g NaCl to be dissolved in 1650g deionized waters；Weigh 28g DMAPS, 64g respectively again
AM is dissolved in NaCl solution；Fully reactor is transferred to after dissolving, is passed through N2Deoxygenation 1h, while being warming up to 55 DEG C, keeps adding 0.45g Ammonium persulfate .s after 30min, and after reaction 2h intermediate product is obtained.20g cationic polyamines 1 are dissolved in 100g deionized waters are again configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 65 DEG C, continue to react 4 hours.Precipitate is obtained with acetone precipitation.Crush after being dried 24h at 110 DEG C, it is final to obtain DMAPS/AM viscosifier.
Embodiment 2
Weigh 112g CaCl2In being dissolved in 910g deionized waters；Weigh 56g DMAPS respectively again, 56g AM are dissolved in CaCl2In solution；Fully reactor is transferred to after dissolving, is passed through N2Deoxygenation 1h, while being warming up to 60 DEG C, keeps adding 0.45g sodium peroxydisulfates after 30min, and reaction 1h obtains intermediate product.20g cationic polyamines 2 are dissolved in 100g deionized waters are again configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 70 DEG C, continue to react 3 hours.Precipitate is obtained with acetone precipitation.Crush after being dried 24h at 120 DEG C, it is final to obtain DMAPS/AM viscosifier.
Embodiment 3
Weigh 40g AlCl3In being dissolved in 660g deionized waters；Weigh 84g DMAPS respectively again, 50g AM are dissolved in AlCl3In solution；Fully reactor is transferred to after dissolving, is passed through N2Deoxygenation 0.5h, while being warming up to 60 DEG C, keeps adding 0.54g potassium peroxydisulfates after 30min, and after reaction 1.5h intermediate product is obtained.25g cationic polyamines 3 are dissolved in 100g deionized waters are again configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 65 DEG C, continue to react 4 hours.Precipitate is obtained with acetone precipitation.Crush after being dried 16h at 120 DEG C, it is final to obtain DMAPS/AM viscosifier.
Embodiment 4
Weigh 19g ZrCl4In being dissolved in 368g deionized waters；Weigh 28g DMAPS respectively again, 64g AM are dissolved in ZrCl4In solution；Fully reactor is transferred to after dissolving, is passed through N2Deoxygenation 1h, while being warming up to 55 DEG C, keeps adding 0.30g sodium peroxydisulfates after 1h, and reaction 1h obtains intermediate product.10g cationic polyamines 2 are dissolved in 50g deionized waters are again configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 70 DEG C, continue to react 4.5 hours.Precipitate is obtained with acetone precipitation.Crush after being dried 20h at 110 DEG C, it is final to obtain DMAPS/AM viscosifier.
Comparative example 1（It is not added with inorganic salt）
56g DMAPS, 56g are weighed respectively
AM is transferred to reactor after being completely dissolved in 910g deionized waters, is passed through N2Deoxygenation 1h, while being warming up to 50 DEG C, keeps adding 0.45g sodium peroxydisulfates after 30min, and reaction 1h obtains intermediate product.20g cationic polyamines 2 are dissolved in 100g deionized waters are again configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 70 DEG C, continue to react 3 hours.Precipitate is obtained with acetone precipitation.Crush after being dried 24h at 120 DEG C, it is final to obtain DMAPS/AM viscosifier.
Comparative example 2（It is not added with cationic polyamine）
Weigh 112g CaCl2In being dissolved in 1010g deionized waters；Weigh 56g DMAPS respectively again, 56g AM are dissolved in CaCl2In solution；Fully reactor is transferred to after dissolving, is passed through N2Deoxygenation 1h, while being warming up to 70 DEG C, keeps adding 0.45g sodium peroxydisulfates after 30min, and after reaction 5h gelatinous solid is obtained, and with acetone precipitation precipitate is obtained.Crush after being dried 24h at 120 DEG C, it is final to obtain DMAPS/AM viscosifier.
Comparative example 3
By commercially available purchase viscosifier 80A51.
Comparative example 4
By commercially available purchase viscosifier xanthan gum.
Above-described embodiment and comparative example evaluate thickening property using the base slurry of saliferous calcic, and concrete evaluation methodology is as follows：
Base slurry is prepared：Add 40g calcium bentonites and 5g sodium carbonate, high-speed stirred 20min that maintenance 24h is placed under room temperature, fresh water-based slurry is obtained in 1000mL water；Continuously add 200g CaCl2, high-speed stirred 20min places maintenance 24h, obtains evaluating with containing 20% CaCl under room temperature2Base is starched.
Evaluation methodology：The base slurry of 350mL is measured, adds 2% viscosifier, high-speed stirred 20min to survey its apparent viscosity after room temperature maintenance 24h.Again after aging 16h at 150 DEG C, apparent viscosity is determined again, calculate apparent viscosity conservation rate.
The different viscosifier temperature-resistant anti-salt anticalcium performance comparison tables of table 1
| Apparent viscosity after high temperature ageing, mPa s | Apparent viscosity conservation rate, % | Yield value after high temperature ageing, mPa s | |
| Embodiment 1 | 50 | 92.6 | 22 |
| Embodiment 2 | 62 | 93.9 | 26 |
| Embodiment 3 | 56 | 93.3 | 24 |
| Embodiment 4 | 62 | 93.9 | 24 |
| Comparative example 1 | 20 | 51.4 | 6 |
| Comparative example 2 | 36 | 71.8 | 9 |
| Comparative example 3 | 6 | 18.8 | 1 |
| Comparative example 4 | 8 | 11.1 | 1 |
Note：The dosage of the xanthan gum of comparative example 4 is 0.5%.
From the result of table 1 can be seen that the present invention viscosifier after high temperature ageing apparent viscosity conservation rate it is higher, illustrate preferable heatproof and salt resistant character；And yield value is also in preferable level after high temperature ageing, it is ensured that drilling fluid system rock of taking under the high temperature conditions carries grittiness energy.
Claims (19)
1. a kind of anticalcium viscosifier copolymerization associated complex, the copolymerization associated complex contains construction unit A, construction unit B and construction unit C, the construction unit A be acrylamide, the construction unit B be zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate（DMAPS）, the construction unit C is the ion association body of construction unit B and cationic polyamine, and on the basis of the total amount of the copolymerization associated complex, the content of the construction unit A is 10-75 weight %, preferably 30-65 weight %；The total content of the zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 8-55 weight %, preferably 20-60 weight %；The content of the cationic polyamine is 1-50 weight %, preferably 3-40 weight %；The copolymerization associated complex is 40-70mPas in 150 DEG C of apparent viscosities after aging 16 hours.
2. according to the copolymerization associated complex described in claim 1, it is characterised in that：The construction unit C has the structure shown in following formula：
Formula（III）
Wherein, dotted line ... represents ion association, X-For inorganic anion；R、R9、R9’、R10、R10' it is respectively following formula（IV）Shown structure：Formula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, t is the integer of 1-5, and z is the integer of 0-5；N, p are respectively the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10；L, l ' and l " value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree is 0.5-2mmol/g.
3. according to the copolymerization associated complex described in claim 2, it is characterised in that：The kinematic viscosity of the cationic polyamine is 150-450mm2/ s, cationic degree is 0.5-1.5mmol/g.
4. according to the copolymerization associated complex described in claim 1, it is characterised in that：The cationic polyamine is by formula（V）Shown end amine and formula（VI）Shown cyclic ethers and formula（VII）Shown haloalkylene oxide is obtained by condensation reaction
Formula（V）
Formula（VI）
Formula（VII）
Wherein, t, n, p are respectively the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10；When x is 0, formula（V）End diamidogen is represented, y is preferably the integer of 1-7；When x is not equal to 0, and during y=2, formula（V）Polyethylene polyamine is represented, x is the integer of 1-10.
5. according to the copolymerization associated complex described in claim 1, it is characterised in that：The cationic polyamine is obtained by following methods：Mol ratio to Deca cyclic ethers in the amine of end, cyclic ethers and end amine at stirring condition and 50-120 DEG C is 2-4：1,1-4 hours are reacted after completion of dropwise addition, 80-150 DEG C is then heated to, Deca haloalkylene oxide under stirring condition, haloalkylene oxide is 0.2-0.7 with the mol ratio of end amine：1,1-4 hours are reacted after completion of dropwise addition, then terminating reaction.
6. according to the copolymerization associated complex described in claim 5, it is characterised in that：The end amine is one or more in ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, TEPA.
7. according to the copolymerization associated complex described in claim 5, it is characterised in that：The cyclic ethers is one or more in oxirane, expoxy propane, tetrahydrofuran.
8. according to the copolymerization associated complex described in claim 5, it is characterised in that：The haloalkylene oxide is one or more in epoxychloropropane, epoxy bromopropane, epoxy chlorobutane.
9. according to the copolymerization associated complex described in any claim in claim 1-8, it is characterised in that：The weight average molecular weight of the copolymerization associated complex is 500,000-500 ten thousand, preferably 1,000,000-300 ten thousand.
10. as described in any claim in claim 1-9 anticalcium viscosifier copolymerization associated complex preparation method, the preparation method comprises the following steps：
（1）Inorganic salt is mixed with water, the inorganic salt solution of 2wt%～30wt% is prepared；
（2）Cationic polyamine and water are hybridly prepared into into cationic polyamine aqueous solution, the mass concentration of the cationic polyamine aqueous solution is 0.5%～3%；
（3）Weigh methylacryoyloxyethyl-N, N- dimethyl propylenes sulfonate and acrylamide and step（1）In inorganic salt solution mixing, methylacryoyloxyethyl-N, N- dimethyl propylenes sulfonate and acrylamide monomer total mass concentration are 5%～20%, and according to acrylamide, methylacryoyloxyethyl-N, on the basis of the total amount of N- dimethyl propylenes sulfonate and cationic polyamine, the consumption of acrylamide is 10-75 weight %, preferably 30-65 weight %；The consumption of methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 15-65 weight %, preferably 20-60 weight %；N is passed through after fully dissolving20.5～1h of deoxygenation, while being warming up to 40～60 DEG C, adds 0.5～2h of initiator for reaction after 5～10min of constant temperature；
（4）By step（2）The cationic polyamine aqueous solution of preparation is added to step（3）In the product for obtaining, mix homogeneously is warming up to 50～70 DEG C simultaneously, continues to react 3～5；With acrylamide, methylacryoyloxyethyl-N, on the basis of the total amount of N- dimethyl propylenes sulfonate and cationic polyamine, the consumption of cationic polyamine is 1-50 weight %, preferably 3-40 weight %；
（5）By step（4）The product for obtaining is washed with acetone soln, and the solid sediment obtained after washing is viscosifier through drying and after crushing.
11. in accordance with the method for claim 10, it is characterised in that：The inorganic salt is one or more in ammonium salt, calcium salt, magnesium salt, mantoquita, zinc salt, aluminium salt, zirconates.
12. according to the method described in claim 10 or 11, it is characterised in that：The inorganic salt is used in the form of a solution, and the inorganic salt be ammonium salt when, the inorganic salt solution concentration be 10wt%～30wt%；When the inorganic salt is calcium salt, magnesium salt, mantoquita, zinc salt, the inorganic salt solution concentration is 5%～15%, preferably 10%～15%；When the inorganic salt is aluminium salt, the inorganic salt solution concentration is 2wt%～10wt%；When the inorganic salt is zirconates, described inorganic salt solution concentration is 2wt%～5wt%.
13. in accordance with the method for claim 10, it is characterised in that：The initiator is one or more in sodium peroxydisulfate, potassium peroxydisulfate, Ammonium persulfate., and the consumption of the initiator is the 0.3-0.7wt% of monomer total amount.
14. in accordance with the method for claim 10, it is characterised in that：The cationic polyamine has following formula（i）Shown structure：
Formula（i）
Wherein, X-For inorganic anion；R、R9、R9`、R10、R10` is respectively following formula（IV）Shown structureFormula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, t is the integer of 1-5, and z is the integer of 0-5；
N, p are respectively the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10；It is 100-500mm that the value of l, l` and l`` causes the kinematic viscosity of the cationic polyamine2/ s, cationic degree is 0.5-2mmol/g.
15. in accordance with the method for claim 14, it is characterised in that：The cationic polyamine is by formula（V）Shown end amine and formula（VI）Shown cyclic ethers and formula（VII）Shown haloalkylene oxide is obtained by condensation reaction
Formula（V）
Formula（VI）
Formula（VII）.
16. in accordance with the method for claim 15, it is characterised in that：The cationic polyamine is obtained by following methods：Mol ratio to Deca cyclic ethers in the amine of end, cyclic ethers and end amine at stirring condition and 50-120 DEG C is 2-4：1,1-4 hours are reacted after completion of dropwise addition, 80-150 DEG C is then heated to, Deca haloalkylene oxide under stirring condition, haloalkylene oxide is 0.2-0.7 with the mol ratio of end amine：1,1-4 hours are reacted after completion of dropwise addition, then terminating reaction.
17. in accordance with the method for claim 16, it is characterised in that：The end amine is one or more in ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, TEPA.
18. in accordance with the method for claim 16, it is characterised in that：The cyclic ethers is one or more in oxirane, expoxy propane, tetrahydrofuran.
19. in accordance with the method for claim 16, it is characterised in that：The haloalkylene oxide is one or more in epoxychloropropane, epoxy bromopropane, epoxy chlorobutane.
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