CN106608973A - Method for preparing tackifier copolymerization associate - Google Patents
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Abstract
The invention discloses a method for preparing a tackifier copolymerization associate. The copolymerization associate comprises a constitutional unit A, a constitutional unit B and a constitutional unit C. The constitutional unit A is N, N-dimethylacrylamide, the constitutional unit B is N-methyl diallyl propylsulfonate (MAPS) which is an amphoteric ionic monomer, and the constitutional unit C is an ionic associate of the constitutional unit B and cationic polyamine. Based on the total amount of the copolymerization associate, the copolymerization associate comprises 10-75% by weight of the constitutional unit A, 8-55% by weight of the amphoteric ionic monomer, and 1-50% by weight of the cationic polyamine. A tackifier obtained through the preparation method can resist temperature as high as 200 DEG C, can resist a saturated NaCl solution, and resist a CaCl2 solution with the concentration being 20%. The tackifier is excellent shale inhibition and filtrate reduction.
Description
Technical field
The present invention relates in Process of Oil Well Drilling polymer for drilling fluid preparation method, more particularly to a kind of drilling fluid high temperature resistant viscosifier and preparation method thereof.
Background technology
In drilling process, in order to ensure that drilling fluid has higher viscosity and good rheological characteristic under low solid phase, it usually needs add viscosifier to improve 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 synthesis two big class of macromolecule, 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 sulfonation group or hydrophobic group being introduced 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 are 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 method for preparing viscosifier copolymerization associated complex.Up to 200 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 method for preparing viscosifier copolymerization associated complex, the copolymerization associated complex contains construction unit A, construction unit B and construction unit C, the construction unit A is N,N-DMAA, and the construction unit B is zwitterionic monomer N- methyl diallyl propane sulfonic acid salt（MAPS）, 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 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 200 DEG C of apparent viscosities after aging 16 hours；The preparation method comprises the 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）Emulsifying agent is added in white oil, leads to N under agitation20.5～1h of deoxygenation, is obtained oil phase, and wherein emulsifying agent and the mass ratio of white oil are 1：（5～10）；
（4）N- methyl diallyl propane sulfonic acid salt and N,N-DMAA are weighed, is subsequently adding to step（1）In the inorganic salt solution of middle preparation, water phase is obtained after fully dissolving, N- methyl diallyl propane sulfonic acid salt and N, N- dimethacrylamide monomers total mass concentration is 20%～40%, and on the basis of the total amount of N,N-DMAA, N- methyl diallyl propane sulfonic acid salt and cationic polyamine is thought, it is N, the consumption of N- DMAAs is 10-75 weight %, preferably 30-65 weight %；The consumption of N- methyl diallyl propane sulfonic acid salt is 15-65 weight %, preferably 20-60 weight %；
（5）By step（4）Obtained water is mutually added dropwise to step（3）In obtained oil phase, while being stirred, initiator is subsequently adding, N is passed through after fully dissolving20.5～1h of deoxygenation, while being warming up to 40～60 DEG C, reacts 1～2h；
（6）By step（2）The cationic polyamine aqueous solution of preparation is added to step（5）In the product for obtaining, mix homogeneously, 50～70 DEG C are warming up to simultaneously after fully emulsified, continue 3～5h of reaction, product is finally obtained, on the basis of the total amount of N,N-DMAA, N- methyl diallyl propane sulfonic acid salt and cationic polyamine, the consumption of cationic polyamine is 1-50 weight %, preferably 3-40 weight %.
In preparation method of the present invention, step（1）In emulsifying agent used be compound emulsifying agents or Tween 80 of the op15 with sorbester p17 and sorbester p17 compound emulsifying agent, op15 or Tween 80 and the mass ratio of sorbester p17 are 1：（9～11）.
In preparation method of the present invention, step（5）Described in oil phase in white oil and water phase in the mass ratio of water be（2～4）：（3～5）.
In preparation method of the present invention, the structural formula of the construction unit A N,N-DMAAs is：
Formula（I）, the structural formula of construction unit B zwitterionic monomers N- methyl diallyl propane sulfonic acid salt (MAPS) 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, integers of the t for 1-5, integers of the z for 0-5；
N, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 1-10；L, l ' and l " value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree are 0.5-2mmol/g.Further preferably the kinematic viscosity of the cationic polyamine is 150-450mm2/ s, cationic degree are 0.5-1.5mmol/g.
Above-mentioned cationic polyamine can balance anion with corresponding with multiple nitrogen cations for various, 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；Integers of the x for 0-10, integers of the y for 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）Represent polyethylene polyamine, integers of the x for 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 to be reacted after completion of dropwise addition, 80-150 DEG C is then heated to, Deca haloalkylene oxide under stirring condition, haloalkylene oxide are 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 is overlapped 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 be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, one or more in TEPA.
Under preferable case, the cyclic ethers is oxirane, expoxy propane, one or more in tetrahydrofuran.
Under preferable case, the haloalkylene oxide is epoxychloropropane, epoxy bromopropane, one or more in epoxy chlorobutane.
In preparation method of the present invention, copolymerization associated complex had both included the structure formed by copolymerization in referring to polymer, also include the structure formed by ion association, 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 preparation method of the present invention, the total content of the various versions that the content of copolymerization associated complex cationic polyamine is provided by cationic polyamine in referring to 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 content not with the zwitterionic structural elements to form construction unit C that associate with cationic polyamine.
In preparation method of the present invention, the content of each construction unit can be determined by way of content of monomer calculating or nuclear magnetic resonance, NMR before and after reaction are with reference to infrared spectrum analysiss.
In preparation method of the present invention, the alkyl of the C1-C5 can be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, one or more in neopentyl.The substituent group of the alkyl of the C1-C5 can for example 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 be determined by way of content of monomer calculating or nuclear magnetic resonance, NMR before and after reaction are with reference to infrared spectrum analysiss.
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 be ammonium salt, calcium salt, magnesium salt, mantoquita, zinc salt, aluminium salt, one or more in zirconates.The inorganic salt is preferably used in the form of a solution.
, by research it has furthermore been found that different types of inorganic salt, the solution concentration for reaching optimum efficiency is different for the present inventor, 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.
In preparation method of the present invention, 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.
In preparation method of 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 structure
Formula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, integers of the t for 1-5, integers of the z for 0-5；N, p are respectively the integer of 1-5, integers of the x for 0-10, integers of the y for 1-10；L, l ' and l ' ' value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree are 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)nIntegers of the H wherein n for 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 can such as 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, 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.
In the inventive method, MAPS used can be synthesized by described below step：Mol ratio is weighed respectively for 2:1～9:1, preferably 2.5:1～8:1 N- amides and PS, and PS is added in N- amides；Then 0.5-4h is reacted at a temperature of 20 DEG C～90 DEG C, preferably react 1-3h at a temperature of 60～80 DEG C, eventually pass filter, extracting, be dried prepared N- methyl diallyl propane sulfonic acid salt.The PS can be added drop-wise in N- amides, it is also possible to be directly disposably added in N- amides, preferably direct disposable feed postition.When using directly disposable feed postition, N- amides and PS mol ratio are preferably 5.2:1～7.8:1；When using Deca mode, N- amides and PS mol ratio are preferably 2.5:1～5:1, PS heating can be melted before Deca.The extraction solvent selects methanol or ethanol, preferred alcohol, and extraction times are 1～3h, and baking temperature is 30～50 DEG C, and drying time is 10～20h.
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 N with certain proportion simultaneously, N- DMAA construction units, zwitterionic structural elements and cationic polyamine construction unit, 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 is not only after high temperature ageing with good apparent viscosity, but also there is preferable shear force, and heatproof, at least up to more than 200 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, phase is by using high concentration inorganic salt solution before the reaction, sulfonic group zwitterionic monomer can be made to combine to form special construction with inorganic salt, as 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, arrange monomer molecule even closer, considerably increase the molecular weight of polymer.Phase is by adding low molecular weight cationic polyamine after the reaction, 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 of polymer temperature influence fracture hydrolysis is caused to reduce, so as to improve the performance of its heatproof, at least up to 180 DEG C, what is had reaches 200 DEG C to heatproof.
Description of the drawings
Fig. 1 and Fig. 2 is respectively MAPS's1HNMR and13CNMR 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.
In the embodiment of the present invention and comparative example, MAPS monomers used can be prepared as follows：Weigh 650g N- amides to pour in reactor, be then placed in thermostat water bath, heat and start stirring.122g PSs being weighed again, being added directly in N- amides, reaction temperature is 80 DEG C, and the crude product of MAPS is obtained after stirring reaction 3h.MAPS crude products are transferred in large stretch of filter paper and are wrapped, be positioned in Soxhlet extraction device, the use of ethanol is solvent extraction 3h, extracting after finishing is placed on filter paper bag in drying baker, dry at 50 DEG C, finally gives pure MAPS monomers.
In the embodiment of the present invention and comparative example, cationic polyamine used is prepared as follows：
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 are 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 are 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 are 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 are 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 are 1.5 mmol/g.
Embodiment 1
2.5gOP15 and 22.5g sorbester p17s are added in 150g white oils, lead to N under agitation2Deoxygenation half an hour, oil phase is obtained standby；NaCl aqueous solutions are configured to after 37.5gNaCl is added in 140g water fully dissolving, then 18gMAPS and 63gDMAM are added in NaCl aqueous solutions, stirring is allowed to fully dissolving；Oil phase is transferred in reactor, water is mutually added dropwise in oil phase while stirring, stirring half an hour obtains emulsification system；0.24g potassium peroxydisulfates are added in emulsification system, N are passed through after fully dissolving2Deoxygenation half an hour, while being warming up to 60 DEG C, after reaction 1h, obtain intermediate product；Again 2g cationic polyamines 1 are dissolved in 10g deionized waters and are 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 reaction 4 hours.Product is Jing after breakdown of emulsion, then is washed with acetone soln, and the solid sediment after washing is viscosifier after being dried 12h crushing at 120 DEG C.
Embodiment 2
1.5gOP15 and 13.5g sorbester p17s are added in 75g white oils, lead to N under agitation2Deoxygenation half an hour, oil phase is obtained standby；By 20gCaCl2CaCl is configured to after fully dissolving in being added to 140g water2Aqueous solution, then 47gMAPS and 46gDMAM are added to into CaCl2In aqueous solution, stirring is allowed to fully dissolving；Oil phase is transferred in reactor, water is mutually added dropwise in oil phase while stirring, stirring half an hour obtains emulsification system；0.32g sodium peroxydisulfates are added in emulsification system, N are passed through after fully dissolving2Deoxygenation half an hour, while obtaining intermediate product after being warming up to 55 DEG C of reaction 1.5h；Again 4g cationic polyamines 2 are dissolved in 10g deionized waters and are 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 reaction 3.5 hours.Product is Jing after breakdown of emulsion, then is washed with acetone soln, and the solid sediment after washing is viscosifier after being dried 12h crushing at 110 DEG C.
Embodiment 3
1.4g Tween 80s and 13.6g sorbester p17s are added in 90g white oils, lead to N under agitation2Deoxygenation half an hour, oil phase is obtained standby；By 10gAlCl3AlCl is configured to after fully dissolving in being added to 130g water3Aqueous solution, then 28gMAPS and 28gDMAM are added to into AlCl3In aqueous solution, stirring is allowed to fully dissolving；Oil phase is transferred in reactor, water is mutually added dropwise in oil phase while stirring, stirring half an hour obtains emulsification system；0.2g potassium peroxydisulfates are added in emulsification system, N are passed through after fully dissolving2Deoxygenation half an hour, while being warming up to 50 DEG C, after reaction 2h, obtain intermediate product；Again 6g cationic polyamines 3 are dissolved in 20g deionized waters and are configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 60 DEG C, continue reaction 5 hours.Product is Jing after breakdown of emulsion, then is washed with acetone soln, and the solid sediment after washing is viscosifier after being dried 16h crushing at 110 DEG C.
Embodiment 4
1.8g Tween 80s and 18.2g sorbester p17s are added in 120g white oils, lead to N under agitation2Deoxygenation half an hour, oil phase is obtained standby；By 5gZrCl4ZrCl is configured to after fully dissolving in being added to 140g water4Aqueous solution, then 14gMAPS and 48gDMAM are added to into ZrCl4In aqueous solution, stirring is allowed to fully dissolving；Oil phase is transferred in reactor, water is mutually added dropwise in oil phase while stirring, stirring half an hour obtains emulsification system；0.3g potassium peroxydisulfates are added in emulsification system, N are passed through after fully dissolving2Deoxygenation half an hour, while being warming up to 60 DEG C, after reaction 1h, obtain intermediate product；Again 4g cationic polyamines 2 are dissolved in 10g deionized waters and are 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 reaction 4 hours.Product is Jing after breakdown of emulsion, then is washed with acetone soln, and the solid sediment after washing is viscosifier after being dried 12h crushing at 120 DEG C.
Comparative example 1（It is not added with inorganic salt）
1.5gOP15 and 13.5g sorbester p17s are added in 75g white oils, lead to N under agitation2Deoxygenation half an hour, oil phase is obtained standby；47gMAPS and 46gDMAM are added in 140g water, stirring is allowed to fully dissolving；Oil phase is transferred in reactor, water is mutually added dropwise in oil phase while stirring, stirring half an hour obtains emulsification system；0.32g sodium peroxydisulfates are added in emulsification system, N are passed through after fully dissolving2Deoxygenation half an hour, while being warming up to 55 DEG C, after reaction 1h, obtain intermediate product；Again 4g cationic polyamines 2 are dissolved in 10g deionized waters and are 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 reaction 3.5 hours.Product is Jing after breakdown of emulsion, then is washed with acetone soln, and the solid sediment after washing is viscosifier after being dried 12h crushing at 110 DEG C.
Comparative example 2（It is not added with cationic polyamine）
1.5gOP15 and 13.5g sorbester p17s are added in 75g white oils, lead to N under agitation2Deoxygenation half an hour, oil phase is obtained standby；By 20gCaCl2CaCl is configured to after fully dissolving in being added to 150g water2Aqueous solution, then 47gMAPS and 46gDMAM are added to into CaCl2In aqueous solution, stirring is allowed to fully dissolving；Oil phase is transferred in reactor, water is mutually added dropwise in oil phase while stirring, stirring half an hour obtains emulsification system；0.32g sodium peroxydisulfates are added in emulsification system, N are passed through after fully dissolving2Deoxygenation half an hour, while being warming up to 65 DEG C, after reaction 5h, obtain tackifier emulsion polymer；Product is Jing after breakdown of emulsion, then is washed with acetone soln, and the solid sediment after washing is viscosifier after being dried 12h crushing at 110 DEG C.
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：In 1000mL water, 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；Continuously add 200g CaCl2, high-speed stirred 20min, placement maintenance 24h under room temperature obtain evaluating with containing 20% CaCl2Base is starched.
Evaluation methodology：The base slurry of 350mL is measured, and adds 2% viscosifier, high-speed stirred 20min its apparent viscosity to be surveyed after room temperature maintenance 24h.Again after aging 16h at 200 DEG C, apparent viscosity is determined again, calculate apparent viscosity conservation rate.
1 different viscosifier temperature-resistant anti-salt anticalcium performance comparison tables of table
Note：The dosage of 4 xanthan gum of comparative example 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 (14)
1. a kind of method for preparing viscosifier copolymerization associated complex, the copolymerization associated complex contains construction unit A, construction unit B and construction unit C, the construction unit A is N,N-DMAA, and the construction unit B is zwitterionic monomer N- methyl diallyl propane sulfonic acid salt（MAPS）, 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 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 200 DEG C of apparent viscosities after aging 16 hours；The preparation method comprises the 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）Emulsifying agent is added in white oil, leads to N under agitation20.5～1h of deoxygenation, is obtained oil phase, and wherein emulsifying agent and the mass ratio of white oil are 1：（5～10）；
（4）N- methyl diallyl propane sulfonic acid salt and N,N-DMAA are weighed, is subsequently adding to step（1）In the inorganic salt solution of middle preparation, water phase is obtained after fully dissolving, wherein, N- methyl diallyl propane sulfonic acid salt and N,N-DMAA monomer gross mass concentration are 20%～40%, and according to N, on the basis of the total amount of N- DMAAs, N- methyl diallyl propane sulfonic acid salt and cationic polyamine, the consumption of N,N-DMAA is 10-75 weight %, preferably 30-65 weight %；The consumption of N- methyl diallyl propane sulfonic acid salt is 15-65 weight %, preferably 20-60 weight %；
（5）By step（4）Obtained water is mutually added dropwise to step（3）In obtained oil phase, while being stirred, initiator is subsequently adding, N2 0.5～1h of deoxygenation is passed through after fully dissolving, while being warming up to 40～60 DEG C, react 1～2h；
（6）By step（2）The cationic polyamine aqueous solution of preparation is added to step（5）In the product for obtaining, mix homogeneously, 50～70 DEG C are warming up to simultaneously after fully emulsified, continue 3～5h of reaction, product is finally obtained, on the basis of the total amount of N,N-DMAA, N- methyl diallyl propane sulfonic acid salt and cationic polyamine, the consumption of cationic polyamine is 1-50 weight %, preferably 3-40 weight %.
2. in accordance with the method for claim 1, it is characterised in that：Emulsifying agent used is the compound emulsifying agent of compound emulsifying agents or Tween 80 of the op15 with sorbester p17 and sorbester p17, and op15 or Tween 80 and the mass ratio of sorbester p17 are 1：（9～11）.
3. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in oil phase in white oil and water phase in the mass ratio of water be（2～4）：（3～5）.
4. in accordance with the method for claim 1, 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, integers of the t for 1-5, integers of the z for 0-5；
N, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 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 are 0.5-2mmol/g.
5. in accordance with the method for 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
T, n, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 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）Represent polyethylene polyamine, integers of the x for 1-10.
6. in accordance with the method for 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 to be reacted after completion of dropwise addition, 80-150 DEG C is then heated to, Deca haloalkylene oxide under stirring condition, haloalkylene oxide are 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.
7. in accordance with the method for claim 6, it is characterised in that：The end amine be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, one or more in TEPA.
8. in accordance with the method for claim 6, it is characterised in that：The cyclic ethers is oxirane, expoxy propane, one or more in tetrahydrofuran.
9. in accordance with the method for claim 6, it is characterised in that：The haloalkylene oxide is epoxychloropropane, epoxy bromopropane, one or more in epoxy chlorobutane.
10. in accordance with the method for 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, integers of the t for 1-5, integers of the z for 0-5；N, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 1-10；L, l ' and l " value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree are 0.5-2mmol/g.
11. in accordance with the method for claim 10, it is characterised in that：The kinematic viscosity of the cationic polyamine is 150-450mm2/ s, cationic degree are 0.5-1.5mmol/g.
12. in accordance with the method for claim 1, it is characterised in that：The inorganic salt be ammonium salt, calcium salt, magnesium salt, mantoquita, zinc salt, aluminium salt, one or more in zirconates.
13. according to the method described in claim 121, 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%.
14. in accordance with the method for claim 1, it is characterised in that：The initiator is sodium peroxydisulfate, potassium peroxydisulfate, one or more in Ammonium persulfate., the 0.3-0.7wt% of the consumption of the initiator for monomer total amount.
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