CN106608976A - Starch-containing thickening agent copolymerization association compound and preparation method thereof - Google Patents
Starch-containing thickening agent copolymerization association compound and preparation method thereof Download PDFInfo
- Publication number
- CN106608976A CN106608976A CN201510683657.7A CN201510683657A CN106608976A CN 106608976 A CN106608976 A CN 106608976A CN 201510683657 A CN201510683657 A CN 201510683657A CN 106608976 A CN106608976 A CN 106608976A
- Authority
- CN
- China
- Prior art keywords
- starch
- weight
- cationic polyamine
- inorganic salt
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Paper (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a starch-containing thickening agent copolymerization association compound and a preparation method thereof. The copolymerization association compound contains a structural unit A, a structural unit B, a structural unit C and a structural unit D, the structural unit A is N,N-dimethylacrylamide, the structural unit B is an amphoteric monomer methacryloyloxyethyl-N,N-dimethylpropanesulfonate (DMAPS), the structural unit C is an ion association body of the structural unit B and cationic polyamine, and the structural unit D is starch; and based on the total amount of the copolymerization association compound, the content of the N,N-dimethylacrylamide is 6-45% by weight, the total content of the amphoteric monomer methacryloyloxyethyl-N,N-dimethylpropanesulfonate is 5-35% by weight, the content of the cationic polyamine is 2-30% by weight, and the content of the starch is 5-35% by weight. Temperature resistance of the thickening agent prepared by the method can reach 150 DEG C, anti-NaCl concentration is saturated, and anti-CaCl2 concentration reaches 20%; and meanwhile, excellent shale inhibition performance and filtrate loss controllability are furthermore achieved.
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 graft starch 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 starch-containing viscosifier copolymerization associated complex and preparation method thereof.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 starch-containing viscosifier copolymerization associated complex, the copolymerization associated complex contains construction unit A, construction unit B, construction unit C and structural units D, the construction unit A is N, N- DMAAs, 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 the construction unit D is starch, and on the basis of the total amount of the copolymerization associated complex, the content of the N,N-DMAA is 6-45 weight %, preferably 10-40 weight %；Zwitterionic monomer methylacryoyloxyethyl-the N,
The total content of N- dimethyl propylene sulfonate is 5-35 weight %, preferably 10-32 weight %；The content of the cationic polyamine is 2-30 weight %, preferably 5-28 weight %；The content of the starch is 5-35 weight %, preferably 10-32 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 N,N-DMAAs 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, 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.
The structural formula of the construction unit D starch is：, specific described starch can be one or more in green starch, tapioca, sweet potato starch, sweet potato starch, potato starch, wheat and barley starch, water caltrop starch, Rhizoma Nelumbinis starch, corn starch, preferred corn starch or potato starch.
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.
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 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, construction unit D 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 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 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 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, wherein construction unit A, it is conventional covalent polymerization methodses between construction unit B, construction unit D, 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 construction unit D 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 present invention also provides a kind of preparation method of above-mentioned tackifier for drilling fluid 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）Weigh starch and part steps（1）The inorganic salt solution mixing of preparation, stirs 20～50min at 60～80 DEG C, gelatinized starch is obtained after process；
（4）To step（3）N is passed through in the gelatinized starch for obtaining2, after 15～60min of reaction, add initiator；
（5）Methylacryoyloxyethyl-N is weighed,
N- dimethyl propylenes sulfonate and N, N- DMAA and step（1）In remainder step（1）The inorganic salt solution mixing of preparation, is added to step until completely dissolved（4）In the gelatinized starch for obtaining, 1～2h is reacted at 50～70 DEG C；Wherein, methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate, N,N-DMAA and starch monomer gross mass concentration are 5%～20%, and according to N,N-DMAA, methylacryoyloxyethyl-N,
On the basis of the total amount of N- dimethyl propylene sulfonate, starch and cationic polyamine, the consumption of N,N-DMAA is 6-45 weight %, preferably 10-40 weight %；The consumption of methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 5-35 weight %, preferably 10-32 weight %；Starch consumption is 5-35 weight %, preferably 10-32 weight %；
（6）By step（2）The cationic polyamine aqueous solution of preparation is added to step（5）In the product for obtaining, mix homogeneously is warming up to 60～80 DEG C simultaneously, continues 3～5h of reaction；Wherein, according to N,N-DMAA, methylacryoyloxyethyl-N, on the basis of the total amount of N- dimethyl propylene sulfonate, starch and cationic polyamine, cationic polyamine consumption is 2-30 weight %, preferably 5-28 weight %；
（7）By step（6）The product for obtaining is washed with acetone soln, and the solid sediment obtained after washing obtains purpose product 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 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.
The preparation method of the copolymerization associated complex provided according to 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.
The preparation method of the copolymerization associated complex that the present invention is provided, described starch can be one or more in green starch, tapioca, sweet potato starch, sweet potato starch, potato starch, wheat and barley starch, water caltrop starch, Rhizoma Nelumbinis starch, corn starch, preferred corn starch or potato starch.
The preparation method of the copolymerization associated complex provided according to the present invention, the step（5）In inorganic salt solution used be step（3）The 1/2～3/5 of middle inorganic salt solution 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 have 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, 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, 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 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 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, 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 150 DEG C, what is had reaches 180 DEG C to heatproof.
Description of the drawings
Fig. 1 and Fig. 2 be respectively DMAPS infrared 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 is measured using 265 oil product kinematic viscosity algoscopy of GB GB/T and dynamic viscosity calculating method；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.
Corn starch used by the embodiment of the present invention and comparative example is the wide corn starch of middle sugared family, and potato starch is Shenyang Fang Chiai ginseng potato starch.
In the embodiment of the present invention and comparative example, DMAPS monomers used can be prepared as follows：
Weigh 785g dimethylaminoethyl methacrylates to pour in reactor, be then placed in thermostat water bath, heat and start stirring.The PS of 122g being weighed again, being added directly in dimethylaminoethyl methacrylate, reaction temperature is 60 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, be positioned in Soxhlet extraction device, the use of ethanol is solvent extraction 2.5h, extracting after finishing is placed on filter paper bag in drying baker, dry 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.
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 structure
Formula（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
170g DMAPS, 140g are weighed respectively
DMAM and 100g corn starchs are standby.6830g deionized waters being weighed respectively again and 1758gNaCl being configured to NaCl solution, solution is divided into into two parts.Add a part of NaCl solution in 80 DEG C of gelatinizing 30min corn starch, be passed through N2 3.7g potassium peroxydisulfates are added after 30min, then is transferred in gelatinized starch reactor after DMAM and DMAPS are added the dissolving of another part NaCl solution, obtain intermediate product after 2h being reacted at 65 DEG C.Again 70g cationic polyamines 1 are dissolved in 200g 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 75 DEG C, continue reaction 4 hours.Cleaned with acetone and be precipitated thing.Precipitate crushes to obtain graft starch viscosifier after being dried 12h at 70 DEG C.
Embodiment 2
150g DMAPS, 112g are weighed respectively
DMAM and 100g potato starch is standby.Weigh 2770g deionized waters and 330g CaCl again respectively2It is configured to CaCl2Solution is divided into volume ratio 6 by solution:4 two parts.Potato starch is added thereto into many a part of CaCl2Solution is passed through N in 70 DEG C of gelatinizing 30min2 1.7g sodium peroxydisulfates are added after 30min, then DMAM and DMAPS is added into remaining few CaCl2Be transferred in gelatinized starch reactor after solution dissolving, obtain intermediate product after 1.5h being reacted at 70 DEG C.Again 60g cationic polyamines 2 are dissolved in 200g 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 80 DEG C, continue reaction 3 hours.Cleaned with acetone and be precipitated thing.Precipitate crushes to obtain graft starch viscosifier after being dried 12h at 80 DEG C.
Embodiment 3
130g DMAPS, 168g are weighed respectively
DMAM and 100g potato starch is standby.Weigh 1785g deionized waters and 105g AlCl again respectively3It is configured to AlCl3Solution is divided into two parts by solution.Potato starch is added into a part of AlCl3Solution is passed through N in 60 DEG C of gelatinizing 30min2 5.3g Ammonium persulfate .s are added after 30min, then DMAM and DMAPS are added into another part AlCl3Be transferred in gelatinized starch reactor after solution dissolving, obtain intermediate product after 2h being reacted at 60 DEG C.Again 60g cationic polyamines 3 are dissolved in 200g 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.Cleaned with acetone and be precipitated thing.Precipitate crushes to obtain graft starch viscosifier after being dried 12h at 80 DEG C.
Embodiment 4
100gDMAPS, 140g are weighed respectively
DMAM and 100g corn starchs are standby.Weigh 1100g deionized waters and 63g ZrCl again respectively4It is configured to ZrCl4Solution is divided into volume ratio 6 by solution:4 two parts.Corn starch is added thereto into many a part of ZrCl4Solution is passed through N in 75 DEG C of gelatinizing 30min2 3g potassium peroxydisulfates are added after 30min, then DMAM and DMAPS is added into remaining few ZrCl4Be transferred in gelatinized starch reactor after solution dissolving, obtain intermediate product after 1.5h being reacted at 65 DEG C.Again 18g cationic polyamines 2 are dissolved in 100g 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 77 DEG C, continue reaction 4.5 hours.Cleaned with acetone and be precipitated thing.Precipitate crushes to obtain graft starch viscosifier after being dried 12h at 75 DEG C.
Comparative example 1（It is not added with inorganic salt）
150g DMAPS, 112g are weighed respectively
DMAM and 100g potato starch is standby.Weigh 2770g deionized waters again respectively, deionized water is divided into into two parts.Add a part of deionized water in 70 DEG C of gelatinizing 30min potato starch, be passed through N2 1.7g sodium peroxydisulfates are added after 30min, it is transferred to after DMAM and DMAPS are added another part deionized water dissolving again in gelatinized starch reactor, again 60g cationic polyamines 2 are dissolved in 200g deionized waters and are configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, it is warming up to 80 DEG C simultaneously, continues reaction 3 hours.Cleaned with acetone and be precipitated thing.Precipitate crushes to obtain graft starch viscosifier after being dried 12h at 80 DEG C.
Comparative example 2（It is not added with cationic polyamine）
150g DMAPS, 112g are weighed respectively
DMAM and 100g potato starch is standby.Weigh 2970g deionized waters and 330g CaCl again respectively2It is configured to CaCl2Solution is divided into volume ratio 6 by solution:4 two parts.Potato starch is added thereto into many a part of CaCl2Solution is passed through N in 70 DEG C of gelatinizing 30min2 1.7g sodium peroxydisulfates are added after 30min, then DMAM and DMAPS is added into remaining few CaCl2Be transferred in gelatinized starch reactor after solution dissolving, obtain colloidal solid, cleaned with acetone and be precipitated thing after 6h being reacted at 75 DEG C.Precipitate crushes to obtain graft starch viscosifier after being dried 12h at 80 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 150 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 (21)
1. a kind of starch-containing viscosifier copolymerization associated complex, the copolymerization associated complex contains construction unit A, construction unit B, construction unit C and structural units D, the construction unit A is N, N- DMAAs, 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 the construction unit D is starch, and on the basis of the total amount of the copolymerization associated complex, the content of the N,N-DMAA is 6-45 weight %, preferably 10-40 weight %；The total content of the zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 5-35 weight %, preferably 10-32 weight %；The content of the cationic polyamine is 2-30 weight %, preferably 5-28 weight %；The content of the starch is 5-35 weight %, preferably 10-32 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, 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.
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 are 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
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.
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 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.
6. according to the copolymerization associated complex described in claim 5, it is characterised in that：The end amine be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, one or more in TEPA.
7. according to the copolymerization associated complex described in claim 5, it is characterised in that：The cyclic ethers is oxirane, expoxy propane, one or more in tetrahydrofuran.
8. according to the copolymerization associated complex described in claim 5, it is characterised in that：The haloalkylene oxide is epoxychloropropane, epoxy bromopropane, one or more in epoxy chlorobutane.
9. according to the copolymerization associated complex described in claim 1, it is characterised in that：The starch is green starch, tapioca, sweet potato starch, sweet potato starch, potato starch, wheat and barley starch, water caltrop starch, Rhizoma Nelumbinis starch, one or more in corn starch, preferred corn starch or potato starch.
10. as described in any claim in claim 1-9 starch-containing 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 starch and part steps（1）The inorganic salt solution mixing of preparation, stirs 20～50min at 60～80 DEG C, gelatinized starch is obtained after process；
（4）To step（3）N is passed through in the gelatinized starch for obtaining2, after 15～60min of reaction, add initiator；
（5）Weigh methylacryoyloxyethyl-N, N- dimethyl propylenes sulfonate and N, N- DMAA and step（1）In remainder step（1）The inorganic salt solution mixing of preparation, is added to step until completely dissolved（4）In the gelatinized starch for obtaining, 1～2h is reacted at 50～70 DEG C；Wherein, methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate, N, N- DMAAs and starch monomer gross mass concentration are 5%～20%, and according to N,N-DMAA, methylacryoyloxyethyl-N, on the basis of the total amount of N- dimethyl propylene sulfonate, starch and cationic polyamine, the consumption of N,N-DMAA is 6-45 weight %, preferably 10-40 weight %；The consumption of methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 5-35 weight %, preferably 10-32 weight %；Starch consumption is 5-35 weight %, preferably 10-32 weight %；
（6）By step（2）The cationic polyamine aqueous solution of preparation is added to step（5）In the product for obtaining, mix homogeneously is warming up to 60～80 DEG C simultaneously, continues 3～5h of reaction；Wherein, according to N,N-DMAA, methylacryoyloxyethyl-N, on the basis of the total amount of N- dimethyl propylene sulfonate, starch and cationic polyamine, cationic polyamine consumption is 2-30 weight %, preferably 5-28 weight %；
（7）By step（6）The product for obtaining is washed with acetone soln, and the solid sediment obtained after washing obtains purpose product through drying and after crushing.
11. in accordance with the method for claim 10, 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.
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 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.
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 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；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.
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
。
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 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.
17. in accordance with the method for claim 16, it is characterised in that：The end amine be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, one or more in TEPA.
18. in accordance with the method for claim 16, it is characterised in that：The cyclic ethers is oxirane, expoxy propane, one or more in tetrahydrofuran.
19. in accordance with the method for claim 16, it is characterised in that：The haloalkylene oxide is epoxychloropropane, epoxy bromopropane, one or more in epoxy chlorobutane.
20. in accordance with the method for claim 10, it is characterised in that：Described starch is green starch, tapioca, sweet potato starch, sweet potato starch, potato starch, wheat and barley starch, water caltrop starch, Rhizoma Nelumbinis starch, one or more in corn starch, preferred corn starch or potato starch.
21. in accordance with the method for claim 10, it is characterised in that：Step（5）In inorganic salt solution used be step（3）The 1/2～3/5 of middle inorganic salt solution total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510683657.7A CN106608976B (en) | 2015-10-21 | 2015-10-21 | A kind of starch-containing tackifier copolymerization associated matter and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510683657.7A CN106608976B (en) | 2015-10-21 | 2015-10-21 | A kind of starch-containing tackifier copolymerization associated matter and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106608976A true CN106608976A (en) | 2017-05-03 |
| CN106608976B CN106608976B (en) | 2019-04-12 |
Family
ID=58610880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510683657.7A Active CN106608976B (en) | 2015-10-21 | 2015-10-21 | A kind of starch-containing tackifier copolymerization associated matter and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106608976B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111329786A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | Multifunctional hand sanitizer containing aminopropanesulfonic acid inner salt type amphoteric structure and preparation method thereof |
| CN113121002A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Flocculating agent and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5620947A (en) * | 1994-12-27 | 1997-04-15 | Exxon Production Research Company | Water-based high temperature well servicing composition and method of using same |
| US6586371B1 (en) * | 1998-02-02 | 2003-07-01 | Schlumberger Technology Corporation | Liquid compositions which reversibly viscosify or gel under the effect of shear |
| CN1542031A (en) * | 2003-11-07 | 2004-11-03 | 四川大学 | Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof |
| WO2008087326A2 (en) * | 2006-12-27 | 2008-07-24 | Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic | Novel powder polymer containing a surface-active monomer, preparation method thereof and use of same as a thickening agent |
| CN101372525A (en) * | 2007-05-11 | 2009-02-25 | 中国科学院成都有机化学有限公司 | Method for preparing non-ionic hydrophobic association polymerization water-soluble polymer from reverse micro emulsion |
| CN103773332A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Drilling fluid and preparation method thereof |
-
2015
- 2015-10-21 CN CN201510683657.7A patent/CN106608976B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5620947A (en) * | 1994-12-27 | 1997-04-15 | Exxon Production Research Company | Water-based high temperature well servicing composition and method of using same |
| US6586371B1 (en) * | 1998-02-02 | 2003-07-01 | Schlumberger Technology Corporation | Liquid compositions which reversibly viscosify or gel under the effect of shear |
| CN1542031A (en) * | 2003-11-07 | 2004-11-03 | 四川大学 | Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof |
| WO2008087326A2 (en) * | 2006-12-27 | 2008-07-24 | Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic | Novel powder polymer containing a surface-active monomer, preparation method thereof and use of same as a thickening agent |
| CN101372525A (en) * | 2007-05-11 | 2009-02-25 | 中国科学院成都有机化学有限公司 | Method for preparing non-ionic hydrophobic association polymerization water-soluble polymer from reverse micro emulsion |
| CN103773332A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Drilling fluid and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121002A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Flocculating agent and preparation method and application thereof |
| CN113121002B (en) * | 2019-12-31 | 2022-07-12 | 中国石油化工股份有限公司 | Flocculating agent and preparation method and application thereof |
| CN111329786A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | Multifunctional hand sanitizer containing aminopropanesulfonic acid inner salt type amphoteric structure and preparation method thereof |
| CN111329786B (en) * | 2020-03-25 | 2023-06-23 | 深圳市施尔洁生物工程有限公司 | Multifunctional hand sanitizer containing aminopropanesulfonic acid inner salt type amphoteric structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106608976B (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106608945B (en) | A kind of copolymerization associated matter and its preparation method and application and drilling fluid | |
| CN106608975A (en) | Grafted starch thickening agent copolymerization association compound and preparation method thereof | |
| CN105399897A (en) | Heatproof salt-resistant polyacrylamide polymer and preparation method thereof | |
| CN105566516A (en) | Structure-oriented composite initiator system, acrylamide polymer and preparation method and application of acrylamide polymer | |
| CN106608976A (en) | Starch-containing thickening agent copolymerization association compound and preparation method thereof | |
| CN106608946A (en) | Tackifier copolymerization associate used for drilling fluid and preparation method of tackifier copolymerization associate | |
| CN104926991B (en) | A kind of preparation method of drilling fluid amphoteric ion copolymer | |
| CN108559475A (en) | A kind of heat-resistant salt-resistant polyvinyl acetate ester microsphere and its preparation and application | |
| CN106608971A (en) | Anti-calcium tackifier copolymerization complex and preparation method thereof | |
| CN102453114B (en) | Redox initiator system, acrylamide polymer and preparation method and application of acrylamide polymer | |
| CN106608974A (en) | Tackifier copolymerization associate used for drilling fluid and preparation method of tackifier copolymerization associate | |
| CN106608944B (en) | A kind of heat-resistance type tackifier copolymerization associated matter and preparation method thereof | |
| CN103483216A (en) | Polymerizable monomer, and preparation method and application thereof | |
| CN106609129A (en) | Copolymerization and association complex used as tackifier and preparation method thereof | |
| CN106608947A (en) | Tackifier copolymerization association compound, and preparation method thereof | |
| CN102453113A (en) | Redox initiator system and acrylamide polymer and preparation method thereof and application thereof | |
| CN106608972A (en) | Preparation method of thickening agent copolymerization association compound | |
| CN102464783B (en) | Water-soluble thermo-thickening copolymer, and preparation method and application thereof | |
| CN106608973A (en) | Method for preparing tackifier copolymerization associate | |
| CN110016325B (en) | Shear strength improving agent for water-based drilling fluid and preparation method thereof | |
| CN102453115B (en) | Redox initiator system, acrylamide polymer and preparation method and application of acrylamide polymer | |
| CN103788296A (en) | Cationic polyacrylamide copolymer high-temperature resisting water-in-water dispersion and low-viscosity preparation method thereof | |
| CN102453111A (en) | Redox initiator system, acrylamide polymer and preparation method and application of acrylamide polymer | |
| CN118852535A (en) | Environment-friendly composite acid thickener for acidizing and fracturing and preparation method thereof | |
| JPS5930995A (en) | Filterability enhancer and dry strength enhancer of paper and paperboard |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |