CN105503623A - Alkyl bis-quaternary ammonium salt monomer, preparation method thereof and associating polymer - Google Patents
Alkyl bis-quaternary ammonium salt monomer, preparation method thereof and associating polymer Download PDFInfo
- Publication number
- CN105503623A CN105503623A CN201511022772.6A CN201511022772A CN105503623A CN 105503623 A CN105503623 A CN 105503623A CN 201511022772 A CN201511022772 A CN 201511022772A CN 105503623 A CN105503623 A CN 105503623A
- Authority
- CN
- China
- Prior art keywords
- formula
- alkyl
- polymer
- quaternary ammonium
- ammonium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
Abstract
The invention provides an alkyl bis-quaternary ammonium salt monomer. The alkyl bis-quaternary ammonium salt monomer has a structure shown in a formula 1 in the specification, wherein in the formula 1, R1 is C2-C6 alkylidene; R is C8-C20 alkyl; and X is halogen. The alkyl bis-quaternary ammonium salt monomer is a long-chain alkyl gemini quaternary ammonium salt cationic monomer. The solubility of hydrophobic monomers can be improved and the C number of long-chain alkyl can be increased through the molecular structure design, so that an obtained polymer has stronger hydrophobic association, thus being conducive to forming a dynamic physical crosslinking network among macromolecules of the polymer, increasing the hydrodynamic volume, substantially increasing the solution viscosity and ensuring that the polymer obtained through polymerization of the alkyl bis-quaternary ammonium salt monomer still has better thickening property in the high temperature and high salinity environment. The invention also provides a preparation method of the alkyl bis-quaternary ammonium salt monomer and an associating polymer.
Description
Technical field
The invention belongs to oilfield chemical auxiliary technical field, particularly relate to a kind of alkyl diquaternary monomers, its preparation method and association polymer.
Background technology
Oil production process can be divided into primary oil recovery, secondary oil recovery and tertiary oil recovery.Once all recovered the oil by physical method with secondary oil recovery, its recovery ratio can reach 30% ~ 40%, but through once, also remained most of crude oil in the stratum of secondary oil recovery.The main oilfield of China enters secondary oil recovery later stage in succession, and in order to improve the recovery ratio in existing oil field, tertiary oil recovery technology obtains increasingly extensive application.
Tertiary oil recovery to be driven by polymer flooding, poly-table binary or poly-table alkali ternary is driven and improved oil recovery factor.Polymer flooding refers to and adds a small amount of polymkeric substance at injection water, relies on to increase aqueous viscosity and reduce reservoir permeability to play and improve sweep efficiency and improve the effect of recovery ratio.Polymer flooding occupies consequence in China's chemical flooding raising recovery efficiency technique.
The polyacrylamide of traditional polymer oil-displacing agent mainly partial hydrolysis, it depends on the repulsive interaction of ion on high molecular and polymer molecular chain and strong polarity side base and reaches Efficient Adhesive Promotion.Often adopt the synthetizing hydrophobic associated polymkeric substance of oil soluble hydrophobic monomer such as N-alkyl acrylamide, alkyl acrylate at present, need in building-up process to adopt exhibiting high surface promoting agent, and in last handling process, need to remove tensio-active agent, be unfavorable for that polymer industryization is produced.
Polymerisable surfactant is obtained polymer oil-displacing agent as polymerization single polymerization monomer polymerization, can solve the problem.But, along with continually developing of oil field, exploitation reservoir condition constantly worsens, oilfield exploitation just progressively enters two classes, the three class oil reservoir blocks of high temperature and high salt, existing polymerisable surfactant is polymerized the shortcoming that the flooding polymers obtained exists high thermal resistance difference and salt resistance difference, under high temperature and high salt environment, thickening property is poor, is difficult to the application meeting such oil reservoir, thus limits the exploitation of such oil reservoir.
Summary of the invention
The object of the present invention is to provide a kind of alkyl diquaternary monomers, its preparation method and association polymer, adopt alkyl diquaternary monomers provided by the invention to be polymerized the association polymer obtained, under high temperature and high salt environment, there is good thickening property.
The invention provides a kind of alkyl diquaternary monomers, there is structure shown in formula 1:
formula 1;
In formula 1, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20, and X is halogen.
Preferably, described R
1for the alkylidene group of C3 ~ C5;
Described R is the alkyl of C12 ~ C18;
Described X is Cl or Br.
The invention provides a kind of preparation method of alkyl diquaternary monomers, comprise the following steps:
A) compound shown in formula 2 and halohydrocarbon RX are reacted, obtain compound shown in formula 3;
B) by described steps A) compound shown in formula 3 that obtains and propylene halide CH
2cHCH
2x reacts, and obtains the alkyl diquaternary monomers shown in formula 1;
formula 2;
formula 3;
formula 1;
Wherein, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20, and X is halogen.
Preferably, shown in described formula 2, the mol ratio of compound and halohydrocarbon is 1:(1 ~ 4).
Preferably, described steps A) in reaction temperature be 30 ~ 60 DEG C;
Described steps A) in reaction time be 24 ~ 36 hours.
Preferably, mol ratio 1:(1.5 ~ 5 of compound and propylene halide shown in described formula 3).
Preferably, described step B) in reaction temperature be 50 ~ 80 DEG C;
Described step B) in reaction time be 18 ~ 30 hours.
Preferably, described step B) after also comprise:
By step B) obtain have shown in formula 1 alkyl diquaternary monomers washing or recrystallization, obtain the alkyl diquaternary monomers of purifying.
Preferably, the washing lotion of described washing comprises ethers and/or chloroform;
The recrystallization solution that described recrystallization uses comprises the aqueous solution of alcohol and/or the aqueous solution of acetone.
The invention provides a kind of association polymer, comprise the repeating unit of structure shown in formula 4 ~ 6:
formula 4;
formula 5;
formula 6;
In formula 6, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20.
The invention provides a kind of alkyl diquaternary monomers, there is structure shown in formula 1, in formula 1, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20, and X is halogen.Alkyl diquaternary monomers in the present invention is a kind of chain alkyl gemini quaternary ammonium salt cationic monomer, such Molecular Structure Design can improve the solvability of hydrophobic monomer, increase the C atomicity of chain alkyl, make the polymer hydrophobic association that obtains stronger, contribute to forming the dynamic physical cross-linked network between polymer macromolecule, its hydrodynamic volume is increased, soltion viscosity significantly raises, and ensure that the polymkeric substance that the alkyl diquaternary monomers in the present invention obtains still has good thickening property under the environment of high temperature and high salt.
In addition, alkyl diquaternary monomers good solubility in the present invention ensure that it adopts conventional aqueous solution polymerization to synthesize association polymer, more economical compared with the method such as micellar copolymerization, letex polymerization adopted with the synthetizing hydrophobic associated polymkeric substance of other water-insoluble hydrophobic monomer, and the polymkeric substance of the high molecular that is more easy to get.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the tackifying test result of the association polymer that the embodiment of the present invention 6 ~ 10 obtains.
Embodiment
The invention provides a kind of alkyl diquaternary monomers, there is structure shown in formula 1:
formula 1;
Described alkyl diquaternary monomers is polymerizable cationic surfactant, in formula 1, and R
1for the alkylidene group of C2 ~ C6, be preferably the alkylidene group of C3 ~ C5, be more preferably the alkylidene group of C4; R is the alkyl of C8 ~ C20, is preferably the alkyl of C12 ~ C18, is more preferably the alkyl of C14 ~ C16; X is halogen, is preferably Cl or Br.
Concrete, described alkyl diquaternary monomers is preferably following structure:
formula 1-1;
formula 1-2;
formula 1-3;
formula 1-4;
formula 1-5.
Present invention also offers a kind of preparation method of alkyl diquaternary monomers, comprise the following steps:
A) compound shown in formula 2 and halohydrocarbon RX are reacted, obtain compound shown in formula 3;
B) by described steps A) compound shown in formula 3 that obtains and propylene halide CH
2cHCH
2x reacts, and obtains the alkyl diquaternary monomers shown in formula 1;
formula 2;
formula 3;
formula 1;
Wherein, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20, and X is halogen.
Compound shown in formula 2 and halohydrocarbon RX preferably mix by the present invention in a solvent, react, and obtain the compound shown in formula 3.Described steps A) reaction be the nucleophilic substitution reaction of amine and halohydrocarbon, reaction process as shown in Equation 7, the present invention is preferably existing by compound and solvent shown in formula 2, and then halohydrocarbon is dripped halohydrocarbon under the condition of constant temperature, stirring in the solution of compound shown in described formula 2, react.The device of the present invention to described reaction does not have special restriction, preferably adopts the four-necked bottle being provided with agitator, thermometer, reflux condensing tube, constant pressure funnel and nitrogen protection device.
formula 7.
Wherein, described R
1for the alkyl of C2 ~ C6, be preferably the alkyl of C3 ~ C5, be more preferably the alkyl of C4; R is the alkyl of C8 ~ C20, is preferably the alkyl of C12 ~ C18, is more preferably the alkyl of C14 ~ C16; X is halogen, is preferably Cl or Br; It is the halohydrocarbon of 8 ~ 20 that described halohydrocarbon (RX namely in formula 7) is preferably carbonatoms, be more preferably the halohydrocarbon that carbonatoms is 12 ~ 18, most preferably be the halohydrocarbon that carbonatoms is 14 ~ 16, halogen in described halohydrocarbon is preferably Cl or Br, concrete, one or more in Dodecyl Bromide, 1-bromo-octadecane and 1-bromotetradecane can be adopted; Described solvent preferably includes dimethyl formamide and/or methyl alcohol.
In the present invention, shown in described formula 2, the temperature of compound and halohydrocarbons reaction is preferably 30 ~ 60 DEG C, is more preferably 35 ~ 55 DEG C, most preferably is 40 ~ 50 DEG C; The time of compound and halohydrocarbons reaction shown in described formula 2 is preferably 24 ~ 36 hours, is more preferably 28 ~ 32 hours.In the present invention, shown in described formula 2, the mol ratio of compound and halohydrocarbon is preferably 1:(1 ~ 4), be more preferably 1:(1.5 ~ 3.5), most preferably be 1:(2.5 ~ 3).
After completing above-mentioned reaction, the present invention preferably adopts Rotary Evaporators to remove compound and solvent shown in formula 2 remaining in system, and then the product washing that will obtain, to carry out purifying, the present invention preferably adopts ethers or acetone to wash it, more preferably adopts ether and/or acetone.
Compound shown in formula 2 after washing is preferably carried out drying by the present invention, obtains compound shown in dry formula 2.The present invention preferably adopts vacuum drying oven to be dried to constant weight to it, and the temperature of described drying is preferably 60 ~ 70 DEG C.
The present invention is preferably by compound and propylene halide CH shown in the formula 3 after purifying
2cHCH
2x mixes in a solvent, reacts, and obtains alkyl diquaternary monomers shown in formula 1.In the present invention, described step B) reaction be the nucleophilic substitution reaction of amine and haloolefin, reaction process as shown in Equation 8, the present invention is preferably first by compound and solvent shown in described formula 3, and then propylene halide is dropped in the solution of compound shown in formula 3 under constant temperature, react.Described propylene halide is preferably the rare or bromopropylene of chlorine third; Described solvent preferably includes alcohols and/or ethyl acetate, more preferably comprises ethanol and/or ethyl acetate.
formula 8.
In the present invention, the temperature that shown in described formula 3, compound and propylene halide react is preferably 50 ~ 80 DEG C, is more preferably 55 ~ 75 DEG C, most preferably is 60 ~ 70 DEG C; The time that shown in described formula 3, compound and propylene halide react is preferably 18 ~ 30, is more preferably 20 ~ 28 hours, most preferably is 24 ~ 26 hours; The mol ratio that shown in described formula 3, compound and propylene halide react is preferably 1:(1.5 ~ 5), be more preferably 1:(2 ~ 4.5), most preferably be 1:(2.5 ~ 4).
After obtaining alkyl diquaternary monomers shown in formula 1, the present invention preferably filters it, then carries out purifying, and the present invention preferably adopts the method for washing or recrystallization to carry out purifying to it, and in the present invention, the washing lotion of described washing preferably includes ethers and/or chloroform; The recrystallization solution that described recrystallization uses preferably includes the aqueous solution and/or the aqueous acetone solution of alcohol, concrete, and described recrystallization can use the aqueous acetone solution of 5%.
Alkyl diquaternary monomers after purifying is preferably carried out drying by the present invention, and the present invention preferably adopts vacuum drying oven to be dried to constant weight, and in the present invention, the temperature of described drying is preferably 60 ~ 70 DEG C.
Present invention also offers a kind of association polymer, comprise the repeating unit of structure shown in formula 4 ~ 6:
formula 4;
formula 5;
formula 6;
In formula 6, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20.
In the present invention, described R
1for the alkylidene group of C2 ~ C6, be preferably the alkylidene group of C3 ~ C5, be more preferably the alkylidene group of C4; R is the alkyl of C8 ~ C20, is preferably the alkyl of C12 ~ C18, is more preferably the alkyl of C14 ~ C16.The molar fraction that the monomer forming structural repeat unit shown in described formula 6 accounts for total monomer is preferably 0.1 ~ 2%; The ratio of the present invention to the repeating unit of structure shown in described formula 4 and formula 5 does not have special restriction, is determined by the add-on of its corresponding monomer.The degree of hydrolysis of described association polymer is preferably 5 ~ 30%, is more preferably 10 ~ 20%; That is, the acrylamide repeating unit having the polyreaction of molar fraction 5 ~ 30% to be formed has changed into sodium acrylate repeating unit.
In the present invention, the viscosity-average molecular weight of described association polymer is preferably 1650 × 10
4~ 1900 × 10
4, be more preferably 1700 × 10
4~ 1850 × 10
4; The solvent time of described association polymer is preferably 1.5 ~ 2.5 hours, and (solvent is total mineralization is 4.9 ten thousand water, Ca
2+, Mg
2+total ion concentration is the simulation salt solution of 1900mg/L).
The present invention preferably obtains above-mentioned association polymer according to following steps:
1) compound shown in formula 1 and acrylamide are mixed in water, then add initiator, carry out polyreaction, obtain polymeric colloid;
2) by described step 1) polymeric colloid that obtains mixes with hydrolytic reagent, and be hydrolyzed, drying obtains association polymer.
After compound shown in formula 1 and acrylamide preferably mix by the present invention in water, the mixing solutions that obtains is placed insulation in a water bath until described mixing solutions temperature to 15 ~ 20 DEG C after, then add initiator, carry out polyreaction.In the present invention, described step 1) in water be preferably pure water, shown in the aqueous solution Chinese style 1 of compound and acrylamide shown in described formula 1, the massfraction of compound is preferably 20 ~ 30%, is more preferably 25%; Described initiator preferably includes Potassium Persulphate and sodium bisulfite; The mass ratio of described Potassium Persulphate and S-WAT is preferably 1:(0.5 ~ 1.5), be more preferably 1:1; The add-on of described Potassium Persulphate is preferably 0.01 ~ 0.03% of compound quality shown in formula 1, is more preferably 0.018 ~ 0.25%; The mol ratio of compound shown in described acrylamide and formula 1 is preferably (99.9 ~ 98): (0.1 ~ 2), is more preferably (99.5 ~ 98.5): (0.5 ~ 1.5).The present invention preferably carries out described polyreaction under the environment of thermal insulation, thinks that polyreaction completes when the temperature of reaction system rose above 1 DEG C in 30 minutes.
After completing described polyreaction, the intermediate polymer obtained mixes with hydrolytic reagent by the present invention, and be hydrolyzed reaction, obtains association polymer.The intermediate polymer obtained (for colloidal state) is preferably cut into the particle of 3 ~ 5mm size by the present invention, and then mixes with hydrolytic reagent, and be hydrolyzed reaction.In the present invention, described hydrolytic reagent preferably includes one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate; The add-on of described hydrolytic reagent is preferably 0.4 ~ 5.0% of described intermediate polymer quality, is more preferably 0.8 ~ 3.0%.
In the present invention, the temperature of described hydrolysis reaction is preferably 90 ~ 100 DEG C, is more preferably 95 DEG C; The time of described hydrolysis reaction is preferably 1 ~ 4 hour, is more preferably 2 ~ 3 hours.After described intermediate polymer and hydrolytic reagent preferably mix by the present invention, transfer them in plastics bag and seal, then be hydrolyzed reaction in constant temperature oven, it should be noted that, to try one's best during sealing excluding air, and retain the ammonia produced when enough controls hold hydrolysis, and when noting hydrolysis, sealing bag does not break.
After hydrolysis reaction completes, the present invention preferably by the product of described hydrolysis freeze-day with constant temperature in an oven, then sieves, and obtains association polymer dry powder.In the present invention, the temperature of described drying is preferably 90 ~ 100 DEG C, is more preferably 95 DEG C; The time of described drying is preferably 0.5 ~ 2 hour, is more preferably 1 ~ 1.5 hour.
The present invention tests the dissolution time of association polymer in the present invention, testing method: solvent is total mineralization is 4.9 ten thousand water, Ca
2+, Mg
2+total ion concentration is the simulation salt solution of 1900mg/L, and solvent temperature is 50 DEG C, and polymer mother liquor concentration is 5000mg/L, adopts observation to investigate the complete dissolution time of polymkeric substance.Result shows, the dissolution time of the association polymer in the present invention is between 1.5 ~ 2.5 hours.
The present invention tests the tackifying of association polymer in the present invention, testing method: solvent is total mineralization is 4.9 ten thousand water, Ca
2+, Mg
2+total ion concentration is the simulation salt solution of 1900mg/L, and target liquid probe temperature is 85 DEG C, adopts Brookfield viscometer DV-III to be 7.34s-in shearing rate
1lower test.Result shows, the association polymer in the present invention still has good thickening property under high salinity condition.
Hydrophobic associated polymer refers to the water-soluble polymers with a small amount of hydrophobic grouping on polymer hydrophilicity macromolecular chain, due to the molecular structure that it is special, makes its solution have special rheological property.In aqueous, the hydrophobic grouping of this base polymer is assembled due to hydrophobic interaction, makes macromolecular chain produce in molecule and Interpolymer Association.In dilute solution, macromole mainly exists with the form of Intramolecular association, macromolecular chain is occurred curling, after polymer concentration is higher than critical association concentration, macromolecular chain is assembled by heat resistance and salt tolerance, form supramolecular structure---the dynamic physical cross-linked network based on Interpolymer Association, hydrodynamic volume increases, and soltion viscosity significantly raises.Small molecules is electrolytical adds the polarity that all can increase solvent with raised temperature, and heat resistance and salt tolerance is strengthened.Under high shear forces, the dynamic physical cross-linked network that hydrophobic association is formed is destroyed, soltion viscosity declines, shearing action reduces or the physical crosslinking eliminated between rear macromolecular chain is formed again, viscosity will be recovered again, and the polymkeric substance irreversible mechano-degradation at high shear rates of general high molecular does not occur.
Hydrophobic monomer in the present invention is a kind of chain alkyl gemini quaternary ammonium salt cationic monomer, the such Molecular Structure Design of gemini quaternary ammonium salt can improve the solvability of hydrophobic monomer, increase the C atomicity of chain alkyl, make multipolymer heat resistance and salt tolerance stronger, simultaneously control the molecular structure of hydrophobic associated polymer by content of hydrophobic monomers regulation range more widely, thus the rheological property of change polymers soln is to meet the demands, hydrophobic monomer good solubility can make to adopt conventional aqueous solution polymerization to get final product synthetizing hydrophobic associated polymkeric substance, the micellar copolymerization adopted with the synthetizing hydrophobic associated polymkeric substance of other water-insoluble hydrophobic monomer, the methods such as letex polymerization are more economical, and the polymkeric substance of the high molecular that is more easy to get.
In addition, the present invention adopts the washing such as ethers, acetone to the purifying of the intermediate product shown in formula 3, and adopt this kind of mode purifying more easy compared with means re-crystallization, product yield increases considerably (>=90%); The purifying of final product (shown in formula 1 structures alone) crude product can adopt the mode of washing, recrystallization, be specially washed with diethylether, 5% isopropylcarbinol aqueous solution recrystallization, 5% aqueous acetone solution recrystallization 2 ~ 3 times, the mode of this kind of recrystallization obtains product purity and yield higher (productive rate > 89%, purity > 90%).
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of alkyl diquaternary monomers provided by the invention, its preparation method and association polymer being described in detail, but can not limiting the scope of the present invention being understood as.
The synthesis of embodiment 1 sodium dodecyl allyl base dibrominated tetramethyl-second two ammonium
130.74g Tetramethyl Ethylene Diamine is added according to the ratio of n (Dodecyl Bromide): n (Tetramethyl Ethylene Diamine): n (dimethyl formamide)=1:2.5:7 in the four-necked bottle that agitator, thermometer, reflux condensing tube, constant pressure funnel and nitrogen protection device are housed; 226.35g dimethyl formamide; under agitation; be warming up to 45 DEG C; under constant temperature, adopt constant pressure funnel slowly to drip 110.25g1-bromododecane; after dropwising, under 45 DEG C of constant temperatures, react 24 ~ 28h.Reaction terminates, and adopts remaining Tetramethyl Ethylene Diamine and dimethyl formamide in Rotary Evaporators removing system.To obtain product washed with diethylether 2 ~ 3 times, and filter, in 50 DEG C of vacuum drying ovens, be dried to constant weight, obtain 149.41g mono-quaternaries, yield is 92%.
According to n (mono-quaternaries): n (dehydrated alcohol)=1:8, 149.64g dehydrated alcohol is added to the 149.41g mono-quaternaries obtained, it is made to dissolve completely, be warming up to 65 DEG C, under constant temperature, by n (mono-quaternaries): n (bromopropylene)=1:3.5, constant pressure funnel is adopted slowly to drip 172.18g bromopropylene, after dropwising, at 65 DEG C of isothermal reaction 18 ~ 24h, obtain white solid product, product is filtered, adopt 5% isopropylcarbinol aqueous solution recrystallization 2 times, acquisition product is dried to constant weight in 60 DEG C of vacuum drying ovens, obtain 188.68g sodium dodecyl allyl base dibrominated tetramethyl-second two ammonium (shown in 1-1), productive rate is 95%, through gas chromatographic detection, its purity is 98%.
The mono-quaternaries of acquisition is carried out magnetic resonance detection by the present invention, and its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (16H), 1.29 (2H), 1.71 (2H), 2.47 (6H), 2.8 (2H), 3.22 (2H), 3.30 (6H), 3.34 (2H) compose result from hydrogen, obtain the chain alkyl mono-quaternaries that product main component is formula 3-1.
formula 3-1
The present invention carries out magnetic resonance detection to described product, and its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (16H), 1.29 (2H), 1.71 (2H), 3.22 (2H), 2.90 (6H), 3.30 (6H), 3.68 (4H), 3.91 (2H), 5.03 (1H), 5.07 (1H), 5.70 (1H), compose result from hydrogen, obtain the chain alkyl bi-quaternary ammonium salt that product main component is formula (1-1).
formula 1-1.
The synthesis of embodiment 2 octadecyl allyl group dibrominated tetramethyl-second two ammonium
According to n (1-bromo-octadecane) in the four-necked bottle that agitator, thermometer, reflux condensing tube, constant pressure funnel and nitrogen protection device are housed: the ratio of n (Tetramethyl Ethylene Diamine): n (methyl alcohol)=1:3.2:6.8 adds 142.24g Tetramethyl Ethylene Diamine; 81.82g methyl alcohol; under agitation; be warming up to 50 DEG C; under constant temperature, adopt constant pressure funnel slowly to drip 125.32g1-bromo-octadecane; after dropwising, under 50 DEG C of constant temperatures, react 28h.Reaction terminates, and adopts remaining Tetramethyl Ethylene Diamine and methyl alcohol in Rotary Evaporators removing system.To obtain product washing with acetone 2 ~ 3 times, and filter, in 60 DEG C of vacuum drying ovens, be dried to constant weight, obtain 155.30g mono-quaternaries, yield is 91.5%.
According to n (mono-quaternaries): n (ethyl acetate)=1:7, 212.15g ethyl acetate is added to the 155.30g mono-quaternaries obtained, it is made to dissolve completely, be warming up to 70 DEG C, under constant temperature, by n (mono-quaternaries): n (bromopropylene)=1:4.0, constant pressure funnel is adopted slowly to drip 166.47g bromopropylene, after dropwising, at 70 DEG C of isothermal reaction 24 ~ 30h, obtain white solid product, product is filtered, adopt washed with diethylether 2 ~ 3 times, acquisition product is dried to constant weight in 60 DEG C of vacuum drying ovens, obtain 190.61g octadecyl allyl group dibrominated tetramethyl-second two ammonium (shown in 1-2), productive rate is 96.8%, through gas chromatographic detection, its purity is 94.5%.
Carry out magnetic resonance detection to described product, its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (28H), 1.29 (2H), 1.71 (2H), 2.26 (6H), 2.80 (2H), 2.90 (6H), 3.22 (2H), 3.34 (2H) compose result from hydrogen, obtain the chain alkyl mono-quaternaries that product main component is formula 3-2.
Carry out magnetic resonance detection to described product, its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (28H), 1.29 (2H), 1.71 (2H), 3.22 (2H), 2.90 (6H), 3.30 (6H), 3.68 (4H), 3.91 (2H), 5.03 (1H), 5.07 (1H), 5.70 (1H), compose result from hydrogen, obtain the chain alkyl bi-quaternary ammonium salt that product main component is formula (1-2).
formula 3-2;
formula 1-2.
The synthesis of embodiment 3 octadecyl allyl group dichloride tetramethyl-second two ammonium
According to n (1-chlorooctadecane) in the four-necked bottle that agitator, thermometer, reflux condensing tube, constant pressure funnel and nitrogen protection device are housed: the ratio of n (Tetramethyl Ethylene Diamine): n (methyl alcohol)=1:3.2:6.8 adds 142.24g Tetramethyl Ethylene Diamine; 81.82g methyl alcohol; under agitation; be warming up to 50 DEG C; under constant temperature, adopt constant pressure funnel slowly to drip 125.32g1-chlorooctadecane; after dropwising, under 50 DEG C of constant temperatures, react 28h.Reaction terminates, and adopts remaining Tetramethyl Ethylene Diamine and methyl alcohol in Rotary Evaporators removing system.To obtain product washing with acetone 2 ~ 3 times, and filter, in 60 DEG C of vacuum drying ovens, be dried to constant weight, obtain 155.30g mono-quaternaries, yield is 91.5%.
According to n (mono-quaternaries): n (ethyl acetate)=1:7, 212.15g ethyl acetate is added to the 155.30g mono-quaternaries obtained, it is made to dissolve completely, be warming up to 80 DEG C, under constant temperature, by n (mono-quaternaries): n (propenyl chloride)=1:4.5, constant pressure funnel is adopted slowly to drip 118.45g propenyl chloride, after dropwising, at 80 DEG C of isothermal reaction 30h, obtain white solid product, product is filtered, adopt washed with diethylether 2 ~ 3 times, acquisition product is dried to constant weight in 60 DEG C of vacuum drying ovens, obtain 163.09g octadecyl allyl group dichloride tetramethyl-second two ammonium (shown in 1-3), productive rate is 89.8%, through gas chromatographic detection, its purity is 92.5%.
Carry out magnetic resonance detection to described intermediate product, its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (28H), 1.29 (2H), 1.71 (2H), 2.26 (6H), 2.80 (2H), 2.90 (6H), 3.22 (2H), 3.34 (2H) compose result from hydrogen, obtain the chain alkyl mono-quaternaries that product main component is formula 3-3.
Carry out magnetic resonance detection to described product, its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (28H), 1.29 (2H), 1.71 (2H), 3.22 (2H), 2.90 (6H), 3.30 (6H), 3.68 (4H), 3.91 (2H), 5.03 (1H), 5.07 (1H), 5.70 (1H), compose result from hydrogen, obtain the chain alkyl bi-quaternary ammonium salt that product main component is formula 1-3.
formula 3-3;
formula 1-3.
The synthesis of embodiment 4 tetradecyl allyl group dibrominated tetramethyl-fourth two ammonium
According to n (1-bromotetradecane) in the four-necked bottle that agitator, thermometer, reflux condensing tube, constant pressure funnel and nitrogen protection device are housed: the ratio of n (tetramethyl butane diamine): n (dimethyl formamide)=1:3.5:7.5 adds 219.60g tetramethyl butane diamine; 238.41g dimethyl formamide; under agitation; be warming up to 55 DEG C; under constant temperature, adopt constant pressure funnel slowly to drip 120.58g1-bromotetradecane; after dropwising, under 55 DEG C of constant temperatures, react 32h.Reaction terminates, and adopts remaining Tetramethyl Ethylene Diamine and dimethyl formamide in Rotary Evaporators removing system.To obtain product washed with diethylether 2 ~ 3 times, and filter, in 60 DEG C of vacuum drying ovens, be dried to constant weight, obtain 165.01g mono-quaternaries, yield is 90.0%.
According to n (mono-quaternaries): n (dehydrated alcohol)=1:6.5, 117.23g dehydrated alcohol is added to the 165.01g mono-quaternaries obtained, it is made to dissolve completely, be warming up to 70 DEG C, under constant temperature, by n (mono-quaternaries): n (bromopropylene)=1:2.8, constant pressure funnel is adopted slowly to drip 132.45g bromopropylene, after dropwising, at 70 DEG C of isothermal reaction 28h, obtain white solid product, product is filtered, adopt 5% aqueous acetone solution recrystallization 2 ~ 3 times, acquisition product is dried to constant weight in 60 DEG C of vacuum drying ovens, obtain 194.92g tetradecyl allyl group dibrominated tetramethyl-fourth two ammonium (shown in 1-4), productive rate is 91.9%, through gas chromatographic detection, its purity is 97.5%.
Carry out magnetic resonance detection to described intermediate product, its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (20H), 1.36 (2H), 1.29 (2H), 1.71 (4H), 2.15 (6H) 2.46 (2H), 3.22 (4H), 3.30 (6H), compose result from hydrogen, obtain the chain alkyl mono-quaternaries that product main component is formula 3-4.
Carry out magnetic resonance detection to described product, its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (20H), 1.29 (2H), 1.71 (6H), 3.22 (6H), 3.30 (12H), 3.91 (2H), 5.03 (1H), 5.07 (1H), 5.70 (1H), compose result from hydrogen, obtain the chain alkyl bi-quaternary ammonium salt that product main component is formula 1-4.
formula 3-4;
formula 1-4.
The synthesis of embodiment 5 tetradecyl allyl group dibrominated 4-methyl hexamethylene diamine
According to n (1-bromotetradecane) in the four-necked bottle that agitator, thermometer, reflux condensing tube, constant pressure funnel and nitrogen protection device are housed: the ratio of n (4-methyl hexamethylene diamine): n (dimethyl formamide)=1:2.5:6.0 adds 195.47g Tetramethyl Ethylene Diamine; 165.50g dimethyl formamide; under agitation; be warming up to 60 DEG C; under constant temperature, adopt constant pressure funnel slowly to drip 125.80g1-bromotetradecane; after dropwising, under 60 DEG C of constant temperatures, react 30h.Reaction terminates, and adopts remaining Tetramethyl Ethylene Diamine and dimethyl formamide in Rotary Evaporators removing system, will obtain product washing with acetone 2 ~ 3 times, filter, in 60 DEG C of vacuum drying ovens, be dried to constant weight, obtain 239.43g mono-quaternaries, yield is 92.5%.
According to n (mono-quaternaries): n (dehydrated alcohol)=1:6.5, 117.23g dehydrated alcohol is added to the 165.01g mono-quaternaries obtained, it is made to dissolve completely, be warming up to 70 DEG C, under constant temperature, by n (mono-quaternaries): n (bromopropylene)=1:2.8, constant pressure funnel is adopted slowly to drip 132.45g bromopropylene, after dropwising, at 70 DEG C of isothermal reaction 28h, obtain white solid product, product is filtered, adopt 5% isopropanol water solution recrystallization 2 ~ 3 times, acquisition product is dried to constant weight in 60 DEG C of vacuum drying ovens, obtain oneself two ammoniums (shown in 1-5) of 220.04g tetradecyl allyl group dibrominated tetramethyl-, productive rate is 91.9%, through gas chromatographic detection, its purity is 96.8%.
Carry out magnetic resonance detection to described intermediate product, its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (20H), 1.36 (2H), 1.29 (6H), 1.71 (4H), 2.15 (6H) 2.46 (2H), 3.22 (4H), 3.30 (6H), compose result from hydrogen, obtain the chain alkyl mono-quaternaries that product main component is formula 3-5.
Carry out magnetic resonance detection to described product, its hydrogen spectrum detected result is,
1h-NMR (DMSO, ppm): 0.88 (3H), 1.26 (20H), 1.29 (6H), 1.71 (6H), 3.22 (6H), 3.30 (12H), 3.91 (2H), 5.03 (1H), 5.07 (1H), 5.70 (1H), compose result from hydrogen, obtain the chain alkyl bi-quaternary ammonium salt that product main component is formula 1-5.
formula 3-5;
formula 1-5.
The synthesis of embodiment 6 association polymer
By acrylamide, sodium dodecyl allyl base dibrominated tetramethyl-second two ammonium feeds intake by the mol ratio of 99.5:0.5, join in 5000mL beaker to dissolve with pure water and be mixed with the mixing solutions that total monomer is 25%, beaker is put into 15 DEG C of water-bath insulations until solution temperature is after 15 DEG C, add Potassium Persulphate and sodium bisulfite composite initiator initiated polymerization, wherein Potassium Persulphate and sodium bisulfite mass ratio are 1:1, and Potassium Persulphate dosage is 0.018% of monomer mass.Polyreaction is carried out under adiabatic environment, inserts thermometer monitors polyreaction and carries out degree, think that polyreaction completes substantially when temperature rises above 1 DEG C in 30 minutes at reaction system center.After polyreaction completes 1 hour, take out colloid, colloid is cut into 3 ~ 5mm size particles, add the hydrolytic reagent NaOH accounting for colloid total mass 2.39%, mix, transferred in plastics bag and seal, then constant temperature 95 DEG C hydrolysis 2h in constant temperature oven.To try one's best when should be noted that sealing excluding air, and the ammonia produced when retaining enough space hydrolysis, when noting hydrolysis, sealing bag does not break.After being hydrolyzed, colloid being spread out and paves on 500 eye mesh screens, put into baking oven constant temperature 95 DEG C of dry 1h, take out the acquisition polymer dry powder that sieves.
The polymer dry powder obtained to embodiment 6 carries out infrared absorption spectrum detection, 3582cm-
1and 3168cm-
1place belongs to unsymmetrically and the symmetrical stretching vibration peak .2935cm-of N-H key
1and 1456cm-
1belong to stretching vibration peak and the flexural vibration peak of c h bond respectively, 1645cm-
1belong to the stretching vibration peak of amide Ⅰ C=O, 1616cm-
1belong to the flexural vibration peak .1558cm-that acid amides II is with N-H
1and 1412cm-
1belong to unsymmetrically and the symmetrical stretching vibration peak of C-O, 1312cm-
1belong to the stretching vibration peak of C-N key, 793cm-
1belong to the absorption peak waving generation in long-chain methylene basal plane.
According to above-mentioned infrared absorption spectrum analysis result, containing groups such as amide group, chain alkyl, carboxyls in this multipolymer, illustrate in this multipolymer to there is acrylamide monomer, long chain alkyl ammonium salt and sodium acrylate structural unit,
The synthesis of embodiment 7 association polymer
Association polymer is prepared according to the method in embodiment 6, unlike, change sodium dodecyl allyl base dibrominated tetramethyl-second two ammonium in embodiment 6 into octadecyl allyl group dibrominated tetramethyl-second two ammonium.
The synthesis of embodiment 8 association polymer
Association polymer is prepared according to the method in embodiment 6, unlike, change sodium dodecyl allyl base dibrominated tetramethyl-second two ammonium in embodiment 6 into octadecyl allyl group dichloride tetramethyl-second two ammonium.
The synthesis of embodiment 9 association polymer
Association polymer is prepared according to the method in embodiment 6, unlike, change sodium dodecyl allyl base dibrominated tetramethyl-second two ammonium in embodiment 6 into tetradecyl allyl group dibrominated tetramethyl-fourth two ammonium.
The synthesis of embodiment 10 association polymer
Association polymer is prepared according to the method in embodiment 6, unlike, sodium dodecyl allyl base dibrominated tetramethyl-second two ammonium in embodiment 6 is changed into oneself two ammoniums of tetradecyl allyl group dibrominated tetramethyl-.
The molecular weight of hydrophobic associated polymer synthesized by embodiment 6 ~ 10 and dissolution time test result as shown in table 1, table 1 is molecular weight and the dissolution time of association polymer in the embodiment of the present invention 6 ~ 10.Wherein molecule measuring method for testing is: use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 test and counting yield viscosity-average molecular weight; Dissolution time testing method: solvent is total mineralization is 4.9 ten thousand water, Ca
2+, Mg
2+total ion concentration is the simulation salt solution of 1900mg/L, and solvent temperature is 50 DEG C, and polymer mother liquor concentration is 5000mg/L, adopts observation to investigate the complete dissolution time of polymkeric substance.
The molecular weight of the association polymer in table 1 embodiment of the present invention 6 ~ 10 and dissolution time
| Embodiment | Viscosity-average molecular weight (× 10 4) | Dissolution time (h) |
| 6 | 1789 | 1.5 |
| 7 | 1658 | 2.5 |
| 8 | 1801 | 2.5 |
| 9 | 1895 | 2.0 |
| 10 | 1852 | 2.0 |
As shown in Table 1, adopt the polymericular weight of bi-quaternary ammonium salt hydrophobic monomer synthesis to be all greater than 1,600 ten thousand, have higher molecular weight, polymkeric substance is at 50 DEG C simultaneously, and high salinity condition dissolution time≤2.5h, possesses good solubility energy.
The present invention tests the tackifying of the association polymer that embodiment 6 ~ 10 obtains.As shown in Figure 1, Fig. 1 is the tackifying test result of the association polymer that the embodiment of the present invention 6 ~ 10 obtains to result.Tackifying testing method: solvent is total mineralization is 4.9 ten thousand water, Ca
2+, Mg
2+total ion concentration is the simulation salt solution of 1900mg/L, and it is 85 DEG C that target liquid surveys probe temperature, adopts Brookfield viscometer DV-III to be 7.34s-in shearing rate
1lower test.
As shown in Figure 1, along with polymer concentration increases, polymer viscosity obviously increases, as polymer concentration >=1500ppm, polymer viscosity is in sharply ascendant trend, and be 85 DEG C in temperature, salt solution total mineralization is under the high temperature and high salinity condition of 4.9 ten thousand, the hydrophobic associated polymer obtained still possesses good tackifying ability, is expected to be applied in high temperature and high salt oil deposit environment.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. an alkyl diquaternary monomers, has structure shown in formula 1:
In formula 1, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20, and X is halogen.
2. alkyl diquaternary monomers according to claim 1, is characterized in that, described R
1for the alkylidene group of C3 ~ C5;
Described R is the alkyl of C12 ~ C18;
Described X is Cl or Br.
3. a preparation method for alkyl diquaternary monomers, comprises the following steps:
A) compound shown in formula 2 and halohydrocarbon RX are reacted, obtain compound shown in formula 3;
B) by described steps A) compound shown in formula 3 that obtains and propylene halide CH
2cHCH
2x reacts, and obtains the alkyl diquaternary monomers shown in formula 1;
Wherein, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20, and X is halogen.
4. preparation method according to claim 3, is characterized in that, shown in described formula 2, the mol ratio of compound and halohydrocarbon is 1:(1 ~ 4).
5. preparation method according to claim 3, is characterized in that, described steps A) in reaction temperature be 30 ~ 60 DEG C;
Described steps A) in reaction time be 24 ~ 36 hours.
6. preparation method according to claim 3, is characterized in that, mol ratio 1:(1.5 ~ 5 of compound and propylene halide shown in described formula 3).
7. preparation method according to claim 3, is characterized in that, described step B) in reaction temperature be 50 ~ 80 DEG C;
Described step B) in reaction time be 18 ~ 30 hours.
8. preparation method according to claim 3, is characterized in that, described step B) after also comprise:
By step B) obtain have shown in formula 1 alkyl diquaternary monomers washing or recrystallization, obtain the alkyl diquaternary monomers of purifying.
9. preparation method according to claim 8, is characterized in that, the washing lotion of described washing comprises ethers and/or chloroform;
The recrystallization solution that described recrystallization uses comprises the aqueous solution and/or the aqueous acetone solution of alcohol.
10. an association polymer, comprises the repeating unit of structure shown in formula 4 ~ 6:
In formula 6, R
1for the alkylidene group of C2 ~ C6, R is the alkyl of C8 ~ C20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511022772.6A CN105503623A (en) | 2015-12-29 | 2015-12-29 | Alkyl bis-quaternary ammonium salt monomer, preparation method thereof and associating polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511022772.6A CN105503623A (en) | 2015-12-29 | 2015-12-29 | Alkyl bis-quaternary ammonium salt monomer, preparation method thereof and associating polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105503623A true CN105503623A (en) | 2016-04-20 |
Family
ID=55711997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511022772.6A Pending CN105503623A (en) | 2015-12-29 | 2015-12-29 | Alkyl bis-quaternary ammonium salt monomer, preparation method thereof and associating polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105503623A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619660A (en) * | 2017-11-02 | 2018-01-23 | 中国石油化工股份有限公司 | Gel acid thickening agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476913A (en) * | 1992-07-06 | 1995-12-19 | Otsuka Kagaku Kabushiki Kaisha | Polymerizable monomer, polymer thereof and process for preparing same |
| CN104910024A (en) * | 2015-05-12 | 2015-09-16 | 四川理工学院 | Surfactant for driving oil |
-
2015
- 2015-12-29 CN CN201511022772.6A patent/CN105503623A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476913A (en) * | 1992-07-06 | 1995-12-19 | Otsuka Kagaku Kabushiki Kaisha | Polymerizable monomer, polymer thereof and process for preparing same |
| CN104910024A (en) * | 2015-05-12 | 2015-09-16 | 四川理工学院 | Surfactant for driving oil |
Non-Patent Citations (2)
| Title |
|---|
| 王斌: "新型疏水缔合水溶性聚合物的合成及溶液性能研究", 《应用化工》 * |
| 章云祥等: "水溶性高聚物的研究进展", 《功能高分子学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619660A (en) * | 2017-11-02 | 2018-01-23 | 中国石油化工股份有限公司 | Gel acid thickening agent and preparation method thereof |
| CN107619660B (en) * | 2017-11-02 | 2020-04-14 | 中国石油化工股份有限公司 | Gelled acid thickener and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448125B (en) | Amphoteric hydrophobically-associating polymer and preparation method thereof | |
| CN102391417B (en) | Hydrophobically associating water-soluble polymer (HAWSP) oil displacement agent and preparation method thereof | |
| CN104371691B (en) | Hydrophobically associating polymer sulfonate oil-displacing agent and synthesizing method thereof | |
| CN103113875A (en) | Water-based fracturing fluid thickener and method for preparing same | |
| CN103320114A (en) | Multiple association type polymer cleaning fracturing fluid thickening agent and preparation method thereof | |
| CN103555311A (en) | AM/NaAA/APO (acrylamide/sodium acrylate/N-allylphenoxyacetamide) ternary polymer flooding agent and synthesis method | |
| CN102372818A (en) | Temperature and salt resistant copolymer for oil field and preparation method thereof | |
| CN104448130A (en) | Temperature-resistant salt-resistant copolymer for oilfield, and preparation method and application thereof | |
| CN105646776A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN102604623A (en) | AM/NaAA/NAC water-soluble polymer oil-displacement agent and synthesizing method thereof | |
| CN104250380A (en) | Dendritic polymer, dendritic polymer monomer, and preparation methods and application of two | |
| CN104099081A (en) | Sand-carrying drag reducer for fracturing and preparation method thereof | |
| CN102660250A (en) | Cation hydrophobic associating polymer oil displacement agent and preparation method thereof | |
| CN105646772A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN104388063A (en) | Micro-crosslinking polymer fluid loss additive for drilling fluid and preparation method of micro-crosslinking polymer fluid loss additive | |
| CN105646774A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN105542070A (en) | Hydrophobic association polymer and preparation method thereof | |
| CN102850487A (en) | Water-soluble hydrophobic associated polymer oil displacement agent and synthesis method thereof | |
| CN105504155A (en) | Hydrophobically associating polymer and preparation method thereof | |
| CN105622451B (en) | A kind of long chain alkyl ammonium salt monomer, its preparation method and association polymer | |
| CN103554360B (en) | Temperature-resistant salt-resistant amphiphilic copolymer as well as preparation method thereof | |
| CN102391849B (en) | Imidazole polymer oil displacement agent and synthesizing method thereof | |
| CN102464782B (en) | Thermo-thickening water-soluble tricopolymer, its preparation method and application | |
| CN105503623A (en) | Alkyl bis-quaternary ammonium salt monomer, preparation method thereof and associating polymer | |
| CN105038733A (en) | High-temperature-resistant polymer tackifier for drilling fluid and preparation method for high-temperature-resistant polymer tackifier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160420 |
|
| RJ01 | Rejection of invention patent application after publication |