CN107022050B - 一种磺酸盐甜菜碱型疏水缔合聚合物及其制备方法 - Google Patents
一种磺酸盐甜菜碱型疏水缔合聚合物及其制备方法 Download PDFInfo
- Publication number
- CN107022050B CN107022050B CN201710342023.4A CN201710342023A CN107022050B CN 107022050 B CN107022050 B CN 107022050B CN 201710342023 A CN201710342023 A CN 201710342023A CN 107022050 B CN107022050 B CN 107022050B
- Authority
- CN
- China
- Prior art keywords
- betaine type
- polymer
- hydrophobic associated
- associated polymer
- sulphonate betaine
- 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.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 51
- 229960003237 betaine Drugs 0.000 title claims abstract description 34
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title claims abstract 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 4
- 238000006073 displacement reaction Methods 0.000 abstract description 3
- 239000002562 thickening agent Substances 0.000 abstract description 3
- 238000006392 deoxygenation reaction Methods 0.000 abstract description 2
- FVNDPBOEFPVRIA-UHFFFAOYSA-N NC(CC)S(=O)(=O)O.CNC.C(C(=C)C)(=O)N Chemical compound NC(CC)S(=O)(=O)O.CNC.C(C(=C)C)(=O)N FVNDPBOEFPVRIA-UHFFFAOYSA-N 0.000 abstract 1
- -1 alkyl (methyl) acrylamides Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical class CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- JGSARLDLIJGVTE-UHFFFAOYSA-N 3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid Chemical compound O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 108010094020 polyglycine Proteins 0.000 description 1
- 150000003140 primary amides Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/606—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing other heteroatoms
-
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
Abstract
本发明公开了一种磺酸盐甜菜碱型疏水缔合聚合物及其制备方法，该磺酸盐甜菜碱型疏水缔合聚合物制备过程如下：首先将丙烯酰胺和丙烯酸在水溶液中混合，调节体系pH为6~8左右，加入3‑(甲基丙烯酰胺丙基二甲氨基）丙磺酸盐、N‑芳香基‑N‑烷基(甲基)丙烯酰胺和十二烷基硫酸钠，搅拌至溶液澄清，通氮气除氧后，加入光引发剂偶氮二异丁脒盐酸盐，在光引发条件下进行聚合。本发明结合双尾疏水缔合聚合物和甜菜碱型聚合物的优点，显著提高了增黏性、耐温性、抗盐性、耐水解性，可用于油田开发中提高原油采收率的驱油剂或酸化压裂增稠剂，其制备方法原理可靠，操作简单，具有广阔的市场前景。
Description
技术领域
本发明涉及一种用于油田提高采收率及酸化压裂的磺酸盐甜菜碱型疏水缔合聚合物及其制备方法。
背景技术
疏水缔合聚合物在共聚物分子链上引入了少量疏水基团，使其溶液具有高效的增黏性、优异的抗盐性以及较好的耐温、抗剪切性，在油田提高采收率及酸化压裂应用广泛。但是，对于高温高矿化度油藏，疏水缔合聚合物的耐温耐盐性能仍有待提高。
含有长链烷基和苯环的双尾疏水单体(吴晓燕等.一种具有表面活性的双尾疏水缔合丙烯酰胺共聚物.广东化工,2014,41(22)：42-44；蒲万芬等.双尾型丙烯酰胺类疏水缔合聚合物的合成与性能评价.现代化工,2016(4)：117-120)，由于引入苯环，有效改善了聚合物耐温性、耐水解性；引入长链烷基，有利改善了聚合物的疏水缔合效果；采用丙烯酰胺类的主体结构，使疏水单体易于与主单体丙烯酰胺聚合反应；采用双尾结构，有效提高疏水单体的耐水解性和疏水缔合效果。因此使得所合成出的疏水缔合聚合物达到耐温耐盐耐水解的目的。
磺酸盐甜菜碱单体是一类含有不易受pH及无机电解质影响的等数目季铵阳离子和磺酸根阴离子的可聚合功能单体，分子整体呈电中性，其化学热稳定性好、水化能力强，其共聚物表现出明显的反聚电解质行为。2002年，LOWE A B等研究发现聚甜菜碱存在近程吸引和远程排斥，其水溶液的表观黏度随着外加电解质(如NaCl等)浓度的升高而升高，表现出明显的反聚电解质行为，使得聚合物具有较好的抗盐性能。2012年，丁伟等用3-(丙烯酰胺丙基二甲氨基)丙磺酸盐与丙烯酰胺共聚，得到共聚物P(AM-DMAPAAS)，该共聚物在盐水中的黏度比在蒸馏水中的大，在含有二价离子(Mg2+或Ca2+)的盐溶液中的黏度比在一价离子盐溶液(Na+或K+)中大，且随着溶液矿化度的增大而增大。2015年，陈洪等以丙烯酰胺为主单体，烯丙基长链烷基季铵盐为疏水单体，磺酸盐甜菜碱为功能单体进行三元共聚制得磺酸盐甜菜碱型疏水缔合聚合物，该聚合物具有耐温耐盐特性，在85℃条件下仍然具有较高黏度。
发明内容
本发明的目的在于提供一种磺酸盐甜菜碱型疏水缔合聚合物，结合双尾疏水缔合聚合物和甜菜碱型聚合物的优点，提高了聚合物的耐温、耐盐、耐水解等性能，可用于油田开发中提高原油采收率的驱油剂或酸化压裂增稠剂，克服了现有技术的缺陷和不足。
本发明的另一目的还在于提供上述磺酸盐甜菜碱型疏水缔合聚合物的制备方法，通过在聚合物分子链上引入磺酸盐甜菜碱型单体，能够显著提高疏水缔合聚合物的增黏性、耐温性、抗盐性、耐水解性等性能，该方法原理可靠，操作简单，具有广阔的市场前景。
为达到以上技术目的，本发明提供以下技术方案。
一种磺酸盐甜菜碱型疏水缔合聚合物，其结构式如下：
式中x、y、m、n为结构单元百分数，x为75～85％，m为0.01～1.0％，n为0.01～0.5％，y＝1-x-m-n；a、b为结构单元数，a为11、13或15，b为1或2；R1为CH3或H。
该聚合物粘均分子量为100～1000万。
所述磺酸盐甜菜碱型疏水缔合聚合物，制备过程如下：首先将丙烯酰胺和丙烯酸在水溶液中混合，调节体系pH为6～8左右，加入3-(甲基丙烯酰胺丙基二甲氨基)丙磺酸盐、N-芳香基-N-烷基(甲基)丙烯酰胺和十二烷基硫酸钠，搅拌至溶液澄清，通氮气除氧后，加入光引发剂偶氮二异丁脒盐酸盐(v50)，在光引发条件下进行聚合，制备出磺酸盐甜菜碱型疏水缔合聚合物。
所述磺酸盐甜菜碱型疏水缔合聚合物的制备方法，依次包括以下步骤：
(1)在蒸馏水中加入丙烯酰胺和丙烯酸，搅拌均匀，用氢氧化钠调节溶液pH值为6～8，再加入3-(甲基丙烯酰胺丙基二甲氨基)丙磺酸盐、疏水单体N-芳香基-N-烷基(甲基)丙烯酰胺和表面活性剂十二烷基硫酸钠，搅拌至溶液澄清透明，反应单体总质量分数为25～28.5wt％，其中丙烯酰胺为20～21.5wt％，丙烯酸为3.5～5wt％，3-(甲基丙烯酰胺丙基二甲氨基)丙磺酸盐为0.2～1.0wt％，N-芳香基-N-烷基(甲基)丙烯酰胺为0.2～0.6wt％，十二烷基硫酸钠为0.4～0.8wt％；
(2)通氮气15min除去水中的溶解氧；
(3)加入光引发剂，置于光引发装置下反应3～5h，反应温度为10～30℃，得到白色粘稠胶体，即为磺酸盐甜菜碱型疏水缔合聚合物。
所述光引发剂为偶氮二异丁脒盐酸盐(v50)。
与现有技术相比，本发明具有以下有益效果：
采用丙烯酰胺类结构的双尾疏水单体，与丙烯酰胺的结构类似，易于与主单体丙烯酰胺进行共聚；苯环结构的引入，可以有效抑制酰胺基的水解，同时能够增加分子链的刚性，改善聚合物耐温性；长链烷基的引入，具有很好的疏水缔合效果；疏水单体为双尾结构，可以有效抑制酰胺基的水解，并且可以提高疏水缔合效果。
本发明通过在聚合物分子链上引入磺酸盐甜菜碱型单体，能够显著提高疏水缔合聚合物的增黏性、耐温性、抗盐性、耐水解性等性能。
本发明有望用于油田开发中作为提高原油采收率的驱油剂或酸化压裂增稠剂，具有广阔的市场前景。
附图说明
图1为磺酸盐甜菜碱型疏水缔合聚合物的红外谱图。
图2为磺酸盐甜菜碱型疏水缔合聚合物的黏度-浓度关系曲线。
图3为磺酸盐甜菜碱型疏水缔合聚合物的黏度-矿化度关系曲线。
图4为磺酸盐甜菜碱型疏水缔合聚合物的黏度-老化天数关系曲线。
具体实施方式
下面通过附图和实施例进一步说明本发明。
一、磺酸盐甜菜碱型疏水缔合聚合物的制备
实施例1：
称取丙烯酰胺(10g)、丙烯酸(2.5g)，加蒸馏水搅拌均匀，调节pH值为7；再加入3-(甲基丙烯酰胺丙基二甲氨基)丙磺酸盐(0.1g)、N-苯乙基-N-十二烷基甲基丙烯酰胺(0.1g)和十二烷基硫酸钠(0.3g)，再加入一定量蒸馏水，使溶液总质量达到50g，搅拌至溶液澄清；通氮气15分钟，除去水中的溶解氧；加入引发剂v50(单体总质量的0.1～0.2wt％)，置于光引发装置下，反应3h。
实施例2：
称取丙烯酰胺(10g)、丙烯酸(2.5g)，加蒸馏水搅拌均匀，调节pH值为7；加3-(甲基丙烯酰胺丙基二甲氨基)丙磺酸(0.1g)、N-苄基-N-十二烷基甲基丙烯酰胺(0.1g)和十二烷基硫酸钠(0.3g)，再加入一定量蒸馏水，使溶液质量达到50g，搅拌至溶液澄清；通氮气15分钟，除去水中的溶解氧；加入引发剂v50(单体总质量的0.1～0.2wt％)，置于光引发装置下，反应3h。
二、磺酸盐甜菜碱型疏水缔合聚合物的结构表征
图1为实施例1所合成聚合物的红外谱图。
从图中可以看到：3408cm-1处为伯酰胺N-H伸缩振动的特征吸收峰，2981cm-1和2897cm-1处为亚甲基反对称伸缩振动和对称伸缩振动的特征吸收峰，1640cm-1处为羰基的特征吸收峰，1531cm-1处为苯环骨架的伸缩振动峰，1398cm-1为亚甲基的面内弯曲振动吸收峰，1320cm-1处为季铵盐中C-N的伸缩振动吸收峰，1088cm-1和1049cm-1处为-SO3 -的对称和不对称振动吸收峰，615cm-1处为伯酰胺-NH2的面外摇摆特征峰。
三、磺酸盐甜菜碱型疏水缔合聚合物的增黏效果分析
将实施例1所合成的聚合物，配制成不同浓度的聚合物溶液。在室温、剪切速度为7.34s-1的条件下，测定聚合物的黏度-浓度关系曲线(如图2所示)。
从图2中可以看出，磺酸基甜菜碱型疏水缔合聚合物的临界缔合浓度较低，增黏效果好，在2000mg/L时黏度达到743.7mPa.s。
四、磺酸盐甜菜碱型疏水缔合聚合物的盐敏性
对实施例1所合成的聚合物进行盐敏性研究。将制备的疏水缔合聚合物在不同矿化度下配制成2000mg/L的聚合物溶液。在室温、剪切速度为7.34s-1的条件下，测定聚合物溶液的表观黏度随矿化度的变化关系(见图3)。从图3中可以看出，随NaCl浓度的升高，聚合物的表观黏度呈现出先降低后升高再降低的趋势，并且聚合物溶液的黏度在12万NaCl高矿化度下保留率仍可以保持在50％以上，表现出很好的抗盐效果。
五、磺酸盐甜菜碱型疏水缔合聚合物的抗老化性能
对实施例1所合成的聚合物进行抗老化性能评价。将制得的疏水缔合聚合物配制成2000mg/L的聚合物溶液，加入除氧剂，置于西林瓶中，封口。在90℃的烘箱中老化，定期测定聚合物溶液的黏度。
从图4中可以看出，聚合物溶液老化30天左右，黏度达到平稳。在温度为90℃、矿化度(NaCl)为10×104mg/L的条件下，聚合物溶液的黏度依然可以保持在60mPa.s以上，表现出良好的耐温抗盐性、抗老化性。
Claims (3)
1.一种磺酸盐甜菜碱型疏水缔合聚合物，其结构式如下：
式中x、y、m、n为结构单元百分数，x为75～85％，m为0.01～1.0％，n为0.01～0.5％，y＝1-x-m-n；a、b为结构单元数，a为11、13或15，b为1或2；R1为CH3或H；
该聚合物粘均分子量为100～1000万。
2.如权利要求1所述的磺酸盐甜菜碱型疏水缔合聚合物的制备方法，依次包括以下步骤：
(1)在蒸馏水中加入丙烯酰胺和丙烯酸，搅拌均匀，用氢氧化钠调节溶液pH值为6～8，再加入3-(甲基丙烯酰胺丙基二甲氨基)丙磺酸盐、疏水单体N-芳香基-N-烷基(甲基)丙烯酰胺和表面活性剂十二烷基硫酸钠，搅拌至溶液澄清透明，其中丙烯酰胺为20～21.5wt％，丙烯酸为3.5～5wt％，3-(甲基丙烯酰胺丙基二甲氨基)丙磺酸盐为0.2～1.0wt％，N-芳香基-N-烷基(甲基)丙烯酰胺为0.2～0.6wt％，十二烷基硫酸钠为0.4～0.8wt％，wt％指的是以上各物质占反应体系的质量分数；
(2)通氮气15min除去水中的溶解氧；
(3)加入光引发剂，置于光引发装置下反应3～5h，反应温度为10～30℃，得到白色粘稠胶体，即为磺酸盐甜菜碱型疏水缔合聚合物。
3.如权利要求2所述的磺酸盐甜菜碱型疏水缔合聚合物的制备方法，其特征在于，所述光引发剂为偶氮二异丁脒盐酸盐。
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710342023.4A CN107022050B (zh) | 2017-05-16 | 2017-05-16 | 一种磺酸盐甜菜碱型疏水缔合聚合物及其制备方法 |
| PCT/CN2017/085328 WO2018209716A1 (zh) | 2017-05-16 | 2017-05-22 | 一种磺酸盐甜菜碱型疏水缔合聚合物及其制备方法 |
| US16/068,898 US10501568B1 (en) | 2017-05-16 | 2017-05-22 | Sulfonate lycine type hydrophobic associated polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710342023.4A CN107022050B (zh) | 2017-05-16 | 2017-05-16 | 一种磺酸盐甜菜碱型疏水缔合聚合物及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107022050A CN107022050A (zh) | 2017-08-08 |
| CN107022050B true CN107022050B (zh) | 2018-02-06 |
Family
ID=59529750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710342023.4A Active CN107022050B (zh) | 2017-05-16 | 2017-05-16 | 一种磺酸盐甜菜碱型疏水缔合聚合物及其制备方法 |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US10501568B1 (zh) |
| CN (1) | CN107022050B (zh) |
| WO (1) | WO2018209716A1 (zh) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11084972B2 (en) | 2017-03-09 | 2021-08-10 | Saudi Arabian Oil Company | Surface charge modified nanosurfactants for reduced retention by reservoir rock |
| US11066594B2 (en) | 2017-03-09 | 2021-07-20 | Saudi Arabian Oil Company | Fluoropolymers to reduce retention of nanosurfactants to carbonate reservoir rock for applications in oil fields |
| US11066914B2 (en) | 2017-03-09 | 2021-07-20 | Saudi Arabian Oil Company | Foam from low cost petroleum sulfonate surfactants for fracturing along with wettability alteration |
| US11078405B2 (en) | 2017-03-09 | 2021-08-03 | Saudi Arabian Oil Company | 3 in 1 foam formulation for enhanced oil recovery including conformance control, ultra-low interfacial tension, and wettability alteration |
| CN110183573B (zh) * | 2019-06-10 | 2019-12-31 | 西南石油大学 | 一种阳离子聚合物增稠剂、制备方法及用于耐高温压裂液 |
| CN111234097B (zh) * | 2020-01-15 | 2021-12-14 | 西南石油大学 | 一种耐盐型五元疏水缔合聚合物及其制备方法和应用 |
| CN111471132B (zh) * | 2020-05-19 | 2022-02-18 | 陕西日新石油化工有限公司 | 一种抗菌防霉柔性凝胶颗粒及驱油剂与驱油剂的制备方法 |
| CN112375177B (zh) * | 2020-10-20 | 2022-06-14 | 爱森（中国）絮凝剂有限公司 | 一种新型疏水缔合聚合物及其制备方法、应用 |
| CN114835863A (zh) * | 2021-02-01 | 2022-08-02 | 中国石油天然气股份有限公司 | 稠化剂及其制备方法 |
| CN112908726B (zh) * | 2021-02-03 | 2022-11-15 | 沈阳大学 | 一种双网络全水凝胶可拉伸固态超级电容器的制备方法 |
| CN113583173B (zh) * | 2021-07-19 | 2022-08-19 | 山东达维石油技术有限公司 | 一种超分子自组装清洁压裂液及其制备方法 |
| CN113563863A (zh) * | 2021-09-02 | 2021-10-29 | 成都理工大学 | 一种气固液三相压裂液体系及其使用方法 |
| CN117143283B (zh) * | 2023-10-26 | 2024-01-09 | 东营市百扬石油科技有限责任公司 | 一种抗盐性压裂液稠化剂及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5074358A (en) * | 1990-07-03 | 1991-12-24 | Alberta Oil Sands Technology And Research Authority | Surfactant-stabilized foams for enhanced oil recovery |
| CN104231169A (zh) * | 2014-10-14 | 2014-12-24 | 西南石油大学 | 一种双尾型丙烯酰胺类疏水缔合聚合物及其制备方法 |
| CN105085331A (zh) * | 2014-05-13 | 2015-11-25 | 中国石油化工股份有限公司 | 一种甲基丙烯酰胺丙基-n, n-二甲基丙磺酸盐的合成方法 |
| CN105439909A (zh) * | 2015-11-19 | 2016-03-30 | 中国石油天然气股份有限公司 | 磺酸盐甜菜碱和磺酸盐甜菜碱型疏水聚合物及制法与应用 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2914647B1 (fr) * | 2007-04-05 | 2011-10-21 | Rhodia Recherches Et Tech | Copolymere comprenant des unites betainiques et des unites hydrophobes et/ou amphiphiles,procede de preparation,et utilisations. |
| JP5984356B2 (ja) * | 2010-11-10 | 2016-09-06 | キヤノン株式会社 | トナー |
| US10550313B2 (en) * | 2013-10-16 | 2020-02-04 | Rhodia Operations | Viscosifier agent for oilfield fluids in hard conditions |
| CN105669499A (zh) * | 2016-03-15 | 2016-06-15 | 西南石油大学 | 一种磺酸盐甜菜碱型丙烯酰胺共聚物驱油剂及其合成方法 |
-
2017
- 2017-05-16 CN CN201710342023.4A patent/CN107022050B/zh active Active
- 2017-05-22 US US16/068,898 patent/US10501568B1/en not_active Expired - Fee Related
- 2017-05-22 WO PCT/CN2017/085328 patent/WO2018209716A1/zh active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5074358A (en) * | 1990-07-03 | 1991-12-24 | Alberta Oil Sands Technology And Research Authority | Surfactant-stabilized foams for enhanced oil recovery |
| CN105085331A (zh) * | 2014-05-13 | 2015-11-25 | 中国石油化工股份有限公司 | 一种甲基丙烯酰胺丙基-n, n-二甲基丙磺酸盐的合成方法 |
| CN104231169A (zh) * | 2014-10-14 | 2014-12-24 | 西南石油大学 | 一种双尾型丙烯酰胺类疏水缔合聚合物及其制备方法 |
| CN105439909A (zh) * | 2015-11-19 | 2016-03-30 | 中国石油天然气股份有限公司 | 磺酸盐甜菜碱和磺酸盐甜菜碱型疏水聚合物及制法与应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107022050A (zh) | 2017-08-08 |
| US10501568B1 (en) | 2019-12-10 |
| US20190359753A1 (en) | 2019-11-28 |
| WO2018209716A1 (zh) | 2018-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107022050B (zh) | 一种磺酸盐甜菜碱型疏水缔合聚合物及其制备方法 | |
| CN107033293B (zh) | 一种具有表面活性的双尾疏水缔合聚合物及其制备方法 | |
| CN104231169B (zh) | 一种双尾型丙烯酰胺类疏水缔合聚合物及其制备方法 | |
| CN102464761B (zh) | 油田用磺化耐温抗盐共聚物及其制备方法 | |
| CN104448128B (zh) | 适用于高温高盐苛刻油藏的聚合物流度控制剂及其制备方法 | |
| CN103666433B (zh) | 用于高温油藏提高采收率的驱油剂组合物及其制备方法 | |
| CN103421137B (zh) | 耐高温驱油用聚丙烯酰胺的制备方法 | |
| CN105439909B (zh) | 磺酸盐甜菜碱和磺酸盐甜菜碱型疏水聚合物及制法与应用 | |
| CN102050926A (zh) | 一种耐温抗盐接枝型聚丙烯酰胺及其制备方法 | |
| CN105646776B (zh) | 一种疏水缔合聚合物及其制备方法 | |
| CN106397694B (zh) | 一种抗高盐梳型微嵌段疏水缔合聚合物及其制备方法 | |
| CN102050913A (zh) | 一种耐温抗盐接枝型聚丙烯酰胺及其制法 | |
| CN103305204A (zh) | 一种耐温耐盐丙烯酰胺三元共聚物磺酸盐驱油剂及合成 | |
| CN1861654A (zh) | 一种水溶性两性离子共聚物及其制备方法 | |
| CN102898590A (zh) | 一种含β-环糊精孪尾疏水缔合聚合物驱油剂及合成方法 | |
| CN108752505A (zh) | 一种疏水改性超支化聚合物及其制备方法 | |
| CN106675543A (zh) | 一种盐增黏水溶性两亲聚合物驱油剂 | |
| US20220025089A1 (en) | Acrylamide copolymer and preparation method therefor and use thereof | |
| CN110016324A (zh) | 一种耐高温水基钻井液提切剂及其制备方法 | |
| CN108503748A (zh) | 一种耐温抗盐功能型聚合物及其制备方法 | |
| CN102464783B (zh) | 一种水溶性热增稠共聚物及其制备方法和应用 | |
| CN107759728B (zh) | 一种具有表面活性的驱油用聚合物及其制备方法和应用 | |
| CN110295033A (zh) | 一种疏水缔合聚合物与表面活性剂的自组装体系及其制备方法和应用 | |
| CN103541701B (zh) | 用于提高高温油藏三次采油采收率的驱油方法 | |
| CN103409125B (zh) | 一种水溶性四元共聚物驱油剂及其合成方法 |
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 |