WO2018209717A1 - 具有表面活性的双尾疏水缔合聚合物及其制备方法 - Google Patents

具有表面活性的双尾疏水缔合聚合物及其制备方法 Download PDF

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WO2018209717A1
WO2018209717A1 PCT/CN2017/085329 CN2017085329W WO2018209717A1 WO 2018209717 A1 WO2018209717 A1 WO 2018209717A1 CN 2017085329 W CN2017085329 W CN 2017085329W WO 2018209717 A1 WO2018209717 A1 WO 2018209717A1
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acrylamide
polymer
meth
tailed
surface active
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李勇明
任强
赵金洲
张烈辉
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西南石油大学
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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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    • 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
    • C09K8/584—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 surfactants
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    • 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
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    • 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
    • C09K8/72—Eroding chemicals, e.g. acids
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    • 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
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  • the invention relates to a surface active two-tailed hydrophobic associating polymer for oil field enhanced oil recovery and acid fracturing and a preparation method thereof.
  • HPAM partially hydrolyzed polyacrylamide
  • HPAM partially hydrolyzed polyacrylamide
  • the viscosity of the solution drops sharply and cannot meet the requirements of enhanced oil recovery and acid fracturing in high temperature and high salt reservoirs.
  • the hydrophobic associative polymer which introduces a small amount of hydrophobic groups on the molecular chain has a high viscosity-increasing property, excellent salt resistance, good temperature resistance and shear resistance, and enhanced oil recovery in the oil field. Acidified fracturing shows good application prospects.
  • hydrophobic monomers which have been reported so far are (meth) acrylate type, styrene type, (meth) acrylamide type and allyl type.
  • Acrylate type hydrophobic monomer which is extremely sensitive to temperature and pH, easily leads to the loss of association effect of the polymer and reduces the viscosity of the polymer solution (yellow snow red, etc., water-soluble hydrophobically associated poly(acrylamide-hexadecyl acrylate) solution Research on the nature.
  • the styrene-type hydrophobic monomer although having a rigid benzene ring, can effectively improve the temperature resistance and hydrolysis resistance of the polymer, but the benzene ring is too close to the molecular main chain, which is disadvantageous for the copolymerization of the hydrophobic monomer and the acrylamide. It is also not conducive to improving the viscosity-increasing effect of polymer solution (Zhong Chuanrong et al. Characterization and heat resistance of AM-STD-NaAMPS ternary hydrophobic association copolymer. Polymer Materials Science and Engineering, 2003, 19(6): 126-130 ).
  • the allyl type hydrophobic monomer because it contains an allyl group, is difficult to copolymerize with the main monomer acrylamide, and the prepared hydrophobically associating polymer has a low molecular weight and the viscosity-increasing effect is not obvious (Roshan et al. Synthesis and Solution Properties of Hydrophobically Associating Polymers of Imidazoline Structures. Chemical Research and Applications, 2015, 27(8): 1151-1156).
  • the acrylamide type hydrophobic monomer has a structure similar to that of acrylamide, which is favorable for the polymerization reaction, but has a certain disadvantage of poor hydrolysis resistance ( ⁇ . Hydrophobic association water-soluble polymer P (AM/NaAA/DiAC16) Viscosity Behavior of Aqueous Solutions. Fine Chemicals, 2007, 24(9): 914-918).
  • Journal of Chemical Engineering, 2015, 66(3): 1215-1220 has the following advantages: introduction of benzene ring, It is beneficial to improve the temperature resistance and hydrolysis resistance of the polymer; the introduction of long-chain alkyl groups is beneficial to improve the hydrophobic association effect of the polymer; the main structure of (meth)acrylamide is used to make the hydrophobic monomer easy to realize.
  • the polymerization reaction with acrylamide; the use of a two-tailed structure is beneficial to improve the hydrolysis resistance and hydrophobic association effect of the hydrophobic monomer.
  • the final hydrophobic monomer takes into account the advantages of various hydrophobic monomers, and can significantly improve the hydrophobic association effect of the polymer, so that the synthesized hydrophobic associative polymer can achieve the purpose of temperature and salt tolerance.
  • polyoxyethylene ether side chain Polymer containing polyoxyethylene ether side chain (L'alloret F et al. Aqueous solution behavior of new thermoassociative polymers. Colloid & Polymer Science, 1995, 273 (12): 1163-1173; Yang Mingzhu et al. New temperature sensitive modified acrylamide Study on the properties of copolymers. Plastics Industry, 2012, 40(4): 35-38), the polyoxyethylene ether chain in the molecule forms hydrogen bonds with water molecules. When the temperature of the solution increases, the hydrogen bonding weakens or breaks.
  • the polyoxyethylene ether chain has a decreased hydrophilicity and enhanced hydrophobicity, so that the polymer can exhibit a good thermal thickening effect in a relatively high temperature range, and can exhibit a high apparent viscosity in a salt solution.
  • the object of the present invention is to provide a surface active two-tailed hydrophobic associative polymer which has the advantages of a two-tailed hydrophobic associative polymer and a polymer containing a polyoxyethylene ether side chain, thereby effectively improving hydrophobic association
  • the polymer has the properties of viscosity increasing, temperature resistance, salt tolerance, hydrolysis resistance and the like, and overcomes the defects and deficiencies of the prior art.
  • Another object of the present invention is to provide a method for preparing the above-mentioned surface-active two-tailed hydrophobic associative polymer, which has the advantages of reliable principle and simple operation, and the synthesized polymer can be widely used in oil field development as an enhanced oil recovery factor.
  • the oil displacing agent or acid fracturing thickener has broad market application prospects.
  • the present invention adopts the following technical solutions.
  • x, y, z, m, n are percentages of structural units, x is 75 to 85%, y is 10 to 20%, z is 0 to 5%, m is 0.1 to 0.2%, and n is 0.2 to 0.5%.
  • the polymer has a viscosity average molecular weight of from 100 to 10,000,000.
  • the surface active two-tailed hydrophobic associative polymer is prepared by free radical micellar polymerization: containing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, surface active macromonic lauryl alcohol
  • a surfactant sodium lauryl sulfate and a hydrophobic monomer N-phenethyl-N-alkyl (meth) acrylamide or N-benzyl group are added.
  • N-alkyl (meth) acrylamide which is formed by solubilizing a hydrophobic monomer with a surfactant
  • the pH value is 6-8
  • the hydrophobic monomer is copolymerized with the water-soluble monomer by photoinitiation to obtain a surface-active two-tailed hydrophobic associative polymer.
  • x, y, z, m, n are percentages of structural units, x is 75 to 85%, y is 10 to 20%, z is 0 to 5%, m is 0.1 to 0.2%, and n is 0.2 to 0.5%.
  • the polymer has a viscosity average molecular weight of from 100 to 10,000,000.
  • the preparation method of the surface active two-tailed hydrophobic associative polymer comprises the following steps in sequence:
  • the photoinitiator is azobisisobutylphosphonium hydrochloride (v50) or 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959).
  • the present invention has the following beneficial effects:
  • the present invention employs a hydrophobic monomer having an acrylamide structure and is easily copolymerized with a water-soluble monomer such as acrylamide;
  • the hydrophobic chain of the hydrophobic monomer contains a benzene ring structure, which inhibits hydrolysis of the amide group and increases molecules.
  • the rigidity of the chain improves the temperature resistance of the polymer;
  • the hydrophobic chain of the hydrophobic monomer contains a long-chain alkyl group, which has a good hydrophobic association effect;
  • the body has a two-tailed structure, which can effectively inhibit the hydrolysis of the amide group and can improve the hydrophobic association effect. Therefore, the hydrophobically associating polymer has better viscosity-increasing property, temperature and salt resistance;
  • the present invention introduces a surface active macromonomer containing a polyoxyethylene ether and a long-chain alkyl group into a polymer molecular chain, so that the polymer has the characteristics of a surfactant, and can significantly increase the viscosity of the hydrophobically associating polymer. Properties such as sex, salt resistance and hydrolysis resistance.
  • Figure 1 is an infrared spectrum of a surface active two-tailed hydrophobically associating polymer.
  • Figure 2 is a graph showing the viscosity-concentration relationship of a surface active two-tailed hydrophobically associating polymer.
  • Figure 3 is a graph showing the viscosity-NaCl concentration of a surface active two-tailed hydrophobically associating polymer.
  • Figure 4 is a graph showing the viscosity-CaCl 2 concentration of a surface active two-tailed hydrophobically associating polymer.
  • Figure 5 is a graph showing the viscosity-aging days of a surface active two-tailed hydrophobically associating polymer.
  • Example 1 is an infrared spectrum of a hydrophobically associating polymer synthesized in Example 1.
  • Example 2 The polymer synthesized in Example 1 was formulated into polymer solutions of different concentrations. The viscosity-concentration curve of the polymer was measured at room temperature and shear rate of 7.34 s -1 (as shown in Figure 2).
  • Fig. 2 It can be seen from Fig. 2 that the hydrophobic interaction of the polymer is strong and the viscosity-increasing effect is obvious.
  • the viscosity of the polymer solution reaches 300 mPa.s at 1000 mg/L, and the viscosity of the polymer solution reaches 753.4 mPa.s at 2000 mg/L.
  • the salt susceptibility study was carried out on the polymer synthesized in Example 1.
  • the prepared hydrophobic associative polymer was formulated into a 1000 mg/L polymer solution at different degrees of salinity.
  • the apparent viscosity of the polymer solution was determined as a function of salinity at room temperature and shear rate of 7.34 s -1 (see Figures 3 and 4).
  • Example 1 The polymer synthesized in Example 1 was evaluated for anti-aging properties.
  • the prepared hydrophobic associative polymer was formulated into a 1000 mg/L polymer solution, an oxygen scavenger was added, placed in a vial, and sealed.
  • the viscosity of the polymer solution was periodically measured by aging in an oven at 90 °C.
  • the polymer solution aged for about 25 days the viscosity is basically stable.
  • the viscosity of the polymer solution can still be maintained above 30 mPa.s, showing good temperature and salt tolerance and aging resistance.

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Abstract

公开了一种具有表面活性的双尾疏水缔合聚合物及其制备方法，该双尾疏水缔合聚合物采用自由基胶束聚合的方法制备：在含有丙烯酰胺、丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、表面活性大单体月桂醇聚氧乙烯醚(甲基)丙烯酸酯的水溶液中，加入表面活性剂十二烷基硫酸钠以及疏水单体N-苯乙基-N-烷基(甲基)丙烯酰胺或N-苄基-N-烷基(甲基)丙烯酰胺，利用表面活性剂将疏水单体增溶在其形成的胶束中，用氢氧化钠调节pH值为6～8，通过光引发的方式，将疏水单体与水溶性单体进行共聚。该聚合物可有效提高疏水缔合聚合物的增黏、耐温、耐盐、耐水解等性能，其制备方法原理可靠，操作简便，具有广阔的市场应用前景。

Description

[根据细则37.2由ISA制定的发明名称]　具有表面活性的双尾疏水缔合聚合物及其制备方法 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具有表面活性的双尾疏水缔合聚合物及其制备方法。
背景技术
传统的聚合物，如部分水解聚丙烯酰胺(HPAM)的耐温性、耐盐性以及抗剪切性能差，在高温高盐油藏条件下，HPAM因水解、热降解以及链卷曲等导致聚合物溶液的粘度急剧下降，不能满足高温高盐油藏提高采收率及酸化压裂的需求。而在分子链上引入少量疏水基团的疏水缔合聚合物，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展现出良好的应用前景。
疏水缔合聚合物的溶液性能在很大程度上取决于疏水单体的结构与性能。疏水单体结构和种类的不同，都会极大影响聚合物的性能。目前已见报道的疏水单体有(甲基)丙烯酸酯型、苯乙烯型、(甲基)丙烯酰胺型和烯丙基型等。丙烯酸酯型疏水单体，对温度和pH极其敏感，容易导致聚合物失去缔合效果而降低聚合物溶液的黏度(黄雪红等，水溶性疏水缔合型聚(丙烯酰胺-丙烯酸十六酯)溶液性质的研究.功能高分子学报,2002,14(1):90-94)。苯乙烯型疏水单体，虽然具有刚性的苯环，可以有效改善聚合物的耐温性和抗水解性，但苯环过于靠近分子主链，这样既不利于疏水单体与丙烯酰胺的共聚，也不利于提高聚合物溶液增黏效果(钟传蓉等，AM-STD-NaAMPS三元疏水缔合共聚物的表征及耐热性能.高分子材料科学与工程,2003,19(6):126-130)。烯丙基型疏水单体，由于含有烯丙基，不易实现与主单体丙烯酰胺的共聚，制备出的疏水缔合聚合物分子量不高，且增黏效果不明显(罗珊等，一种咪唑啉结构疏水缔合聚合物合成与溶液性质.化学研究与应用,2015,27(8):1151-1156)。丙烯酰胺型疏水单体，其结构与丙烯酰胺类似，有利于聚合反应的进行，但存在着一定的耐水解性差的缺点(耿同谋.疏水缔合水溶性聚合物P(AM/NaAA/DiAC16)水溶液的黏度行为.精细化工,2007,24(9):914-918)。
与单尾疏水单体相比，含有苯环和长链烷基的双尾疏水单体(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；姜峰等.双尾型丙烯酰胺类疏水缔合共聚物的合成与表征.化工学报,2015,66(3):1215-1220)具有以下优势：引入了苯环，有利于改善聚合物耐温性、耐水解性；引入了长链烷基，有利于改善聚合物的疏水缔合效果；采用了(甲基)丙烯酰胺类的主体结构，使疏水单体容易实现与丙烯酰胺的聚合反应；采用了双尾结构，有利于提高疏水单体的耐水解性及疏水缔合效果。最终疏水单体兼顾各类疏水单体的优点，可以更加显著提高聚合物的疏水缔合效果，使合成出的疏水缔合聚合物达到耐温耐盐的目的。
含有聚氧乙烯醚侧链的聚合物(L'alloret F et al.Aqueous solution behavior of new thermoassociative polymers.Colloid&Polymer Science,1995,273(12):1163-1173；杨明珠等.新型温敏改性丙烯酰胺共聚物的性能研究.塑料工业,2012,40(4):35-38)，其分子中的聚氧乙烯醚链与水分子形成氢键，当溶液温度升高，氢键作用逐渐减弱或断裂，聚氧乙烯醚链亲水性下降，疏水性增强，使得聚合物能在较高温度范围内表现出良好的热增稠效应，而且在盐溶液中能够显示出较高的表观黏度。
发明内容
本发明的目的在于提供一种具有表面活性的双尾疏水缔合聚合物，该聚合物同时具有双尾疏水缔合聚合物和含有聚氧乙烯醚侧链的聚合物的优点，有效提高疏水缔合聚合物的增黏性、耐温、耐盐、耐水解等性能，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具有表面活性的双尾疏水缔合聚合物的制备方法，该方法原理可靠，操作简便，合成的聚合物可广泛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，具有广阔的市场应用前景。
为达到上述技术目的，本发明采用以下技术方案。
一种具有表面活性的双尾疏水缔合聚合物，其结构式如下：
Figure PCTCN2017085329-appb-000001
式中x、y、z、m、n为结构单元百分数，x为75～85％，y为10～20％，z为0～5％，m为0.1～0.2％，n为0.2～0.5％，x+y+z+m+n＝1；a、b、c为结构单元数，a为7、9、11、13或15，b为1或2，c为5、7、10、23或40；R1、R2为CH3或H。
该聚合物粘均分子量为100～1000万。
所述具有表面活性的双尾疏水缔合聚合物采用自由基胶束聚合的方法制备：在含有丙烯酰胺、丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、表面活性大单体月桂醇聚氧乙烯醚(甲基)丙烯酸酯的水溶液中，加入表面活性剂十二烷基硫酸钠以及疏水单体N-苯乙基-N-烷基(甲基)丙烯酰胺或N-苄基-N-烷基(甲基)丙烯酰胺，利用表面活性剂将疏水单体增溶在其形成的 胶束中，用氢氧化钠调节pH值为6～8，通过光引发的方式，将疏水单体与水溶性单体进行共聚，得到具有表面活性的双尾疏水缔合聚合物。反应原理如下：
Figure PCTCN2017085329-appb-000002
式中x、y、z、m、n为结构单元百分数，x为75～85％，y为10～20％，z为0～5％，m为0.1～0.2％，n为0.2～0.5％，x+y+z+m+n＝1；a、b、c为结构单元数，a为7、9、11、13或15，b为1或2，c为5、7、10、23或40；R1、R2为CH3或H。
该聚合物粘均分子量为100～1000万。
所述具有表面活性的双尾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、丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、表面活性大单体月桂醇聚氧乙烯醚(甲基)丙烯酸酯，搅拌均匀，用氢氧化钠调节溶液pH值为6～8，再加入疏水单体N-苯乙基-N-烷基(甲基)丙烯酰胺或N-苄基-N-烷基(甲基)丙烯酰胺与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25～30wt％，其中丙烯酰胺为20～21.5wt％，丙烯酸为3.5～5wt％，2-丙烯酰胺-2-甲基丙磺酸为0～2wt％，月桂醇聚氧乙烯醚(甲基)丙烯酸酯为0.2～0.6wt％，N-苯乙基-N-烷基(甲基)丙烯酰胺或N-苄基-N-烷基(甲基)丙烯酰胺为0.2～0.6wt％；十二烷基硫酸钠为0.8～2.0wt％；
(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℃，得到白色胶体，即为具有表面活性的双尾疏水缔合聚合物。
所述光引发剂为偶氮二异丁脒盐酸盐(v50)或2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮(Irgacure2959)。
与现有技术相比，本发明具有以下有益效果：
(1)本发明采用丙烯酰胺类结构的疏水单体，容易与丙烯酰胺等水溶性单体进行共聚；疏水单体的疏水链中含有苯环结构，可以抑制酰胺基的水解，同时能够增加分子链的刚性，改善聚合物耐温性；疏水单体的疏水链中含有长链烷基，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。因此该疏水缔合聚合物有着较好的增黏性、耐温抗盐性；
(2)本发明在聚合物分子链上引入含有聚氧乙烯醚和长链烷基的表面活性大单体，使聚合物具有表面活性剂的特点，能够显著提高疏水缔合聚合物的增黏性、抗盐性、耐水解性等性能。
附图说明
图1为具有表面活性的双尾疏水缔合聚合物的红外谱图。
图2为具有表面活性的双尾疏水缔合聚合物的黏度-浓度关系曲线。
图3为具有表面活性的双尾疏水缔合聚合物的黏度-NaCl浓度关系曲线。
图4为具有表面活性的双尾疏水缔合聚合物的黏度-CaCl2浓度关系曲线。
图5为具有表面活性的双尾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、具有表面活性的双尾疏水缔合聚合物的制备
实施例1：
称取10g丙烯酰胺、2.5g丙烯酸、0.1g表面活性大单体月桂醇聚氧乙烯醚(甲基)丙烯酸酯，加蒸馏水搅拌均匀，调节pH值为7；加0.1g N-苯乙基-N-十二烷基甲基丙烯酰胺和0.3g十二烷基硫酸钠，再加一定量蒸馏水，使溶液质量达到50g，搅拌至溶液澄清透明；通氮气15min，除去水中的溶解氧；加入引发剂V50(单体总质量的0.016wt％)，置于光引发装置下，反应4h。
实施例2：
称取9.9g丙烯酰胺、1.6g丙烯酸、1.0g 2-丙烯酰胺-2-甲基丙磺酸、0.3g表面活性大单体月桂醇聚氧乙烯醚(甲基)丙烯酸酯，加蒸馏水搅拌均匀，调节pH值为7；加0.3gN-苄基-N-十二烷基甲基丙烯酰胺和0.7g十二烷基硫酸钠，再加一定量蒸馏水，使溶液质量达到50g，搅拌至溶液澄清透明；通氮气15min，除去水中的溶解氧；加入引发剂v50(单体总质量的0.1wt％)，置于光引发装置下，反应4h。
实施例3：
称取9.9g丙烯酰胺、1.6g丙烯酸、1.0g 2-丙烯酰胺-2-甲基丙磺酸、0.3g表面活性大单体月桂醇聚氧乙烯醚(甲基)丙烯酸酯，加蒸馏水搅拌均匀，调节pH值为7；加0.3g N-苯乙基-N-十二烷基甲基丙烯酰胺和0.7g十二烷基硫酸钠(十二烷基硫酸钠)，再加一定量蒸馏水，使溶液质量达到50g，搅拌至溶液澄清透明；通氮气15min，除去水中的溶解氧；加入引发剂V50(单体总质量的0.016wt％)，置于光引发装置下，反应4h。
实施例4：
称取10g丙烯酰胺、2.5g丙烯酸、0.3g表面活性大单体月桂醇聚氧乙烯醚(甲基)丙烯酸酯，加蒸馏水搅拌均匀，调节pH值为7；加0.3g N-苯乙基-N-十四烷基甲基丙烯酰胺和0.7g十二烷基硫酸钠，再加一定量蒸馏水，使溶液质量达到50g，搅拌至溶液澄清透明；通氮气15min，除去水中的溶解氧；加入引发剂Irgacure2959(单体总质量的0.016wt％)，置于光引发装置下，反应4h。
二、具有表面活性的双尾疏水缔合聚合物的结构表征
图1为实施例1所合成的疏水缔合聚合物的红外谱图。
从图中可以看到：3408cm-1处为伯酰胺N-H伸缩振动吸收峰，2926cm-1处为亚甲基振动吸收峰，1639cm-1处为伯酰胺N-H弯曲振动吸收峰，1670cm-1处为羰基的特征吸收峰，1530cm-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，1057cm-1处为乙氧基的伸缩振动峰，630cm-1处为伯酰胺-NH2的面外摇摆特征峰。
三、具有表面活性的双尾疏水缔合聚合物的增黏效果分析
将通过实施例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，聚合物疏水缔合作用强，增黏效果明显，1000mg/L时聚合物溶液黏度达到300mPa.s，2000mg/L时聚合物溶液黏度达到753.4mPa.s。
四、具有表面活性的双尾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1000mg/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和图4)。
从图3和图4中可以看出，随矿化度的升高，聚合物的表观黏度呈现出先降低后升高再降低的趋势，盐增稠的区域较宽，并且聚合物溶液的黏度在20万NaCl和1万CaCl2高矿化度下保留率可以保持在10％以上，表现出很好的抗盐效果。
五、具有表面活性的双尾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1000mg/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。
图5中可以看出，聚合物溶液老化25天左右，黏度基本达到平稳。在温度为90℃、矿化度为10×104mg/L的条件下，聚合物溶液的黏度依然可以保持在30mPa.s以上，表现出良好的耐温耐盐性及抗老化性。

Claims (4)

  1. 一种具有表面活性的双尾疏水缔合聚合物，其结构式如下：
    Figure PCTCN2017085329-appb-100001
    式中x、y、z、m、n为结构单元百分数，x为75～85％，y为10～20％，z为0～5％，m为0.1～0.2％，n为0.2～0.5％，x+y+z+m+n＝1；a、b、c为结构单元数，a为7、9、11、13或15，b为1或2，c为5、7、10、23或40；R1、R2为CH3或H。
  2. 如权利要求1所述的具有表面活性的双尾疏水缔合聚合物，其特征在于，该聚合物粘均分子量为100～1000万。
  3. 如权利要求1或2所述的具有表面活性的双尾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、丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、表面活性大单体月桂醇聚氧乙烯醚(甲基)丙烯酸酯，搅拌均匀，用氢氧化钠调节溶液pH值为6～8，再加入疏水单体N-苯乙基-N-烷基(甲基)丙烯酰胺或N-苄基-N-烷基(甲基)丙烯酰胺与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25～30wt％，其中丙烯酰胺为20～21.5wt％，丙烯酸为3.5～5wt％，2-丙烯酰胺-2-甲基丙磺酸为0～2wt％，月桂醇聚氧乙烯醚(甲基)丙烯酸酯为0.2～0.6wt％，N-苯乙基-N-烷基(甲基)丙烯酰胺或N-苄基-N-烷基(甲基)丙烯酰胺为0.2～0.6wt％，十二烷基硫酸钠为0.8～2.0wt％；
    (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℃，得到白色胶体，即为具有表面活性的双尾疏水缔合聚合物。
  4. 如权利要求3所述的具有表面活性的双尾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或2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100999875A (zh) * 2006-01-11 2007-07-18 丹东恒星精细化工有限公司 丙烯酸酯乳化增稠剂及生产方法
WO2012170373A2 (en) * 2011-06-08 2012-12-13 Nalco Company An environmentally friendly dispersion system used in the preparation of inverse emulsion polymers
US20140287967A1 (en) * 2010-01-26 2014-09-25 S.P.C.M. S.A. Water-soluble polymers for oil recovery
CN104140507A (zh) * 2014-07-24 2014-11-12 山东大学 一种含超长疏水长链改性的丙烯酰胺水溶性聚合物及其制备方法
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
CN105418862A (zh) * 2015-12-29 2016-03-23 四川光亚聚合物化工有限公司 一种疏水缔合聚合物及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105646772B (zh) * 2015-12-29 2018-03-27 四川光亚聚合物化工有限公司 一种疏水缔合聚合物及其制备方法
CN105461855B (zh) * 2015-12-29 2018-04-06 四川光亚聚合物化工有限公司 一种疏水缔合聚合物及其制备方法
CN105646777A (zh) * 2015-12-29 2016-06-08 四川光亚聚合物化工有限公司 一种疏水缔合聚合物及其制备方法
CN106397694B (zh) * 2016-10-18 2018-12-04 西南石油大学 一种抗高盐梳型微嵌段疏水缔合聚合物及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100999875A (zh) * 2006-01-11 2007-07-18 丹东恒星精细化工有限公司 丙烯酸酯乳化增稠剂及生产方法
US20140287967A1 (en) * 2010-01-26 2014-09-25 S.P.C.M. S.A. Water-soluble polymers for oil recovery
WO2012170373A2 (en) * 2011-06-08 2012-12-13 Nalco Company An environmentally friendly dispersion system used in the preparation of inverse emulsion polymers
CN104140507A (zh) * 2014-07-24 2014-11-12 山东大学 一种含超长疏水长链改性的丙烯酰胺水溶性聚合物及其制备方法
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
CN105418862A (zh) * 2015-12-29 2016-03-23 四川光亚聚合物化工有限公司 一种疏水缔合聚合物及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113265022A (zh) * 2021-04-20 2021-08-17 长江大学 一种渗吸驱油剂及制备方法
CN115404067A (zh) * 2021-05-26 2022-11-29 大庆油田有限责任公司 一种耐盐聚合物和驱油剂体系及制备方法
CN115404067B (zh) * 2021-05-26 2023-10-03 大庆油田有限责任公司 一种耐盐聚合物和驱油剂体系及制备方法

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