WO2011147054A1 - 一种树枝状梳形聚合物增稠剂及其制备和应用 - Google Patents

一种树枝状梳形聚合物增稠剂及其制备和应用 Download PDF

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WO2011147054A1
WO2011147054A1 PCT/CN2010/000835 CN2010000835W WO2011147054A1 WO 2011147054 A1 WO2011147054 A1 WO 2011147054A1 CN 2010000835 W CN2010000835 W CN 2010000835W WO 2011147054 A1 WO2011147054 A1 WO 2011147054A1
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monomer
dendritic
acid
comb
comb polymer
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PCT/CN2010/000835
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English (en)
French (fr)
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罗健辉
朱怀江
白凤鸾
王平美
丁彬
杨静波
刘强
刘玉章
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中国石油天然气股份有限公司
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Priority to US13/508,866 priority Critical patent/US8822389B2/en
Publication of WO2011147054A1 publication Critical patent/WO2011147054A1/zh

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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
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • 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
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • 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
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides

Definitions

  • Dendritic comb polymer thickener and preparation and application thereof
  • the present invention relates to a dendritic comb polymer thickener and its preparation and use.
  • Polyacrylamide has poor salt resistance and must be prepared with fresh water to obtain an economical viscosity.
  • the viscosity of the polymer solution is also relatively stable. To this end, solving the problem of salt resistance of polyacrylamide has become one of the research hotspots in the field of oilfield chemistry in the world.
  • a comb-shaped salt-tolerant polymer thickener (comb-shaped polymer) of the Chinese invention patent (CN 011367989) has been widely used in oil-type reservoirs, directly formulated with sewage and has a viscosity-increasing ratio in sewage.
  • the polyacrylamide is increased by more than 50%, and the effect of oil and precipitation is very significant. It becomes a kind of oil reservoir in the oil field (good permeability).
  • the third oil recovery in the second-class oilfield is the key to the next oil recovery in the oilfield. Since the permeability of the second-class oil reservoir is lower than that of the first-class reservoir, it is required to use lower molecular weight, good salt resistance, dissolution rate and polymerization. A novel anti-salt polymer with consistent acrylamide.
  • the object of the present invention is to solve the problem of salt resistance of lower molecular weight polymers,
  • the molecular weight is lower than that of the comb-shaped salt-resistant polymer, has good water solubility, strong ability to thicken the aqueous medium, and the polymer molecule exhibits a dendritic comb structure in an aqueous solution, and has excellent salt resistance, and is suitable for oil field type II oil reservoirs.
  • the polymer-driven copolymer thickener enables the oil field to use the produced water to formulate the polymer-driven polymer, and the viscosity of the polymer solution is more than 30% higher than the similar molecular weight common polyacrylamide, thereby improving the polymerization of the second-class reservoir.
  • a dendritic comb polymer thickener which is a copolymer obtained by copolymerizing a monomer (A) and a monomer (B), characterized in that the monomer (A) is one or more water-soluble.
  • An unsaturated ethylenic monomer which may be one or more of acrylamide, vinylpyrrolidone, 2-acrylamido-2-methylpropanesulfonic acid, acrylic;
  • the body (B) is at least one of the general structures:
  • R 2 may be the same or different, optional H or ( ⁇ C 12 fluorenyl; R 3 , R 4 , R 5 may be the same or different, optional H or ( ⁇ ( 8 alkyl, ( ⁇ (: 8 aryl), ( ⁇ (: 8 alkyl ether or ( ⁇ ( 8 ⁇ ); A optional C00—or 0H. Ri, R 2
  • the screening mainly affects the elasticity of the copolymer solution. As the carbon number increases, the elasticity of the copolymer solution increases.
  • the screening of R 3 , R 4 and R 5 mainly affects the salt resistance of the copolymer solution, and as the carbon number increases, The salt resistance of the copolymer solution is enhanced.
  • the monomer (B) is prepared by dissolving 30 to 60% of a hydroxy acid or a polyhydric alcohol in ethanol. Further, 6 to 12% of a dihalogenene is added, and the mixture is heated under reflux and a 40 to 50% caustic soda solution is added dropwise to neutral, and ethanol and water are distilled off to obtain.
  • the hydroxy acid may be selected from the group consisting of hydroxyglutaric acid, dihydroxymaleic acid, galactonic acid, malic acid, citric acid, tartaric acid and the like or a mixture of the above compounds.
  • the polyol may be selected from the group consisting of glycerin, butyl triol, pentanetriol, hexanetriol, heptanetriol, octanetriol, isobaerythritol, butyltetraol, and the like or a mixture of the above compounds.
  • the dihaloolefin may be selected from the group consisting of dichloroethylene, dichloropropene, dichlorobutene, dibromoethylene, dibromopropene, dibromobutene, etc. or a mixture of the above compounds.
  • the content of the monomer (A) in the dendritic comb polymer thickener of the present invention is 70 to 99.99%, preferably 90 to 99.9%, based on the total mass percentage of the monomer (A) and the monomer (B).
  • the content of the body (B) is 0.01 to 30% by weight of the total mass of the monomer (A) and the monomer (B), preferably 0.1 to 10%, and the mass concentration of the monomer and water in the polymerization system is 10 to 50. %, the preferred embodiment is 15 to 40%.
  • the initiator used in the dendritic comb polymer thickener of the present invention is an initiator used in the publication.
  • the polymerization method used in the dendritic comb polymer thickener of the present invention is a solution polymerization, emulsion polymerization and suspension polymerization method used in the publication.
  • the polymerization conditions are deoxygenation by nitrogen for 30 minutes, and 0.15 to 0.2% of an initiator is added, 40
  • the thermoelastic hydrogel product was obtained by thermostating at 60 ° C for 6 to 14 hours.
  • a solid product can be obtained by drying by a common technique such as acetone precipitation, a kneader, a dryer or the like as needed.
  • the structural formula of the monomer (B) is: Add sodium hydroxide to adjust the pH of the solution to 8 and deoxygenate for 30 minutes with nitrogen. Add 0.1. The ammonium persulfate and 0.1% white powder were thermostated at 40 ° C for 8 hours to obtain a viscoelastic hydrogel product. The product was granulated by a granulator and dried in a rotary drier at 90 ° C for 3 hours to obtain a solid product.
  • the pH of the solution was adjusted with sodium carbonate to 9, and deoxidized by nitrogen for 30 minutes, 0.1% ammonium persulfate and 0.1% sodium hydrogen sulfite, and kept at 60 ° C for 6 hours to obtain a viscoelastic hydrogel product.
  • Example 3 The solid product obtained in Example 3 was subjected to performance comparison test under the same conditions as ordinary polyacrylamide. Test results are shown in Table 1
  • the molecular weight of the dendritic comb polymer is similar to that of ordinary polyacrylamide, but the viscosity in Daqing Qingshui or Daqing Sewage is higher than that of ordinary polyacrylamide, especially in The viscosity in Daqing wastewater is 50% higher than that of ordinary polyacrylamide.
  • the core test from Fig. 1 shows that under the same conditions, the dendritic comb polymer can increase the recovery factor by 0.91% compared with the ordinary polyacrylamide under the same conditions.
  • the dendritic comb polymer has low molecular weight and good salt-tolerant thickening performance, which can meet the requirements of oilfield second-class polymer flooding. It also shows that the molecular design of dendritic comb polymer is successful.
  • the total salinity of Daqing Qingshui is 1000mg/L, of which Ca 2+ +Mg 2+ is 15mg/L ; the total salinity of Daqing wastewater is 4000mg/L, of which Ca 2+ +Mg 2+ is 60mg/L.
  • the monomer (B) of the present invention is characterized in that two side chains having two ionic groups or polar groups are attached to the unsaturated carbon, and the ionic group or the polar group is located at the tail of the side chain, so
  • the inventive monomer (B) is water-soluble and can be uniformly mixed with the monomer (A) solution to easily copolymerize a high molecular weight polymer, and the synthesized copolymer can be completely dissolved in an aqueous medium.
  • the preparation of the monomer (B) is easy, 30 ⁇ 60% hydroxy acid or polyol, dissolved in ethanol and then added 6 ⁇ 12% dihaloene, heated under reflux and added 40 ⁇ 50% caustic soda solution to the middle
  • the monomer (B) of the present invention is obtained by distilling off ethanol and water.
  • the dendritic comb polymer of the invention has an inorganic salt content of up to 30%, Ca 2 +, Mg 2 + polyvalent cations up to 2% of the medium, and the temperature ranges from room temperature to 90 ,, and the viscosity of the aqueous medium can be obtained.
  • the amount of the injecting water medium is 0.05 to 1%.
  • the polymer solution of the present invention has excellent water solubility and excellent salt resistance due to the use of the dendritic comb polymer thickener obtained by copolymerization of the above monomer (A) and monomer (B). Water soluble dendritic comb polymer thickener.
  • the dendritic comb polymer of the invention has a molecular weight much lower than that of the comb-shaped salt-resistant polymer, and solves the problem of salt resistance of the lower molecular weight polymer, and the polymer can be used to prepare the polymer-driven polymer, and the viscosity of the polymer solution It is more than 30% higher than the similar molecular weight common polyacrylamide. It can be used in polymer oil reservoirs with a permeability of less than 400mD. It can improve the economic benefits and popularization and application of polymer flooding in the second-class reservoirs.
  • the dendritic comb polymer of the present invention can also be used for oil field water shutoff profile control, deep profile control and deep liquid flow steering.

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Description

一种树枝状梳形聚合物增稠剂及其制备和应用
技术领域
本发明涉及一种树枝状梳形聚合物增稠剂及其制备和应用。
背景技术
聚丙烯酰胺抗盐性能差， 必须使用淡水配制， 才能得到经济的粘度， 聚合物溶液的粘度也较稳定。 为此， 解决聚丙烯酰胺的抗盐问题就成为 世界油田化学领域的研究热点之一。
中国发明专利 （CN 011367989) 的一种梳形抗盐聚合物增稠剂 （梳 形聚合物）， 已在油田一类油藏得到大量应用， 用污水直接配制且在污水 中的增粘性能比聚丙烯酰胺提高了 50%以上， 增油降水效果非常显著， 成为油田一类油藏 （渗透性较好） 三次采油用新一代驱油剂， 但这种梳 形抗盐聚合物工业品的分子量比聚丙烯酰胺大， 溶解速度比聚丙烯酰胺 慢， 在油田二类油藏 （渗透性较一类油藏差） 应用时， 注入性能存在一 些问题。 油田二类油藏开展三次采油是油田下一步提高采收率的重点， 由于油田二类油藏的渗透率比一类油藏低， 需采用分子量较低、 抗盐性 能好、 溶解速度与聚丙烯酰胺一致的新型抗盐聚合物。
针对油田二类油藏三次采油的需求， 我们发展了梳形抗盐聚合物增 稠剂， 研制成功一种辫状梳形抗盐聚合物增稠剂， 并分别申请了美国发 明专利 (US 7304116) 和中国发明专利 (CN 2005100752911 ), 该聚合物 在分子量较低的情况下， 抗盐性能好， 但由于在中性水中溶解速度较慢， 必须在一定碱性条件下的溶解速度才与聚丙烯酰胺一致， 因此， 辫状梳 形抗盐聚合物增稠剂用于油田二类油藏复合驱的效果很好， 而用于油田 二类油藏聚合物驱的新型抗盐聚合物还需攻关研究。
发明内容
本发明的目的是解决较低分子量聚合物的抗盐问题， 提供 一种分子量比梳形抗盐聚合物低， 具有良好水溶性、 增稠水介 质能力强， 聚合物分子在水溶液中呈现树枝状梳形结构， 且抗 盐性能优良， 适用于油田二类油藏聚合物驱的共聚物增稠剂， 使油田可以采用产出水配制聚合物驱用聚合物， 并且聚合物溶 液的粘度比相近分子量普通聚丙烯酰胺高 30%以上，从而提高二 类油藏聚合物驱的经济效益和推广应用领域。
本发明的具体内容为：
一种树枝状梳形聚合物增稠剂， 它是由单体（A )和单体（B ) 共聚而成的共聚物， 其特征在于， 单体 （A ) 为一种或多种水溶 性不饱和带烯链的单体， 该单体可以是丙烯酰胺， 乙烯基吡咯 垸酮类， 2-丙烯酰胺基 -2-甲基丙磺酸类， 丙烯酸类中的一种或 多种； 单体 （B ) 是至少一种通式结构为：
Figure imgf000004_0001
的单体， 通式中： R2可以相同， 也可以不相同， 可选 H或（^〜 C12垸基； R3、 R4、 R5可以相同， 也可以不相同， 可选 H或（^〜( 8 烷基、 （^〜(：8垸基芳基、 （^〜(：8烷基醚或 （^〜( 8垸基酯； A 可选 C00—或 0H。 Ri、 R2的筛选主要影响共聚物溶液的弹性， 随碳数的 增加， 共聚物溶液的弹性增大； R3、 R4、 R5的筛选主要影响共聚 物溶液的抗盐性能， 随碳数的增加， 共聚物溶液的抗盐能力增 强。
单体 （B ) 的制备是将 30〜60%羟基酸或多元醇， 溶于乙醇 中再加入 6〜12%二卤代烯， 加热回流并滴加 40〜50%苛性钠溶 液至中性， 蒸馏除去乙醇和水而得。 羟基酸可选羟基戊二酸、 二羟基马来酸、 半乳糖二酸、 苹果酸、 柠檬酸、 亚酒石酸等或 上述化合物的混合物。 多元醇可选甘油、 丁三醇、 戊三醇、 己 三醇、 庚三醇、 辛三醇、 异戊四醇、 丁四醇等或上述化合物的 混合物。 二卤代烯可选二氯乙烯、 二氯丙烯、 二氯丁烯、 二溴 乙烯、 二溴丙烯、 二溴丁烯等或上述化合物的混合物。
本发明的树枝状梳形聚合物增稠剂中的单体 （A) 含量占单 体 （A) 和单体 （B) 总质量百分比的 70〜99.99%， 优选方案为 90〜99.9%， 单体 （B) 的含量占单体 （A) 和单体 （B) 总质量 百分比的 0.01〜30%， 优选方案为 0.1〜： 10%， 聚合体系中单 体与水的质量浓度为 10〜50%， 优选方案为 15〜40%。
本发明的树枝状梳形聚合物增稠剂中所用的引发剂为公开文献采用 的引发剂。 如过硫酸钾、 过硫酸铵、 过硫酸钠 -亚硫酸钾、 过硫酸铵-亚 硫酸氢钠、 过硫酸铵-雕白粉、 过硫酸钾-雕白粉、 偶氮二异丁腈、 过硫 酸铵 -雕白粉-偶氮二异丁腈、 过硫酸铵-亚硫酸氢钠-偶氮二异丁腈、 过 硫酸铵-雕白粉-偶氮二异丁腈。
本发明的树枝状梳形聚合物增稠剂中所用的聚合方法为公开文献采 用的溶液聚合、 乳液聚合和悬浮聚合方法， 聚合条件为通氮气脱氧 30分 钟， 加入 0.15〜0.2%引发剂， 40〜60°C下恒温 6〜14小时， 得到粘弹性 水凝胶产物。 需要时可由普通技术如丙酮沉淀、 捏合机、 干燥机等干燥 而得到固态产品。
附图说明 图 1聚合物在二类油藏中的驱油效率对比
具体实施方式
实施例中， 除另有说明外， 各等份和百分比均以质量为单 位。
单体 （B) 的制备：
实施例 1
将 30〜60%羟基酸或多元醇， 溶于乙醇中再加入 6〜12%二 卤代烯， 加热回流并滴加 40〜50%苛性钠溶液至中性， 蒸馏除 去乙醇和水即得本发明单体 （B)。
树枝状梳形聚合物增稠剂的制备：
实施例 2
在含 15%的丙烯酰胺， 5%单体 （B) 的水溶液中， 单体 （B) 的结构式为:
Figure imgf000006_0001
通氮气脱氧 30分钟， 加入 0.2%偶氮二异于腈引发剂， 60Ό下 恒温 14小时， 得到粘弹性水凝胶产物。 产物在捏合机中， 90°C 下干燥 8小时， 得到固态产品。
实施例 3
在含 12%丙烯酸胺， 6%丙烯酸， 2%单体（B)的水溶液中， 单体 （B) 的结构式为:
Figure imgf000006_0002
加氢氧化钠调节溶液的 pH=8， 通氮气脱氧 30 分钟， 加入 0.1 %过硫酸铵和 0.1%雕白粉， 于 40°C下恒温 8小时， 得到粘弹 性水凝胶产物。 产物经造粒机造粒， 在回转干燥机中， 90°C下 干燥 3小时， 得到固态产品。
实施例 4
在含 7%丙烯酰胺， 10%乙烯基吡咯垸酮， 3%单体（B)的水 溶液中， 单体 （B) 的结构式为：
Figure imgf000007_0001
通氮气脱氧 30分钟， 加入 0.15%偶氮二异丁腈引发剂， 于 60 °C下恒温 14小时， 得到粘弹性水凝胶产物。
实施例 5
在含 15%丙烯酰胺， 8%2—丙烯酰胺基一 2—甲基丙磺酸， 4%单体（B)的水溶液中， 单体 （B) 的结构式为：
Figure imgf000007_0002
用碳酸钠调节溶液的 pH至 9， 通氮气脱氧 30分钟， 0.1%过硫 酸铵和 0.1%亚硫酸氢钠， 于 60°C下恒温 6小时， 得到粘弹性 水凝胶产物。
实施例 6
将实施例 3 得到的固体产品与普通聚丙烯酰胺在相同条件 下进行性能比较测试。 测试结果见表 1
工业实用性 从表 1 的测试结果可以看到， 树枝状梳形聚合物的分子量 与普通聚丙烯酰胺相近， 但无论在大庆清水， 还是在大庆污水 中的粘度均比普通聚丙烯酰胺的高， 特别是在大庆污水中的粘 度比普通聚丙烯酰胺的提高了 50%。 从图 1 的岩心试验表明， 在二类油藏进行聚合物驱， 相同条件下， 采用树枝状梳形聚合 物可比普通聚丙烯酰胺提高采收率多 0.91个百分点。 说明树枝 状梳形聚合物分子量较低、 抗盐增稠性能较好， 可以适应油田 二类 藏聚合物驱的要求， 也说明树枝状梳形聚合物的分子设 计是成功的。
树枝状梳形聚合物的基本性能
Figure imgf000008_0001
注： 大庆清水总矿化度 1000mg/L， 其中 Ca2++Mg2+为 15mg/L; 大庆污水总矿化度 4000mg/L, 其中 Ca2++Mg2+为 60mg/L。
本发明单体 （B) 的特点是与不饱和碳相连着二个含有两个 离子基团或极性基团的侧链， 且离子基团或极性基团位于侧链 的尾部， 因此本发明单体 （B) 是水溶性的， 可与单体 （A) 溶 液均相混合， 易于共聚出高分子量聚合物， 合成出的共聚物能 完全溶于水介质。 单体 （B) 的制备是容易， 将 30〜60%羟基酸 或多元醇， 溶于乙醇中再加入 6〜12%二卤代烯， 加热回流并滴 加 40〜50%苛性钠溶液至中性， 蒸馏除去乙醇和水而得本发明 单体 （B)。 本发明的树枝状梳形聚合物的无机盐含量最多占 30 %， Ca2 +、 Mg2 +多价阳离子最多占 2 %介质中， 温度在室温至 90 Ό范围 内， 水介质的粘度可得到增加， 并在较长时间中具有良好的粘 度保留率， 增稠剂的用量为注入水介质质量的 0. 05— 1 %。
由于采用了上述单体 （A ) 和单体 （B ) 共聚而得到的树枝 状梳形聚合物增稠剂的技术方案， 使得本发明聚合物具有极好 的水溶性， 得到抗盐性能优良的水溶性树枝状梳形聚合物增稠 剂。
本发明的树枝状梳形聚合物分子量大大低于梳形抗盐聚合 物， 解决较低分子量聚合物的抗盐问题， 可以采用产出水配制 聚合物驱用聚合物， 并且聚合物溶液的粘度比相近分子量普通 聚丙烯酰胺高 30%以上， 可用于油田二类油藏 （渗透率小于 400mD ) 聚合物驱， 提高二类油藏聚合物驱的经济效益和推广应 用领域。 本发明的树枝状梳形聚合物还可用于油田堵水调剖、 深部调驱和深部液流转向。

Claims

权利 要求
1 . 一种树枝状梳形聚合物增稠剂， 它是由单体 （A ) 和 单体 （B ) 共聚而成的共聚物， 其特征在于： 单体 （A ) 为一 种或多种水溶性不饱和带烯链的单体， 单体 （B ) 是至少一种 通式结构为：
Figure imgf000010_0001
体， 通式结构中 、 R2选择 H或 〜C12垸基； R3、 R»、 R5选择 H或 (^〜(：8垸基、 烷基芳基、（^〜( 8垸基醚或 基酯； A选择 COO-或 OH;
单体（A) 的含量占单体（A)和单体 （B) 总质量的 70〜99.99%， 单体（B) 的含量占单体（A)和单体（B) 总质量的 0.01〜30%。
2. 根据权利要求 1所述的树枝状梳形聚合物增稠剂， 其特征在于： 单体（A)是丙烯酰胺、 乙烯基吡咯垸酮类、 2-丙烯酰胺基 -2-甲基丙磺酸 类、 丙烯酸类中的一种或多种；
3. 一种权利要求 1所述的树枝状梳形聚合物增稠剂的制备方法， 其 特征在于： （1 )单体（B) 的制备是将 30〜60%羟基酸或多元醇， 溶于乙 醇中再加入 6〜12%二卤代烯， 加热回流并滴加 40〜50%苛性钠溶液至中 性， 蒸馏除去乙醇和水而得； (2)单体（A)和单体（B)根据权利要求 1 质量比配制， 聚合体 系中单体（A)和单体（B) 与水的质量浓度为 10〜50%；
(3)通氮气脱氧 30分钟， 加入 0. 15〜0. 2%引发剂， 40〜60°C下恒 温 6〜14小时， 得到粘弹性水凝胶产物。
4. 根据权利要求 3所述的树枝状梳形聚合物增稠剂的制备方法， 其 特征在于： 羟基酸可选羟基戊二酸、 二羟基马来酸、 半乳糖二酸、 苹果 酸、 柠檬酸、 亚酒石酸等或上述化合物的混合物。 多元醇可选甘油、 丁 三醇、 戊三醇、 己三醇、 庚三醇、 辛三醇、 异戊四醇、 丁四醇等或上述 化合物的混合物。
5. 根据权利要求 3所述的树枝状梳形聚合物增稠剂的制备方法， 其 特征在于： 二卤代烯可选二氯乙烯、 二氯丙烯、 二氯丁烯、 二溴乙烯、 二溴丙烯、 二溴丁烯或上述化合物的混合物。
6.—种权利要求 1所述的树枝状梳形聚合物增稠剂的应用， 其特征在于： 此增稠剂用做油田渗透率小于 400mD 油藏的聚合 物驱， 用量为注入水介质质量的 0. 05— 1 %。
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