WO2013013354A1 - 一种两亲高分子及其用途 - Google Patents

一种两亲高分子及其用途 Download PDF

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WO2013013354A1
WO2013013354A1 PCT/CN2011/001576 CN2011001576W WO2013013354A1 WO 2013013354 A1 WO2013013354 A1 WO 2013013354A1 CN 2011001576 W CN2011001576 W CN 2011001576W WO 2013013354 A1 WO2013013354 A1 WO 2013013354A1
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amphiphilic polymer
formula
mol
structural unit
molecular weight
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PCT/CN2011/001576
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English (en)
French (fr)
Inventor
王金本
徐晓慧
史学峰
韩玉淳
王毅琳
阎海科
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中国科学院化学研究所
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Application filed by 中国科学院化学研究所 filed Critical 中国科学院化学研究所
Priority to ES11869894.3T priority Critical patent/ES2630738T3/es
Priority to US14/235,016 priority patent/US9738741B2/en
Priority to EP11869894.3A priority patent/EP2738189B1/en
Priority to CA2842783A priority patent/CA2842783C/en
Priority to EA201490338A priority patent/EA025931B1/ru
Priority to DK11869894.3T priority patent/DK2738189T3/en
Publication of WO2013013354A1 publication Critical patent/WO2013013354A1/zh

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Definitions

  • the invention relates to an amphiphilic polymer and the use thereof, and the amphiphilic polymer is suitable for oil field drilling, cementing, fracturing, crude oil gathering and transportation, sewage treatment, sludge treatment and papermaking, and can be used as an enhanced oil recovery drive.
  • the solution viscosity and viscosity stability of the tertiary oil recovery polymer are important indicators for measuring the effectiveness of the use.
  • the temperature of the reservoir, the formation water and the salinity of the injected water directly affect the viscosity-increasing ability of the polymer solution.
  • polyacrylamide Although it has obvious viscosity-increasing effect in fresh water, as the oilfield temperature, formation water or mineralization of injected water increases, the hydrodynamic radius of the polymer macromolecule decreases and simultaneously The increased adsorption of the material on the rock surface also reduces the effective concentration of the solution, resulting in a decrease in the viscosity of the solution.
  • Amphiphilic polymers are an important class of water-soluble polymers that form a spatial network in solution by introducing a small amount of hydrophobic groups on the hydrophilic macromolecular chain to produce intramolecular or intermolecular hydrophobic interactions.
  • the structure thus has a significant viscosity-increasing effect.
  • By increasing the content of hydrophobic groups on the polymer chain or increasing the molecular weight it can resist the effects of high temperature and high salinity to some extent, but it may also cause the polymer to have poor solubility, a large increase in dissolution time, and easy shearing of macromolecular chains. Degradation and easy adsorption to rock formations and other issues. These problems are particularly acute as formation temperatures and water salinity increase.
  • Heavy oil resources have become one of the important strategic succession resources in China, but mining is very difficult.
  • the main reason is that the viscosity of heavy oil is large, and the gum, asphaltene or wax content is high. It is not easy to flow in formations, wellbore and oil pipelines.
  • due to the large oil-to-water ratio it is also easy to cause problems such as rapid water seepage, high water content, and easy sand production in the formation.
  • the present invention relates to an amphiphilic polymer having repeating units as described below: structural unit A, high sterically hindered structural unit B, and both parents which function to adjust molecular weight, molecular weight distribution, and charge characteristics Structural unit C.
  • the structural unit A which modulates the molecular weight, molecular weight distribution and charge characteristics comprises (meth)acrylamide-based monomer units and/or (meth)acrylic monomer units A 2 ;
  • the (meth)acrylamide monomer unit and the (meth)acrylic monomer unit A 2 are included .
  • the molecular weight of the amphiphilic polymer can usually be selected as needed, and the use is relatively between 100 and 20 million.
  • the (meth)acrylamide monomer unit A has a structure represented by the following formula (1):
  • 1 is 11 or a methyl group
  • R 2 and R 3 are each independently an alkyl group selected from H and C r C 3
  • R 2 and R 3 are preferably H.
  • the (meth)acrylic monomer unit A 2 is (meth)acrylic acid and/or (meth)acrylic acid salt; and the methacrylic acid salt is preferably sodium methacrylate.
  • the (meth)acrylamide monomer unit A accounts for 70 to 99 mol%, preferably 70 to 90 mol%, more preferably 70 to 78 mol%, of all repeating units of the entire amphiphilic polymer. .
  • the (meth)acrylic monomer unit A 2 accounts for 1 to 30 mol%, preferably 1 to 28 mol%, more preferably 20 to 28 mol%, based on the total of all repeating units of the amphiphilic polymer.
  • the structural unit A which functions to adjust the molecular weight, the molecular weight distribution, and the charge characteristic has a structure represented by the following formula (2):
  • 1 is 11 or methyl;
  • R 2 and R 3 are each independently selected from the group consisting of H, C r C 3 alkyl; R 2 and R 3 are preferably H; selected from H or methyl;
  • Gr is -OH Or -0"Na + ;
  • m and n represent the mole percentage of the structural unit in all repeating units of the entire amphiphilic polymer;
  • m is 70-99 mol%, preferably 70-90 mol%, more preferably 70-78 mol%
  • n is from 1 to 30 mol%, preferably from 1 to 28 mol%, more preferably from 20 to 28 mol%.
  • R r R 3 in formula (2) is preferably H, and Gr is preferably -0"Na + .
  • the high sterically hindered structural unit B contains at least a structure G, which is an annular hydrocarbon structure formed on the basis of two adjacent carbon atoms of the main chain or is selected from the formula (3)
  • the structure indicated, optionally in the structural unit B, contains the structure shown in the formula (4):
  • R6 is selected from the group represented by the following formulas (5) to (6): CH 2 — 0(CH 2 ) 2 COOCH 2 CH 3
  • a is an integer of 1 to 11; preferably 1 to 7;
  • R 7 is H
  • R 8 is selected from H, -S0 3 H and a salt thereof, -(CH 2 ) 2 CH 3 C1
  • CH 3 2Cr; ⁇ , ⁇ Each is an integer from 1 to 15, preferably from 1 to 11.
  • the high sterically hindered structural unit ⁇ contains the structure G and the structure shown in the formula (4).
  • the structure G in the above high sterically hindered structural unit B accounts for 0.02-2 mol%, preferably 0.02-1.0 mol%, more preferably 0.1-0.5 mol%, of all repeating units of the entire amphiphilic polymer. .
  • the structure represented by the formula (4) in the above high sterically hindered structural unit B accounts for 0.05 to 5 mol%, preferably 0.1 to 2.5 mol%, more preferably in the total repeating unit of the entire amphiphilic polymer. It is 0.1 to 1.5 mol%.
  • the high element B has the structure shown in the formula (7):
  • the structure represented by the formula (3) is preferably a structure represented by the formula (3), Yan NHCOCH,
  • R 7 and R 8 are as defined in formula (4);
  • X and y respectively represent the mole percentage of the structural unit in all repeating units of the entire amphiphilic polymer;
  • X is 0.02-2 mol%, preferably 0.02-1.0 Mol%, more preferably 0.1 to 0.5 mol%;
  • y is 0.05 to 5 mol%, preferably 0.1 to 2.5 mol%, more preferably 0.1 to 1.5 mol%.
  • the two structures do not have the formula (8):
  • R 9 is H or a methyl group.
  • r is an integer from 3 to 21, s is an integer from 2 to 9, and t is an integer from 3 to 15, and X is C1—or Br—.
  • r is 3-17, s is 2-5, and t is 3-1 1 .
  • the above-mentioned amphiphilic structural unit C accounts for 0.05 to 10 mol%, preferably 0.1 to 5.0 mol%, more preferably 0.5 to 1.5 mol%, based on the total of all repeating units of the amphiphilic polymer.
  • m, n are as defined in the formula (2); R 7 , R 8 , G, x, y are as defined in the formula (7); R 9 , R 1 () l ⁇ 5.0 ⁇ %, more preferably 0.5-1.5, as described in the formula (8), z represents the mole percentage of the structural unit in the entire repeat unit of the amphiphilic polymer, z is 0.05-10 mol%, preferably 0. l-5.0 mol%, more preferably 0.5-1.5 Mol %.
  • the amphiphilic polymer of the present invention has a molecular weight of from 1,000,000 to 20,000,000; preferably from 3 million to 11 million.
  • the amphiphilic polymer of the present invention can be produced by a method known in the art, for example, by structural unit monomers, high space sites which function to adjust molecular weight, molecular weight distribution and charge characteristics.
  • the blocking structural unit monomer and the amphiphilic structural unit monomer are polymerized by an initiator; the polymerization reaction may be a polymerization method well known in the art such as suspension polymerization, emulsion polymerization, solution polymerization, precipitation polymerization, and the like.
  • a typical preparation method is as follows: Dispersing or dissolving the above monomers in a water system by stirring, and initiating polymerization under nitrogen gas to form an amphiphilic polymer.
  • the related art for preparing an amphiphilic polymer in the prior art can be used for the preparation of the amphiphilic polymer of the present invention.
  • the monomers used in the preparation of the amphiphilic polymer can be directly obtained commercially or directly prepared according to the prior art to ij.
  • the synthesis route of some monomers is described in detail in the specific examples.
  • Example 1 is a graph showing the viscosity-concentration relationship of an amphiphilic polymer prepared in Example 5 of Example 1 of the present invention at 60 ° C in 1 X 10 4 mg/L salinity brine.
  • Example 2 is a graph showing the viscosity-temperature relationship of an amphiphilic polymer obtained in Example 1 of Example 1 in a concentration of 1 750 mg/L in 1 X 10 4 mg/mineralized saline. The best way to implement the invention
  • amphiphilic polymer synthesized in this embodiment is represented by the formula (V):
  • amphiphilic polymer synthesized in this embodiment is represented by the formula ( ):
  • the figure shows that the amphiphilic polymer solutions of Examples 1-5 still have good tackifying ability under high temperature and high salinity conditions.
  • the high steric hindrance unit in the amphiphilic polymer reduces the degree of rotational freedom in the main chain, increases the rigidity of the macromolecular chain, makes the macromolecular chain difficult to distort and tends to stretch, resulting in an increase in macromolecular hydrodynamic radius, and
  • the amphiphilic structural unit forms an association microdomain by intramolecular or intermolecular interaction, which significantly improves the solution viscosity-increasing ability under high temperature and high salt conditions.
  • Test method 25ml of three oilfield electro-de-oil samples were added to a 50ml plugged test tube at a temperature of 25 ° C. Continue to add 25 ml of an aqueous solution of amphiphilic polymers of different concentrations prepared by steaming water, and tightly tighten the tube stopper. Use manual mode to shake or place the test tube in the shaker box. Shake it horizontally 80-100 times. The amplitude should be greater than 20cm. After mixing thoroughly, loosen the test tube plug. The viscosity reduction rate of crude oil is calculated according to the following formula:
  • Viscosity reduction rate (%) xlOO
  • Table 1 shows that the amphiphilic polymers of Examples 6-10 have a good viscosity reducing effect on the three oil samples. As the concentration of the amphiphilic polymer solution increases, the viscosity reduction rate increases. When the concentration of the solution is the same, the viscosity of the oil sample increases and the corresponding viscosity reduction rate increases. The amphiphilic polymer effectively emulsifies and disperses the crude oil through the synergistic action of the high steric hindrance unit and the amphiphilic structural unit, and the viscosity of the crude oil is remarkably lowered.
  • amphiphilic polymer of the present invention for oil field drilling, cementing, fracturing, crude oil gathering, sewage treatment, sludge treatment and papermaking, or as an enhanced oil recovery agent, heavy oil viscosity reducer, Fracturing fluid, clay stabilizer, sewage treatment agent, paper retention aid or reinforcing agent.
  • the solution When used as an oil displacing agent, the solution still has a significant viscosity-increasing effect under high temperature and high salt conditions, which can improve the recovery rate of crude oil.
  • a heavy oil viscosity reducer by effectively dispersing and emulsifying the heavy oil, the viscosity of the heavy oil is significantly reduced, and the flow resistance of the heavy oil in the formation and the wellbore is reduced.

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Abstract

本发明提供了一种两亲高分子及该高分子的用途。该两亲高分子具有重复结构单元：调节分子量与分子量分布以及荷电特性作用的结构单元、高空间位阻结构单元和两亲结构单元，适用于油田钻井、固井、压裂、原油集输、污水处理、污泥处理和造纸等领域，可用作强化采油驱油剂、稠油降粘剂、压裂液、粘土稳定剂、污水处理剂、造纸用助留助滤剂或补强剂等。

Description

一种两亲高分子及其用途 技术领域
本发明涉及一种两亲高分子及其用途， 该两亲高分子适用于油田钻井、 固井、 压裂、 原油集输、 污水处理、 污泥处理和造纸等领域， 可用作强化采油驱油剂、 稠 油降粘剂、 压裂液、 粘土稳定剂、 污水处理剂、 造纸用助留助滤剂或补强剂等。 背景技术
三次采油用聚合物的溶液粘度和粘度稳定性是衡量其使用效果的重要指标。油 藏温度、 地层水和注入水矿化度的高低， 直接影响聚合物溶液的增粘能力。 对于部 分水解聚丙烯酰胺而言， 虽然其在淡水中具有明显的增粘作用， 但随着油田温度、 地层水或注入水矿化度的增加， 聚合物大分子流体力学半径减小， 同时聚合物在岩 石表面的吸附量增大也使溶液有效浓度降低， 导致溶液粘度不断下降。 两亲高分子 是一类重要的水溶性聚合物， 通过在亲水性大分子链上引入少量的疏水基团， 产生 分子内或分子间疏水相互作用， 使大分子在溶液中形成空间网状结构， 因而具有显 著的增粘效果。 通过增加高分子链上疏水基团含量或增大分子量可以在一定程度上 抵御高温、 高盐度的影响， 但也可能导致聚合物溶解能力变差、 溶解时间大幅增加 以及大分子链容易剪切降解和容易吸附于岩层等问题。 随着地层温度和水矿化度的 增大， 这些问题尤为严重。
稠油资源已经成为我国重要的战略接替资源之一，但开采难度很大， 主要原因 是稠油的粘度大， 胶质、沥青质或含蜡量高， 在地层、井筒及输油管线中不易流动， 另外由于油水流度比大， 还易造成油井见水快、 含水率高、 地层易出砂等严重影响 生产的问题。
如何保持高分子溶液的增粘与稳粘性、提高其乳化和分散稠油、降低稠油粘度 的能力， 对于提高原油采收率以及最大限度挖潜地下残余原油具有重要意义。 发明公开
本发明以下内容中， 除另有定义外， 相同的可变基团、 分子式 /结构式等均具 有相同的定义。
本发明涉及一种两亲高分子，所述两亲高分子具有如下所述的重复单元： 起调 节分子量、 分子量分布以及荷电特性作用的结构单元 A、 高空间位阻结构单元 B和 两亲结构单元 C。
在一个实施例中，所述调节分子量、分子量分布以及荷电特性作用的结构单元 A包括 (甲基)丙烯酰胺类单体单元 和/或 (甲基)丙烯酸类单体单元 A2;优选同时包 括 (甲基)丙烯酰胺类单体单元 和 (甲基)丙烯酸类单体单元 A2。 在本领域中， 两亲 高分子的分子量通常可根据需要进行选择， 使用比较多的是 100-2000万之间。
优选的， 所述 (甲基)丙烯酰胺类单体单元 A具有如下式 (1)所示的结构：
Figure imgf000003_0001
式 (1)
式 (1)中， 1^为11或甲基； R2和 R3各自独立的选自 H、 CrC3的烷基； R2和 R3 优选为 H。
优选的，所述 (甲基)丙烯酸类单体单元 A2为 (甲基)丙烯酸和 /或 (甲基)丙烯酸盐; 甲基丙烯酸盐优选为甲基丙烯酸钠。
优选的，所述 (甲基)丙烯酰胺类单体单元 A在整个两亲高分子所有重复单元中 所占的摩尔百分数为 70-99mol%， 优选为 70-90mol%， 更优选 70-78mol%。
优选的，所述 (甲基)丙烯酸类单体单元 A2在整个两亲高分子所有重复单元中所 占的摩尔百分数为 l-30mol%， 优选 l-28mol%， 更优选 20-28mol%。
在另一个实施例中，所述起调节分子量、分子量分布以及荷电特性作用的结构 单元 A具有如下式 (2)所示的结构：
Figure imgf000003_0002
式 (2)
其中， 1^为11或甲基； R2和 R3各自独立的选自 H、 CrC3的烷基； R2和 R3优 选为 H; 选自 H或甲基； Gr为 -OH或 -0"Na+; m和 n表示该结构单元在整个两亲 高分子所有重复单元中所占的摩尔百分数； m为 70-99mol%， 优选为 70-90mol%， 更优选 70-78mol% ; n为 l-30mol%， 优选 l-28mol%， 更优选 20-28mol%。
在另一个实施例中， 式 (2)中 RrR3优选为 H， Gr优选为 -0"Na+。
在另一个实施例中，所述高空间位阻结构单元 B至少含有结构 G，所述结构 G 为以主链相邻两个碳原子为基础形成的环状烃结构或选自式 (3)表示的结构，结构单 元 B中任选的含有式 (4)所示的结构：
式 (3) 式 (4)
式 (3)中， 为11或甲基； 优选为 H; R6选自如下式 (5)-(6)所示的基团: CH2— 0(CH2)2COOCH2CH3
—— CH2—— OCCH2)2COOCH2CH3
Figure imgf000004_0001
CH2— 0(CH2)2COOCH2CH3
式 (5) 式 (6)
式 (5)中， a为 1-11的整数； 优选为 1-7;
式 (4)中， R7为 H; R8选自 H、 -S03H及其盐、 -(CH2)2CH3C1、
-CH2N+(CH3)2(CH2 CH3Cr或 -CH2N+(CH3)2(CH2)2N+(CH3)2(CH2)。CH32Cr; ξ、 σ分别 为 1-15的整数， 优选 1-11。
优选的， 所述高空间位阻结构单元 Β含有结构 G和式 (4)所示的结构。
在另一个实施例中， 所述以主链相邻两个碳原子为基础形成的环状烃结构选
Figure imgf000004_0002
或
优选的， 上述高空间位阻结构单元 B中结构 G在整个两亲高分子所有重复单 元中所占的摩尔百分数为 0.02-2mol%， 优选 0.02-1.0mol%， 更优选为 0.1-0.5mol%。
优选的， 上述高空间位阻结构单元 B中式 (4)所示的结构在整个两亲高分子所 有重复单元中所占的摩尔百分数为 0.05-5mol%， 优选为 0.1-2.5mol%， 更优选为 0.1-1.5mol%。
在另一个实施例中， 所述高 元 B具有式 (7)所示的结构：
Figure imgf000004_0003
式 (7)
式 (7) 所述， 优选为式 (3)所表示的结构、
Figure imgf000004_0004
严 NHCOCH,
Figure imgf000004_0005
R7和 R8的定义如式 (4)所述； X和 y分别表示该结构单元在整个两亲高分子所 有重复单元中所占的摩尔百分数； X为 0.02-2mol%， 优选 0.02-1.0mol%， 更优选为 0.1-0.5mol%; y为 0.05-5mol%， 优选为 0.1-2.5mol%， 更优选为 0.1-1.5mol%。 在另一个实施例中， 所述两未 具有式 (8)所示的结构:
Figure imgf000005_0001
式 (8)
式 (8)中， R9为 H或甲基， 。为 -N+(CH3)2(CH2)rCH3X—、 -N+((CH2)SCH3)3X—或 -N+(CH3)((CH2)tCH3)2X—； r为 3-21的整数， s为 2-9的整数， t为 3-15的整数， X 为 C1—或 Br―。 优选地， r为 3-17， s为 2-5， t为 3-1 1。
优选的， 上述两亲结构单元 C在整个两亲高分子所有重复单元中所占的摩尔 百分数为 0.05-10mol%， 优选 0.1-5.0mol%， 更优选 0.5-1.5mol %。
在另一个实施 ：
Figure imgf000005_0002
式 (9)
式 (9)中， ， m， n的定义如式 (2)所述； R7， R8， G， x， y的定义如式 (7)所述; R9， R1()的定义如式 (8)所述， z表示该结构单元在整个两亲高分子所有重复单元中 所占的摩尔百分数， z为 0.05- 10mol%， 优选 0. l-5.0mol%， 更优选 0.5-1.5mol %。
本
Figure imgf000005_0003
( I )
Figure imgf000006_0001
Figure imgf000007_0001
(Vffl)
Figure imgf000008_0001
( X)
本发明上述两亲高分子的分子量为 100万 -2000万之间； 优选为 300万 -1100 万之间。
分子量 M的测定方法： 使用乌氏粘度计测定特性粘数 [；；]， 并将测得的 [；；]代 入下面公式中计算得到；
M = 802[/7] 本发明所述两亲高分子可采用本技术领域所已知的方法制备，例如： 通过起调 节分子量、 分子量分布以及荷电特性作用的结构单元单体、 高空间位阻结构单元单 体和两亲结构单元单体在引发剂作用下聚合而成； 聚合反应可以为悬浮聚合、 乳液 聚合、 溶液聚合、 沉淀聚合等本领域熟知的聚合方法。
典型的制备方法为： 在水体系中通过搅拌的方式分散或溶解上述各单体，在氮 气保护下引发聚合形成两亲性高分子。 现有技术中制备两亲高分子的相关技术均可 用于本发明的两亲高分子的制备。
制备两亲高分子所采用的单体均可直接商购获得，或依据现有技术直接制备得 至 ij， 一些单体的合成路线在具体实施例中有详细说明。
附图说明
图 1为本发明实施例 1一实施例 5制得的两亲高分子在 1 X 104mg/L矿化度盐水 中 60°C下的粘浓关系曲线。
图 2为本发明实施例 1一实施例 5制得的两亲高分子在 1 X 104mg/矿化度盐水中 浓度为 1750mg/L时的粘温关系曲线。 实施发明的最佳方式
下面结合具体实施例对本发明作进一步说明， 但本发明并不限于以下实施例( 实施例 1
Figure imgf000009_0001
本实施例的未高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜， 各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 78%、 20 % 0.25%、 0.5%、 1.25%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节 反应溶液， 使其 pH为 8左右， 通氮气 30 min除去其中的氧气。 在氮气保护下加入 引发剂， 再通氮气 10 min后封口，在 18°C下反应， 反应约 5 h反应结束， 反应完全。 所得产品经过干燥， 得到粉末状两亲高分子.两亲高分子的分子量 970x l04。
实施例 2
本实
Figure imgf000009_0002
本实施例两亲高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜， 各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 75%、 23 % 0.25%、 0.25%、 1.5%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节 反应溶液， 使其 pH为 8左右， 通氮气 40 min除去其中的氧气。 在氮气保护下加入 引发剂， 再通氮气 10 min后封口，在 22°C下反应， 反应约 5 h反应结束， 反应完全。 所得产品经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 1030x l04。
实施例 3
本实
Figure imgf000010_0001
本实施例两亲高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜， 各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 73%、 26%、 0.1%、 0.1%、 0.8%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节反应溶 液， 使其 pH为 9左右， 通氮气 30 min除去其中的氧气。在氮气保护下加入引发剂， 再通氮气 lO min后封口， 在 25°C下反应， 反应约 6 h反应结束， 反应完全。 所得产 品经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 620x l04。
实施例 4
本实
Figure imgf000010_0002
b 。 /—。+
Figure imgf000011_0001
本实施例两亲高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜， 各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 75%、 23%、 0.1%、 0.4%、 1.5%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节反应溶 液， 使其 pH为 9左右， 通氮气 30 min除去其中的氧气。在氮气保护下加入引发剂， 再通氮气 lO min后封口， 在 25 °C下反应， 反应约 6 h反应结束， 反应完全。 所得产 品经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 390x l04。
实施例 5
本实施例合成的两亲高分子如式 (V)所示：
Figure imgf000012_0001
本实施例两亲高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜， 各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 78%、 21%、 0.1%、 0.1%、 0.8%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节反应溶 液， 使其 pH为 8左右， 通氮气 30 min除去其中的氧气。在氮气保护下加入引发剂， 再通氮气 lO min后封口， 在 25 °C下反应， 反应约 6 h反应结束， 反应完全。 所得产 品经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 390x l04。
实施例 6
本
Figure imgf000012_0002
(VI) 本实施例两未高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜，各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 73.5%、 25%、 0.5%、 0.5%、 0.5%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节反应溶 液， 使其 pH为 8左右， 通氮气 30 min除去其中的氧气。在氮气保护下加入引发剂， 再通氮气 lO min后封口， 在 45 °C下反应， 反应约 3 h反应结束， 反应完全。 所得产 品经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 680χ 104。
实施例 7
本实施例合成的两亲高分子如式 ( )所示：
Figure imgf000013_0001
本实施例两亲高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜， 各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 75%、 23%、 0.25%、 0.25%、 1.5%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节反应 溶液， 使其 pH为 9左右， 通氮气 30 min除去其中的氧气。 在氮气保护下加入引发 剂， 再通氮气 10 min后封口， 在 55 °C下反应， 反应约 3 h反应结束， 反应完全。 所 得产品经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 690x l04。
实施例 8
Figure imgf000013_0002
Figure imgf000013_0003
(環) 本实施例两未高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜， 各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 70%、 28%、 0.15%、 0.75%、 1.1%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节反应 溶液， 使其 pH为 8左右， 通氮气 30 min除去其中的氧气。 在氮气保护下加入引发 剂， 再通氮气 10 min后封口， 在 55°C下反应， 反应约 3 h反应结束， 反应完全。 所 得产品经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 390x l04。
实施例 9
Figure imgf000014_0001
(IX)
本实施例两亲高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜，各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 75%、 23.5%、 0.5%、 0.5%、 0.5%, 搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节反应溶 液， 使其 pH为 8左右， 通氮气 30 min除去其中的氧气。在氮气保护下加入引发剂， 再通氮气 lO min后封口， 在 50°C下反应， 反应约 2.5 h反应结束， 反应完全。 所得 产品经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 430x l04。
实施例 10
本
Figure imgf000014_0002
本实施例两未高分子的合成：
先将占总反应体系重量 3/4的水加入反应釜中， 再将占总反应体系重量 1/4的 各种单体加入反应釜， 各重复单元的摩尔百分数 m、 n、 x、 y、 z依次为 74%、 23%、 0.5%、 1.5%、 1%，搅拌使它们完全溶解， 并向其中加入 pH值调节剂调节反应溶液， 使其 pH为 8左右， 通氮气 30 min除去其中的氧气。 在氮气保护下加入引发剂， 再 通氮气 lO min后封口， 在 50°C下反应， 反应约 2 h反应结束， 反应完全。 所得产品 经过干燥， 得到粉末状两亲高分子。 两亲高分子的分子量为 560x l04。
测定实施例
测定例 1
使用矿化度 l X 104mg/L的盐水配制不同浓度的两亲高分子溶液， 测定溶液浓 度、 温度与溶液粘度的关系， 结果见图 1和图 2。
图中表明， 在高温和高矿化度条件下， 实施例 1-5的两亲高分子溶液仍具有良 好的增粘能力。 两亲高分子中的高空间位阻单元减小了主链内旋转自由度、 增加了 大分子链的刚性，使大分子链难于蜷曲而趋向伸展，导致大分子流体力学半径增大， 同时， 两亲结构单元通过分子内或分子间作用形成缔合微区， 显著提高了高温高盐 条件下的溶液增粘能力。
测定例 2
测试方法： 温度为 25°C下， 将三种油田电脱原油样品 25ml加入 50ml具塞试 管中， 继续加入 25ml以蒸熘水配制的不同浓度两亲高分子的水溶液， 盖紧试管塞 后， 采用手工方式振荡或将试管放置在振荡箱内， 水平振荡 80-100次， 振幅应大于 20cm, 充分混合后， 松动试管塞。 原油降粘率按照下式计算：
原油样品粘度-混合后体系粘度
降粘率 （％)= xlOO
原油样品粘度
表 1 实施例 6—实施例 10制得的两亲高分子稠油降粘实验结果（油水比 1 : 1
25 °C )
Figure imgf000015_0001
1200mg/L 260 680 780
85.56 89.85 95.67
400mg/L 820 2050 4250
54.44 69.40 76.39
600mg/L 470 1370 1975
73.89 79.55 89.03 实施例 800mg/L 315 850 1325
8 82.50 87.31 92.64
lOOOmg/L 230 675 930
87.22 89.93 94.83
1200mg/L 200 590 850
88.89 91.19 95.28
400mg/L 925 2270 4700
48.61 66.12 73.89
600mg/L 630 1420 2550
65.00 78.81 85.83 实施例 800mg/L 450 940 1480
9 75.00 85.97 91.78
lOOOmg/L 380 680 1050
78.89 89.85 94.17
1200mg/L 340 530 880
81.11 92.09 95.11
400mg/L 820 1900 5100
54.44 71.64 71.67
600mg/L 530 1250 2900
70.56 81.34 83.89 实施例 800mg/L 390 825 1890
10 78.33 87.69 89.50
lOOOmg/L 305 650 1400
83.06 90.30 92.22
1200mg/L 260 575 1175
85.56 91.42 93.47 表 1说明， 实施例 6-10的两亲高分子对于三种油样具有很好的降粘效果。 随 两亲高分子溶液浓度增加， 降粘率增大。 溶液浓度相同时， 油样粘度提高则相应降 粘率增大。两亲高分子通过高空间位阻单元与两亲结构单元的协同作用，有效乳化、 分散原油， 显著降低了原油粘度。
工业应用
本发明的两亲高分子的用途， 其用于油田钻井、 固井、 压裂、 原油集输、 污水 处理、 污泥处理和造纸， 或用作强化采油驱油剂、 稠油降粘剂、 压裂液、 粘土稳定 剂、 污水处理剂、 造纸用助留助滤剂或补强剂等。
特别适用于原油开采领域， 如可用作强化采油聚合物驱油剂和稠油降粘剂。作 为驱油剂使用时， 溶液在高温高盐条件下仍具有显著增粘效果， 能够提高原油采收 率。 作为稠油降粘剂时， 通过有效分散和乳化稠油， 显著降低稠油粘度、 减小稠油 在地层和井筒中流动阻力。

Claims

权利要求
1、 一种两亲高分子， 其特征在于： 具有调节分子量与分子量分布以及荷电特 性作用的结构单元 A、高空间位阻结构单元 B和两亲结构单元 C作为重复结构单元。 所述高空间位阻结构单元 B含有结构 G和式 (4)所示的结构， 其中所述结构 G为以 主链相邻两个碳原子为基础形成的环状烃结构或选自式 (3)表示的结构：
Figure imgf000017_0001
式 (3)中， 为11或甲基； 优选为 H; R6选自如下式 (5)-(6)所示的基团：
^CH2-0(CH2)aCH3
CH— O― CH
I 2 \ CH2— 0(CH2)2COOCH2CH3
\ ^CH2-o(CH2)aCH3 ― NH― c― ― 0(CH2)2COOCH2CH3
CH2— O― CH \
\CH2- ο(α¾)3α¾ CH2 - 0(CH2)2COOCH2CH3 式 (5) 式 (6) 式 (5)中， a为 1-11的整数。
式 (4)中， R7为 H; R8选自 H、 -S03H及其盐、 -(CH2)2CH3C1、
-CH2N+(CH3)2(CH2 CH3Cr或 -CH2N+(CH3)2(CH2)2N+(CH3)2(CH2)。CH32Cr; ξ、 σ分别 为 1-15的整数。
其中所述两亲结构单元 C具有式 (8)所示的结构：
Figure imgf000017_0002
式 (8) 式 (8)中， R9为 H或甲基， 。为 -N+(CH3)2(CH2)rCH3X—、 -N+((CH2)SCH3)3X—或 -N+(CH3)((CH2)tCH3)2X； r为 3-21的整数， s为 2-9的整数， t为 3-15的整数， X— 为 C1—或 Br―。
2、 如权利要求 1所述的两亲高分子， 其特征在于： 所述起调节分子量、 分子 量分布以及荷电特性作用的结构单元 A包括 (甲基)丙烯酰胺类单体单元 和/或 (甲 基)丙烯酸类单体单元 A2。
3、 如权利要求 2所述的两亲高分子， 其特征在于： 以两亲高分子所有重复单 元总数为 100mol%计，所述 (甲基)丙烯酰胺类单体单元 在整个两亲高分子所有重 复单元中所占的摩尔百分数为 70-99mol%; 所述 (甲基)丙烯酸类单体单元 A2在整个 两亲高分子所有重复单元中所占的摩尔百分数为 l-30mol%。
4、 如权利要求 1所述的两亲高分子， 其特征在于： 结构 G在整个两亲高分子 所有重复单元中所占的摩尔百分数为 0.02-2mol%;式 (4)所示的结构在整个两亲高分 子所有重复单元中所占的摩尔百分数为 0.05-5mol%。
5、 如权利要求 1所述的两亲高分子， 其特征在于： 以两亲高分子所有重复单 元总数为 100mol%计， 所述式 (8)表示的结构单元在整个两亲高分子所有重复单元 中所占的摩尔百分数为 0.05-10mol%。
6、 如权利要求 1所述的两亲高分子， 其特征在于： 所述调节分子量、 分子量 分布以及荷电特性作用 结构：
Figure imgf000018_0001
式 (2) 式 (2)中， 1^为11或甲基； R2和 R3各自独立的选自 H、 d-C3的烷基； R4选自 H或甲基； Gr为 -OH或 -0"Na+; m和 n表示该结构单元在整个两亲高分子中所占的 摩尔百分数； m为 70-99mol%; n为 l-30mol%。
7、 如权利要求 1所述的两亲高分子， 其特征在于： 所述以主链相邻两个碳原 子
Figure imgf000018_0002
8、 如权利要求 1所述的两亲高分子， 其特征在于： 所述高空间位阻结构单元 B具有式 (7)所示的结构：
Figure imgf000019_0001
式 (7) 式 (7)中， 1所述， 1 7和 的定义如式 (4)中所述， X和 y 分别表示该结构单元在整个两亲高分子所有重复单元中所占的摩尔百分数， X为 0.02-2mol%, y为 0.05-5mol%。
9、 如权利要求 1所述的两亲高分子， 其特征在于： 所述两亲高分子具有式 (9) 所示的结构：
Figure imgf000019_0002
式 (9) 式 (9)中， 选自 H或甲基； m和 n表示该结构单元在整个两亲高分子中所占 的摩尔百分数； m为 70-99mol%; n为 l-30mol% ; G、 R7、 R8、 x和 y的定义如上 述式 (7)所述； R9， R1()的定义如上述式 (8)所述， z表示该结构单元在整个两亲高分 子所有重复单元中所占的摩尔百分数， z为 0.05-10mol%。
10、 如权利要求 1所述的两亲高分子， 所述高分子是下述式（I )-(X)化合物：
Figure imgf000020_0001
Figure imgf000020_0002
Figure imgf000020_0003
Figure imgf000021_0001
Figure imgf000021_0002
(VI)
Figure imgf000022_0001
IX)
Figure imgf000023_0001
11、 如权利要求 1-10任一项所述的两亲高分子， 其特征在于： 分子量为 100 万 -2000万之间。
12、 权利要求 1-11任一项所述的两亲高分子的用途， 其特征在于： 用于油田 钻井、 固井、 压裂、 原油集输、 污水处理、 污泥处理和造纸， 或用作强化采油驱油 剂、稠油降粘剂、压裂液、粘土稳定剂、 污水处理剂、造纸用助留助滤剂或补强剂。
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EA025931B1 (ru) 2017-02-28
CN102382242B (zh) 2013-10-23
CA2842783C (en) 2016-03-29
US20140316092A1 (en) 2014-10-23
DK2738189T3 (en) 2017-02-20
CA2842783A1 (en) 2013-01-31
ES2630738T3 (es) 2017-08-23
EP2738189A4 (en) 2015-08-19
US9738741B2 (en) 2017-08-22
MY166452A (en) 2018-06-27
EP2738189B1 (en) 2016-11-09
EA201490338A1 (ru) 2014-05-30
CN102382242A (zh) 2012-03-21

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