CN103788293A - Acrylamide series copolymer, preparation method thereof and applications thereof - Google Patents

Acrylamide series copolymer, preparation method thereof and applications thereof Download PDF

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CN103788293A
CN103788293A CN 201210422133 CN201210422133A CN103788293A CN 103788293 A CN103788293 A CN 103788293A CN 201210422133 CN201210422133 CN 201210422133 CN 201210422133 A CN201210422133 A CN 201210422133A CN 103788293 A CN103788293 A CN 103788293A
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CN103788293B (en )
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杜凯
赵方园
刘希
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention discloses an acrylamide series copolymer, a preparation method thereof and applications thereof. The acrylamide series copolymer comprises a structure unit A, a structure unit B, a structure unit C and a structure unit D, wherein the structure unit A is a structure unit shown as the formula (1) and/or a structure unit shown as the formula (2); the structure unit B is at least one structural unit shown as the formula (3), the formula (4), the formula (5) and the formula (6); the structure unit C is a structure unit shown as the formula (7) and/or a structure unit shown as the formula (8); the structure unit D is a structure unit shown as the formula (9) and/or a structure unit shown as the formula (10); and the viscosity average molecular weight of the acrylamide series copolymer is two million to eighteen million. The acrylamide series copolymer has high drag reduction efficiency, good heat resistance, good salt resistance, good high-shear resistance, good water solubility, good compatibleness with clay inhibitors (alcohols) and low damage to stratums.

Description

一种丙烯酰胺系共聚物及其制备方法和应用 Acrylamide copolymer and its preparation method and application

技术领域 FIELD

[0001 ] 本发明涉及一种丙烯酰胺系共聚物及其制备方法和应用。 [0001] The present invention relates to an acrylamide copolymer and its preparation method and application.

背景技术 Background technique

[0002] 作为非常规油气资源利用的典型代表——页岩气(油)资源的开采已经成为全球非常规油气资源领域的一场革命,目前页岩气的开发与利用已成为世界各国着重关注与发展的重点技术。 [0002] As a typical representative of unconventional oil and gas resources utilization - shale gas (oil) resources has become a revolution in the world of unconventional oil and gas resources, the development and utilization of shale gas has become the world focus on focus on technology and development. 由于页岩气藏等极致密油气藏具有渗透率极低(一般小于0.5mD)、压裂压力高、易造成地层伤害的特点。 Because extremely dense, like shale gas reservoirs with very low permeability (typically less than 0.5md), high fracture pressure, easily causing formation damage characteristics. 必须采用“减阻水(滑溜水)压裂”工艺开采。 We must be "slickwater (slick water) fracturing" process mining.

[0003] “减阻水(滑溜水)压裂”是水力压裂的一种。 [0003] "slickwater (slick water) fracturing" is a hydraulic fracturing. 与目前常规压裂体系(改性瓜胶交联体系)相比,减阻水(滑溜水)压裂不是依靠高粘性胶体携砂,而是以高的泵注排量携砂,实现将储层压裂成网状裂缝的最终目的。 Compared with the current conventional fracturing system (modified guar gum crosslinking system), slickwater (slick water) instead of relying on the high viscosity fracturing sand carrying colloid, but in the high injection pump displacement carrying sand, achieve reservoir fracture splitting into a laminate web of the ultimate goal. 减阻水(滑溜水)压裂较常规压裂体系在成本上有较大优势的同时对地层的伤害较小。 Slickwater (slick water) compared with conventional fracturing fracturing system have a greater advantage in terms of cost while a smaller formation damage.

[0004] 减阻水压裂液核心助剂为水基降阻剂,在实际施工中,水基减阻剂的加入克服工作液在管线中的摩擦阻力,保证了泵注排量的提高,使压力最大限度地作用于压开地层和延伸地层裂缝,目前可用作水基降阻剂的主要有胍胶及其衍生物、纤维素衍生物、丙烯酰胺类聚合物。 [0004] The core aids slickwater fracturing fluid reduction agent is water-based, in actual construction, the water-based drag reducing agent was added to overcome the frictional resistance of the working fluid in a pipeline, to ensure the improvement of pumping displacement, to maximize the pressure acting on the pressure of the formation and the extension formation fractures open, current can be used as water-reducing agent based mainly guar gum and derivatives thereof, cellulose derivatives, acrylamide-based polymer.

[0005]目前,采用胍胶及其衍生物、纤维素及其衍生物作为减阻水压裂中的减阻剂一定程度上提高了泵注排量、降低了管线中的摩擦阻力(US 5697444,US 5271466),但仍无法满足减阻水压裂的要求,主要由于上述生物高分子存在以下缺点:(1)降阻性能有限;(2)由于胍胶及其衍生物、纤维素及其衍生物具有少量不溶物极易对地层造成伤害;(3)溶解时间较长。 [0005] Currently, the use of guar gum and derivatives thereof, cellulose and its derivatives as slickwater fracturing improved to some extent on the drag reducing agent injection pump displacement to reduce the frictional resistance (US 5697444 pipeline , US 5271466), but still can not meet the requirements of slickwater fracturing, mainly due to the presence of the biopolymer the following disadvantages: (1) drop resistance performance is limited; (2) due to the guar gum and derivatives thereof, cellulose and easily cause formation damage derivatives having a little insoluble matter; and (3) a long time to dissolve.

[0006] 在减阻水压裂施工中,多采用丙烯酰胺类聚合物(部分水解聚丙烯酰胺)作为减阻水压裂中的减阻剂,很大程度上提高了泵注排量、降低了管线中的摩擦阻力,但作为页岩气藏减阻水压裂的减阻剂使用,存在以下重要缺陷:(1)为了减少压裂过程中的“水敏效应”,抑制页岩中粘土组分的水化膨胀,帮助压裂液的返排减少“水堵”,必须在压裂液中加入部分醇,但部分水解丙烯酰胺及其乳液产品与醇的配伍性较差,极易产生沉淀;(2)部分水解聚丙烯酰胺作为页岩气藏减阻水压裂的减阻剂使用抗滤失性能较差,此种减阻水压裂液极易滤失到地层当中;(3)耐温抗盐性较差,尤其在高矿化度高二价离子含量条件下,分子结构不稳定,降阻效果下降较快;(4)传统的高相对分子质量的丙烯酰胺类聚合物不易降解,容易对极度致密的页岩地层造成永久型伤害。 [0006] In the slickwater fracturing, the use of acrylamide-based polymer (partially hydrolyzed polyacrylamide) slickwater fracturing, as a drag reducing agent, greatly improves the pumping displacement, reduced the frictional resistance of the line, but as shale gas reservoirs slickwater fracturing drag reducing agent, the following important disadvantages: (1) in order to reduce the fracturing process "water sensitive" effect, inhibiting shale clay hydration expansion component to help reduce fracturing fluid flowback "water blocks", must be added the alcohol part in the fracturing fluid, but partially hydrolyzed acrylamide and its compatibility with alcohols poor emulsion products, easy to produce the precipitate; (2) a partially hydrolyzed polyacrylamide shale gas slickwater fracturing fluid loss using an anti-drag reducer performance is poor, such slickwater fracturing fluid loss into the formation which can easily filtered; (3 ) temperature and salt poor, especially under conditions of high content of divalent ions in the high salinity, the molecular structure is unstable, the reduction in resistance decreased rapidly; (4) a conventional high molecular weight acrylamide-based polymer easily degradation, likely to cause permanent damage to the extremely tight shale formations.

[0007] 专利US 20090298721A1公开了一种减阻水压裂液的配方:向1000加仑去离子水中加入0.5加仑丙烯酰胺-Co-丙烯酸共聚物(FR-56™)等阴离子型丙烯酰胺共聚物乳液作为减阻剂,再加入0.15wt%碳酸钠或EDTA-2Na等络合剂,该减阻水压裂液具有优良的降阻性能,室内平均降阻率达到65.0%,对耐盐性(尤其对二价钙离子的耐受性)有了一定程度的改善,但该种减阻水压裂体系作为页岩气减阻水压裂液使用,存在如下问题:(1)与醇的配伍性较差,与甲醇等醇作用极易产生沉淀;(2)抗滤失性能较差,此种减阻水压裂液极易滤失到地层当中;(3)在实际施工中“水敏效应”显著;(4)极易产生“水堵”;(5)耐高速剪切性能差,在高速剪切作用下不稳定,降阻率下降很快;(6)耐温耐盐性较差,尤其在高矿化度高二价离子含量条件下,分子结构不稳定,降阻效果下降较快;(7)不易降解,容 [0007] Patent US 20090298721A1 discloses one kind of formulations slickwater fracturing fluids: to 1000 gallons of deionized water was added 0.5 gallons -Co- acrylamide acrylic acid copolymer (FR-56 ™) and other anionic acrylamide copolymer emulsion as the drag reducing agent, sodium carbonate was added 0.15wt% or complexing agent such as EDTA-2Na, slickwater fracturing fluid which has excellent barrier properties drop, the average indoor rate 65.0% reduction in resistance, salt tolerance (especially tolerance to divalent calcium ions) has been improved to some extent, but such systems as slickwater fracturing shale slickwater fracturing fluid used, the following problems: (1 compatibility) with an alcohol poor effect of an alcohol such as methanol and easy to produce precipitate; poor (2) anti fluid loss properties, such slickwater fracturing fluid loss into the formation which can easily filtered; (3) in actual construction, "effect of water Sensitivity "significant; (4) easy to produce" water blocks "; (5) high shear resistance performance is poor, unstable at high speed shearing action, reducing the resistivity decreases rapidly; (6) temperature poor salt , especially in conditions of high content of divalent ions in the high salinity, the molecular structure is unstable, the reduction in resistance decreased rapidly; (7) easily degradable, Yung 对极度致密的页岩地层造成永久型伤害,污染地层,继而影响油气产量。 Extremely tight shale formations to cause permanent damage, pollution formation, thereby affecting the oil and gas production.

[0008] 与上述部分水解聚丙烯酰胺相比,阳离子型高分子量的丙烯酰胺共聚物作为减阻剂(US 356226,US 3868328)也有报道。 [0008] Compared with the above-described partially hydrolyzed polyacrylamide, a high molecular weight cationic acrylamide copolymers as drag reducing agents (US 356226, US 3868328) have also been reported. US 3868328公开了一种聚合物,该聚合物含有(3-丙烯酰胺基-3-甲基)丁基三甲基氯化铵和/或还原剂,加或不加酸。 US 3868328 discloses a polymer containing a (3-acrylamido-3-methyl) butyl-trimethylammonium chloride and / or a reducing agent, with or without an acid. 此种结构共聚物与醇的配伍性较好,与粘土抑制剂(如KCl)相容性较好,“水敏效应”不显著,不易“水堵”,但是此类降阻剂大分子也不易降解,容易对极度致密的页岩地层造成永久型伤害。 Such a structure of the copolymer compatibility with alcohols preferably, clay inhibitors (e.g., KCl) good compatibility, "water-sensitive" effect is not significant, easily "water blocks", but also macromolecules such reducing agent resistant to degradation, likely to cause permanent damage to the extremely tight shale formations.

[0009] 但是如何进一步提闻减阻剂耐闻速到切性能,提闻压裂液对粘土的抑制性及抗滤失性,提高在高温高盐高剪切条件下的减阻率的稳定性同时具有可降解性能,减少聚合物对地层的伤害,仍是一个亟需解决的问题。 [0009] However, how to further improve the smell DRA smell speed to cut resistance properties, mention smell of clay inhibition and anti fluid loss fracturing fluid, improve the stability of drag reduction at high temperature, high shear conditions of high salt resistance while having biodegradable properties, reduce polymer formation damage, is still an urgent problem.

发明内容 SUMMARY

[0010] 本发明的目的是克服上述现有技术的缺陷,提供一种高分子量、减阻率高、水溶性好、与粘土抑制剂有良好配伍性,具有可降解性,对地层伤害小,而且溶解时间短的丙烯酰胺系共聚物,以及该丙烯酰胺系共聚物的制备方法和应用。 [0010] The object of the present invention is to overcome the above drawbacks of the prior art, to provide a high molecular weight, drag reduction rate, good water solubility, good compatibility clay inhibitors, having biodegradability, less formation damage, and a short time to dissolve acrylamide copolymer, and the preparation and use of acrylamide based copolymer.

[0011] 本发明人经过研究,意外地发现,将可聚合功能性单体通过共聚的方法,引入到含有丙烯酰胺大分子链上,通过控制聚合条件得到高分子量的共聚物,同时可以提高在高温闻盐闻到切条件下的减阻率,提闻与粘土抑制剂的配伍性,减少水敏和水堵现象的发生,具有可降解性,可降低对地层的伤害,从而得到本发明。 [0011] The present inventors study, unexpectedly been found that the polymerizable functional monomer copolymerized by introducing into the macromolecular chain containing acrylamide, a copolymer of high molecular weight by controlling the polymerization conditions can be improved at the same time salt smell smell temperature under cut drag reduction conditions provide compatibility with the clay smell inhibitor, reduce the incidence of water-sensitive and water-blocking phenomenon, having degradability, formation damage can be reduced, whereby the present invention.

[0012] 本发明提供一种丙烯酰胺系共聚物,其中,所述丙烯酰胺系共聚物含有结构单元A、结构单元B、结构单元C和结构单元D,其中,所述结构单元A为式(I)所示的结构单元和/或式(2)所示的结构单元, 所述结构单元B为式(3)、式(4)、式(5)和式(6)所示的结构单元中的至少一种,所述结构单元C为式(7)所示的结构单元和/或式(8)所示的结构单元,所述结构单元D为式(9)所示的结构单元和/或式(10)所示的结构单元;且以所述丙烯酰胺系共聚物中结构单元的总摩尔数为基准,所述结构单元A的含量为5-95摩尔%,所述结构单元B的含量为2.5-90摩尔%,所述结构单元C的含量为0.5-90摩尔%,所述结构单元D的含量为0.0001-1摩尔% ;优选地,所述结构单元A的含量为10-70摩尔%,所述结构单元B的含量为20-50摩尔%,所述结构单元C的含量为5-40摩尔%,所述结构单元D的含量为0.001-0.5摩尔% ; [0012] The present invention provides a copolymer of acrylamide, wherein the acrylamide copolymer comprising structural units A, structural units B, C structural unit and the structural unit D, where the structural unit A of the formula ( the structural unit I in) structural units and / or formula (2), the structural unit B of the formula (3), formula (4), (5) and (6) a structural unit structural unit in at least one structural unit, the structural unit C of formula (7) and / or formula (8), the structural unit D of the formula (9) and structural unit and / or formula (10); and the total number of moles of said acrylamide copolymer of the structural unit as a reference, the content of the structural unit a is from 5 to 95 mol%, the structural unit B an amount of 2.5 to 90 mol%, the content of the structural unit C is 0.5 to 90 mol%, the content of the structural unit D 0.0001 mol%; content preferably, the structural unit a is a 10- 70 mol%, the content of the structural unit B is 20-50 mol%, the content of the structural unit C of 5 to 40 mol%, the content of the structural unit D is 0.001 to 0.5 mol%; 述丙烯酰胺系共聚物的粘均分子量为200万-1800万,优选为400万-1500万; Said acrylamide copolymer viscosity-average molecular weight of 2,000,000 -1,800 million and 15 million preferably 4,000,000;

Figure CN103788293AD00091
Figure CN103788293AD00101

[0018]其中,R1' R4、V 和R4,各自独立地为C1-C4 的亚烷基;R2、R3> R2' R3' R5、R6> R7>R8、R9、Rn、R14、R15、R5,、R6,、R7,、R8,、R9,、Rn,、R14,和R15' 各自独立地为C1-C4 的烷基;R10、R12、R13、Rltl'、R12'和R13'各自独立地为C1-C20的直链或支链亚烷基;M*H、K和Na中的至 [0018] wherein, R1 'R4, V, and R4, are each independently a C1-C4 alkylene group; R2, R3> R2' R3 'R5, R6> R7> R8, R9, Rn, R14, R15, R5 ,, R6,, R7,, R8,, R9,, Rn ,, R14, and R15 'are each independently a C1-C4 alkyl; R10, R12, R13, Rltl', R12 'and R13' are each independently a straight-chain or branched alkylene group of C1-C20; M * H, K and Na is to

少一种为Cl—,Br^, I-,SCN—, At least one of Cl-, Br ^, I-, SCN-,

Figure CN103788293AD00111

[0019] 本发明还提供一种丙烯酰胺系共聚物的制备方法,该制备方法包括,在烯烃的溶液聚合反应条件下,在引发剂存在下,使一种单体混合物在水中进行聚合反应,其中,所述单体混合物含有单体E、单体F、单体G和单体H,所述单体E为式(15)所示的单体和/或式 [0019] The present invention further provides a process for preparing an acrylamide-based copolymer, the method comprising preparing, in the solution polymerization of olefins under reaction conditions, in the presence of an initiator, a monomer mixture of a polymerization reaction in water, wherein said E monomer mixture containing a monomer, a monomer F., monomer and monomer G H, E is a monomer represented by the formula (15) monomers and / or of formula

(16)所示的单体,所述单体F为式(17)、式(18)、式(19)和式(20)所示的单体中的至少一种,所述单体G为式(21)所示的单体和/或式(22)所示的单体,所述单体H为式(23)所示的单体和/或式(24)所示的单体; (16) a monomer, the monomer of formula F (17), formula (18), a monomer of formula (19) and (20) shown in at least one of said monomers G monomer is a monomer represented by the formula (21) and / or formula (22), H is the monomer of formula (23) shown in monomer and / or formula (24) shown in FIG. ;

Figure CN103788293AD00112

[0023] [0023]

Figure CN103788293AD00121

[0024]其中,HR/ 和R/ 各自独立地为C1-C4 的亚烷基;r2、r3、r2,、r3,、r5、r6、r7、r8、R9> Rn、Rh、R15、R5,、R6,、R7,、V、V、Rn'、V 和V 各自独立地为C1-C4 的烷基;R10R12,R13> V、R12'和V各自独立地为C1-C20的直链或支链亚烷基;M为H、K和Na中的至少一种;X_ 为Cl—,Br^, I,SCN—, [0024] wherein, HR / and R / are each independently a C1-C4 alkylene group; r2, r3, r2,, r3,, r5, r6, r7, r8, R9> Rn, Rh, R15, R5, , R6,, R7,, V, V, Rn ', V and V are each independently a C1-C4 alkyl; R10R12, R13> V, R12', and V are each independently a C1-C20 linear or branched alkylene chain; M is H, at least one of K and Na; X_ as Cl-, Br ^, I, SCN-,

Figure CN103788293AD00122

[0025] 此外,本发明还提供一种丙烯酰胺系共聚物的制备方法,该制备方法包括将水相和油相混合形成反相乳液,然后在乳液聚合反应条件下,将该反相乳液与引发剂接触,所述水相为含有单体混合物的水溶液,所述油相含有油和乳化剂,接触的条件使得单体混合物发生聚合反应,其中,所述单体混合物含有单体E、单体F、单体G和单体H,所述单体E为上述式(15)所示的单体和/或式(16)所示的单体,所述单体F为上述式(17)、式(18)、式(19)和式(20)所示的单体中的至少一种,所述单体G为上述式(21)所示的单体和/或式(22)所示的单体,所述单体H为上述式(23)所示的单体和/或式(24)所示的单体。 [0025] Further, the present invention also provides a process for preparing an acrylamide-based copolymer, which method comprises preparing the aqueous and oil phases mixed to form a reverse phase emulsion, and then under the reaction conditions in the emulsion polymerization, inverse emulsion and the contacting an initiator, the aqueous phase is an aqueous solution containing a monomer mixture, condition of the oil phase containing oil and emulsifiers, such that the contact polymerization reaction of the monomer mixture, wherein the monomer mixture comprises a monomer E, single body F, G monomers and monomer H, the E monomer is a monomer represented by the formula (15) and / or formula (16) a monomer represented by the above formula is a monomer F (17 ), formula (18), a monomer of formula (19) and (20) shown in at least one of said monomers G is a monomer represented by the formula (21) and / or formula (22) monomer represented by the H monomer is a monomer represented by the above formula (23) shown in monomer and / or formula (24).

[0026] 另外,本发明还提供了通过上述方法制备得到的丙烯酰胺系共聚物,以及所述丙烯酰胺系共聚物在减阻剂中的应用。 [0026] Further, the present invention provides an acrylamide-based copolymer obtained by the above method was prepared, and applying the acrylamide copolymer in the drag reducing agent.

[0027] 本发明的丙烯酰胺系共聚物具有高的粘均分子量,实施例1-6中制得的共聚物的粘均分子量均可达到400万以上;在水中的不溶物含量仅为0.01重量% ;在浓度为2重量%、4重量%、8重量%、10重量%、12重量%的NaCl或KCl溶液中以及在pH值在2.5-10的条件下,减阻率均可达到60%以上;在2500rpm的剪切速率下,该聚合物在水/醇溶液不产生沉淀,可以完全溶解;在PH值小于2.5的条件下时,该聚合物能降解,对地层的伤害小于10%。 [0027] acrylamide copolymer of the present invention has a high viscosity average molecular weight, viscosity of the obtained copolymer 1-6 embodiment can reach average molecular weight of 4,000,000 or more; insoluble in water content of only 0.01 wt. %; at a concentration of 2 wt%, 4 wt%, 8 wt%, 10 wt%, 12 wt% NaCl or KCl solution, and the pH value at 2.5 to 10, drag reduction can reach 60% above; at a shear rate of 2500rpm, the polymer does not produce a water / alcohol solution was precipitated, can be completely dissolved; under conditions when the PH value of less than 2.5, the polymer can degrade, formation damage is less than 10%. 说明本发明的丙烯酰胺系共聚物在高盐、高剪切条件下仍具有高的减阻率,与压裂液配方中常用的防膨剂(如KC1)、助排剂(如甲醇)有很好的相容性,且对地层低伤害。 DESCRIPTION acrylamide copolymer of the present invention still have high drag reduction at high salt, high shear conditions, fracturing fluid formulations with conventional anti-swelling agent (e.g., The KC1), drainage aids (e.g., methanol) have good compatibility, and low formation damage. 此外,本发明提供的丙烯酰胺系共聚物的两种制备方法(溶液聚合法和反相乳液聚合法)具有简便且单体转化率高的优点。 In addition, both preparations acrylamide-based copolymer of the present invention provides (inverse emulsion polymerization and solution polymerization method) is simple and high monomer conversion advantage.

[0028] 本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。 [0028] Other features and advantages of the present invention will be described in detail in a subsequent portion of the detailed description.

具体实施方式 detailed description

[0029] 以下对本发明的具体实施方式进行详细说明。 [0029] The following detailed description of specific embodiments of the present invention. 应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。 It should be understood that the specific embodiments described herein are only to illustrate and explain the present invention and are not intended to limit the present invention.

[0030](一)丙烯酰胺系共聚物 [0030] (a) acrylamide copolymer

[0031] 本发明提供一种丙烯酰胺系共聚物,其特征在于,所述丙烯酰胺系共聚物含有结构单元A、结构单元B、结构单元C和结构单元D,其中,所述结构单元A为式(I)所示的结构单元和/或式(2)所示的结构单元,所述结构单元B为式(3)、式(4)、式(5)和式(6)所示的结构单元中的至少一种,所述结构单元C为式(7)所示的结构单元和/或式(8)所示的结构单元,所述结构单元D为式(9)所示的结构单元和/或式(10)所示的结构单元;且以所述丙烯酰胺系共聚物中结构单元的总摩尔数为基准,所述结构单元A的含量为5-95摩尔%,所述结构单元B的含量为2.5-90摩尔%,所述结构单元C的含量为0.5-90摩尔%,所述结构单元D的含量为0.0001-1摩尔% ;优选地,所述结构单元A的含量为10-70摩尔%,所述结构单元B的含量为20-50摩尔%,所述结构单元C的含量为5-40摩尔%,所述结构单元D的含量为0.001-0.5摩尔 [0031] The present invention provides an acrylamide copolymer, characterized in that said acrylamide copolymer comprising structural units A, structural units B, C structural unit and the structural unit D, where the structural unit A is a structural unit represented by the formula (I) and / or formula (2) structural units, the structural unit B of formula (3), formula (4), (5) and (6) shown in FIG. structure structural unit at least one structural unit, the structural unit C of the formula (7) and / or formula (8), the structural unit D of the formula (9) shown in FIG. means a structural unit and / or the formula (10); and the total number of moles of said acrylamide copolymer of the structural unit as a reference, the content of the structural unit a is from 5 to 95 mol%, of the structure unit B content is from 2.5 to 90 mol% of the content of the structural unit C is 0.5 to 90 mol%, the content of the structural unit D 0.0001 mol%; content preferably, the structural unit a is 10-70 mol%, the content of the structural unit B is 20-50 mol%, the content of the structural unit C of 5 to 40 mol%, the content of the structural unit D is 0.001 to 0.5 mole % ;更优选地,所述结构单元A的含量为50-70摩尔%,所述结构单元B的含量为20-40摩尔%,所述结构单元C的含量为5-20摩尔%,所述结构单元D的含量为0.005-0.2摩尔% ;所述丙烯酰胺系共聚物的粘均分子量为200万-1800万,优选为400万-1500万; %; More preferably, the content of the structural unit A 50 to 70 mol%, the content of the structural unit B is 20-40 mol%, the content of the structural unit C of 5 to 20 mol%, the content of the structural unit D is 0.005 to 0.2 mol%; viscosity of the acrylamide copolymer of average molecular weight of 2,000,000 -1,800 million and 15 million preferably 4,000,000;

Figure CN103788293AD00131
Figure CN103788293AD00141

[0036] 其中,RJPR/各自独立地为C1-C4的亚烷基,优选为亚甲基;R4和R/各自独立地为C1-C4的亚烷基,优选为亚正丙基,进一步优选为-CH2CH2CH2- ;R2、R3> R2\ R3\ R5> R6>R7、R8、R9、Rn、R14、R15、R5'、R6'、R/、R8'、R9'、Rn'、R14' 和R15' 各自独立地为C1-C4 的烷基,优选为甲基;R1Q和R1Q'各自独立地为C1-C20的直链或支链亚烷基,优选为Cl-ClO的直链或支链亚烷基,更优选为亚甲基;R12、R13、R12'和R13'各自独立地为C1-C20的直链或支链亚烷基,优选为C1-C3的直链或支链亚烷基,更优选为亚乙基,最优选为-CH2CH2- ;M为H、K和 [0036] wherein, RJPR / each independently a C1-C4 alkylene group, preferably methylene; R4 and R / are each independently a C1-C4 alkylene group, preferably n-propylene, more preferably It is -CH2CH2CH2-; R2, R3> R2 \ R3 \ R5> R6> R7, R8, R9, Rn, R14, R15, R5 ', R6', R /, R8 ', R9', Rn ', R14', and R15 'are each independently a C1-C4 alkyl group, preferably methyl; R1q are satisfied and R1Q' are each independently a C1-C20 linear or branched alkylene group, preferably Cl-ClO straight chain or branched chain alkylene group, more preferably a methylene group; R12, R13, R12 'and R13' are each independently a C1-C20 linear or branched alkylene, preferably C1-C3 straight or branched alkylene group, more preferably an ethylene group, and most preferably -CH2CH2-; M is H, K, and

Na中的至少一种,优选为H -X为Cl—, Br—,i, SCN , At least one of Na, H -X is preferably Cl-, Br-, i, SCN,

Figure CN103788293AD00142

优选为Cl—。 Preferably Cl-. [0037] 本发明的发明人在研究中发现,由特定的结构单元A、结构单元B、结构单元C与结构单元D组成的四元聚合物能取得极好的降阻效果。 The inventors of the [0037] present invention is found in the study, a tetrapolymer specific structural units A, structural units B, C and the structural unit consisting of the structural unit D can achieve excellent reduction in resistance.

[0038] 例如,所述结构单元B为式(11)所示的结构单元和/或式(12)所示的结构单元,所述结构单元C为式(13)所示的结构单元,所述结构单元D为式(14)所示的结构单元, The structural unit [0038] For example, the structural unit B is a structural unit represented by the formula (11) and / or formula (12), the structural unit C of formula (13), the D is said structural unit represented by the formula (14) a structural unit,

Figure CN103788293AD00151

[0042] 其中,R1为C1-C4的亚烷基,优选为亚甲基;R4为C1-C4的亚烷基,优选为亚正丙基,进一步优选为-CH2CH2CH2- ;R10为C1-C20的直链或支链亚烷基,优选为C1-C10的直链或支链亚烷基,更优选为亚甲基;R12'和R13'为C1-C20的直链或支链亚烷基,优选为C1-C3的直链或支链亚烷基,更优选为亚乙基,最优选为-CH2CH2-。 [0042] wherein, Rl is a C1-C4 alkylene group, preferably methylene; R4 is a C1-C4 alkylene group, preferably n-propylene, more preferably -CH2CH2CH2-; R10 is C1-C20 a straight-chain or branched alkylene, preferably C1-C10 straight or branched chain alkylene group, more preferably a methylene group; R12 'and R13' is C1-C20 linear or branched alkylene group preferably C1-C3 straight or branched chain alkylene group, more preferably an ethylene group, and most preferably -CH2CH2-.

[0043] 本发明中,所述C1-C4的烷基的实例可以包括但不限于:甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基和叔丁基。 [0043] In the present invention, examples of the C1-C4 alkyl groups may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert butyl.

[0044] 所述亚烷基是指烷烃失去两个氢原子后的残基,所述两个氢原子可以为同一个碳原子上的两个氢原子,也可以不同碳原子上的两个氢原子,可以是直链的,也可以是支链的,例如,所述亚乙基可以是-CH2CH2-或-CH (CH3) _。 [0044] The alkylene group means a residue obtained by loss of two hydrogen atoms, an alkane, the two hydrogen atoms may be two hydrogen atoms on the same carbon atom, two hydrogen may be on different carbon atoms atoms, may be straight chain or may be branched, e.g., the ethylene may be -CH2CH2- or -CH (CH3) _.

[0045] 本发明中,所述亚烷基可以是直链的,也可以是支链的。 [0045] In the present invention, the alkylene group may be linear, it may be branched. 所述C1-C20的直链或支链亚烷基的实例可以包括但不限于:亚甲基、亚乙基、亚正丙基、亚异丙基、亚正丁基、亚仲丁基、亚异丁基、亚叔丁基、亚正戊基、亚异戊基、亚叔戊基、亚新戊基、亚正己基、亚正庚基、亚正辛基、亚正癸基、亚正十二烷基、亚十六烷基和亚二十烷基。 Examples of the C1-C20 linear or branched alkylene group may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butyl, isobutylene, tert-butylene, n-pentylene, ethylene isopentyl, tert-pentyl group alkylene, alkylene neopentyl, ethylene n-hexyl, n-heptyl ethylene, isopropylene, n-octyl, n-decyl alkylene, alkylene n-dodecyl, cetyl Asia and sub-eicosyl.

[0046] (二)溶液聚合法 [0046] (ii) a solution polymerization method

[0047] 本发明还提供一种丙烯酰胺系共聚物的制备方法,该制备方法包括,在烯烃的溶液聚合反应条件下,在引发剂存在下,使一种单体混合物在水中进行聚合反应,其中,所述单体混合物含有单体E、单体F、单体G和单体H,所述单体E为式(15)所示的单体和/或式(16)所示的单体,所述单体F为式(17)、式(18)、式(19)和式(20)所示的单体中的至少一种,所述单体G为式(21)所示的单体和/或式(22)所示的单体,所述单体H为式(23)所示的单体和/或式(24)所示的单体;且以所述单体混合物中单体的总摩尔数为基准,所述单体E的含量为5-95摩尔%,所述单体F的含量为2.5-90摩尔%,所述单体G的含量为 [0047] The present invention further provides a process for preparing an acrylamide-based copolymer, the method comprising preparing, under reaction conditions in the polymerization of olefins in solution, in the presence of an initiator, a monomer mixture of a polymerization reaction in water, wherein said E monomer mixture containing a monomer, a single monomer F., monomer and monomer G H, E is a monomer represented by the formula (15) and / or formula (16) shown in FIG. body, F is the monomer of formula (17), formula (18), a monomer of formula (19) and (20) shown in at least one of said monomers G is of formula (21) shown in FIG. monomer of monomers and / or formula (22) shown in the monomer, the monomer is of formula H (23) as shown and / or formula (24); and at said monomer the total moles of the monomers in the mixture, the content of the monomer E is 5-95 mol%, the content of the monomer is 2.5 to 90 mole% F, G of the content of the monomer

0.5-90摩尔%,所述单体H的含量为0.0001-1摩尔% ;优选地,所述单体E的含量为10-70摩尔%,所述单体F的含量为20-50摩尔%,所述单体G的含量为5-40摩尔%,所述单体H的含量为0.001-0.5摩尔% ;更优选地,所述单体E的含量为50-70摩尔%,所述单体F的含量为20-40摩尔%,所述单体G的含量为5-20摩尔%,所述单体H的含量为0.005-0.2摩尔% ;所述聚合反应的条件使得聚合反应后所得聚合物的粘均分子量为200万-1800万,优选为400 万-1500 万; 0.5 to 90 mol%, a content of the monomer H 0.0001 mol%; preferably, the content of the monomer E is 10-70 mol%, of the monomer content of 20 to 50 mol% F the content of the monomer is 5 to 40 mol% G, H content of the monomer is 0.001 to 0.5 mol%; more preferably, the content of the monomer E is 50-70 mol%, said single body F content of 20 to 40 mol%, the content of the monomer is 5-20 mol% G, H content of the monomer is 0.005 to 0.2 mol%; polymerization conditions such that the resulting polymerization reaction viscosity-average molecular weight of 2,000,000 -1,800 million and 15 million preferably 4,000,000;

[0048] [0048]

Figure CN103788293AD00161
Figure CN103788293AD00171

[0052] 其中,RJPR/各自独立地为C1-C4的亚烷基,优选为亚甲基;R4和R/各自独立地为C1-C4的亚烷基,优选为亚正丙基,进一步优选为-CH2CH2CH2- ;R2、R3> R2\ R3\ R5> R6>R7、R8、R9、Rn、R14、R15、R5'、R6'、R/、R8'、R9'、Rn'、R14' 和R15' 各自独立地为C1-C4 的烷基,优选为甲基;R1Q和R1Q'各自独立地为C1-C20的直链或支链亚烷基,优选为Cl-ClO的直链或支链亚烷基,更优选为亚甲基;R12、R13、R12'和R13'各自独立地为C1-C20的直链或支链亚烷基,优选为C1-C3的直链或支链亚烷基,更优选为亚乙基,最优选为 [0052] wherein, RJPR / each independently a C1-C4 alkylene group, preferably methylene; R4 and R / are each independently a C1-C4 alkylene group, preferably n-propylene, more preferably It is -CH2CH2CH2-; R2, R3> R2 \ R3 \ R5> R6> R7, R8, R9, Rn, R14, R15, R5 ', R6', R /, R8 ', R9', Rn ', R14', and R15 'are each independently a C1-C4 alkyl group, preferably methyl; R1q are satisfied and R1Q' are each independently a C1-C20 linear or branched alkylene group, preferably Cl-ClO straight chain or branched chain alkylene group, more preferably a methylene group; R12, R13, R12 'and R13' are each independently a C1-C20 linear or branched alkylene, preferably C1-C3 straight or branched alkylene group, more preferably an ethylene group, and most preferably

Figure CN103788293AD00172

M为H、K和 M is H, K, and

[0053] 根据本发明,所述聚合反应开始时,所述单体混合物的重量与水和单体混合物的总重量的比例为本领域技术人员所公知的各种比例,所述单体混合物的重量与水和单体混合物的总重量的比例优选为0.05-0.5:1,进一步优选为0.15-0.4:1,最优选为0.2-0.35: [0053] According to the invention, the start of the polymerization reaction, well known to those skilled in the various proportions by weight ratio of the total weight of the monomer mixture and the monomer mixture with the water present, of the monomer mixture the weight ratio of the total weight of the monomer mixture and water is preferably 0.05 to 0.5: 1, more preferably 0.15 to 0.4: 1, most preferably 0.2-0.35:

1 1

[0054] 根据本发明,所述引发剂可以为本领域各种引发剂。 [0054] According to the invention, the initiator may be present various initiators art. 例如,选自偶氮系引发剂和氧化还原系引发剂。 For example, selected from azo initiators and redox based initiators. 以所述单体混合物中单体的总摩尔数为基准,所述偶氮系引发剂的用量为0-10摩尔%,所述氧化还原系引发剂的用量为0-10摩尔%,且所述偶氮系引发剂和氧化还原系引发剂的总用量优选满足:所述引发剂的总用量为单体混合物中单体的总摩尔数的 In total moles of the monomer mixture of the monomers of the azo initiator in an amount of 0-10 mol%, the redox initiator used is 0-10 mol%, and the said azo initiator and a redox agent is the total amount of initiator is preferably satisfied: the total number of initiated monomer mixture is used in an amount of total moles of monomer

0.0001-10 摩尔%。 0.0001 mol%.

[0055] 本发明中,优选地,所述偶氮系引发剂选自偶氮二异丁腈、偶氮二异庚腈、偶氮双甲基戍酸盐、2,2' -偶氮二异丁基脉盐酸盐和2,2' -偶氮二[2-(2-咪唑啉-2-丙烷)-二盐酸盐]中的至少一种,进一步优选为2,2' -偶氮二异丁基脒盐酸盐和2,2' -偶氮二[2-(2-咪唑啉-2-丙烷)-二盐酸盐]中的至少一种。 [0055] In the present invention, preferably the azo initiator selected from azobisisobutyronitrile, azobis iso-heptyl-carbonitrile, azobis methyl Shu acid, 2,2 '- azobis isobutyl pulse hydrochloride and 2,2 '- azobis [2- (2-imidazolin-2-propane) - dihydrochloride] at least one, more preferably 2,2' - even nitrogen diisobutylaluminum hydrochloride and 2,2 '- azobis [2- (2-imidazolin-2-propane) - dihydrochloride] in at least one. 所述氧化还原系引发剂包括氧化剂和还原剂,优选地,所述氧化剂与所述还原剂的摩尔比为0.5-2:1,满足上述比例的条件下,所述氧化剂的用量优选为单体混合物中单体的总摩尔数的0.0001-0.01摩尔%,进一步优选为0.001-0.008摩尔% ;优选情况下,所述氧化剂选自过硫酸铵、过硫酸钾、过硫酸钠和过氧化氢中的至少一种,进一步优选为过硫酸铵、过硫酸钾和过硫酸钠中的至少一种;所述还原剂的用量优选为单体混合物中单体的总摩尔数的0.0001-0.005摩尔%,优选为单体混合物中单体的总摩尔数的0.001-0.004摩尔% ;所述还原剂可以为无机还原剂(助还原剂),优选地,所述无机还原剂选自亚硫酸氢钠、亚硫酸钠、雕白粉、硫代硫酸钠、硫酸亚铁、保险粉、抗坏血酸和脲中的至少一种,进一步优选为亚硫酸氢钠和/或硫代硫酸钠。 The redox initiators include an oxidizing agent and a reducing agent, preferably the oxidizing agent and the reducing agent molar ratio of 0.5-2: 1, under conditions satisfying the above ratio, the oxidizing agent used is preferably a monomer 0.0001 mol% of the total number of moles of monomers in the mixture, more preferably 0.001-0.008 mole%; preferably, the oxidizing agent is selected from ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide in the at least one, more preferably ammonium persulfate, potassium persulfate and sodium least one of; the reducing agent used is preferably from 0.0001 to 0.005 mol% of the total number of moles of monomers in the monomer mixture, preferably 0.001-0.004 mol% of the total moles of monomer in the monomer mixture; the reducing agent may be an inorganic reducing agent (co-reducing agent), preferably, the inorganic reducing agent selected from sodium bisulfite, sodium sulfite, Rongalite, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite, ascorbic acid and at least one of urea, more preferably sodium hydrogen sulfite and / or sodium thiosulfate.

[0056] 在本发明中,需要特别指出地,所述单体H在聚合过程中同时起到扩链剂和有机还原剂的作用,不需要在聚合反应过程中再添加有机还原剂,这可能是因为所述单体H中的双键基团可参与聚合反应的同时,末端的叔胺基团可参与氧化还原引发反应,在末端甲基上产生自由基,继而在端甲基上继续引发单体聚合,形似“架桥”。 [0056] In the present invention, it is necessary to point out, the monomer acts as a chain extender H organic reducing agent and at the same time during the polymerization process, does not need to add the organic reducing agent during the polymerization reaction, which may because the double bond of the monomer H groups can participate in the polymerization reaction, and tertiary amine end groups can participate in a redox reaction initiator, to generate free radicals in the terminal methyl group, then continue on the initiator terminal methyl polymerization of the monomers, the shape of "bridging."

[0057] 另外,本发明提供的丙烯酰胺系共聚物对地层的伤害降低,这可能是由于该聚合物中具有酯羰基,易在酸性条件下发生降解反应。 [0057] Further, an acrylamide-based copolymer of the present invention provides a reduced formation damage, which may be due to the polymer having the ester carbonyl group, prone to degradation under acidic conditions.

[0058] 根据本发明,所述聚合反应还可以在各种助剂存在下进行,所述助剂可以选自螯合剂和/或其他助剂;以所述单体混合物中单体的总摩尔数为基准,所述螯合剂的用量为0-2摩尔%,优选为0.0001-1摩尔%,进一步优选为0.0001-0.05摩尔%,所述其他助剂的用量可以为0-2摩尔%,优选为0.0001-1摩尔%,进一步优选为0.0001-0.2摩尔% ;优选地,所述螯合剂和其他助剂的用量使得:以所述单体混合物中单体的总摩尔数为基准,所述助剂的用量为0.0001-4摩尔%。 [0058] According to the present invention, the polymerization reaction may also be carried out in the presence of various adjuvants, the adjuvant may be selected from a chelating agent and / or other auxiliaries; the total moles of the monomers in the monomer mixture reference number of the chelating agent in an amount of 0-2 mol%, preferably from 0.0001 to 1 mol%, more preferably 0.0001 to 0.05 mol%, the other additives may be used in an amount of 0-2 mol%, preferably 0.0001 to 1 mol%, more preferably 0.0001 to 0.2 mol%; preferably, the amount of the chelating agent and other additives such that: the total number of moles of the monomer mixture of the monomers, the co- used in an amount of 0.0001 mol%.

[0059] 所述螯合剂可以选自乙二胺四乙酸二钠(EDTA)、三乙二胺五乙酸、柠檬酸、柠檬酸盐和聚羟基丙烯酸中的至少一种,进一步优选为EDTA、柠檬酸盐和三乙二胺五乙酸中的一种或多种,所述柠檬酸盐可以为柠檬酸钾、柠檬酸钠、柠檬酸钙和柠檬酸铵等。 [0059] The chelating agents may be selected from disodium ethylenediaminetetraacetate (EDTA), triethylene diamine penta-acetic acid, citric acid, citrates, and acrylic acid polyhydroxy at least one, more preferably EDTA, citric and one or more salts of triethylenediamine pentaacetic acid, the citrate may be as the potassium citrate, sodium citrate, calcium citrate, and ammonium citrate.

[0060] 所述其他助剂可以选自尿素、甲酸钠、异丙醇和次磷酸钠中的至少一种,优选为尿素和/或甲酸钠。 [0060] The other additives may be at least one selected from urea, sodium formate, isopropyl alcohol and sodium hypophosphite is preferably urea and / or sodium formate.

[0061] 本发明的发明人发现,在同时存在上述各种引发剂和助剂的条件下,溶液聚合法能够得到粘均分子量很高的丙烯酰胺系共聚物。 [0061] The present inventors found that, in the simultaneous presence of the aforementioned various conditions and auxiliaries initiators, a solution polymerization method can be obtained a high viscosity average molecular weight acrylamide copolymer.

[0062] 根据本发明,所述聚合反应的条件可以为本领域常规的条件。 [0062] According to the present invention, the polymerization conditions may be conventional in the field conditions. 例如,所述聚合反应在惰性气体存在下进行,所述聚合`反应条件可以包括:温度为0-80°C,时间为1-24小时,pH值为5-13 ;优选情况下,温度为4-60°C,时间为4-36小时,pH值为5_9,所述pH值通过加入酸或碱进行调节,所述酸优选为无机酸,所述无机酸优选为盐酸、硫酸、磺酸、硝酸和磷酸中的至少一种;所述碱可以是无机碱或有机胺类化合物,如可以选自氢氧化钠、氢氧化钾、氨水、甲胺、乙胺、乙醇胺和三乙醇胺中的至少一种,优选为氢氧化钠。 For example, the polymerization reaction is carried out in the presence of an inert gas, the polymerization reaction conditions may `comprising: a temperature of 0-80 ° C, time 1 to 24 hours, pH = 5-13; Preferably, the temperature is 4-60 ° C, time is 4-36 hours, pH = 5_9, said pH is adjusted by adding an acid or a base, the acid is preferably an inorganic acid, the inorganic acid preferably hydrochloric acid, sulfuric acid, sulfonic acid , nitric acid, phosphoric acid, and at least one of; the base can be an inorganic base or an organic amine compound, as can be selected from sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, ethanolamine and triethanolamine, at least one, preferably sodium hydroxide.

[0063] 本发明的发明人在研究中发现,采取下述条件能够进一步提高聚合物的分子量:即,优选地,所述聚合反应包括依次进行的三个阶段:第一阶段的反应条件包括:温度为 [0063] The inventors of the present invention found in the study, the following conditions take molecular weight polymers can be further improved: That is, preferably, the three stages of the polymerization reaction comprises successively: the reaction conditions of the first stage comprises: temperature

0-10°C,优选为4-10°C,时间为1-15小时,优选为3-10小时;第二阶段的反应条件包括:温度为15-30°C,优选为20-30°C,时间为3_8小时,优选为3_5小时;第三阶段的反应条件包括:温度为35-60°C,优选为45-55°C,时间为2_14小时,优选为2_12小时。 0-10 ° C, preferably 4-10 ° C, to 15 hours, preferably 10 hours; the second stage reaction conditions comprise: a temperature of 15-30 ° C, preferably 20-30 ° C, time is 3_8 hours, preferably 3_5 hours; the reaction conditions of the third stage comprising: a temperature of 35-60 ° C, preferably 45-55 ° C, 2_14 time hours, preferably 2_12 hours.

[0064] 此外,本发明的发明人在研究中发现,当选择特定的单体F、单体G与单体H进行反应时,能够进一步提高所得的聚合物的降阻效果。 [0064] Further, the present inventors found that in the study, when selecting a specific monomer F., G monomer is reacted with the monomer H, can be further improved reduction in resistance of the resulting polymer. 例如,优选地,所述单体F为式(25)所示的单体和/或式(26)所示的单体,所述单体G为式(27)所示的单体,所述单体H为式(28)所示的单体, For example, the monomer preferably, F is the monomer represented by the formula (25) and / or formula (26), G is the monomer of formula (27) shown in the monomer, the said monomer represented by formula (28) H is a monomer of formula,

Figure CN103788293AD00191

[0067] 其中,R1为C1-C4的亚烷基,优选为亚甲基;R4为C1-C4的亚烷基,优选为亚正丙基,进一步优选为-CH2CH2CH2- ;R10为C1-C20的直链或支链亚烷基,优选为C1-C10的直链或支链亚烷基,更优选为亚甲基;R12'和R13'为C1-C20的直链或支链亚烷基,优选为C1-C3的直链或支链亚烷基,更优选为亚乙基,最优选为-CH2CH2-。 [0067] wherein, Rl is a C1-C4 alkylene group, preferably methylene; R4 is a C1-C4 alkylene group, preferably n-propylene, more preferably -CH2CH2CH2-; R10 is C1-C20 a straight-chain or branched alkylene, preferably C1-C10 straight or branched chain alkylene group, more preferably a methylene group; R12 'and R13' is C1-C20 linear or branched alkylene group preferably C1-C3 straight or branched chain alkylene group, more preferably an ethylene group, and most preferably -CH2CH2-.

[0068](三)反相乳液聚合法 [0068] (c) Inverse Emulsion

[0069] 此外,本发明还提供一种丙烯酰胺系共聚物的制备方法,该制备方法包括将水相和油相混合形成反相乳液,然后在乳液聚合反应条件下,将该反相乳液与引发剂接触,所述水相为含有单体混合物的水溶液,所述油相含有油和乳化剂,接触的条件使得单体混合物发生聚合反应,其中,所述单体混合物含有单体E、单体F、单体G和单体H,所述单体E为式 [0069] Further, the present invention also provides a process for preparing an acrylamide-based copolymer, which method comprises preparing the aqueous and oil phases mixed to form a reverse phase emulsion, and then under the reaction conditions in the emulsion polymerization, inverse emulsion and the contacting an initiator, the aqueous phase is an aqueous solution containing a monomer mixture, condition of the oil phase containing oil and emulsifiers, such that the contact polymerization reaction of the monomer mixture, wherein the monomer mixture comprises a monomer E, single body F, G monomers and monomer H, E is the monomer of formula

(15)所示的单体和/或式(16)所示的单体,所述单体F为式(17)、式(18)、式(19)和式(20)所示的单体中的至少一种,所述单体G为式(21)所示的单体和/或式(22)所示的单体,所述单体H为式(23)所示的单体和/或式(24)所示的单体;且以所述单体混合物中单体的总摩尔数为基准,所述单体E的含量为5-95摩尔%,所述单体F的含量为2.5-90摩尔%,所述单体G的含量为0.5-90摩尔%,所述单体H的含量为0.0001-1摩尔% ;优选地,所述单体E的含量为10-70摩尔%,所述单体F的含量为20-50摩尔%,所述单体G的含量为5_40摩尔%,所述单体H的含量为0.001-0.5摩尔% ;更优选地,所述单体E的含量为50-70摩尔%,所述单体F的含量为20-40摩尔%,所述单体G的含量为5-20摩尔%,所述单体H的含量为0.005-0.2摩尔% ;所述聚合反应的条件使得聚合反应后所得聚合物的粘均分子量为200万-1800万,优选为400万-15 (15) monomers and / or formula (16) shown in the monomer, the monomer of formula F (17), formula (18), a single formula (19) and (20) shown in FIG. monomer body in at least one of said monomers G is represented by the formula (21) and / or formula (22), H is the monomer of formula (23) a monomer represented by and / or formula (24) shown in the monomer; and the total moles of the monomer mixture of the monomers, of the monomer content of 5 to 95 mol% of E, F is the monomer content of 2.5 to 90 mol%, the content of the monomer is 0.5 to 90 mol% G, H of the monomer content of from 0.0001 mol%; preferably, the content of the monomer E is 10-70 mol% of the monomer content of 20 to 50 mole% of F, G of the content of the monomer 5_40 mol% of the monomer content of H is from 0.001 to 0.5 mol%; more preferably, said single E content of the body is 50-70 mol%, of the monomer content of 20 to 40 mole% F, G of the monomer content of 5 to 20 mol%, the content of the monomer is 0.005 to 0.2 H mol%; polymerization conditions such that the viscosity of the resulting polymer after polymerization average molecular weight of 2,000,000 -1,800 million and preferably 400 000 -15 00万。 000,000.

[0070] 式(15)-式(24)所示单体的阐述及优选情况与前文描述相同,在此不再赘述。 Preferably shown and described with the foregoing monomers described formula (24) the same, are not repeated here - [0070] Formula (15).

[0071] 根据本发明,所述水相为含有单体混合物的水溶液。 [0071] According to the invention, the aqueous phase is an aqueous solution containing the monomer mixture. 所述单体混合物的重量与水和单体混合物的总重量的比例的阐述及优选情况与前文描述相同,此处不做赘述。 Preferably forth and water and the weight ratio of the total weight of the monomer mixture of the monomer mixture of the same with the foregoing description, it is not repeated here.

[0072] 根据本发明,对所述水相和油相的重量比例没有特别的限制,只要使所述水相与油相充分混合形成反相乳液即可,优选情况下,所述水相和油相的重量比例可以为1: [0072] According to the present invention, there is no particular limitation on the weight ratio of the aqueous phase and oil phase, the aqueous phase as long as the mixed oil phase inverse emulsion can be formed, preferably the case, and the aqueous phase oil phase weight ratio may be 1:

0.1-2,进一步优选为1:0.3-0.8。 0.1-2, more preferably 1: 0.3-0.8.

[0073] 根据本发明,所述油可以为本领域各种用于乳液聚合的与水互不相容的非极性或极性小的有机溶剂,例如可以为甲苯、二甲苯、己烷、环己烷、正庚烷、异构石蜡、异构烷烃、汽油、煤油和白油中的至少一种,优选情况下,所述油选自甲苯、二甲苯、正庚烷、异构烷烃、环己烷和煤油中的至少一种。 Incompatible with water or non-polar organic solvent less polar [0073] According to the present invention, the oil may be used in various emulsion polymerization art, for example, toluene, xylene, hexane, cyclohexane, n-heptane, isomerized paraffins, isoparaffins, gasoline, kerosene, white oil, and at least one, preferably, said oil is selected from toluene, xylene, n-heptane, isoparaffins, at least one of cyclohexane and kerosene.

[0074] 根据本发明,所述油相含有油和乳化剂。 [0074] According to the present invention, the oil phase containing oil and emulsifiers. 对所述油的用量没有特别的要求,可以在较宽的范围内变动,只要所述油与乳化剂混合形成油相即可,优选情况下,以所述乳液的总重量为基准,所述油的用量可以为10-60重量%,进一步优选为20-35重量%。 The amount of oil is not particularly required, may vary within a wide range, so long as the oil and emulsifier to form an oil phase, Preferably, the total weight of the emulsion as a reference, the oil the amount may be 10 to 60 wt%, more preferably 20-35 wt%.

[0075] 根据本发明,所述乳化剂可以为本领域各种用于乳液聚合的非离子型乳化剂,例如可以为失水山梨醇脂肪酸酯、烷基酚聚氧乙烯醚、异构醇聚氧乙烯醚、月桂醇聚氧乙烯醚、丙二醇脂肪酸酯、月桂醇聚醚、苄基酚氧聚氧乙烯醚、苯乙基酚聚氧乙烯醚、聚氧乙烯失水山梨醇脂肪酸脂、失水山梨醇脂肪酸酯环氧乙烷加成物、苄基二甲基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚和脂肪胺聚氧乙烯醚中的至少一种,优选情况下,所述乳化剂选自失水山梨醇脂肪酸酯、聚氧乙烯失水山梨醇脂肪酸脂、壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚、苄基酚氧聚氧乙烯醚、苯乙基酚聚氧乙烯醚、异构十三醇聚氧乙烯醚、月桂醇聚氧乙烯醚和苄基二甲基酚聚氧乙烯醚中的至少一种,进一步优选为由上述两种或两种以上的乳化剂组成的亲水亲油平衡值为5-9的复合乳化剂,例如 [0075] According to the invention, the emulsifying agent may be used art various non-ionic emulsion polymerization, for example, as sorbitan fatty acid esters, polyoxyethylene alkylphenol ether, isomeric alcohols polyoxyethylene ethers, polyoxyethylene lauryl alcohol ether, propylene glycol fatty acid esters, laureth, benzyl phenoxy polyoxyethylene ether, phenethyl phenol polyoxyethylene ethers, polyoxyethylene sorbitan fatty acid ester, of at least one, preferably the sorbitan fatty acid ester ethylene oxide adduct, benzyl dimethyl phenol polyoxyethylene ethers, polyoxyethylene ethers of fatty alcohols and polyoxyethylene fatty amine polyglycol ether, the said emulsifier is selected from sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, benzyl phenoxy polyoxyethylene ethers, acetophenone phenol polyoxyethylene ether, iso-tridecyl alcohol polyoxyethylene ether, polyoxyethylene lauryl ether and benzyl dimethyl phenol polyoxyethylene ether of at least one, more preferably a combination of two or above more emulsifiers hydrophilic-lipophilic balance value of the emulsifier 5-9, e.g. 可以为失水山梨醇脂肪酸酯和壬基酚聚氧乙烯醚。 It may be a sorbitan fatty acid ester, and polyoxyethylene nonylphenyl ether.

[0076] 根据本发明,对所述乳化剂的用量没有特别地限定,可以在较宽的范围内变动,只要所述乳化剂与油混合形成油相即可`,优选情况下,以所述乳液的总重量为基准,所述乳化剂的用量可以为1-10重量%,进一步优选为2-9重量%。 [0076] According to the present invention, an amount of the emulsifier is not particularly limited, and may vary within a wide range, so long as the emulsifier mixed with the oil to form an oil phase `Preferably, to the emulsion the total weight of the emulsifier may be used in an amount of 1 to 10 wt%, more preferably 2-9 wt%.

[0077] 根据本发明,所述引发剂可以为本领域中各种引发剂,所述引发剂的阐述及优选情况与前文描述相同,此处不再赘述。 [0077] According to the invention, the initiator may be present in a variety of art initiators, the initiator and forth Preferably the agent is the same as the foregoing description is not repeated here.

[0078] 本发明中,优选情况下,可先将偶氮系引发剂加入水相,再与油相混合形成反相乳液,然后将反相乳液与氧化还原系引发剂接触,通过氧化还原引发剂引发聚合反应。 [0078] In the present invention, preferably, the first azo initiator may be added to the aqueous phase, and then mixed with the oil phase inverse emulsion is formed, and then the inverse emulsion and redox initiator contacting through redox initiator polymerization initiator.

[0079] 根据本发明,所述聚合反应还可以在各种助剂存在下进行,所述助剂可以选自螯合剂和/或其他助剂,所述助剂的阐述及优选情况与前文描述相同,在此处不再赘述。 [0079] According to the present invention, the polymerization reaction may also be carried out in the presence of various adjuvants, the adjuvants may be and / or other additives selected from chelating agents, and set forth the preferred case with the aid of the foregoing description same, not repeat them here.

[0080] 根据本发明中,对所述螯合剂的加料时机没有特别的要求,只要使螯合剂与金属离子发生螯合作用以使对共聚物起到稳定化作用即可,可以选择在水相加入或者在油相中加入,优选情况下,为了使螯合剂更充分的发挥稳定作用,可以选择在水相中加入螯合剂。 [0080] According to the present invention, there is no particular restriction on the addition timing of the chelating agent, as long as the chelating agent and metal ion chelation occurs to make copolymers can play a stabilizing effect may be selected in the aqueous phase was added in the oil phase was added or, preferably, the chelating agent to more fully stabilizing role, the option to add a chelating agent in the aqueous phase. [0081 ] 根据本发明,所述螯合剂的阐述及优选情况与前文描述相同,此处不再赘述。 [0081] According to the present invention, preferably where the chelating agent and forth with the same foregoing description is not repeated here.

[0082] 同样,本发明的发明人在研究中发现,采取下述条件能够进一步提高聚合物的分子量:即,优选地,所述聚合反应包括依次进行的两个阶段:第一阶段的反应条件包括:温度为0-20°C,优选为5-10°C,时间为1-15小时,优选为1_5小时;第二阶段的反应条件包括:温度为20-60°C,优选为25-55°C,时间为2_8小时,优选为2_5小时。 [0082] Similarly, the present inventors found that in the study, the following conditions take molecular weight polymers can be further improved: That is, preferably, the polymerization reaction comprises two stages carried out sequentially: the first stage reaction conditions comprising: a temperature of 0-20 ° C, preferably 5-10 ° C, to 15 hours, preferably 1_5 hours; the second stage reaction conditions comprise: a temperature of 20-60 ° C, preferably 25 55 ° C, time 2_8 hours, preferably 2_5 hours.

[0083] 根据本发明,该方法还包括在所述聚合反应后将所述聚合反应所得产物与转相剂接触。 [0083] According to the invention, the method further comprising the resultant reaction product into contact with a phase inversion agent in the polymerization reaction after the polymerization. 所述转相剂可以为本领域用于乳液聚合的各种转相剂,只要使所述聚合反应所得产物在压裂液应用中快速在水中溶解即可,例如可以为聚氧乙烯失水山梨醇脂肪酸酯、壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚、苄基酚聚氧乙烯醚、苯乙基酚聚氧乙烯醚、异构十醇聚氧乙烯醚、异构十一醇聚氧乙烯醚、异构十三醇聚氧乙烯醚和脂肪胺聚氧乙烯醚的非离子型乳化剂中的至少一种,优选情况下,所述转相剂选自聚氧乙烯失水山梨醇脂肪酸脂、异构十醇聚氧乙烯醚、异构十一醇聚氧乙烯醚、异构十三醇聚氧乙烯醚、壬基酚聚氧乙烯醚和辛基酚聚氧乙烯醚中的至少一种。 The phase transfer agent may be present a variety of phase-transfer agent for the emulsion polymerization art, so long as the polymerization reaction the resulting product can be quickly dissolved in water in the fracturing fluid applications, for example, polyoxyethylene sorbitan poly alcohol fatty acid esters, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, benzyl phenol polyoxyethylene ether, phenethyl phenol polyoxyethylene ether, isomeric ten alcohol polyoxyethylene ether, isomers ten a polyoxyethylene ether alcohol, iso-tridecyl alcohol polyoxyethylene ethers and polyoxyethylene fatty amine polyglycol ether nonionic emulsifier is at least one, preferably, the phase transfer agent is selected from polyoxyethylene loss sorbitan fatty acid ester, isomeric ten alcohol polyoxyethylene ether, isomeric undecyl alcohol polyoxyethylene ether, iso-tridecyl alcohol polyoxyethylene ether, polyoxyethylene nonylphenol ether and polyoxyethylene octylphenol ether at least one.

[0084] 根据本发明,对所述转相剂的用量没有特别的要求,只要可以使所述聚合反应所得产物在压裂液应用中快速在水中溶解即可,所述转相剂的用量使得:以所述乳液的总重量为基准,所述转相剂的用量可以为0.5-10重量%,优选为1-4重量%。 [0084] According to the present invention, no special requirements for the amount of phase transfer agent, the polymerization reaction may be as long as the resulting product can be quickly dissolved in water in the fracturing fluid applications, the phase transfer agent in an amount such that : based on the total weight of the emulsion as a reference, the phase transfer agent may be used in an amount of 0.5 to 10 wt%, preferably 1-4 wt%.

[0085] 此外,本发明的发明人在研究中发现,当选择特定的单体F、单体G与单体H进行反应时,能够进一步提高所得的聚合物的降阻效果。 [0085] Further, the present inventors found that in the study, when selecting a specific monomer F., G monomer is reacted with the monomer H, can be further improved reduction in resistance of the resulting polymer. 例如,优选地,所述单体F为式(25)所示的单体和/或式(26)所示的单体,所述单体G为式(27)所示的单体,所述单体H为式(28)所示的单体,式(25)-式(28)所示单体的阐述及优选情况与前文描述相同,在此不再赘述。 For example, the monomer preferably, F is the monomer represented by the formula (25) and / or formula (26), G is the monomer of formula (27) shown in the monomer, the H is said monomer of formula (28) a monomer represented by the formula (25) - (28) described and illustrated in the foregoing description preferred case where the same monomer, are not repeated here.

[0086] 本发明还提供了根据上述两种方法制得的丙烯酰胺系共聚物。 [0086] The present invention further provides an acrylamide-based copolymer prepared by the above two methods in accordance with.

[0087] 此外,本发明还提供了所述丙烯酰胺系共聚物在减阻剂中的应用。 [0087] Further, the present invention also provides the use of the acrylamide copolymer in the drag reducing agent. 采用本发明提供的所述丙烯酰胺系共聚物作为压裂液减阻剂,可以获得高而稳定的减阻率,具体的应用方法为本领域技术人员所熟知的技术。 Employing the acrylamide copolymer of the present invention provides a fracturing fluid drag reducing agent, a high and stable rate of drag reduction, the specific application methods well known to those skilled in the art.

[0088] 以下通过实施例对本发明的具体实施方式进行详细说明。 [0088] The following detailed description of specific embodiments of the invention by way of example. 应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。 It should be understood that the specific embodiments described herein are only to illustrate and explain the present invention and are not intended to limit the present invention.

[0089] 特性粘数[η]根据GB12005.1-89聚丙烯酰胺特性粘数测定方法进行测定;粘均分子量按照公式Mv ([!^/。^,其中!^*』※^)—3,α =0.80进行计算;溶解时间按GB12500.8-89进行测定,(样品质量均按样品内纯聚合物质量计),测得的粉末状样品溶解时间均小于20min,乳液样品溶解时`间均小于5min ;分子结构及结构单元的组成采用IR光谱和13C-NMR测定;水不溶物含量按SY/T 5862-1993测定;室内减阻率按SY/T 6376-2008测定;降阻剂对岩心的伤害性按石油天然气行业标准SY/T 5107-2005《水基压裂液性能评价方法》中压裂液滤液对岩心基质渗透率损害实验进行。 [0089] The intrinsic viscosity [[eta]] was measured according to the method GB12005.1-89 polyacrylamide intrinsic viscosity measured; viscosity-average molecular weight according to the equation Mv - 3 ([^ / ^, ^ * where "※ ^!.!) , α = 0.80 is calculated; dissolution time was measured by the GB12500.8-89, (pure polymer mass of the sample within the sample are by mass), powdery sample was measured dissolution time is less than 20min, an emulsion sample was dissolved between ` less than 5min; composition using 13C-NMR and IR spectrum to determine the molecular structure and the structural unit; water insoluble matter by SY / T 5862-1993 measurement; drag reduction rate measured by the indoor SY / T 6376-2008; reducing agent for noxious cores by oil and gas industry standard SY / T 5107-2005 "water-based fracturing fluid performance evaluation method" in the fracturing fluid filtrate matrix permeability of core damage experiments.

[0090] 下述实施例中式(29)所示的单体Ml和式(33)所示的单体M3均购自Sigma-Aldrich公司,除此之外,除非特殊说明,实施例、对比例和测试例中用到的聚合物和试剂等均均为市售品。 Example M3 monomers of formula [0090] The following examples (29) and a monomer represented by the formula Ml formula (33) were purchased from Sigma-Aldrich Corporation, in addition, unless otherwise noted, embodiments, Comparative and polymers and reagents used in test Example etc. are commercially available products.

[0091] 实施例1 [0091] Example 1

[0092] 本实施例用于说明本发明提供的溶液聚合法制备丙烯酰胺系共聚物。 [0092] The present embodiment used in the solution polymerization of acrylamide-based copolymer of the present invention is provided to illustrate the preparation.

[0093] 室温下,将36.8g的丙烯酰胺(AM)、37.6g的式(29)所示的单体Ml、5.98g的双丙酮丙烯酰胺和0.41g的式(30)所示的M2单体(根据文献MacromolecularBioscience, 2006,6 (7),540-554的方法制得,以下相同)加入到反应瓶中,加入去离子水149.28g,搅拌使单体完全溶解,并搅拌均匀。 [0093] At room temperature, 36.8g acrylamide (AM), 37.6g of formula (29) a monomer represented by Ml, 5.98g diacetone acrylamide and 0.41g of formula (30) shown M2 single body (literature MacromolecularBioscience, 2006,6 (7), 540-554 obtained by the method, the same applies hereinafter) was added to the reaction flask, deionized water was added 149.28g, stirred to completely dissolve the monomer, and stir. 分别向烧瓶中加入I重量%的EDTA水溶液17.94g,I重量%2,2'-偶氮二异丁基脒盐酸盐水溶液2.lg,尿素0.12g,充分搅拌使其混合均匀。 I were added to the flask wt% aqueous EDTA 17.94g, I wt% of 2,2'-azobis isobutyl amidine hydrochloride solution 2.lg, urea 0.12g, sufficiently stirred to mix uniformly. 用I重量%的氢氧化钠溶液pH至7.5,加入0.5重量%亚硫酸氢钠溶液0.62g,控制体系初始温度至4°C,通氮气除氧30分钟后,加入I重量%过硫酸铵水溶液0.62g,并继续通氮除氧20分钟。 With I wt% sodium hydroxide solution to the pH 7.5, 0.5% by weight solution of 0.62 g of sodium hydrogen sulfite, the initial temperature control system to 4 ° C, deoxygenated nitrogen for 30 minutes, was added I wt% aqueous ammonium persulfate solution 0.62g, nitrogen and oxygen was continuously for 20 minutes. 将反应器密闭,保持在4°C,反应8小时后,将温度升至20°C后反应5小时,然后将温度升至50°C反应2小时,将得到的胶状产物取出,经造粒、干燥、粉碎即可获得高分子量丙烯酰胺系共聚物Pl。 The reactor was sealed and kept at 4 ° C, the reaction for 8 hours, the temperature was raised to 20 ° C after the reaction for 5 hours, and then the temperature was raised to 50 ° C for 2 hours, the resulting gum product is removed by making granulated, dried, pulverized to obtain a high molecular weight acrylamide copolymer Pl.

[0094] 对Pl进行IR光谱测定,IR光谱中,1660CHT1和1635CHT1处分别出现归属于酰胺基的酰胺I带吸收峰(C=O伸缩振动)和酰胺II带吸收峰(NH弯曲振动),在1546cm—1、1449cm_\l364cm_1处出现双丙酮丙烯酰胺C=O吸收峰,在1430CHT1处出现CN的伸缩振动吸收峰,1729cm-1出现了M2单体酯羰基的特征伸缩振动峰,1356和HOlcnT1出现典型的甲基对称弯曲振动吸收峰,2792cm—1为季铵基的甲基CH不对称伸缩振动吸收峰。 [0094] The Pl subjected to IR spectroscopy, IR spectroscopy, 1660CHT1 and at 1635CHT1 amide I appear attributable to an amide group, respectively, with absorption peaks (C = O stretching vibration) and the amide II band absorption peak (NH bending vibration), in 1546cm-1,1449cm_ \ l364cm_1 diacetone acrylamide occurs at C = O absorption peak appears CN stretching vibration absorption peak at 1430CHT1, 1729cm-1 peak vibration occurred M2 monomer wherein the ester carbonyl stretch, 1356 and appear HOlcnT1 typical methyl symmetric bending vibration absorption peaks, 2792cm-1-yl methyl CH quaternary ammonium asymmetric stretching vibration absorption peaks. 可以确定得到的共聚物分子具有式(31)所示的结构,通过黏度法测得其粘均分子量Mv为800万,单体转化率为99.9%以上。 The resulting copolymer may determine the molecular structure shown in formula (31), as measured by obtaining the viscosity viscosity average molecular weight Mv of 8,000,000, a monomer conversion of more than 99.9%. 其中,式(31)以及XpXyypyyZpZ2和u仅表示出结构单元的类型和数目,而不表示结构单元的连接方式。 Wherein, the formula (31) and the type and the number shows only a structural unit XpXyypyyZpZ2 and u, without showing connection structural units. χ。 χ. X2> Yi> y2> Z1^ Z2和u的具体数值由投料量确定,分子结构式和结构单元的组成采用定量13C谱测定,得到(Xl+X2): (yi+y2): (Zl+Z2):u=l: X2> Yi> y2> Z1 ^ Z2 and specific values ​​of u is determined by the feeding amount, the constituent molecules of the formula and the structural unit of the quantitative 13C spectroscopy, to give (Xl + X2): (yi + y2): (Zl + Z2) : u = l:

0.38:0.07:0.003。 0.38: 0.07: 0.003.

Figure CN103788293AD00221

[0096] 对比例I [0096] Comparative Example I

[0097] 按照实施例1的方法制备丙烯酰胺系共聚物,不同的是,不加入双丙酮丙烯酰胺和M2单体,从而得到共聚物DP1,测得其粘均分子量Mv为1010万。 [0097] acrylamide copolymer prepared as in Example 1, except that, without the addition of diacetone acrylamide monomer and M2 to obtain a copolymer DP1, obtaining the measured viscosity average molecular weight Mv of 10.1 million.

[0098] 对比例2 [0098] Comparative Example 2

[0099] 按照实施例1的方法制备丙烯酰胺系共聚物,不同的是,将丙烯酰胺与相同摩尔数的(3-丙烯酰胺基-3-甲基)丁基三甲基氯化铵进行聚合反应,从而得到二元共聚物DP2,测得其粘均分子量Mv为1180万。 [0099] acrylamide copolymer prepared as in Example 1, except that the acrylamide and the same number of moles of (3-acrylamido-3-methyl) butyl-trimethylammonium chloride is polymerized reaction, thereby obtaining a binary copolymer DP2 is, obtaining the measured viscosity average molecular weight Mv of 11.8 million.

Figure CN103788293AD00231

[0101] 实施例2 [0101] Example 2

[0102] 本实施例用于说明本发明提供的溶液聚合法制备丙烯酰胺系共聚物。 [0102] The present embodiment used in the solution polymerization of acrylamide-based copolymer of the present invention is provided to illustrate the preparation.

[0103] 室温下,将38.60g的甲基丙烯酰胺、74.07g的式(29)所示的单体Ml、15.6g的双丙酮丙烯酰胺和0.01g的式(30)所示的M2单体加到聚合瓶中,加入346.8g去离子水,搅拌使单体完全溶解。 The [0103] room temperature, 38.60g of methacrylamide, Ml monomer represented by the formula (29) 74.07g of diacetone acrylamide, and 15.6g of Formula (30) 0.01g of monomer M2 It was added to the polymerization flask, 346.8g deionized water and stirred to completely dissolve the monomers. 分别向烧瓶中加入0.1重量%的柠檬酸钠水溶液0.24g,加入I重量%2.2' -偶氮二异丁基脒盐酸盐水溶液2.13g,加入尿素0.08g,充分搅拌使其混合均匀。 To the flask were added 0.1 wt% aqueous solution of sodium citrate 0.24g, was added 2.2% by weight of I '- azobis isobutyl amidine hydrochloride solution 2.13g, urea was added 0.08g, sufficiently stirred to mix uniformly. 用I重量%的氢氧化钠溶液pH至8,加入0.1重量%亚硫酸氢钠溶液2.53g,控制体系初始温度至10°C,通氮气除氧30分钟后,加入1%过硫酸铵水溶液Ig并继续通氮除氧10分钟。 With I wt% sodium hydroxide solution to pH 8, was added 0.1% by weight solution of 2.53 g of sodium hydrogen sulfite, the initial temperature control system to 10 ° C, deoxygenated nitrogen for 30 minutes, a 1% aqueous ammonium persulfate solution was added Ig oxygen and nitrogen was continuously for 10 minutes. 将反应器密闭,保持在10°C,反应3小时后,升温至30°C,反应3小时后,升温至55°C反应7小时,将得到的胶状产物取出,经造粒、干燥、粉碎即可获得高分子量的丙烯酰胺系共聚物P2。 The reactor was sealed and maintained at 10 ° C, after the reaction for 3 hours, warmed to 30 ° C, after 3 hours, the reaction was warmed to 55 ° C for 7 hours and the resulting gum product is removed, granulated, dried, pulverized to obtain a high molecular weight acrylamide copolymer P2.

[0104] 对P2进行IR光谱测定,IR光谱中1660(^1和1635(^1处分别出现归属于酰胺基的酰胺I带吸收峰(C=O伸缩振动)和酰胺II带吸收峰(NH弯曲振动),在1546cm—1、1449cm_\l364cm_1处出现双丙酮丙烯酰胺C=O吸收峰,在1430CHT1处出现CN的伸缩振动吸收峰,1729CHT1出现了M2单体酯羰基的特征伸缩振动峰,2923,28520^1处出峰分别归属于-CH2-、-CH3的CH伸缩振动,2792cm—1为季铵基的甲基CH不对称伸缩振动吸收峰。1467cm—1出峰归属于-CH2-、-CH3的CH弯曲振动。可以确定得到的共聚物分子具有式(32)所示的结构,通过黏度法测得其粘均分子量Mv为1320万,单体转化率为99.9%以上。其中,式(32)以及Xp x2、Y1^ y2、Z1^ Z2和u仅表示出结构单元的类型和数目,而不表示结构单元的连接方式。Xp X2> Yi> y2> Z1^ z2和u的具体数值由投料量确定,分子结构式和结构单元的组成采用定量13C 谱测定,得到(Xl+X2): (yi+y2): (Zl+Z2 [0104] The P2 spectrometric IR, IR spectrum 1660 (^ 1 and 1635 (the ^ 1 attributable to amide group of the amide I band absorption peak (C = O stretching vibration) and the amide II band absorption peak appeared (NH bending vibration), in \ l364cm_1 appears at 1546cm-1,1449cm_ diacetone acrylamide, C = O absorption peak appears CN stretching vibration absorption peak at 1430CHT1, 1729CHT1 vibration peaks appeared M2 monomer wherein the ester carbonyl stretch, 2923 , a peak at 28520 ^ are attributed to -CH2 -, - CH stretching vibration of CH3, 2792cm-1-methyl quaternary ammonium group of the asymmetric stretching vibration of CH .1467cm-1 absorption peak attributable to -CH2 -, - CH3 the CH bending vibration may be determined to obtain a copolymer having the molecular structure represented by the formula (32), as measured by obtaining the viscosity viscosity average molecular weight Mv of 13,200,000, a monomer conversion of more than 99.9%., in the formula (32 ) and Xp x2,, z2 type and number of Y1 ^ y2 Z1 ^ u and shows only a structural unit, without showing connection .Xp X2> Yi> structural unit y2> Z1 ^ z2 particular values ​​and by feeding u determining the amount, molecular structure and composition of the structural units was measured by quantitative 13C spectrum, to give (Xl + X2): (yi + y2): (Zl + Z2 ):u=l:0.79:0.20:0.0001。 ): U = l: 0.79: 0.20: 0.0001.

Figure CN103788293AD00241

[0106] 实施例3 [0106] Example 3

[0107] 本实施例用于说明本发明提供的溶液聚合法制备丙烯酰胺系共聚物。 [0107] The present embodiment used in the solution polymerization of acrylamide-based copolymer of the present invention is provided to illustrate the preparation.

[0108] 室温下,将38.38g的丙烯酰胺(AM),37.31g的式(33)所示的单体Μ3、30.46g的双丙酮丙烯酰胺和0.21g的式(30)所示的M2单体加入到反应瓶中,加入去离子水424.6g,搅拌使单体完全溶解,并搅拌均匀。 [0108] A mixture of 38.38g acrylamide (AM), 37.31g of formula (33) diacetone acrylamide monomer represented Μ3,30.46g and 0.21g of formula (30) shown M2 single thereof was added to the reaction flask, 424.6g deionized water was added, and stirred to completely dissolve the monomers, and stir. 分别向烧瓶中加入I重量%的EDTA水溶液10.03g, I重量%2.2' -偶氮二异丁基脒盐酸盐水溶液4.87g,尿素0.03g,充分搅拌使其混合均匀。 I were added to the flask wt% aqueous solution of EDTA 10.03g, I wt% 2.2 '- azobis isobutyl amidine hydrochloride solution 4.87g, urea 0.03g, sufficiently stirred to mix uniformly. 用固体氢氧化钠将PH调至7.5。 PH was adjusted with solid sodium hydroxide to 7.5. 加入0.5重量%亚硫酸氢钠溶液1.1g,控制体系初始温度至8°C,通氮气除氧30分钟后,加入I重量%过硫酸铵水溶液1.lg,并继续通氮除氧20分钟。 0.5% by weight solution of 1.1 g of sodium hydrogen sulfite, controlling the initial temperature of the system to 8 ° C, deoxygenated nitrogen for 30 minutes, was added I wt% ammonium persulfate aqueous 1.LG, nitrogen and oxygen was continuously for 20 minutes. 将反应器密闭,保持在8V'反应10小时后,将温度升至20°C后反应4小时,然后将温度升至45°C反应12小时,将得到的胶状产物取出,经造粒、干燥、粉碎即可获得高分子量丙烯酰胺系共聚物P3。 The reactor was sealed and held after 8V '10 hours of reaction, the reaction temperature was raised to 20 ° C 4 hours and then the temperature was raised to 45 ° C for 12 hours, the resulting gummy product was taken out, granulated, dried and pulverized to obtain high molecular weight acrylamide copolymer P3.

[0109] 对P3进行IR光谱测定,IR光谱中,1660CHT1和1635CHT1处分别出现归属于酰胺基的酰胺I带吸收峰(C=O伸缩振动)和酰胺II带吸收峰(NH弯曲振动),在1546cm—1、1449cm_\l364cm_1处出现双丙酮丙烯酰胺C=O吸收峰,在1430CHT1处出现CN的伸缩振动吸收峰,在KMOcnT1处出现OS的伸缩振动吸收峰,在601CHT1处出现CS的伸缩振动吸收峰,1729cm-1出现了M2单体酯羰基的特征伸缩振动峰。 [0109] The P3 subjected to IR spectroscopy, IR spectroscopy, 1660CHT1 and at 1635CHT1 amide I appear attributable to an amide group, respectively, with absorption peaks (C = O stretching vibration) and the amide II band absorption peak (NH bending vibration), in 1546cm-1,1449cm_ \ l364cm_1 occurs at diacetone acrylamide absorption peak of C = O, CN stretching vibration occurs at the absorption peak at 1430CHT1, OS stretching vibration occurs at the absorption peak at KMOcnT1, CS stretching vibration absorption occurs at the 601CHT1 peak, 1729cm-1 peak vibration occurred M2 monomer wherein the ester carbonyl stretch. 可以确定得到的共聚物分子具有式 It may determine the resulting copolymer molecule having the formula

(34)所示的结构,通过黏度法测得其粘均分子量Mv为1420万,单体转化率为99.9%以上。 Structure shown in (34), as measured by obtaining the viscosity viscosity average molecular weight Mv of 14.2 million, more than 99.9% monomer conversion. 其中,式(34)以及Xl、x2、y1、y2、Zl、Z2和u仅表示出结构单元的类型和数目,而不表示结构单元的连接方式。 Wherein, the formula (34) and Xl, x2, y1, y2, Zl, Z2, and the type and number u shows only a structural unit, without showing connection structural units. Xp x2> Y1^ y2> Z1^ z2和u的具体数值由投料量确定,分子结构式和结构单元的组成采用定量13C 谱测定,得至Ij (χ!+χ2): (y!+y2): (ZjZ2):u=l:0.33:0.33:0.002。 Xp x2> Y1 ^ y2> Z1 ^ z2 and specific values ​​of u is determined by the feeding amount, the constituent molecules of the formula and the structural unit of quantitative spectroscopy. 13C, to give to Ij (χ + χ2!): (! Y + y2): (ZjZ2): u = l: 0.33: 0.33: 0.002.

Figure CN103788293AD00251

[0112] 实施例4 [0112] Example 4

[0113] 本实施例用于说明本发明提供的乳液聚合法制备丙烯酰胺系共聚物。 [0113] Preparation examples serve to illustrate the present acrylamide copolymer of the present invention provides an emulsion polymerization process.

[0114] (I)将40.85g的甲基丙烯酰胺,33.16g的式(33)所示的单体M3、27.07g的双丙酮丙烯酰胺和0.21g的式(30)所示的M2单体加入到配置瓶中,加入187.72g去离子水,搅拌使单体完全溶解,分别向烧瓶中加入I质量%的EDTA水溶液14.61g,加入I重量%偶氮二异丁基脒盐酸盐水溶液1.03g,加入尿素0.09g,充分搅拌使其混合均匀,用固体氢氧化钠将PH调至7.1,得到水相。 [0114] (I) of the methacrylamide 40.85g, 33.16g of formula (33) of a monomer M3,27.07g shown diacetone acrylamide and 0.21g of formula (30) shown in the monomer M2 was added to a vial configuration, 187.72g of deionized water was added and stirred to completely dissolve the monomers were added to the flask I mass% aqueous solution of EDTA 14.61g, I wt% was added azobis isobutyl amidine hydrochloride solution 1.03 g, urea was added 0.09g, sufficiently stirred and mixed, adjusted with solid sodium hydroxide to PH 7.1, to give an aqueous phase.

[0115] (2)将失水山梨醇脂肪酸酯(span60, Sigma-Aldrich公司,以下相同)10.66g,烧基酹聚氧乙烯醚(Igepal CA720, Sigma-Aldrich公司,以下相同)6.67g、127.07g煤油混合成油相,并将步骤(1)中得到水相全部加入到油相中,通过高速混匀形成反相乳液加入到反应器中。 [0115] (2) a sorbitan fatty acid ester (span60, Sigma-Aldrich Corporation, hereinafter the same) 10.66 g, sprinkle burning polyoxyethylene ether group (Igepal CA720, Sigma-Aldrich Corporation, hereinafter the same) 6.67g of, 127.07g synthetic kerosene mixed phase, and in step (1) was added all the aqueous phase to the oil phase, is added to the invert emulsion formed in the reactor by a high speed mixing.

[0116] (3)控制体系初始温度5°C,通氮气除氧30分钟后,加入I重量%亚硫酸氢钠水溶液0.7g,再加入I重量%过硫酸铵水溶液1.0g并继续通氮除氧10分钟。 [0116] (3) control of the initial temperature of the system 5 ° C, deoxygenated nitrogen for 30 minutes, I wt% was added 0.7g of sodium hydrogen sulfite solution, then add I wt% aqueous solution of ammonium persulfate 1.0g and continue through the other nitrogen oxygen for 10 minutes. 将反应器密闭,保持在5°C,反应5小时后,升温至55°C,反应2小时。 The reactor was sealed and kept at 5 ° C, the reaction for 5 hours, warmed to 55 ° C, reacted for 2 hours. 待反应温度冷却到室温后,加入4.45g壬基酚聚氧乙烯醚(Sigma-Aldrich公司,以下相同),用80目滤布过滤得到乳液状产品。 After the reaction was cooled to room temperature, was added 4.45g of polyoxyethylene nonylphenol ether (Sigma-Aldrich Corporation, hereinafter the same), with 80 mesh filter cloth to obtain an emulsion-like product. 将反相乳液产品用丙酮和甲醇混合溶剂沉淀出来后,即可获得高分子量的丙烯酰胺系共聚物P4。 After the inverse emulsion product precipitated with a mixed solvent of acetone and methanol, to obtain high molecular weight acrylamide copolymer P4.

[0117] 对P4进行IR光谱测定,IR光谱中1660CHT1和1635(^1处分别出现归属于酰胺基的酰胺I带吸收峰(C=O伸缩振动)和酰胺II带吸收峰(NH弯曲振动),在1546cm—1、1449cm_\l364cm_1处出现双丙酮丙烯酰胺C=O吸收峰,在1430CHT1处出现CN的伸缩振动吸收峰,1729cm-1出现了M2单体酯羰基的特征伸缩振动峰,在KMOcnT1处出现OS的伸缩振动吸收峰,在601CHT1处出现CS的伸缩振动吸收峰,2936cm-1出现-CH3吸收峰。可以确定得到的共聚物分子具有式(35)所示的结构,通过黏度法测得其粘均分子量Mv为1345万,单体转化率为99.9%以上。其中,式(35)以及Xp x2> y2、Z1^ Z2和u仅表示出结构单元的类型和数目,而不表示结构单元的连接方式。Xp X2> Yi> y2> Z1^ Z2和u的具体数值由投料量确定,分子结构式和结构单元的组成采用定量13C谱测定,得到Xl、X2、y1、y2、Zl、z2和U=I:0.33:0.33:0.002。 [0117] The P4 spectrometric IR, IR spectrum 1660CHT1 and 1635 (at ^ 1 attributable to amide group of the amide I band absorption peak (C = O stretching vibration) and the amide II band absorption peak appeared (NH bending vibration) in 1546cm-1,1449cm_ \ l364cm_1 diacetone acrylamide occurs at C = O absorption peak appears CN stretching vibration absorption peak at 1430CHT1, 1729cm-1 peak vibration occurred M2 monomer wherein the ester carbonyl stretch at KMOcnT1 OS stretching vibration occurs at the absorption peak, the structure of the CS stretching vibration absorption peaks, 2936cm-1 -CH3 absorption peak appears may be determined to obtain a copolymer having the molecular formula (35) occurs at 601CHT1, the viscosity as measured by obtaining the viscosity average molecular weight Mv of 13,450,000, a monomer conversion of more than 99.9%., in the formula (35) and Xp x2> y2, Z2, and the type and number Z1 ^ u shows only a structural unit, without showing the structure connection unit .Xp X2> Yi> y2> Z1 ^ Z2 and specific values ​​of u is determined by the feeding amount, composition quantitative 13C spectrum to determine the molecular formula and structural unit obtained Xl, X2, y1, y2, Zl, z2 and U = I: 0.33: 0.33: 0.002.

Figure CN103788293AD00261

[0119] 对比例3 [0119] Comparative Example 3

[0120] 按照实施例4的方法制备丙烯酰胺系共聚物,不同的是,不加入双丙酮丙烯酰胺和M2单体,从而得到共聚物DP3,测得其粘均分子量Mv为1050万。 [0120] acrylamide copolymer prepared as in Example 4, except that, without the addition of diacetone acrylamide monomer and M2 to obtain a copolymer DP3, obtaining the measured viscosity average molecular weight Mv of 10.5 million.

[0121] 对比例4 [0121] Comparative Example 4

[0122] 按照实施例4的方法制备丙烯酰胺系共聚物,不同的是,将甲基丙烯酰胺与相同摩尔数的(3-丙烯酰胺基-3-甲基)丁基三甲基氯化铵进行聚合反应,从而得到二元共聚物DP4,测得其粘均分子量Mv为1140万。 [0122] acrylamide copolymer prepared as in Example 4, except that the methacrylamide with the same number of moles of (3-acrylamido-3-methyl) butyl-trimethylammonium chloride a polymerization reaction, thereby obtaining a binary copolymer of DP4, obtaining the measured viscosity average molecular weight Mv of 11.4 million.

[0123] 实施例5 [0123] Example 5

[0124] 本实施例用于说明本发明提供的乳液聚合法制备丙烯酰胺系共聚物。 [0124] Preparation examples serve to illustrate the present acrylamide copolymer of the present invention provides an emulsion polymerization process.

[0125] (I)将41.70g的甲基丙烯酰胺,36.17g的式(29)所示的单体Ml、5.92g的双丙酮丙烯酰胺和0.008g的式(30)所示的M2单体加入到配置瓶中,加入335.19g去离子水,搅拌使单体完全溶解,分别向烧瓶中加入I质量%的EDTA水溶液7.83g,加入I重量%偶氮二异丁基脒盐酸盐水溶液2.03g,加入尿素0.10g,充分搅拌使其混合均匀,用I重量%的氢氧化钠溶液pH至7.1,得到水相。 [0125] (I) of the methacrylamide 41.70g, 36.17 g of a formula (29) a monomer represented by Ml, diacetone acrylamide and 5.92g 0.008g of formula (30) shown in the monomer M2 was added to a vial configuration, 335.19g of deionized water was added and stirred to completely dissolve the monomers, were added to I mass% EDTA solution to the flask 7.83g, was added I wt% azobis isobutyl amidine hydrochloride solution 2.03 g, urea was added 0.10g, sufficiently stirred and mixed with I wt% sodium hydroxide solution to the pH 7.1, to obtain an aqueous phase.

[0126] (2)将失水山梨醇脂肪酸酯(span60) 30.22g,烷基酚聚氧乙烯醚(Ig印al CA720)30g, 263.96g煤油混合成油相,并将步骤(1)中得到的水相全部加入到油相中,通过高速混匀形成反相乳液加入到反应器中。 [0126] (2) a sorbitan fatty acid ester (span60) 30.22g, alkylphenol ether (Ig printing al CA720) 30g, 263.96g synthetic kerosene mixed phase, and in step (1) the resulting aqueous phase was added to the entire oil phase was added to the reactor through a high speed kneading formed inverse emulsion.

[0127] (3)控制体系初始温度10°C,通氮气除氧30分钟后,加入I重量%亚硫酸氢钠水溶液0.73g,再加入I重量%过硫酸铵水溶液1.3g并继续通氮除氧10分钟。 [0127] (3) control of the initial temperature of the system 10 ° C, deoxygenated nitrogen for 30 minutes, was added I wt% aqueous solution of 0.73 g of sodium hydrogen sulfite, was added I wt% aqueous solution of ammonium persulfate 1.3g and continue through the other nitrogen oxygen for 10 minutes. 将反应器密闭,保持在10°C,反应I小时后,升温至25°C,反应5小时。 The reactor was sealed and maintained at 10 ° C, the reaction after I h warmed to 25 ° C, reacted for 5 hours. 待反应温度冷却到室温后,加入 After the reaction temperature was cooled to room temperature,

30.16g壬基酚聚氧乙烯醚,用100目滤布过滤得到乳液状产品。 30.16g nonylphenol ether, with 100 mesh filter cloth to obtain an emulsion-like product. 将反相乳液产品用丙酮和甲醇混合溶剂沉淀出来后,即可获得高分子量的丙烯酰胺系共聚物P5。 After the inverse emulsion product precipitated with a mixed solvent of acetone and methanol, to obtain high molecular weight acrylamide copolymer P5.

[0128] 对P5进行IR光谱测定,IR光谱中1660(^1和1635(^1处分别出现归属于酰胺基的酰胺I带吸收峰(C=O伸缩振动)和酰胺II带吸收峰(NH弯曲振动),在1546cm—1、1449CHT1、1364CHT1处出现双丙酮丙烯酰胺C=O吸收峰,在1430CHT1处出现CN的伸缩振动吸收峰,1729cm-1出现了M2单体酯羰基的特征伸缩振动峰,2792^1为季铵基的甲基CH不对称伸缩振动吸收峰,2923,2852cm-1处出峰分别归属于-CH2-、_CH3的CH伸缩振动,1467cm^出峰归属于-CH2-、-CHd^CH弯曲振动。可以确定得到的共聚物分子具有式(36)所示的结构,通过黏度法测得其粘均分子量Mv为1380万,单体转化率为99.9%以上。其中,式(36)以及XpXpypy2' Zp Z2和u仅表示出结构单元的类型和数目,而不表示结构单元的连接方式。Xl、X2, Y1, y2、Z1, Z2和u的具体数值由投料量确定,分子结构式和结构单元的组成采用定量13C 谱测定, 得至Ij (χ!+χ2): (yi+y2): (z!+z2):u= [0128] The P5 spectrometric IR, IR spectrum 1660 (^ 1 and 1635 (the ^ 1 attributable to amide group of the amide I band absorption peak (C = O stretching vibration) and the amide II band absorption peak appeared (NH bending vibration) occurs in diacetone acrylamide 1546cm-1,1449CHT1,1364CHT1 C = O absorption peak at a, CN stretching vibration occurs at the absorption peak 1430CHT1, 1729cm-1 peak vibration occurred M2 monomer wherein the ester carbonyl stretching , 2792 ^ a quaternary ammonium methyl group CH asymmetric stretching vibration absorption peaks, the peak at 2923,2852cm-1 are attributed to -CH2 -, _ CH stretching vibration of CH3, 1467cm ^ peak attributable to -CH2 -, - CHd ^ CH bending vibration may be determined to obtain a copolymer having the molecular structure represented by the formula (36), as measured by obtaining the viscosity viscosity average molecular weight Mv of 13,800,000, a monomer conversion of more than 99.9% of which (36 ) and 'Z2 XpXpypy2 Zp and the type and number u shows only a structural unit, rather than specific values ​​represents a structural unit connection .Xl, X2, Y1, y2, Z1, Z2 and u is determined by the feeding amount, the molecular structure of formula and the structural unit composed of quantitative spectroscopy 13C, to give Ij (χ + χ2!): (yi + y2): (! z + z2): u = l:0.36:0.07:0.0001。 l: 0.36: 0.07: 0.0001.

[0129] 实施例6 [0129] Example 6

[0130] 本实施例用于说明本发明提供的乳液聚合法制备丙烯酰胺系共聚物。 [0130] Preparation examples serve to illustrate the present acrylamide copolymer of the present invention provides an emulsion polymerization process.

[0131] (I)将33.76g的AM,78.55g的式(29)所示的单体Ml和16.07g的双丙酮丙烯酰胺和0.5g的式(30)所示的M2单体加入到配置瓶中,加入385.14g去离子水,搅拌使单体完全溶解,分别向烧瓶中加入I质量%的EDTA水溶液8.5g,加入I重量%偶氮二异丁基脒盐酸盐水溶液2.1g,加入尿素0.08g,充分搅拌使其混合均匀,用I重量%的氢氧化钠溶液pH至7.1,得到水相。 [0131] (I) 33.76g of the AM, 78.55g of formula (29) and a monomer represented by Ml diacetone acrylamide and 0.5g 16.07g of formula (30) was added to the monomer M2 represented by the configuration flask, 385.14g of deionized water and stirred to complete dissolution of the monomers were added to the flask I mass% aqueous solution of EDTA 8.5g, was added I wt% azobis isobutyl amidine hydrochloride solution 2.1g, was added urea 0.08g, sufficiently stirred and mixed with I wt% sodium hydroxide solution to the pH 7.1, to obtain an aqueous phase.

[0132] (2)将失水山梨醇脂肪酸酯(span60) 10.54g,烷基酚聚氧乙烯醚(Ig印al CA720)IOg, 133.52g煤油混合成油相,并将步骤(1)中得到的水相全部加入到油相中,通过高速混匀形成反相乳液加入到反应器中。 [0132] (2) a sorbitan fatty acid ester (span60) 10.54g, alkylphenol ether (Ig printing al CA720) IOg, 133.52g synthetic kerosene mixed phase, and in step (1) the resulting aqueous phase was added to the entire oil phase was added to the reactor through a high speed kneading formed inverse emulsion.

[0133] (3)控制体系初始温度8°C,通氮气除氧30分钟后,加入I重量%亚硫酸氢钠水溶液0.98g,再加入I重量%过硫酸铵水溶液1.3g并继续通氮除氧10分钟。 [0133] (3) control of the initial temperature of the system 8 ° C, deoxygenated nitrogen for 30 minutes, I wt% was added 0.98g of sodium hydrogen sulfite solution, then add I wt% aqueous solution of ammonium persulfate 1.3g and continues through the other nitrogen oxygen for 10 minutes. 将反应器密闭,保持在8°C,反应3小时后,升温至40°C,反应4小时。 The reactor was sealed and kept at 8 ° C, after the reaction for 3 hours, warmed to 40 ° C, for 4 hours. 待反应温度冷却到室温后,加入13.35g壬基酚聚氧乙烯醚,用80目滤布过滤得到乳液状产品。 After the reaction was cooled to room temperature, was added 13.35g nonylphenol ether, filtered with 80 mesh filter cloth to obtain an emulsion-like product. 将反相乳液产品用丙酮和甲醇混合溶剂沉淀出来后,即可获得高分子量的丙烯酰胺系共聚物P6。 After the inverse emulsion product precipitated with a mixed solvent of acetone and methanol, to obtain a high molecular weight acrylamide copolymer of P6.

[0134] 对P6进行IR光谱测定,IR光谱中1660(^1和1635(^1处分别出现归属于酰胺基的酰胺I带吸收峰(C=O伸缩振动)和酰胺II带吸收峰(NH弯曲振动),在1546cm—1、1449cm_\l364cm_1处出现双丙酮丙烯酰胺C=O吸收峰,在1430CHT1处出现CN的伸缩振动吸收峰,1729cm-1出现了M2单体酯羰基的特征伸缩振动峰,2792^1为季铵基的甲基CH不对称伸缩振动吸收峰。可以确定得到的共聚物分子具有式(37)所示的结构,通过黏度法测得其粘均分子量Mv为760万,单体转化率为99.9%以上。其中,式(37)以及Xl、x2、Yl, y2、z1、z2和u仅表示出结构单元的类型和数目,而不表示结构单元的连接方式。Xp x2> Y1^ y2、z1、z2和u的具体数值由投料量确定,分子结构式和结构单元的组成采用定量13C谱测定,得 [0134] The P6 spectrometric IR, IR spectrum 1660 (^ 1 and 1635 (the ^ 1 attributable to amide group of the amide I band absorption peak (C = O stretching vibration) and the amide II band absorption peak appeared (NH bending vibration), in \ l364cm_1 appears at 1546cm-1,1449cm_ diacetone acrylamide, C = O absorption peak appears CN stretching vibration absorption peak at 1430CHT1, 1729cm-1 shows the feature of monomer M2 ester carbonyl stretching vibration peak , 2792 ^ 1-methyl quaternary ammonium group CH asymmetric stretching vibration absorption peaks may determine the resulting copolymer molecules having structural formula (37), as measured by obtaining the viscosity viscosity average molecular weight Mv of 7,600,000, a monomer conversion was 99.9%, in the formula (37) and Xl, x2, Yl, y2, z1, z2, and the type and number u shows only a structural unit, a structural unit without showing connection of .Xp x2> Y1 ^ y2, specific values ​​z1, z2 and u is determined by the feeding amount, composition and molecular structure of the structural unit 13C spectroscopy quantitative yield

到(x!+x2): (y!+y2): (ZjZ2):u=l:0.8:0.2:0.005。 To (x + x2!): (Y + y2!): (ZjZ2): u = l: 0.8: 0.2: 0.005.

Figure CN103788293AD00281

[0137] 测试例I [0137] Test Example I

[0138] 水不溶物是根据SY/T 5862-1993中规定的方法测定的。 [0138] water-insoluble substance according to the method specified in SY / T 5862-1993 in the assay. 将P1-P6、DP1-DP4和羟丙基瓜胶(JXY油井压裂羟丙基瓜胶粉,山东聚鑫化工有限公司,以下相同)进行水溶性测定,结果如表1所不。 The P1-P6, DP1-DP4, and hydroxypropyl guar (hydroxypropyl guar fracturing JXY powder, Shandong Xin Chemical Co., Ltd., hereinafter the same) of water-soluble measured results shown in Table 1 are not.

[0139]表1 [0139] TABLE 1

[0140] [0140]

Figure CN103788293AD00291

[0141] 从上表中可以看出,本发明提供的两种方法制备的丙烯酰胺系共聚物P1-P6中水不溶物明显低于现场施工中常用做减阻剂的羟丙基瓜胶,这说明与羟丙基瓜胶相比,使用本发明提供的P1-P6作为页岩气压裂用减阻剂对地层的伤害低。 [0141] As can be seen from the table, the acrylamide copolymer P1-P6 prepared by two methods of the present invention provides a water-insoluble substance was significantly lower than on-site construction of DRA commonly done hydroxypropyl guar gum, this shows that compared to the hydroxypropyl guar gum, using P1-P6 according to the present invention as provided with DRA shale gas fracturing low formation damage.

[0142] 测试例2 [0142] Test Example 2

[0143] 在2500rpm剪切速率下,分别将P1_P6、DP1-DP4和部分水解聚丙烯酰胺(HPAM,淄博天健化工有限公司、牌号TJY-1、粘均分子量为1000-1300万,下同)各自分别地缓慢加入到体积比为80/20和60/40的水/醇溶液(本测试例中使用甲醇)中,P1-P6、DP1-DP4和部分水解聚丙烯酰胺的用量为水/醇溶液的0.01重量%(样品质量按样品内纯聚合物质量计),溶解时间为30min,结果如表2所示。 [0143] at a shear rate of 2500rpm, respectively P1_P6, DP1-DP4, and partially hydrolyzed polyacrylamide (of HPAM, Tianjian Zibo Chemical Co., Ltd., trademark TJY-1, 1000-1300 Wan viscosity average molecular weight, the same below) (test Example using methanol present) are each separately added slowly to a volume ratio of 80/20 and 60/40 of water / alcohol solution, P1-P6, DP1-DP4, and the amount of partially hydrolyzed polyacrylamide water / alcohol 0.01% by weight of the solution (sample mass by the sample mass of the neat polymer), dissolution time of 30min, the results shown in table 2.

[0144]表 2 [0144] TABLE 2

[0145] [0145]

Figure CN103788293AD00301

[0147] 从表2中可以看出,本发明提供的两种方法制备的丙烯酰胺系共聚物P1-P6作为页岩气压裂用减阻剂,与部分水解聚丙烯酰胺相比,与醇的配伍性好。 [0147] As can be seen from Table 2, acrylamide copolymers prepared according to the present invention provides two methods P1-P6 as shale gas fracturing a drag reducing agent, as compared with the partially hydrolyzed polyacrylamide, with an alcohol good compatibility.

[0148] 测试例3 [0148] Test Example 3

[0149] 在温度为25°C的条件下,将P1-P6、DP1-DP4、HPAM和羟丙基瓜胶分别溶于纯水和浓度为2重量%、4重量%、8重量%、10重量%、12重量%的NaCl或KCl溶液中,将其配制成的500mg/L和1000mg/L的溶液(样品质量按样品内纯聚合物质量计),然后根据SY/T6376-2008中规定的方法在GLM-1管路摩阻测定装置上测定上述溶液的减阻率,(测试条件:测试段管路的内径为8mm,测试段管路的长度为9m,泵注排量为30L/min)结果如表3和表4所示。 [0149] at a temperature of 25 ° C conditions, the P1-P6, DP1-DP4, HPAM and hydroxypropyl guar gum are dissolved in purified water in a concentration of 2 wt%, 4 wt%, 8%, 10 wt%, 12 wt% NaCl or KCl solution, which was formulated to 500mg / L and 1000mg / L solution (sample mass by the mass of the sample of the pure polymer), and then according to a predetermined SY / T6376-2008 the method of measuring drag reduction rate of the solution in the GLM-1 line friction measuring apparatus (test conditions: the inner diameter of the pipeline test section was 8mm, length of the test section duct is 9m, pumping displacement of 30L / min ) results as shown in table 3 and table 4.

[0150]表 3 [0150] TABLE 3

Figure CN103788293AD00311
Figure CN103788293AD00321
Figure CN103788293AD00331
Figure CN103788293AD00341

[0156] 从表3和表4中可以看出,本发明提供的两种方法制备的丙烯酰胺系共聚物P1-P6作为页岩气压裂用减阻剂,与羟丙基瓜胶、HPAM和DP1-DP4相比,与粘土抑制剂(如,KCl)配伍性好,抗盐性能优异。 [0156] From Tables 3 and 4 can be seen, an acrylamide-based copolymer prepared according to the present invention provides two methods P1-P6 as shale gas fracturing a drag reducing agent, hydroxypropyl guar gum, of HPAM DP1-DP4, and compared with the clay inhibitors (e.g., KCI) good compatibility, excellent salt resistance.

[0157] 测试例4 [0157] Test Example 4

[0158] 减阻率是根据SY/T 6376-2008中规定的方法测定的。 [0158] The method of drag reduction is predetermined SY / T 6376-2008 in the assay. 将P1-P6、DP1-DP4分别溶于纯水,将其配制成500mg/L的溶液(样品质量按样品内纯聚合物质量计),通过加入HCl或NaOH,调节体系的pH值在2.5-10之间变化,结果如表5所示。 The P1-P6, DP1-DP4 are dissolved in purified water, which is formulated as 500mg / L solution (sample mass by the mass of the sample of the pure polymer), by addition of HCl or NaOH, adjusting the pH of the system at 2.5 10 changes between the results shown in table 5.

[0159]表 5 [0159] TABLE 5

Figure CN103788293AD00342

[0161] 从表5中可以看出,本发明提供的两种方法制备的丙烯酰胺系共聚物P1-P6作为页岩气压裂用减阻剂较在很大的PH值范围内都具有良好的降阻效果。 [0161] As can be seen from Table 5, an acrylamide-based copolymer prepared according to the present invention provides two methods P1-P6 shale gas fracturing as compared with the drag reducing agent in a wide range of PH have good the reduction in resistance.

[0162] 测试例5 [0162] Test Example 5

[0163] 降阻剂对岩心的伤害性按石油天然气行业标准SY/T 5107-2005《水基压裂液性能评价方法》中压裂液滤液对岩心基质渗透率损害实验进行,在美国岩心公司地层伤害测试仪(型号为FDS-800)上进行测试,岩心的基质渗透率为2md。 [0163] The reducing agent to the core by noxious oil and gas industry standard SY / T 5107-2005 "aqueous-based fracturing fluid performance evaluation method" in the fracturing fluid to the core matrix and the filtrate permeability damage experiment, in U.S. Core Laboratories formation damage tester (model FDS-800) on the test core matrix permeability 2md.

[0164] 将P1-P6、DP1_DP4分别溶于纯水,将其配制成1000mg/L的溶液(样品质量按样品内纯聚合物质量计),通过加入HCl,调节溶液的pH值为2,在美国岩心公司地层伤害测试仪(型号为FDS-800)上测试其对岩心的伤害性,结果如表6所不。 [0164] The P1-P6, DP1_DP4 were dissolved in purified water, formulated into 1000mg / L solution (sample mass by the mass of the sample of the pure polymer), by the addition of HCl, adjusting the pH of the solution 2, noxious tested for core formation damage U.S. core Laboratories tester (model FDS-800), the results in table 6 are not.

[0165]表 6 [0165] TABLE 6

[0166] [0166]

Figure CN103788293AD00351

[0167] 从上表中可以看出,本发明提供的两种方法制备的丙烯酰胺系共聚物P1-P6对于岩心的伤害明显低于现场施工中常用做减阻剂的对比样品,这说明使用P1-P6作为页岩气压裂用减阻剂对地层的伤害低。 [0167] As can be seen from the table, the acrylamide copolymer P1-P6 prepared by two methods of the present invention provides for core damage was significantly lower than on-site construction of DRA commonly used to make comparative sample, indicating that the use of P1-P6 as shale gas fracturing with DRA low formation damage.

[0168] 上述测试结果说明,本发明提供的丙烯酰胺系共聚物具有良好的水溶性,对地层的伤害低;而且能完全溶解于水醇溶液中,与醇的配伍性好;由于与醇和粘土抑制剂(NaCl或KCl)的配伍性提高,提高了抗滤失性能;并且在高盐、较宽的PH值条件下仍具有高的减阻率;具有可降解性,在PH值小于2.5时可降解,对地层的伤害低。 [0168] The test results indicated that the acrylamide-based copolymer of this invention has good water solubility, low formation damage; and completely soluble in aqueous alcohol solution, good compatibility with alcohol; alcohol due to clay improved compatibility inhibitor (NaCl or KCl), and improved resistance to fluid loss properties; and still have a high drag reduction at high salt wider PH value condition; having biodegradability, the PH value of less than 2.5 biodegradable, low formation damage. 此外,本发明提供的丙烯酰胺系共聚物的制备方法具有简便且单体转化率高的优点。 Moreover, preparation of an acrylamide-based copolymer of the present invention to provide a simple and has the advantages of high monomer conversion.

Claims (18)

  1. 1.一种丙烯酰胺系共聚物,其特征在于,所述丙烯酰胺系共聚物含有结构单元A、结构单元B、结构单元C和结构单元D,其中,所述结构单元A为式(I)所示的结构单元和/或式(2)所示的结构单元,所述结构单元B为式(3)、式(4)、式(5)和式(6)所示的结构单元中的至少一种,所述结构单元C为式(7)所示的结构单元和/或式(8)所示的结构单元,所述结构单元D为式(9)所示的结构单元和/或式(10)所示的结构单元;且以所述丙烯酰胺系共聚物中结构单元的总摩尔数为基准,所述结构单元A的含量为5-95摩尔%,所述结构单元B的含量为2.5-90摩尔%,所述结构单元C的含量为0.5-90摩尔%,所述结构单元D的含量为.0.0001-1摩尔% ;优选地,所述结构单元A的含量为10-70摩尔%,所述结构单元B的含量为.20-50摩尔%,所述结构单元C的含量为5-40摩尔%,所述结构单元D的含量为0.001-0.5摩尔% ;所述丙烯酰胺 An acrylamide copolymer, characterized in that said acrylamide copolymer comprising structural units A, structural units B, C structural unit and the structural unit D, where the structural unit A of formula (I) structural unit and / or the formula (2) shown in structural unit B is a structural unit of the formula (3), formula (4), (5) and formula (6) in the structural units and / or at least one structural unit, the structural unit is a structural unit represented by the formula C (7) and / or formula (8), the structural unit D of formula (9) a structural unit represented by the formula (10); and the total number of moles of said acrylamide copolymer of the structural unit as a reference, the content of the structural unit a is from 5 to 95 mol%, the content of the structural unit B of from 2.5 to 90 mol%, the content of the structural unit C is 0.5 to 90 mol%, the content of the structural unit D is .0.0001-1 mol%; preferably, the content of the structural unit a is 10-70 mol%, the content of the structural unit B is .20-50% by mole, the content of the structural unit C of 5 to 40 mol%, the content of the structural unit D is 0.001 to 0.5 mol%; the acrylamide 共聚物的粘均分子量为200万-1800万,优选为400万-1500万; Copolymer viscosity-average molecular weight of 2,000,000 -1,800 million and 15 million preferably 4,000,000;
    Figure CN103788293AC00021
    Figure CN103788293AC00031
    其中,Rp R4、R/ 和R4,各自独立地为C1-C4 的亚烷基;R2、R3> R2,、R/、R5> R6> R7> R8> R9>Rn、R14、R15、R5,、R6,、R7,、R8,、R9,、Rn,、R14,和R15' 各自独立地为C1-C4 的烷基;R10、R12、R13、R1Q'、R12'和R13'各自独立地为C1-C20的直链或支链亚烷基;M为H、K和Na中的至少一种; X-为Cl—,Br— Wherein, Rp R4, R /, and R4, are each independently a C1-C4 alkylene group; R2, R3> R2,, R /, R5> R6> R7> R8> R9> Rn, R14, R15, R5, , R6,, R7,, R8,, R9,, Rn ,, R14, and R15 'are each independently a C1-C4 alkyl; R10, R12, R13, R1Q', R12 'and R13' are each independently C1-C20 linear or branched alkylene group; M is H, at least one of K and Na; X-is Cl-, Br-
    Figure CN103788293AC00032
  2. 2.根据权利要求1所述的丙烯酰胺系共聚物,其中,所述结构单元B为式(11)所示的结构单元和/或式(12)所示的结构单元,所述结构单元C为式(13)所示的结构单元,所述结构单元D为式(14)所示的结构单元, 2. acrylamide copolymer according to claim 1, wherein the structural unit B is a structural unit represented by the formula (11) and / or formula (12) a structural unit, the structural unit C of formula (13) a structural unit represented by the structural unit D of formula (14) shown in the structural unit,
    Figure CN103788293AC00033
    Figure CN103788293AC00041
    其中,R1和R4为C1-C4的亚烷基;R10、R12'和R13'为C1-C20的直链或支链亚烷基。 Wherein, R1, and R4 are a C1-C4 alkylene group; R10, R12 'and R13' is C1-C20 linear or branched alkylene group.
  3. 3.一种丙烯酰胺系共聚物的制备方法,该制备方法包括,在烯烃的溶液聚合反应条件下,在引发剂存在下,使一种单体混合物在水中进行聚合反应,其特征在于,所述单体混合物含有单体E、单体F、单体G和单体H,所述单体E为式(15)所示的单体和/或式(16)所示的单体,所述单体F为式(17)、式(18)、式(19)和式(20)所示的单体中的至少一种,所述单体G为式(21)所示的单体和/或式(22)所示的单体,所述单体H为式(23)所示的单体和/或式(24)所示的单体; 3. A method of preparing an acrylamide-based copolymer, the method comprising preparing, in the solution polymerization of olefins under reaction conditions, in the presence of an initiator, a monomer mixture of a polymerization reaction in water, characterized by said monomer mixture comprising monomer E, F. monomers, the monomers and monomer G H, E is the monomer of formula (15) shown in monomer and / or formula (16) shown in the monomer, the F is a monomer of said monomer of formula (17), formula (18), a monomer of formula (19) and (20) shown in at least one of said monomers G is represented by the formula (21) and / or formula (22) shown in the monomer, the monomer is of formula H (23) monomer and / or formula (24) shown in the monomer;
    Figure CN103788293AC00042
    Figure CN103788293AC00051
    其中,Rp R4、R/ 和R4,各自独立地为C1-C4 的亚烷基;R2、R3> R2,、R/、R5> R6> R7> R8> R9>Rn、R14、R15、R5,、R6,、R7,、R8,、R9,、Rn,、R14,和R15' 各自独立地为C1-C4 的烷基;R10R12、R13、R1Q'、R12'和R13'各自独立地为C1-C20的直链或支链亚烷基;M为H、K和Na中的至少一种;X-为 Wherein, Rp R4, R /, and R4, are each independently a C1-C4 alkylene group; R2, R3> R2,, R /, R5> R6> R7> R8> R9> Rn, R14, R15, R5, , R6,, R7,, R8,, R9,, Rn ,, R14, and R15 'are each independently a C1-C4 alkyl group; R10R12, R13, R1Q', R12 'and R13' are each independently C1- C20 linear or branched alkylene group; M is H, K and Na in at least one of; X-is
    Figure CN103788293AC00052
  4. 4.一种丙烯酰胺系共聚物的制备方法,该制备方法包括将水相和油相混合形成反相乳液,然后在乳液聚合反应条件下,将该反相乳液与引发剂接触,所述水相为含有单体混合物的水溶液,所述油相含有油和乳化剂,接触的条件使得单体混合物发生聚合反应,其中,所述单体混合物含有单体E、单体F、单体G和单体H,所述单体E为权利要求3中所述式(15)所示的单体和/或式(16)所示的单体,所述单体F为权利要求3中所述式(17)、式(18)、式(19)和式(20)所示的单体中的至少一种,所述单体G为权利要求3中所述式(21)所示的单体和/或式(22)所示的单体,所述单体H为权利要求3中所述式(23)所示的单体和/或式(24)所示的单体。 4. A method of preparing an acrylamide-based copolymer, which method comprises preparing the aqueous and oil phases mixed to form a reverse phase emulsion, and then under the conditions of emulsion polymerization, inverse emulsion and contacting the initiator, the water phase is an aqueous solution containing a monomer mixture, the oil phase containing oil and emulsifiers, such contact conditions polymerization reaction of the monomer mixture, wherein the monomer mixture containing the monomer E, F. monomer, and a monomer G monomer H, E is the monomer of the monomer of formula 3 (15) and / or formula (16) as claimed in claim monomer represented by F is the monomer as claimed in claim 3 formula (17), formula (18), formula (19) and (20) monomers represented by at least one of said monomers G is shown in (21) as claimed in claim 3 in the single formula and / or formula (22) shown in the monomer, the monomer is 3 H in the formula (23) shown in monomer and / or formula (24) a monomer of the claims.
  5. 5.根据权利要求4所述的制备方法,其中,所述水相与油相的重量比为1:0.1-2,优选为I:0.3-0.8。 The production method according to claim 4, wherein the weight ratio of water phase to oil phase is 1: 0.1-2, preferably I: 0.3-0.8.
  6. 6.根据权利要求4所述的制备方法,其中,以所述乳液的总重量为基准,所述油的用量为10-60重量%,所述乳化剂的用量为1-10重量%,优选地,所述油的用量为20-35重量%,所述乳化剂的用量为2-9重量%。 6. The production method according to claim 4, wherein, based on the total weight of the emulsion as a reference, the oil in an amount of 10-60% by weight, the emulsifier in an amount of 1-10% by weight, preferably , the oil in an amount of 20-35% by weight, the emulsifier in an amount of 2-9% by weight.
  7. 7.根据权利要求4所述的制备方法,其中,该方法还包括在所述聚合反应后将所述聚合反应所得产物与转相剂接触。 7. The production method according to claim 4, wherein the method further comprises the resultant reaction product into contact with a phase inversion agent in the polymerization reaction after the polymerization.
  8. 8.根据权利要求7所述的制备方法,其中,以所述乳液的总重量为基准,所述转相剂的用量为0.5-10重量%,优选为1-4重量%。 8. A method of preparing an amount according to claim 7, wherein, based on the total weight of the emulsion as a reference, the phase transfer agent is 0.5 to 10 wt%, preferably 1-4 wt%.
  9. 9.根据权利要求3或4所述的制备方法,其中,以所述单体混合物中单体的总摩尔数为基准,所述单体E的含量为5-95摩尔%,所述单体F的含量为2.5-90摩尔%,所述单体G的含量为0.5-90摩尔%,所述单体H的含量为0.0001-1摩尔% ;优选地,所述单体E的含量为10-70摩尔%,所述单体F的含量为20-50摩尔%,所述单体G的含量为5_40摩尔%,所述单体H的含量为0.001-0.5摩尔% ;所述聚合反应的条件使得聚合反应后所得聚合物的粘均分子量为200万-1800万,优选为400万-1500万 9. The production method according to claim 3 or claim 4, wherein, based on the total moles of the monomer mixture of the monomers, of the monomer content of 5 to 95 mol% of E, said monomer content of from 2.5 to 90 mole% F, G of the monomer content is 0.5 to 90 mol% of the monomer content of from 0.0001 mol% of H; preferably, the content of the monomer E is 10 -70% by mole content of the monomer is 20 to 50 mole% F, G of the content of the monomer 5_40 mol%, the content of the monomer is 0.001 to 0.5 mole% H; said polymerization reaction after the polymerization reaction conditions such that the resulting polymer viscosity average molecular weight of 2,000,000 -1,800 million and preferably 4,000,000 15 million
  10. 10.根据权利要求3或4所述的制备方法,其中,所述单体F为式(25)所示的单体和/或式(26)所示的单体,所述单体G为式(27)所示的单体,所述单体H为式(28)所示的单体, 10. The production method according to claim 3 or claim 4, wherein the monomer is a monomer of formula F (25) a monomer represented by and / or formula (26) shown in the monomer G is of formula (27) a monomer represented by the formula H (28) a monomer represented by,
    Figure CN103788293AC00061
    其中,R1和R4为C1-C4的亚烷基;R10、R12'和R13'为C1-C20的直链或支链亚烷基。 Wherein, R1, and R4 are a C1-C4 alkylene group; R10, R12 'and R13' is C1-C20 linear or branched alkylene group.
  11. 11.根据权利要求3或4所述的制备方法,其中,所述单体混合物的重量与水和单体混合物的总重量的比值为0.05-0.5:1,优选为0.15-0.4:1。 11. The production method according to claim 3 or claim 4, wherein the ratio by weight of the total weight of the monomer mixture and water of the monomer mixture is from 0.05 to 0.5: 1, preferably from 0.15 to 0.4: 1.
  12. 12.根据权利要求3或4所述的制备方法,其中,所述引发剂选自偶氮系引发剂和氧化还原系引发剂,以所述单体混合物中单体的总摩尔数为基准,所述偶氮系引发剂的用量为0-10摩尔%,所述氧化还原系引发剂的用量为0-10摩尔%,且所述引发剂的总用量为.0.001-10摩尔% ;所述偶氮系引发剂选自偶氮二异丁腈、偶氮二异庚腈、偶氮双甲基戊酸盐、2,2' -偶氣二异丁基脉盐酸盐和2,2' -偶氣二[2_(2-咪唑琳_2_丙烷)-二盐酸盐]中的至少一种,所述氧化还原系引发剂包括氧化剂和还原剂,所述氧化剂与所述还原剂的摩尔比为0.5-2:1,所述氧化剂选自过硫酸铵、过硫酸钾、过硫酸钠和过氧化氢中的至少一种;所述还原剂为无机还原剂,所述无机还原剂选自亚硫酸氢钠、亚硫酸钠、雕白粉、硫代硫酸钠、硫酸亚铁、保险粉、抗坏血酸和脲中的至少一种。 12. The production method according to claim 3 or claim 4, wherein said initiator is selected from azo initiator and a redox initiator to the total moles of the monomer mixture of the monomers, the amount of the azo initiator is 0-10 mol%, the amount of the redox-based initiator is 0-10 mol%, and the total amount of initiator agent is .0.001-10 mol%; the azo initiator selected from azobisisobutyronitrile, azobis iso-heptyl-carbonitrile, azobis methyl valerate, 2,2 '- even diisobutylaluminum gas pulse hydrochloride and 2,2' - even gas-bis [2_ (2-imidazolin Lin _2_ propane) - dihydrochloride] at least one of the redox-based initiator comprising an oxidizing agent and a reducing agent, said oxidizing agent with said reducing agent molar ratio of 0.5-2: 1, the oxidizing agent is selected from ammonium persulfate, potassium persulfate, sodium persulfate and at least one of hydrogen peroxide; the reducing agent is an inorganic reducing agent, the reducing agent is selected from inorganic since sodium bisulfite, sodium sulfite, Rongalit, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite, ascorbic acid and at least one of urea.
  13. 13.根据权利要求3或4所述的制备方法,其中,所述聚合反应在助剂存在下进行,所述助剂选自螯合剂和其他助剂中的至少一种;以所述单体混合物的总摩尔数为基准,所述螯合剂的用量为0-2摩尔%,所述其他助剂的用量为0-2摩尔%,且以所述单体混合物中单体的总摩尔数为基准,所述助剂的总用量为0.0001-4摩尔% ;所述螯合剂选自乙二胺四乙酸二钠、三乙二胺五乙酸、柠檬酸、柠檬酸盐和聚羟基丙烯酸中的至少一种,所述其他助剂选自尿素、甲酸钠、异丙醇和次磷酸钠中的至少一种。 13. A method of preparation according to claim 3 or claim 4, wherein the polymerization reaction is carried out in the presence of adjuvant, said adjuvant is selected from at least one chelating agent and the other additives; to the monomer the total number of moles of the mixture used as a reference, the chelating agent in an amount of 0-2 mol%, the amount of further auxiliaries 0-2 mol%, and the total number of moles of the monomers of the monomer mixture reference, a total amount of the aid is 0.0001 mol%; the chelating agent is selected from edetate disodium, triethylenediamine pentaacetic acid, citric acid, citrates, and acrylic acid at least polyhydroxy one of the other additives are selected from urea, sodium formate, at least one of isopropyl alcohol and sodium hypophosphite.
  14. 14.根据权利要求3-13中任意一项所述的制备方法,其中,所述聚合反应在惰性气体存在下进行,所述聚合反应条件包括:温度为0-80°C,时间为1-24小时,pH值为5-13。 3-13 prepared according to any method of any one of claims, wherein the polymerization reaction is carried out in the presence of an inert gas, the polymerization conditions comprise: a temperature of 0-80 ° C, time is 1 24 hours, pH = 5-13.
  15. 15.根据权利要求3所述的制备方法,其中,所述聚合反应包括依次进行的三个阶段,第一阶段的反应条件包括:温度为0-10°C,时间为1-15小时;第二阶段的反应条件包括:温度为15-30°C,时间为3-8小时;第三阶段的反应条件包括:温度为35-60°C,时间为2_14小时 15. The production method according to claim 3, wherein said polymerization reaction comprises three stages sequentially, the conditions of the first reaction stage comprising: a temperature of 0-10 ° C, to 15 hours; the first the reaction conditions of two-stage comprising: a temperature of 15-30 ° C, the time is 3-8 hours; the reaction conditions of the third stage comprising: a temperature of 35-60 ° C, 2_14 time hours
  16. 16.根据权利要求4所述的制备方法,其中,所述聚合反应包括依次进行的二个阶段,第一阶段的反应条件包括:温度为0-20°C,时间为1-15小时;第二阶段的反应条件包括:温度为20-60°C,时间为2-8小时。 16. The production method according to claim 4, wherein said polymerization reaction comprises two stages sequentially, the first stage reaction conditions comprise: a temperature of 0-20 ° C, to 15 hours; the first the reaction conditions of two-stage comprising: a temperature of 20-60 ° C, the time is 2-8 hours.
  17. 17.根据权利要求3-16中任意一项所述的制备方法制得的丙烯酰胺系共聚物。 17. 3-16 acrylamide copolymer prepared according to any one obtained by the method according to claim.
  18. 18.权利要求1-2和17中任意一项所述的丙烯酰胺系共聚物在减阻剂中的应用。 1-2 and 17 is applied to any one of the acrylamide copolymer in the drag reducing agent of claim 18.
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