CN103570865A - Acrylamide series terpolymer, preparation method, and applications thereof - Google Patents

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

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CN103570865A
CN103570865A CN 201210265039 CN201210265039A CN103570865A CN 103570865 A CN103570865 A CN 103570865A CN 201210265039 CN201210265039 CN 201210265039 CN 201210265039 A CN201210265039 A CN 201210265039A CN 103570865 A CN103570865 A CN 103570865A
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acrylamide
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CN103570865B (en )
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杜凯
赵方园
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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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Abstract

The invention relates to an acrylamide series terpolymer, a preparation method, and applications thereof. The acrylamide series terpolymer comprises a structural unit A, a structural unit B, and a structural unit C, wherein the structural unit A comprises a structural unit represented by the formula (1), the structural unit B comprises a structural unit represented by the formula (2), and the structural unit C comprises a structural unit represented by the formula (3). The acrylamide series terpolymer improves the solubility of the terpolymer in alcohol and clay inhibitor, has high drag reduction efficiency under a high salinity condition when the terpolymer is used as a drag reducer, and has a very good drag reducing effect in a pH range from 4 to 10.

Description

一种丙烯酰胺系三元共聚物及其制备方法和应用 Acrylamide terpolymers its preparation method and application

技术领域 FIELD

[0001] 本发明涉及一种丙烯酰胺系三元共聚物及其制备方法,以及所述丙烯酰胺系三元共聚物作为减阻剂的应用。 [0001] The present invention relates to a propylene terpolymer and a preparation method, and terpolymers of acrylamide amide of the application as a drag reducing agent.

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,与目前常规压裂体系(改性瓜尔胶交联体系)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。 [0003] "slickwater (slick water) fracturing" is a kind of hydraulic fracturing, compared to current conventional fracturing system (modified guar crosslinking system), slickwater (slickwater) Fracturing not rely on high viscosity colloid carrying sand, but at a high pumping displacement carrying sand, reservoir fracturing achieve the ultimate goal of a mesh fracture. 减阻水(滑溜水)压裂较常规压裂体系在成本上有较大优势,同时对地层的伤害较小。 Slickwater (slick water) compared with conventional fracturing fracturing system has great advantages in terms of cost, while the smaller formation damage.

[0004] 减阻水压裂液核心助剂为水基减阻剂,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,目前可用作水基减阻剂的主要有瓜尔胶及其衍生物、纤维素衍生物、丙烯酰胺类聚合物。 [0004] slickwater fracturing fluid is water-based core DRA aid, 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, the current is used as the water-based DRA major guar and derivatives thereof, cellulose derivatives, acrylamide-based polymer.

[0005]目前,采用瓜尔胶、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(US5697444,US5271466),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减阻性能有限,明显不及丙烯酰胺类聚合物;②由于瓜尔胶、纤维素及其衍生物具有少量不溶物极易对地层造成伤害。 [0005] Currently, the use of guar gum, cellulose and its derivatives to improve the pumping slickwater fracturing, as a displacement of the drag reducing agent to a certain extent, in reducing the frictional resistance line (US5697444, US5271466), but still can not meet the requirements of slickwater fracturing, mainly due to the presence of the biopolymer following disadvantages: ① drag reduction performance is limited, significantly less acrylamide-based polymer; ② Since guar gum, cellulose and its derivatives has a small insolubles easily cause formation damage. ③溶解时间较长。 ③ longer dissolution time.

[0006] 在减阻水压裂施工中,多采用丙烯酰胺类聚合物(基本采用部分水解丙烯酰胺或阴离子型丙烯酰胺共聚物)作为减阻水压裂液中的减阻剂,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液的减阻剂使用,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,帮助减阻水压裂液的返排、减少“水堵”,必须在压裂液中加入部分醇。 [0006] In the slickwater fracturing, the use of acrylamide-based polymer (substantially using partially hydrolyzed acrylamide or anionic acrylamide copolymer) as slickwater fracturing fluid drag reducing agent, to a large extent Note the increased displacement pump, reducing the frictional resistance of the line, but as a drag reducing agent shale gas slickwater fracturing fluid, the following important disadvantage: ① to reduce fracturing of the "water-sensitive "effect, inhibiting shale hydration swelling clay components, help slickwater fracturing fluid flowback, reducing" water blocks ", must be added the alcohol part in the fracturing fluid. 部分水解丙烯酰胺或阴离子型丙烯酰胺共聚物及其乳液产品与醇的配伍性较差,极易产生沉淀。 Partially hydrolyzed anionic acrylamide or acrylamide copolymers and an emulsion product with an alcohol compatibility is poor, easy to produce precipitation. ②部分水解丙烯酰胺或阴离子型丙烯酰胺共聚物作为页岩气藏减阻水压裂液的减阻剂使用时,抗滤失性能较差,此种减阻水压裂液极易滤失到地层当中。 ② partially hydrolyzed anionic acrylamide or acrylamide copolymers drag reducing agent when poor as shale gas reservoirs slickwater fracturing fluid against fluid loss properties, such slickwater fracturing fluid leakoff to easily among formation. ③耐温抗盐性较差,尤其在高矿化度(高的二价离子含量)条件下,分子结构不稳定,减阻效果下降较快。 ③ temperature and salt resistance is poor, especially in the high salinity (high divalent ion content) conditions, the molecular structure is unstable, drag reduction decreased rapidly.

[0007] US20090298721A1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。 [0007] US20090298721A1 discloses one kind of formulations slickwater fracturing fluids: 1,000 gallons to 0.5 gallons of deionized water was added -Co- acrylamide acrylic acid copolymer (FR-56 ™) and other anionic acrylamide copolymer emulsion as Save blocking agent, was added 0.15wt.% sodium carbonate or complexing agent such as EDTA-2Na. 该减阻水压裂液具有优良的减阻性能,室内平均减阻率达到65.0%、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。 The slickwater fracturing fluid having superior drag reduction, drag reduction rate of the average indoor 65.0%, salt tolerance (especially the divalent calcium ion tolerance) has been improved to some extent, but such drag reducing aqueous fracturing system as shale slickwater fracturing fluid used, the following problems: ① compatibility and poor alcohol, methanol and the like alcohol can easily effect precipitation. 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。 ② anti-poor fluid loss properties, such slickwater fracturing fluid loss into the formation which can easily filtered off. ③在实际施工中“水敏效应”显著。 ③ in the actual construction of the "water-sensitive" effect is significant. ④极易产生“水堵”。 ④ easy to produce "water blocks." ⑤耐高速剪切性能差,在高速剪切作用下,减阻率下降很快;⑥耐温耐盐性较差,尤其在高矿化度(高的二价离子含量)条件下,分子结构不稳定,减阻效果下降较快。 ⑤ Resistance to high shear performance difference, at high shear, drag reduction decreased rapidly; ⑥ Temperature salt is poor, especially at high salinity (high divalent ion content) conditions, the molecular structure unstable, drag reduction decreased rapidly.

[0008] 阳离子型高分子量的丙烯酰胺共聚物作为减阻剂(US3868328)也有报道,与上述部分水解丙烯酰胺或阴离子型丙烯酰胺共聚物相比,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”。 [0008] The high molecular weight cationic acrylamide copolymer as a drag reducing agent (US3868328) have been reported, as compared with the partially hydrolyzed anionic acrylamide or acrylamide copolymers, copolymers of compatibility with such a structure is preferably an alcohol , clay inhibitors (e.g., KCl) good compatibility, "water-sensitive" effect is not significant, easily "water block."

[0009] 如何进一步提高减阻剂耐高速剪切性能,提高压裂液对粘土的抑制性及抗滤失性,在高温、高盐、高剪切条件下使减阻率的稳定性提闻仍是一个尚未解决的问题。 [0009] How to further improve the performance of drag reducing agent to high shear resistance, improved inhibition of clay and anti fluid loss fracturing fluid, so that drag reduction at a high temperature, high salt, high shear conditions of stability mentioned smell It is still an unresolved issue.

发明内容 SUMMARY

[0010] 本发明的目的是提供一种超高分子量、减阻率高、水溶性好、与粘土抑制剂及减堵剂有良好配伍性,以及溶解时间短的丙烯酰胺系三元共聚物,以及该丙烯酰胺系三元共聚物的制备方法和应用。 [0010] The object of the present invention is to provide a high molecular weight, high drag, good water solubility, clay inhibitors and reducing agent has good compatibility blocking, and a short dissolution time terpolymer of acrylamide, as well as the preparation and use of acrylamide terpolymers.

[0011] 本发明提供一种丙烯酰胺系三元共聚物,其特征在于,该丙烯酰胺系三元共聚物 [0011] The present invention provides a terpolymer of acrylamide, wherein the acrylamide terpolymer

含有结构单元A、结构单元B和结构单元C,其中,所述结构单元A为具有式(1)所示结构的 Containing structural units A, structural units B and structural units C, where, A is a structural unit having the formula (1) shown in the structure of

结构单元,所述结构单元B为具有式(2)所示结构的结构单元,所述结构单元C为具有式 Structural units, the structural unit B having the formula (2) a structural unit represented by the structure, the structural unit having the formula C

(3)所示结构的结构单元,且以所述丙烯酰胺系三元共聚物中结构单元的总摩尔数为基准, (3) a structural unit represented by the structure, and the total number of moles of the terpolymer acrylamide structural unit as a reference,

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 The content of the structural unit A is from 5 to 95 mol%, the content of the structural unit B is from 2.5 to 90 mol%, of the structure

单元C的含量为0.5-90摩尔% ;优选地,所述结构单元A的含量为10-70摩尔%,所述结构 Unit C content is 0.5 to 90 mol%; preferably, the content of the structural unit A is 10 to 70 mol%, of the structure

单元B的含量为20-50摩尔%,所述结构单元C的含量为10-40摩尔% ;所述丙烯酰胺系三 Unit B content is 20-50 mol%, the content of the structural unit C of 10 to 40 mole%; the three acrylamide

元共聚物的粘均分子量为1500万-2500万,优选为1800万-2200万; Copolymer viscosity average molecular weight 15 million 25 million, preferably 18 million -2200 Wan;

Figure CN103570865AD00061

[0013] 其中,R1、 R4为氢原子或甲基;R2为叔碳原子与咪唑环上氮原子之间的共价键,或 [0013] wherein, R1, R4 is a hydrogen atom or a methyl group; R2 is a tertiary carbon atom on the imidazole ring with a covalent bond between the nitrogen atom, or

者为C1-C4的亚烷基;R3为C1-C20的直链烷基或C3-C20的支链烷基;R5为氢原子、C3-C20的支 Who is a C1-C4 alkylene group; R3 is a linear C1-C20 alkyl group or a branched C3-C20 alkyl group; R5 is a hydrogen atom, C3-C20 branched

链烷基、C1-C20的直链烷基中部分氢原子被羟基取代的烃基或C3-C20的支链烷基中部分氢原 Chain alkyl, branched alkyl groups C1-C20 straight chain alkyl group in part of hydrogen atoms substituted with hydroxy or C3-C20 hydrocarbon group part of hydrogen atoms in the

子被羟基取代的烃基:X-为Cl-、Br- I-、SCN-、 Sub-hydroxy substituted hydrocarbon group: X- is Cl-, Br- I-, SCN-,

Figure CN103570865AD00062

[0014] 本发明还提供一种丙烯酰胺系三元共聚物的制备方法,该方法包括在烯烃的溶液聚合反应条件下、在引发剂存在下,使单体混合物在水中进行聚合反应,所述单体混合物含有单体D、单体E和单体F,所述单体D为具有式(11)所示结构的单体,所述单体E为具有式(12)所示结构的单体,所述单体F为具有式(13)所示结构的单体,且以所述单体混合物中单体的总摩尔数为基准,所述单体D的含量为5-95摩尔%,所述单体E的含量为2.5-90摩尔%,所述单体F的含量为0.5-90摩尔% ;优选地,所述单体D的含量为10-70摩尔%,所述单体E的含量为20-50摩尔%,所述单体F的含量为10-40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1500万-2500万,优选为1800万-2200万; [0014] The present invention further provides a process for preparing acrylamide terpolymers, which comprises the solution polymerization of olefins under reaction conditions, in the presence of an initiator, polymerization of the monomer mixture in water, the the monomer mixture containing a monomer D, E monomers and monomer F., said monomer having the formula D (11) structure of the monomer, the monomer having the formula E (12) a single structure shown body, the monomer having the formula F (13) of the monomer represented by the structure, and the total moles of monomers in the monomer mixture is a reference content of the monomer D is 5-95 mol% the content of the monomer E is 2.5 to 90 mol%, the content of the monomer is 0.5 to 90 mol% F; preferably, the content of the monomer D is 10-70 mol%, of the monomer E content of 20 to 50 mol% of the content of the monomer is 10 to 40 mole% of F; condition of the polymerization reaction such that polymerization of the resulting polymer after viscosity-average molecular weight of 15 million 25 million, preferably 18 million -2200 Wan;

Figure CN103570865AD00071

[0016] 其中,R1-R5以及Χ_与上述定义相同。 [0016] wherein, R1-R5 as defined above and Χ_.

[0017] 另外,本发明提供通过上述方法制备的丙烯酰胺系三元共聚物。 [0017] Further, the present invention provides acrylamide terpolymer prepared by the above method.

[0018] 本发明还提供上述丙烯酰胺系三元共聚物作为减阻剂的应用。 [0018] The present invention provides the acrylamide terpolymer use as drag reducing agents.

[0019] 本发明通过将可聚合功能性单体通过三元共聚的方法,引入到含有丙烯酰胺、阳离子单体的大分子链上,通过控制聚合条件得到超高分子量的三元共聚物。 [0019] The present invention is by the polymerizable functional monomer of the terpolymer by the process, is introduced into the ultra high molecular weight terpolymers containing acrylamide, cationic monomer of the macromolecular chains, is obtained by controlling the polymerization conditions. 该三元共聚物保持了线性大分子优异粘弹性,并且具有耐高温、耐盐和耐高剪切的性能,将该三元共聚物用于减阻剂,可以提高在高温、高盐、高剪切条件下的减阻率;由于与醇(例如:甲醇、乙醇)和粘土抑制剂(例如=NaCl或KCl)的配伍性提高,从而提高对粘土的抑制性及抗滤失性能,减少水敏效应和水堵现象的发生,由此可保证高的泵注排量携砂,实现将储层压裂成网状裂缝的最终目的。 The terpolymer maintains the excellent viscoelastic linear macromolecules, and high temperature, salt, and high shear resistance performance, the terpolymers for drag reducing agents, can improve the high temperature, high salt, high drag reduction under shear conditions; as with an alcohol (e.g.: methanol, ethanol) and clay inhibitor (e.g. = NaCl or KCl) to improve compatibility, thereby improving the anti-depressants and fluid loss properties of the clay, water reducing Min blocking effect and the occurrence of the phenomenon of water, whereby to secure a high injection pump displacement carrying sand, reservoir fracturing achieve the ultimate goal of a mesh fracture. 与现有技术中使用的瓜尔胶减阻剂、阳离子丙烯酰胺共聚物(DP2)及二元丙烯酰胺系聚合物(DPI)相比,本发明提供的丙烯酰胺系三元共聚物P1-P3提高了与醇和粘土抑制剂的溶解性,作为减阻剂在高盐度条件下具有超过60%的减阻率,并且在pH为 Guar drag reducing agents used in the prior art, the cationic acrylamide copolymer (DP2 is) and the binary propylene-based polymer amide (DPI) as compared to the present invention provides acrylamide terpolymer P1-P3 increase the solubility of the alcohol and clay inhibitor, a drag reducing agent has a drag reduction rate of more than 60% under conditions of high salinity, and pH of

4-10的范围内具有高减阻率。 Having a high rate of drag reduction in the range of 4-10.

具体实施方式 detailed description

[0020] 本发明提供一种丙烯酰胺系三元共聚物,其中,该丙烯酰胺系三元共聚物含有结构单元A、结构单元B和结构单元C,其中,所述结构单元A为具有式(I)所示结构的结构单元,所述结构单元B为具有式(2)所示结构的结构单元,所述结构单元C为具有式(3)所示结构的结构单元,且以所述丙烯酰胺系三元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% ;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10-40摩尔% ;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20-30摩尔%,所述结构单元C的含量为10-20摩尔% ;所述丙烯酰胺系三元共聚物的粘均分子量为1500万-2500万,优选为1800万-2200万; [0020] The present invention provides a terpolymer of acrylamide, wherein the acrylamide terpolymers contain structural units A, structural units B and structural units C, where, A is a structural unit having the formula ( I) and the structural unit structure, to the structural unit B is propylene having the formula (2) shown in structural unit structure, the structural unit having the formula C (3) structural unit represented by the structure, and the total moles of the terpolymer amide structural units, the content of the structural unit a is from 5 to 95 mol%, the content of the structural unit B is from 2.5 to 90 mol%, the structural unit C content of 0.5 to 90 mol%; preferably, the content of the structural unit a is 10 to 70 mol%, the content of the structural unit B is 20-50 mol%, the structural unit content of from 10 to 40 C mol%; more preferably, the content of the structural unit a 50 to 70 mol%, the content of the structural unit B is 20-30 mol%, the content of the structural unit C is 10-20 mol%; the said adhesive acrylamide terpolymer average molecular weight of 15 million 25 million, preferably 18 million -2200 Wan;

Figure CN103570865AD00081

[0022] 其中,Rp R4为氢原子或甲基;R2为叔碳原子与咪唑环上氮原子之间的共价键,或者为C1-C4的亚烷基;R3为C1-C2tl的直链烷基或C3-C2tl的支链烷基;R5为氢原子、C3-C2ci的支链烷基X1-C2tl的直链烷基中部分氢原子被羟基取代的烃基或C3-C2tl的支链烷基中部分氢原 [0022] wherein, Rp R4 is a hydrogen atom or a methyl group; R2 is a tertiary carbon atom on the imidazole ring with a covalent bond between the nitrogen atom, or is a C1-C4 alkylene group; R3 is a linear C1-C2tl alkyl or C3-C2tl branched alkyl; R5 is a hydrogen atom, a linear alkyl, branched C3-C2ci X1-C2tl alkyl group part of hydrogen atoms in the hydrocarbon group substituted with a hydroxyl group or a branched C3-C2tl alkoxy original group part of hydrogen

子被羟基取代的烃基X为Cr、Br' I-、SCN_、 Sub-hydroxy substituted hydrocarbon group X is Cr, Br 'I-, SCN_,

Figure CN103570865AD00082

H3COZ 'Ο-或獲、。 H3COZ 'Ο- or eligible.

[0023] 本发明所述的丙烯酰胺系三元共聚物,在优选情况下,R3为C1-C4的直链烷基或C3-C4的支链烷基;r5为氢原子、C3-C10的支链烷基、C1-C10的直链烷基中一个氢原子被羟基取代的烃基或C3-Cltl的支链烷基中一个氢原子被羟基取代的烃基;X_为Cl—、Br—、I-或 [0023] acrylamide terpolymer of the present invention, in the preferred case, R3 is a linear C1-C4 alkyl group or a branched C3-C4 alkyl; R5 is a hydrogen atom, C3-C10 of branched alkyl, branched alkyl C1-C10 straight chain alkyl group of a hydrogen atom is a hydroxyl substituted hydrocarbyl or C3-Cltl of a hydrogen atom is a hydroxyl-substituted hydrocarbyl; X_ as Cl-, Br-, I- or

Figure CN103570865AD00083

[0024] 本发明中,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,也可以为不同碳原子上的两个氢原子;所述亚烷基可以是直链的,也可以是支链的,例如,所述亚乙基可以是-CH2CH2-或-CH(CH3) -ο本发明中所述C1-C4的亚烷基可以包括但不限于甲烷、乙烷、丙烷、正丁烷或异丁烷中失去两个氢原子后的烃基。 [0024] In the present invention, 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, it may be a different carbon atoms two hydrogen atoms; and the alkylene group may be linear, may be branched, e.g., the ethylene may be -CH2CH2- or -CH (CH3) -ο the present invention, C1-C4 alkylene group may include, but are not limited to, methane, ethane, propane, n-hydrocarbyl after two hydrogen atoms are lost butane or isobutane. 所述C1-C2tl的直链或支链的烷基可以包括但不限于:甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、正己基、正庚基、正辛基、正癸基、正十二烷基、十六烷基或二十烷基。 A straight-chain or branched-chain alkyl group of the C1-C2tl may include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, hexadecyl or eicosyl.

[0025] 本发明的发明人在研究中发现,由特定的结构单元Α、结构单元B与结构单元C组成的三元聚合物能取得极好的减阻效果。 [0025] The present inventors have found in the study, [alpha] by a specific structural unit, the structural unit B terpolymer and consisting of structural units C can achieve excellent drag reduction.

[0026] 在优选的情况下,所述结构单元A为具有式(4)所示结构的结构单元,所述结构单元B为具有式(5)和/或式(6)所示结构的结构单元,所述结构单元C为具有式(7)- (10)所示结构的结构单元中的至少一种, [0026] In the preferred case, the structural unit A having the formula (4) a structural unit structure, the structural unit B is a structure having the formula (5) and / or formula (6) as shown in structure unit, the structural unit having the formula C (7) - at least one structural unit represented by the structure (10),

Figure CN103570865AD00084
Figure CN103570865AD00091

[0030] 本发明还提供一种丙烯酰胺系三元共聚物的制备方法,该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,所述单体混合物含有单体D、单体E和单体F,所述单体D为具有式(11)所示结构的单体,所述单体E为具有式(12)所示结构的单体,所述单体F为具有式(13)所示结构的单体,且以所述单体混合物中单体的总摩尔数为基准,所述单体D的含量为5-95摩尔%,所述单体E的含量为2.5-90摩尔%,所述单体F的含量为0.5-90摩尔% ;优选地,所述单体D的含量为10-70摩尔%,所述单体E的含量为20-50摩尔%,所述单体F的含量为10-40摩尔% ;更优选地,所述单体D的含量为50-70摩尔%,所述单体E的含量为20-30摩尔%,所述单体F的含量为10-20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1500万-2500万,优选 [0030] The present invention also provides a method of preparing an acrylamide-based terpolymers, which comprises the reaction of olefins under solution polymerization conditions, in the presence of an initiator, a monomer mixture of a polymerization reaction in water, the monomer mixture containing a monomer D, E monomers and monomer F., said monomer having the formula D (11) structure of the monomer, the monomer having the formula E (12) as shown in structure of monomers having the formula F (13) of the monomer represented by the structure, and the total moles of the monomer mixture of the monomers, the content of the monomer D is 5-95 mol%, the content of the monomer E is 2.5 to 90 mol%, the content of the monomer is 0.5 to 90 mol% F; preferably, the content of the monomer D is 10-70 mol%, the E content of the monomer is 20-50 mole%, of the monomer content of 10 to 40 mole% of F; more preferably, the content of the monomer D is 50-70 mol%, of the monomers E an amount of 20-30 mol% of the monomer content of 10 to 20 mol% F; with the proviso that the viscosity of the polymerization the resulting polymer after polymerization average molecular weight of 25 million to 15 million, preferably 为1800万-2200万; 18 million -2200 Wan;

Figure CN103570865AD00092

[0032] 其中,所述R1-R5' τ的阐述及优选情况与前文描述相同,在此不做赘述。 [0032] wherein R1-R5 'τ set forth and preferably the same as the case of the foregoing description, and is not repeated herein.

[0033] 根据本发明的方法,单体混合物的重量可以在较大范围内选取,只要保证水能够充分散发聚合反应产生的热量即可,例如: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0.05-0.5:1,优选为0.15-0.4:1,进一步优选为0.2_0.4:1。 [0033] The method of the present invention, the weight of the monomer mixture can be selected over a wide range, as long as the water can be sufficiently dissipate heat generated by the polymerization reaction, for example: the start of the polymerization reaction, the monomer mixture the ratio of the weight of the total weight of the monomer mixture and water is 0.05 to 0.5: 1, preferably from 0.15 to 0.4: 1, more preferably 0.2_0.4: 1.

[0034] 根据本发明的方法,聚合反应中可以使用各类用于溶液聚合的引发剂,其中,可以单独使用一类引发剂,也可以组合使用两类以上的引发剂。 [0034] The method of the present invention, the polymerization reaction solution may be used for various types of polymerization initiators, which may be used alone for a class of initiators may be used in combination of two or more initiators. 在优选的情况下,所述引发剂选自偶氮引发剂和氧化还原引发剂,以摩尔计,所述偶氮系引发剂的用量可以为单体混合物中单体的总摩尔数的0-10摩尔%,所述氧化还原系引发剂的用量可以为单体混合物中单体的总摩尔数的0-10摩尔%,且所述引发剂的用量为单体混合物中单体的总摩尔数的0.0001-10 摩尔%。 In the preferred case, the initiator is selected from azo initiators and redox initiators, in moles, of the azo initiator used may 0- the total number of moles of monomers in the monomer mixture 10 mol%, the redox initiator used may be 0-10 mol% of the total moles of monomers in the monomer mixture, and the amount of initiator in the monomer mixture of the total moles of monomer of 0.0001 mol%. [0035] 在本发明的方法中,所述偶氮引发剂可以选自偶氮二异丁腈、4,4'-偶氮双(4-氰基戊酸)、2,2' -偶氮二异丁基脒盐酸盐和偶氮二咪唑啉基丙烷二盐酸盐中的至少一种。 [0035] In the method of the present invention, the azo initiators can be selected from azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 2,2 '- azobis at least one diisobutylaluminum hydrochloride and azobis imidazolinyl propane dihydrochloride salt.

[0036] 在本发明的方法中,所述氧化还原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可以为0.1-10:1。 [0036] In the method of the present invention, the molar ratio of redox initiators include an oxidizing agent and a reducing agent, the oxidizing agent and the reducing agent may be 0.1 to 10: 1. 所述氧化剂可以选自过硫酸铵、过硫酸钾、过硫酸钠和过氧化氢中的至少一种。 The oxidizing agent may be selected from ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide is at least one. 所述还原剂可以为无机还原剂和/或有机还原剂,例如,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、硫酸亚铁和保险粉中的至少一种; 所述有机还原剂选自N,N' -二甲基乙二胺、N,N' - 二甲基-1,3-丙二胺、N,N,N',N' -四甲基乙二胺、N,N-二甲基乙胺和3-甲氨基丙胺中的至少一种。 The reducing agent may be an inorganic reducing agent and / or an organic reducing agent, for example, the inorganic reducing agent selected from sodium hydrogen sulfite, sodium sulfite, Rongalit, sodium thiosulfate, ferrous sulfate, and sodium hydrosulfite at least one species; the organic reducing agent is selected from N, N '- dimethylethylenediamine, N, N' - dimethyl-1,3-propanediamine, N, N, N ', N' - tetramethyl ethylene diamine, at least one N, N- dimethyl-ethanamine and 3-methylamino-propylamine in.

[0037] 根据本发明的方法,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、扩链剂和其他助剂中的一种或多种。 [0037] The method of the present invention, the polymerization reaction can also be carried out in the presence of various adjuvants, the adjuvant may be selected from a chelating agent, one or more chain extender agents and other additives in. 以所述单体混合物中单体的总摩尔数为基准,所述助剂的用量可以为0.0001-6摩尔%。 In total moles of the monomer mixture of the monomers, the additives may be used in an amount of 0.0001-6 mol%. 其中,以所述单体混合物中单体的总摩尔数为基准,所述螯合剂的用量可以为0-2摩尔%,优选为0.0001-2摩尔% ;所述扩链剂的用量可以为0-2摩尔%,优选为0.0001-2摩尔% ;所述其他助剂的用量可以为0-2摩尔%,优选为0.0001-2 摩尔%。 Wherein the total number of moles of the monomer mixture of the monomers, the chelating agent may be used in an amount of 0-2 mol%, preferably 0.0001 mol%; the chain extender may be used in an amount 0 -2 mol%, preferably 0.0001 mol%; the amount of other additives may be 0-2 mol%, preferably 0.0001 mol%.

[0038] 所述螯合剂可以选自乙二胺四乙酸及其盐(如EDTA_2Na)、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和/或柠檬酸盐,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中的至少一种。 [0038] The chelating agent can be selected from ethylenediaminetetraacetic acid and salts thereof (e.g. EDTA_2Na), triethylene diamine penta-acetic acid, citric acid, citrates, and acrylic acid polyhydroxy at least one, more preferably EDTA and / or citrate, the citrate salt may be potassium citrate, at least one of sodium citrate, ammonium citrate, and calcium citrate in.

[0039] 所述扩链剂可以选自N,N' -二甲基乙二胺、N,N,N',N' -四甲基乙二胺、N,N-二甲基乙胺、3-甲氨基丙胺、N,N'- 二甲基-1,3-丙二胺、1-( 二甲基氨基)-2-丙胺和二亚乙基三胺中的至少一种。 [0039] The chain extender may be selected from N, N '- dimethylethylenediamine, N, N, N', N '- tetramethylethylenediamine, N, N- dimethylethylamine, 3-methylamino-propylamine, N, N'- dimethyl-1,3-propanediamine, at least one 1- (dimethylamino) -2-propanamine and diethylene triamine. 在优选的情况下,所述扩链剂为N,N' - 二甲基乙二胺、N,N' - 二甲基-1,3-丙二胺、N,N,N',N' -四甲基乙二胺和N,N-二甲基乙胺中的一种或多种。 In the preferred case, the chain extender is N, N '- dimethylethylenediamine, N, N' - dimethyl-1,3-propanediamine, N, N, N ', N' - tetramethylethylenediamine and N, N- dimethylethylamine of one or more.

[0040] 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。 [0040] 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.

[0041] 本发明的发明人发现,在同时存在上述引发剂和助剂的条件下,能够得到粘均分子量很高的聚合物。 [0041] The present inventors found that, in the above-described simultaneous presence of an initiator under conditions and auxiliaries, it is possible to obtain a very high viscosity average molecular weight of the polymer.

[0042] 根据本发明的方法,所述聚合反应的条件可以为常规的溶液聚合反应条件。 [0042] The method of the present invention, the polymerization conditions may be conventional polymerization conditions a solution. 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0-60°C,时间为8-24小时,pH值为6-11。 For example, the polymerization reaction is carried out in the presence of an inert gas, the polymerization conditions may include: a temperature of 0-80 ° C, time 1 to 24 hours, pH = 5-13; Preferably, the temperature is 0 -60 ° C, time is 8-24 hours, pH = 6-11. `当需要加入酸调节体系PH值时,所述酸优选为无机酸,所述无机酸可以为盐酸、硫酸、磺酸、硝酸和磷酸中的至少一种。 `When the addition of acid when required to adjust the PH value of the system, the acid is preferably an inorganic acid, the inorganic acid may be at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. 当需要加入碱调节体系PH值时,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。 When the system needs to adjust the PH value of the addition of a base, the base may 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.

[0043] 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 [0043] The present inventors have 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0-5°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_6小时;第三阶段的反应条件包括:温度为35-60°C、优选为40-55°C,时间为2_14小时、优选为4_12小时。 0-10 ° C, preferably 0-5 ° 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_6 hours; the reaction conditions of the third stage comprising: a temperature of 35-60 ° C, preferably 40-55 ° C, 2_14 time hours, preferably 4_12 hours.

[0044] 此外,本发明的发明人在研究中发现,当选择特定的单体D、单体E与单体F进行反应时,能够进一步提高所得的聚合物的减阻效果。 [0044] Further, the present inventors found that in the study, when selecting a specific monomer D, E monomer is reacted with the monomer F, the polymer can be further improved drag reduction obtained. [0045] 在优选的情况下,单体D为具有式(14)所示结构的单体,所述单体E为具有式(15)和/或式(16)所示结构的单体,所述单体F为具有式(17)至式(20)所示结构的单体中的至少一种, [0045] In the preferred case, the monomer D is a monomer having the formula (14) shown in the monomer structure, the monomer having the formula E (15) and / or formula (16) structure, F is a monomer having the formula (17) at least one (20) of a monomer represented by the structure of formula to,

Figure CN103570865AD00111

[0049] 上述式(11)至式(20)所示结构的单体均可以通过商购得到。 [0049] The above formula (11) to (20) of the monolithic structure can be illustrated by a commercially available supplier.

[0050] 本发明还提供了根据上述方法制得的丙烯酰胺系三元共聚物。 [0050] The present invention further provides a terpolymer of the acrylamide obtained by the above method.

[0051] 此外,本发明还提供了所述丙烯酰胺系三元共聚物作为减阻剂的应用。 [0051] Further, the present invention also provides the use of the acrylamide terpolymer as a drag reducer.

[0052] 下面,通过以下实施例对本发明进行更详细的说明。 [0052] Hereinafter, more detailed description of the present invention by the following examples.

[0053] 实施例中所用式(21)、式(23)和式(25)所示的单体均购自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通过商购获得。 Examples of the monomer used in the formula (21), formula (23) and (25) shown in [0053] embodiments were purchased from Sigma-Aldrich Corporation, in addition, unless otherwise noted, embodiments, and comparative tests the polymer used in Examples and reagents were purchased commercially adopted.

[0054] 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虬二吖^^^^^其中!^*』※^)—3,α =0.80进行计算;溶解时间按GB12500.8-89进行测定,测得的溶解时间均小于2小时;分子结构及组成采用IR光谱测定;水不溶物含量按SY/T5862-1993测定;室内减阻率按SY/T6376-1998测定。 [0054] The intrinsic viscosity [[eta]] was measured according to measurement method GB12005.1-89 polyacrylamide intrinsic viscosity number; viscosity-average molecular weight according to the formula wherein Qiu two acridine ^^^^^ ^ * "※ ^) - 3,! calculate α = 0.80; dissolution time was measured by the GB12500.8-89, dissolution times measured were less than 2 hours; the molecular structure and composition were determined by IR spectroscopy; water insoluble matter by SY / T5862-1993 determination; Save chamber press resistivity SY / T6376-1998 measured.

[0055] 实施例1 [0055] Example 1

Figure CN103570865AD00112

[0057] 室温下,将38.1g丙烯酰胺(AM)、28.2g式(21)所示的单体和6.6g丙烯酸甲酯加入到反应瓶中,加入去离子水170.lg,搅拌使单体完全溶解,并分散均匀。 [0057] A mixture of 38.1g of acrylamide (AM), 28.2g of formula (21) and a monomer represented by 6.6g of methyl acrylate was added to the reaction flask was added deionized water 170.lg, stirring the monomer is completely dissolved, and dispersed uniformly. 分别向烧瓶中加入I重量%的EDTA水溶液5.5g,I重量%偶氮二异丁基脒盐酸盐水溶液2.1g,扩链剂N, N' - 二甲基乙二胺0.166g,尿素0.llg,充分搅拌使其混合均匀。 I were added to the flask wt% aqueous EDTA 5.5g, I wt%, azobis isobutyl amidine hydrochloride solution 2.1g, chain extender N, N '- dimethylethylenediamine 0.166g, urea 0 .llg, sufficiently stirred to mix uniformly. 用I重量%的氢氧化钠溶液调节体系PH至7.5。 I PH to 7.5 wt% with sodium hydroxide solution to adjust the system. 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1.lg,并继续通氮除氧20分钟。 The initial temperature control system to 4 ° C, the deoxygenated nitrogen for 30 minutes, I wt% ammonium persulfate aqueous 1.LG, nitrogen and oxygen was continuously for 20 minutes. 将反应器密闭,保持在4°C,反应10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5小时,将得到的胶状产物取出,经造粒、干燥、粉碎获得丙烯酰胺系三元共聚物Pl。 The reactor was sealed and kept at 4 ° C, after 10 hours of reaction, the reaction temperature was raised to 20 ° C for 5 hours and then the temperature was raised to 50 ° C for 5 hours, the resulting gum product is removed, by making granulated, dried, pulverized to obtain acrylamide terpolymer Pl.

[0058] 对Pl进行IR光谱测定,其中,1730CHT1处出现归属于丙烯酸酯单元C=O伸缩振动;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(N — H弯曲振动);在1430CHT1处出现C一N的伸缩振动吸收峰;1356和HOlcnT1出现典型的甲基对称弯曲振动吸收峰JlOOcnT1处小峰归属于咪唑环上C=CH的伸缩振动;2923cm_\2852cm_1处出峰分别归属于-CH2-、_CH3的CH伸缩振动:1508-16540^1出峰归属于咪唑环上C=C伸缩振动:1467011-1出峰归属于-CH2-、-CHj^CH弯曲振动:1034-1229(^-1出峰归属于咪唑环上C=N伸缩振动:12600^1出峰归属于酯键上CO伸缩振动#25-9110^1出峰归属于咪唑环Ar-H平面外弯曲振动。由上述IR光谱中的特征峰可以确定得到的共聚物分子具有式(22)所示的结构,通过粘度法测得Pl的粘均分子量Mv为1820万,单体转化率为99.9%以上。其中,式(22)中X、y和z仅表示出结构单元的 [0058] The Pl spectrometric IR, wherein, 1730CHT1 at home C = O stretching vibration in acrylate units occurred; 1660CHT1 and at 1635CHT1 appears attributable to the amide group are amide I band absorption peak (C = O stretching vibration) and amide II band absorption peak (N - H bending vibration); appears stretching vibration of C-N absorption peak at 1430CHT1; 1356 and HOlcnT1 the typical meth symmetric bending vibration absorption peak JlOOcnT1 small peak attributable to the imidazole ring C = CH stretching vibration; at 2923cm_ \ 2852cm_1 peaks are attributed to -CH2 -, _ CH stretching vibration of CH3: 1508-16540 ^ imidazol-1 ascribed to C = C ring stretching: 1467011-1 peak attributable to -CH2 -, - CHj ^ CH bending vibration: 1034-1229 (^ - imidazol-1 ascribed to C = N ring stretching vibration: 12600 ^ a peak attributed to the stretching vibration of the ester bond CO ^ 1 peak # 25-9110 attributable to the imidazole ring Ar-H bending vibration plane. IR spectrum of the above-described characteristic peaks can be determined in the resulting copolymer molecules having structural formula (22), as measured by viscosity Pl viscosity average molecular weight Mv of 1820 Wan, the monomer conversion was 99.9%, in the formula (22) in the X, y and z are shown only the structural unit 类型和数目,而不表示结构单元的连接方式。X、y和z的具体数值由投料量确定。 Type and number, and does not mean a structural unit .X connection, y and z are the specific values ​​determined by the feeding amount.

Figure CN103570865AD00121

[0060] 对比例I [0060] Comparative Example I

[0061] 按照实施例1的方法制备丙烯酰胺系聚合物,不同的是不加入丙烯酸甲酯、并且丙烯酰胺的加入量为42.5g、式(21)所示的单体的加入量为31g,得到丙烯酰胺系二元共聚物DPl,该丙烯酰胺系二元共聚物DPl的粘均分子量为1750万。 [0061] Following the procedure of Example 1 was prepared acrylamide-based polymer, except that methyl acrylate was not added, and is added in an amount of 42.5 g of acrylamide, of formula (21) was added to the amount of monomer represented 31g, acrylamide obtained binary copolymer DPl, the DPL acrylamide binary copolymer viscosity average molecular weight of 17,500,000. 通过IR光谱分析,除了缺少丙烯酸甲酯所具有的特征峰,DPl中的结构单元所表现出的特征峰的出峰位置与Pl中相同的结构单元所表现的特征峰的出峰位置类似。 Similarly the characteristic peak positions of the peak position of the peak by IR spectroscopy, in addition to the lack of a characteristic peak of methyl acrylate has the structural unit of the DPl exhibited characteristic peaks in the same structural unit as represented Pl.

[0062] 对比例2 [0062] Comparative Example 2

[0063] 按照实施例1的方法,不同的是合成38.1g丙烯酰胺与42.lg(3_丙烯酰胺基-3-甲基)丁基三甲基氯化铵的共聚物DP2,测得该共聚物的粘均分子量为1810万。 [0063] Following the procedure of Example 1, except that 38.1g of acrylamide and synthetic 42.lg (3_ acrylamido-3-methyl) butyl-trimethylammonium chloride copolymer DP2 is, the measured viscosity-average molecular weight of the copolymer was 18.1 million.

[0064] 实施例2 [0064] Example 2

Figure CN103570865AD00131

[0066] 室温下,将38. lg AM、63. 2g式(23)所示的单体和21. 6g甲基丙烯酸羟丙酯加入到反应瓶中,加入355. 5g去离子水,搅拌使单体完全溶解,分别向烧瓶中加入1质量%的EDTA 水溶液4. 65g,加入1重量%偶氮二异丁基脒盐酸盐水溶液1. 23g,加入扩链剂N,N' - 二甲基乙二胺0. 12g,加入0. 1%亚硫酸氢钠溶液1. 13g,加入尿素0. llg,充分搅拌使其混合均勻。 [0066] A mixture of 38. lg AM, 63. 2g so that the formula (23) and a monomer represented by 21. 6g hydroxypropyl methacrylate was added to the reaction flask was added 355. 5g of deionized water, stirring complete dissolution of the monomers, 1% by mass aqueous solution of EDTA were added to the flask 4. 65g, added 1% by weight of azobis isobutyl amidine hydrochloride solution 1. 23g, the chain extender is added N, N '- dimethyl ethylenediamine 0. 12g, was added 0.1% sodium bisulfite solution 1. 13g, urea was added 0. llg, sufficiently stirred to mix uniformly. 控制体系初始温度至4°C,通氮气除氧30分钟后,加入1重量%过硫酸铵水溶液1. 0g 并继续通氮除氧10分钟。 The initial temperature control system to 4 ° C, the deoxygenated nitrogen for 30 minutes, 1 wt% aqueous ammonium persulfate solution was continuously 1. 0g nitrogen and oxygen for 10 minutes. 将反应器密闭,保持在2V,反应8小时后,升温至25°C,反应6 小时后,升温至50°C反应12小时,将得到的胶状产物取出,经造粒、干燥、粉碎获得丙烯酰胺系三元共聚物P2。 The reactor was sealed and kept at 2V, after 8 hours, allowed to warm to 25 ° C, after 6 hours of reaction, the reaction temperature was raised to 50 ° C for 12 hours and the resulting gum product is removed, granulated, dried, pulverized to obtain acrylamide terpolymers P2.

[0067] 对P2进行IR光谱测定,IR光谱中1730CHT1处出现归属于甲基丙烯酸羟丙酯单元C=0伸缩振动;IR光谱中1660cm—1和1635cm—1处分别出现归属于酰胺基的酰胺I带吸收峰(C=0伸缩振动)和酰胺II带吸收峰(NH弯曲振动);在3630(^_1出峰归属于0-H伸缩振动、 1260CHT1出峰归属于C-0伸缩振动、在1050CHT1出峰归属于0-H的弯曲振动;在1430cm_1处出现CN的伸缩振动吸收峰;1310CHT1处小峰归属于咪唑环上C=CH的伸缩振动jgZScnT1、 2852cm-1处出峰分别归属于_CH2_、_CH3的CH伸缩振动;1508-1654CHT1出峰归属于咪唑环上C=C伸缩振动;146701^出峰归属于-CH2-、-CH3的CH弯曲振动;1034-122901^出峰归属于咪唑环上C=N伸缩振动^S-gilcnT1出峰归属于咪唑环Ar-H平面外弯曲振动。由上述IR光谱中的特征峰可以确定得到的共聚物分子具有式(24)所示的结构,通过粘度法测得其粘均分子量Mv为1913万,单体转化率为99. 9%以 [0067] The P2 spectrometric IR, IR spectra attributed to the 1730CHT1 hydroxypropyl methacrylate units C = 0 stretching vibration occurs; IR spectrum at 1660cm-1 and 1635cm-1 were assigned to the amide group of the amide occurs I band absorption peak (C = 0 stretching vibration) and the amide II band absorption peak (NH bending vibration); in 3630 (^ _ a peak attributed to a 0-H stretching vibration, 1260CHT1 a peak attributed to a C-0 stretching vibration, the 1050CHT1 peak attributable to bending vibration 0-H; the emergence of the CN at 1430cm_1 stretching vibration absorption peak; the 1310CHT1 small peak attributable to the imidazole ring C = stretching vibration jgZScnT1 CH, and at 2852cm-1 peaks are attributed to _CH2_ , _CH3 the CH stretching vibration; 1508-1654CHT1 an imidazole ring peak attributed to C = C stretching vibration; 146701 ^ peak attributable to -CH2 -, - CH bending vibration is CH3; ^ 1034-122901 peak attributable to an imidazole ring the C = N stretching vibration ^ S-gilcnT1 bending vibration peak attributed to the outer plane of the imidazole ring Ar-H. IR spectrum obtained by the characteristic peak may be determined in the copolymer molecules having the formula (24) configuration, viscosity measurements obtaining the viscosity average molecular weight Mv of 19,130,000, a monomer conversion of 99.9% to 。其中,式(24)以及x2、y2和z2 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。x2、y2和z2的具体数值由投料量确定。 Where formula (24), and x2, the type and number of the structural unit only shown y2 and z2, showing connections without structural unit .x2, y2, and z2 specific values ​​determined by the feeding amount.

Figure CN103570865AD00132
Figure CN103570865AD00141

[0071] 室温下,将35.6g甲基丙烯酰胺、84.Sg式(25)所示的单体28.8g4_羟基丁基丙烯酸酯到反应瓶中,加入595g去离子水,搅拌使单体完全溶解,分别向烧瓶中加入I重量%的EDTA水溶液7.56g,加入I重量%偶氮二异丁基脒盐酸盐水溶液2.13g,加入扩链剂N,N'-二甲基乙二胺0.01g,加入0.1重量%亚硫酸氢钠溶液2.13g,加入尿素0.20g,充分搅拌使其混合均匀。 [0071] A mixture of 35.6g of methacrylamide, 84.Sg of formula (25) 28.8g4_-hydroxybutyl acrylate monomer represented by the reaction flask was added 595g deionized water and stirred to complete the monomers was dissolved, were added to I% by weight of EDTA to an aqueous solution of 7.56g flask, I wt% azobis isobutyl amidine hydrochloride 2.13 g of an aqueous solution, a chain extender is added N, N'- dimethylethylenediamine 0.01 g, was added 0.1 wt% sodium bisulfite solution, 2.13g, was added urea 0.20g, sufficiently stirred to mix uniformly. 控制体系初始温度至2°C,通氮气除氧30分钟后,加入1%过硫酸铵水溶液3.0g并继续通氮除氧10分钟。 The initial temperature control system to 2 ° C, the deoxygenated nitrogen for 30 minutes, 3.0g of 1% aqueous ammonium persulfate solution was continuously and deoxygenated nitrogen for 10 minutes. 将反应器密闭,保持在2°C,反应8小时后,升温至30°C,反应5小时后,升温至50°C反应4小时,将得到的胶状产物取出,经造粒、干燥、粉碎获得丙烯酰胺系三元共聚物P3。 The reactor was sealed and kept at 2 ° C, 8 hours after the reaction was heated to 30 ° C, the reaction for 5 hours, warmed to 50 ° C for 4 hours, the resulting gum product is removed, granulated, dried, pulverized to obtain acrylamide terpolymer P3.

[0072] 对P3进行IR光谱测定,IR光谱中1730CHT1处出现归属于4_羟基丁基丙烯酸酯单元C=O伸缩振动JeeOcnT1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3630cm—1出峰归属于OH伸缩振动、1260CHT1出峰归属于CO伸缩振动、在ΙΟδΟα1出峰归属于OH的弯曲振动;在1430cm_1处出现CN的伸缩振动吸收峰:1310011-1处小峰归属于咪唑环上C=CH的伸缩振动:2923011'2852cm-1处出峰分别归属于-CH2-、_CH3的CH伸缩振动;1508-1654CHT1出峰归属于咪唑环上C=C伸缩振动;146701^出峰归属于-CH2-、-CH3的CH弯曲振动;1034-122901^出峰归属于咪唑环上C=N伸缩振动#25-911(^1出峰归属于咪唑环Ar-H平面外弯曲振动。由上述IR光谱中的特征峰可以确定得到的共聚物P3分子具有式(26)所示的结构,通过粘度法测得其粘均分子量Mv为1875万,单体转化率为99.9%以上。其中,式(26)以 [0072] The P3 spectrometric IR, IR spectrum appeared at 1730CHT1 attributable to 4_ hydroxybutyl acrylate units JeeOcnT1 C = O stretching vibration attributable to the occurrence and the 1635CHT1 amide group are amide I absorption band (C = O stretching vibration) and the amide II band absorption peak (NH bending vibration); at 3630cm-1 peak attributed to the OH stretching vibration, 1260CHT1 a peak attributed to CO stretching vibration and bending vibration ΙΟδΟα1 peak attributed to the OH; in 1430cm_1 CN stretching vibration occurs at the absorption peak: 1310011-1 small peak attributable to the imidazole ring CH stretching vibration of C =: peaks at 2923011'2852cm-1 are attributed to -CH2 -, _ CH stretching vibration is CH3; 1508-1654CHT1 a peak attributed to the imidazole ring stretching vibration of C = C; 146701 ^ peak attributable to -CH2 -, - CH bending vibration is CH3; ^ 1034-122901 peak attributable to the imidazole ring stretching vibration of C = N # 25-911 (^ a peak attributed to the outer plane of the imidazole ring Ar-H bending vibration. IR spectrum obtained by the characteristic peak may be determined in the copolymer molecule having a structural formula P3 (26) as shown, as measured by viscosity method obtaining viscosity Mv average molecular weight of 18,750,000, a monomer conversion of more than 99.9%., in the formula (26) x3、y3和z3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。x3、y3和z3的具体数值由投料量确定。 Type and number x3, y3 and z3 shows only a structural unit, a structural unit without showing connection of .x3, y3 and z3 specific values ​​determined from the charged amounts.

Figure CN103570865AD00142

[0074] 测试例I [0074] Test Example I

[0075] 水不溶物含量是根据SY/T5862-1993中规定的方法测定的。 [0075] Water insoluble matter according to the method specified in SY / T5862-1993 assay. 将P1_P3、DP1_DP2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_P3, DP1_DP2 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.

[0076]表1 [0076] TABLE 1

[0077] [0077]

Figure CN103570865AD00151

[0078] 从表1中可以看出,P1-P3中水不溶物含量明显低于羟丙基瓜尔胶,说明由本发明提供的方法制备的丙烯酰胺系三元共聚物P1-P3作为页岩气压裂用减阻剂,与羟丙基瓜胶相比,对地层的伤害低。 [0078] As can be seen from Table 1, water-insoluble matter content significantly lower than P1-P3 hydroxypropyl guar, description acrylamide terpolymer P1-P3 produced by the method provided by the present invention is as shale gas fracturing a drag reducing agent, as compared with hydroxypropyl guar gum, low formation damage.

[0079] 测试例2 [0079] Test Example 2

[0080] 在2500rpm剪切速率下,分别将P1_P3、DP1-DP2和部分水解聚丙烯酰胺(HPAM,淄博天健化工有限公司、牌号TJY-3、粘均分子量为1800-2000万,下同)各自分别地缓慢加入到体积比为80/20、60/40的水/醇(本测试例中使用甲醇)溶液中,P1-P3、DP1-DP2和HPAM的用量为水/醇溶液的0.01重量%,溶解时间为30min,结果如表2所示。 [0080] at a shear rate of 2500rpm, respectively P1_P3, DP1-DP2 and partially hydrolyzed polyacrylamide (of HPAM, Tianjian Zibo Chemical Co., Ltd., trademark TJY-3, viscosity average molecular weight 1800-2000 Wan, the same below) are each separately added slowly to the volume ratio of water / alcohol 80/20, 60/40 (in this test Example using methanol) solution, P1-P3, DP1-DP2 HPAM and an amount of water / alcohol solution of 0.01 wt. %, the dissolution time was 30min, the results shown in table 2.

[0081]表 2 [0081] TABLE 2

[0082] [0082]

Figure CN103570865AD00152

[0083] 从表2中可以看出,本发明提供的方法制备的丙烯酰胺系三元共聚物Ρ1-Ρ3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。 [0083] As can be seen from Table 2, acrylamide terpolymer prepared by the process of the present invention provides Ρ1-Ρ3 shale gas fracturing as a drag reducing agent, as compared with the partially hydrolyzed polyacrylamide, with an alcohol good compatibility.

[0084] 测试例3 [0084] Test Example 3

[0085] 在温度为25°C的条件下,将P1-P3、DP1-DP2、HPAM和羟丙基瓜尔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,然后根据SY/T6376-1998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。 [0085] at a temperature of 25 ° C conditions, the P1-P3, DP1-DP2, HPAM and hydroxypropyl guar gum are dissolved in purified water in a concentration of 2 wt%, 4 wt%, 8 wt.%, 10 wt%, 12 wt% NaCl or KCl solution, which was formulated to 500mg / L and 1000mg / L solution, and then according to the method specified in SY / T6376-1998 GLM-1 line friction measuring apparatus Determination of the drag reduction rate of the solution (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), the results as shown in table 3 and table 4.

[0086]表 3 [0086] TABLE 3

[0087] [0087]

Figure CN103570865AD00161

[0088]表 4 [0088] TABLE 4

[0089] [0089]

Figure CN103570865AD00162
Figure CN103570865AD00171

[0091 ] 从表3和表4中可以看出,本发明提供的方法制备的丙烯酰胺系三元共聚物P1-P3作为页岩气压裂用减阻剂,与羟丙基瓜胶、HPAM相比,与粘土抑制剂(如,NaCl或KCl)配伍性好,抗盐性能优异。 [0091] From Tables 3 and 4 can be seen, acrylamide terpolymer P1-P3 produced by the method provided by the invention as a drag reducing agent shale gas fracturing, hydroxypropyl guar gum, of HPAM compared with the clay inhibitors (e.g., NaCl or KCl) good compatibility, excellent salt resistance.

[0092] 测试例4 [0092] Test Example 4

[0093] 减阻率是根据SY/T6376-1998中规定的方法测定的。 [0093] The method of drag reduction is set forth in the SY / T6376-1998 assay. 将P1_P3、DP1_DP2分别溶于纯水,将其配制成500mg/L的溶液,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_P3, DP1_DP2 were dissolved in purified water, which is formulated as 500mg / L solution, by addition of HCl or NaOH, adjusting the pH of the system vary between 2.5 and 10, the results shown in Table 5.

[0094]表 5 [0094] TABLE 5

[0095] [0095]

Figure CN103570865AD00172

[0096] 从表5中可以看出,本发明提供的方法制备的丙烯酰胺系三元共聚物P1-P3作为页岩气压裂用减阻剂在很大的PH值范围内都具有良好的减阻效果。 [0096] As can be seen from Table 5, the method of preparing acrylamide of the present invention provides a terpolymer P1-P3 used as the shale gas fracturing have good drag reducing agents over a wide range of PH value drag reduction.

[0097] 上述测试结果说明本发明提供的丙烯酰胺系三元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,使得压裂水中的水分不易流失,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。 [0097] The above test results indicate acrylamide terpolymers of the present invention provides excellent water solubility, low formation damage; and completely soluble in water / alcohol solution, good compatibility with alcohol; due to improved compatibility alcohol clay inhibitor (NaCl or KCl), so that water is less likely to fracture water loss, fluid loss performance improved resistance; and still have a high drag reduction at high salt wider PH value condition. 此外,本发明提供的丙烯酰胺系三元共聚物的制备方法具有简便且单体转化率高的优点。 In addition, preparation of acrylamide terpolymers of the present invention provides a simple and has the advantages of high monomer conversion.

Claims (12)

  1. 1.一种丙烯酰胺系三元共聚物,其特征在于,该丙烯酰胺系三元共聚物含有结构单元A、结构单元B和结构单元C,其中,所述结构单元A为具有式(I)所示结构的结构单元,所述结构单元B为具有式(2)所示结构的结构单元,所述结构单元C为具有式(3)所示结构的结构单元,且以所述丙烯酰胺系三元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% ;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10-40摩尔% ;所述丙烯酰胺系三元共聚物的粘均分子量为1500万-2500万,优选为1800万-2200万; A terpolymer of acrylamide, wherein the acrylamide terpolymers contain structural units A, structural units B and structural units C, where, A is a structural unit having the formula (I) a structural unit represented by the structure, the structural unit B having the formula (2) shown in structural unit structure, the structural unit having the formula C (3) structural unit represented by the structure, and to the acrylamide-based the total number of moles of the ternary copolymer the structural units, the content of the structural unit a is from 5 to 95 mol%, the content of the structural unit B is from 2.5 to 90 mol%, the content of the structural unit C is 0.5 to 90 mol%; preferably, the content of the structural unit a is 10 to 70 mol%, the content of the structural unit B is 20-50 mol%, the content of the structural unit C of 10 to 40 mol% ; sticky acrylamide the terpolymer of weight average molecular weight 15 million 25 million, preferably 18 million -2200 Wan;
    Figure CN103570865AC00021
    其中,Rp R4为氢原子或甲基;R2为叔碳原子与咪唑环上氮原子之间的共价键,或者为C1-C4的亚烷基;R3为C1-C2tl的直链烷基或C3-C2tl的支链烷基;R5为氢原子、C1-C20的直链烷基、C3-C20的支链烷基、C1-C20的直链烷基中部分氢原子被羟基取代的烃基或C3-C2tl的支链烷基中部分氢原子被羟基取代的烃基;x_为Cr、Br' I _、SCN_、 Wherein, Rp R4 is a hydrogen atom or a methyl group; R2 is a tertiary carbon atom on the imidazole ring with a covalent bond between the nitrogen atom, or is a C1-C4 alkylene group; R3 is a linear alkyl group or C1-C2tl C3-C2tl branched alkyl; R5 is a hydrogen atom, a C1-C20 straight chain alkyl, C3-C20 branched alkyl, C1-C20 straight chain alkyl group part of hydrogen atoms in a hydrocarbon group substituted with a hydroxyl group or C3-C2tl branched alkyl group part of hydrogen atoms in the hydroxyl-substituted hydrocarbyl; X_ of Cr, Br 'I _, SCN_,
    Figure CN103570865AC00022
  2. 2.根据权利要求1所述的丙烯酰胺系三元共聚物,其中,R3为C1-C4的直链烷基或C3-C4的支链烷基;R5为氢原子、C1-C10的直链烷基、C3-C10的支链烷基、C1-C10的直链烷基中一个氢原子被羟基取代的烃基或C3-Cltl的支链烷基中一个氢原子被羟基取代的烃基-X为Cl-、 Br-、I-或 Acrylamide The terpolymer according to claim 1, wherein, R3 is a linear C1-C4 alkyl group or a branched C3-C4 alkyl; R5 is a hydrogen atom, a C1-C10 linear alkyl, C3-C10 branched alkyl, C1-C10 straight chain alkyl group of one hydrogen atom is a branched alkyl group or a hydroxyl-substituted hydrocarbyl group of C3-Cltl one hydrogen atom is a hydroxyl-substituted hydrocarbyl is -X cl-, Br-, I- or
    Figure CN103570865AC00023
  3. 3.根据权利要求2所述的丙烯酰胺系三元共聚物,其中,所述结构单元A为具有式(4)所示结构的结构单元,所述结构单元B为具有式(5)和/或式(6)所示结构的结构单元,所述结构单元C为具有式(7) - (10)所示结构的结构单元中的至少一种, 3. The acrylamide terpolymer according to claim 2, wherein said structural unit having the formula A (4) a structural unit structure, the structural unit B having the formula (5) and / or or a structural unit represented by the structure (6), the structural unit having the formula C (7) - at least one (10) of the structural unit represented by the structure,
    Figure CN103570865AC00024
    Figure CN103570865AC00031
  4. 4.一种丙烯酰胺系三元共聚物的制备方法,该方法包括在烯烃的溶液聚合反应条件下、在引发剂存在下,使单体混合物在水中进行聚合反应,所述单体混合物含有单体D、单体E和单体F,所述单体D为具有式(11)所示结构的单体,所述单体E为具有式(12)所示结构的单体,所述单体F为具有式(13)所示结构的单体,且以所述单体混合物中单体的总摩尔数为基准,所述单体D的含量为5-95摩尔%,所述单体E的含量为2.5-90摩尔%,所述单体F的含量为0.5-90摩尔% ;优选地,所述单体D的含量为10-70摩尔%,所述单体E的含量为20-50摩尔%,所述单体F的含量为10-40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1500万-2500万,优选为1800万-2200万; 4. A method of preparing a terpolymer of acrylamide, which comprises reacting an olefin in the reaction solution polymerization conditions, in the presence of an initiator, a monomer mixture of a polymerization reaction in water, the monomer mixture contains a single body D, E monomers and monomer F., said monomer having the formula D (11) structure of the monomer, the monomer having the formula E (12) of the unitary structure shown, the single body F having the formula (13) shown in the monomer structure, and the total moles of the monomer mixture of the monomers, the content of the monomer D is 5-95 mol%, of the monomer E content of from 2.5 to 90 mol% of the content of the monomer is 0.5 to 90 mol% F; preferably, the content of the monomer D is 10-70 mol%, the content of the monomer E is 20 -50 mol% of the monomer content of 10 to 40 mole% of F; with the proviso that the viscosity of the polymerization the resulting polymer after polymerization average molecular weight of 25 million to 15 million, preferably 18 million -2200 Wan ;
    Figure CN103570865AC00032
    其中,R1-R5以及X-如上述权利要求1或2所定义的。 Wherein, R1-R5 and X- as above defined in claim 1 or claim 2.
  5. 5.根据权利要求4所述的方法,其中,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0.05-0.5:1,优选为0.15-0.4:1。 5. The method of claim 4, wherein the start of the polymerization reaction, the weight ratio 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.
  6. 6.根据权利要求4或5所述的方法,其中,所述引发剂选自偶氮引发剂和氧化还原引发剂,所述偶氮系引发剂的用量为单体混合物中单体的总摩尔数的0-10摩尔%,所述氧化还原系引发剂的用量为单体混合物中单体的总摩尔数的0-10摩尔%,且所述引发剂的用量为单体混合物中单体的总摩尔数的0.0001-10摩尔% ;所述偶氮引发剂选自偶氮二异丁腈、.4,4'-偶氮双(4-氰基戊酸)、2,2'-偶氮二异丁基脒盐酸盐和偶氮二咪唑啉基丙烷二盐酸盐中的至少一种;所述氧化还原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0.1-10:1,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和/或有机还原剂,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、硫酸亚铁和保险粉中的至少一种,所述 The method according to claim 4 or 5, wherein the total moles of initiator selected from azo initiators and redox initiators, the azo initiators are used in an amount of monomers in the monomer mixture number of 0-10 mol%, the redox initiator is 0-10 mole% of the total moles of monomer mixture used in an amount of monomers, and the amount of initiator in the monomer mixture of monomers 0.0001 to 10 mol% of the total number of moles; the azo initiator is selected from azobisisobutyronitrile, .4,4'- azobis (4-cyanovaleric acid), 2,2'-azobis at least one diisobutylaluminum hydrochloride and azobis imidazolinyl propane dihydrochloride salt; molar ratio of the redox initiators include an oxidizing agent and a reducing agent, the oxidizing agent and the reducing agent is 0.1-10: 1, said oxidizing agent is selected from ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide, at least one of the reducing agent is an inorganic reducing agent and / or an organic reducing agent, the inorganic at least one reducing agent selected from sodium bisulfite, sodium sulfite, Rongalit, sodium thiosulfate, ferrous sulfate, and sodium hydrosulfite, said 机还原剂选自Ν,Ν' - 二甲基乙二胺、N,N' - 二甲基-1,3-丙二胺、N,N,N',N' -四甲基乙二胺、N,N-二甲基乙胺和3-甲氨基丙胺中的至少一种。 Machine reducing agent is selected Ν, Ν '- dimethylethylenediamine, N, N' - dimethyl-1,3-propanediamine, N, N, N ', N' - tetramethylethylenediamine at least one N, N- dimethyl-ethanamine and 3-methylamino-propylamine in.
  7. 7.根据权利要求4-6中任意一项所述的方法,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、扩链剂和其他助剂中的一种或多种;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0.0001-2摩尔%,所述扩链剂的用量为0-2摩尔%,优选为0.0001-2摩尔%,所述其他助剂的用量为0-2摩尔%,优选为0.0001-2摩尔%,且以所述单体混合物中单体的总摩尔数为基准,所述助剂的用量为0.0001-6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;所述扩链剂选自N,N' - 二甲基乙二胺、N,N,N',N' -四甲基乙二胺、N,N-二甲基乙胺、3-甲氨基丙胺、N,N' - 二甲基-1,3-丙二胺、1-( 二甲基氨基)-2_丙胺和二亚乙基三胺中的至少一种;所述其他助剂选自尿素、甲酸钠、异丙 The method according to any one of claims 4-6, wherein the polymerization reaction is carried out in the presence of adjuvant, said adjuvant is selected from chelants, one chain extender, and other additives in or more; the total number of moles of the monomer mixture of the monomers, of the chelating agent in an amount of 0-2 mol%, preferably 0.0001 mol%, the chain extender in an amount of 0 -2 mol%, preferably 0.0001 mol%, the other additives in an amount of 0-2 mol%, preferably 0.0001 mol%, and the total moles of monomers in the monomer mixture reference, the adjuvant is an amount of 0.0001-6 mol%; disodium edetate said chelating agent is selected from at least one triethylenediamine pentaacetic acid, citric acid, citrates, and acrylic acid polyhydroxy species; the chain extender is selected from N, N '- dimethylethylenediamine, N, N, N', N '- tetramethylethylenediamine, N, N- dimethylethylamine, 3- methylamino propylamine, N, N '- dimethyl-1,3-propanediamine, 1- (dimethylamino) propylamine and at least one -2_ diethylene triamine; the other co agent is selected from urea, sodium formate, isopropyl 醇和次磷酸钠中的至少一种。 At least one of alcohol and sodium hypophosphite.
  8. 8.根据权利要求4-7中任意一项所述的方法,其中,所述聚合反应在惰性气体存在下进行,所述聚合反应的条件包括:温度为0-80°C,时间为1-24小时,pH值为5-13。 The method according to any one of claims 4-7, 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.
  9. 9.根据权利要求8所述的方法,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。 9. A method according to claim 8, wherein the polymerization reaction comprises three stages sequentially, the conditions of the first reaction stage comprising: a temperature of 0-10 ° C, to 15 hours; second the reaction conditions for 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 hours time.
  10. 10.根据权利要求4-9中任意一项所述的方法,其中,单体D为具有式(14)所示结构的单体,所述单体E为具有式(15)和/或式(16)所示结构的单体,所述单体F为具有式(17)至式(20)所示结构的单体中的至少一种, 10. The method according to any one of claims 4-9, wherein monomer D having the formula (14) shown in the monomer structure, the monomer having the formula E (15) and / or formula (16) shown in the monomer structure, the monomer having the formula F (17) at least one (20) of a monomer represented by the structure of formula to,
    Figure CN103570865AC00041
  11. 11.根据权利要求4-10中任意一项所述的方法制备的丙烯酰胺系三元共聚物。 Acrylamide terpolymer prepared by the process of any one of claims 4-10 11. A according to claim.
  12. 12.权利要求1-3和11中任意一项所述的丙烯酰胺系三元共聚物作为减阻剂的应用。 12. 1-3 acrylamide terpolymer of claim 11 and any one of claim 1 as a drag reducing agent.
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US4460758A (en) * 1983-11-02 1984-07-17 Exxon Research And Engineering Co. Drag reduction agents for aqueous salt solutions
CN102050914A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Ultra-high molecular weight sulfonic acid type acrylamide and preparation method thereof
CN102604622A (en) * 2012-02-20 2012-07-25 西南石油大学 Oil displacing agent containing imidazole ring quaternary ammonium salt polymer and preparation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3868328A (en) * 1972-03-09 1975-02-25 Calgon Corp Friction reducing compounds for use in hydraulic fracturing fluids
US4460758A (en) * 1983-11-02 1984-07-17 Exxon Research And Engineering Co. Drag reduction agents for aqueous salt solutions
CN102050914A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Ultra-high molecular weight sulfonic acid type acrylamide and preparation method thereof
CN102604622A (en) * 2012-02-20 2012-07-25 西南石油大学 Oil displacing agent containing imidazole ring quaternary ammonium salt polymer and preparation method

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