Chemical Structure Effect of (Meth) Acrylic Ester Copolymers and Modified Poly (Etliylene-co-Vinyl Acetate) Copolymer on Paraffin Deposition Prevention in Crude Oil

Acrylic and methacrylic esters copolymers in various compositions: were synthesized in order to study the chemical structure effect over their effectiveness as pour point reducers in crude oil. Copolymerization results data from octadecyl methacrylate, hexadecyl methacrylate with methyl methacrylate and octadecyl acrylate, hexadecyl acrylate with methyl acrylate revealed superior results for acrylate monomers compared to methacrylate ones. Copolymers of ethylene and vinyl acetate (EVA) containing 19, 31 and 40% of vinyl acetate were chemically modified aiming to improve their performance as pour point reducer in crude oil. Ester pendant groups were introduced in the copolymer main chains resulting in meaningful increase of their performance as additive.     

Chemical Structure Effect of (Meth) Acrylic Ester Copolymers and Modified Poly (Etliylene-co-Vinyl Acetate) Copolymer on Paraffin Deposition Prevention in Crude Oil

ABSTRACT

Acrylic and methacrylic esters copolymers in various compositions: were synthesized in order to study the chemical structure effect over their effectiveness as pour point reducers in crude oil. Copolymerization results data from octadecyl methacrylate, hexadecyl methacrylate with methyl methacrylate and octadecyl acrylate, hexadecyl acrylate with methyl acrylate revealed superior results for acrylate monomers compared to methacrylate ones. Copolymers of ethylene and vinyl acetate (EVA) containing 19, 31 and 40% of vinyl acetate were chemically modified aiming to improve their performance as pour point reducer in crude oil. Ester pendant groups were introduced in the copolymer main chains resulting in meaningful increase of their performance as additive.     

Investigation of the properties of novel nitrogen-containing poly(meth)acrylate oil thickening agents

A comparative study of the properties of poly(decyl methacrylate) and decyl methacrylate copolymers with N-tert-nonylacrylamide as viscosity index improver-dispersant additives for petroleum oils has been performed. Tests in the I-20A oil have shown that the introduction of substituted acrylamide units improves the thickening and dispersing properties of the poly(meth)acrylate additives, but it reduces their resistance to mechanical degradation.     

丙烯酰胺共聚物作柴油低温流动改进剂的应用研究

合成了丙烯酰胺-丙烯酸烷基酯系列共聚物,考察了该系列共聚物作为柴油低温流动改进剂的作用效果、结构与性能的关系,同时对其作用机理进行了初步分析探讨。结果表明：该共聚物对降低柴油的冷滤点有较好的效果,同时还可以降低柴油的凝点和浊点;共聚物结构对其使用性能有重要影响,在一定范围内,随着共聚物中丙烯酰胺摩尔分数的增加,其降低柴油冷滤点的效果增强;柴油的感受性与丙烯酸酯的碳链长度有一定的匹配性,当二者匹配时效果较好。     

β-Pinene – acrylate copolymer as a potential biodegradable multifunctional additives for lube oil

Viscosity index improver (VII) and Pour point depressant (PPD) performances of the β-pinene based newly developed greener additives were tested in base oil in terms of viscosity index (VI) and pour point (PP), respectively. It is observed that, incorporation of β-pinene induces excellent biodegradability in the acrylate system. Among the two systems, β-pinene – dodecyl acrylate copolymers showed higher VI and pour point depression efficiency than the corresponding decyl acrylate copolymers. The study also indicated that VI and PP values of the additive doped base oils depend on the nature of mineral base oils as well as on the type and concentration of the additives. The synthesized copolymers of each of them with β-pinene (BP) were characterized by spectral, gel permeation chromatographic (GPC) and thermogravimetric analysis. For a comparison the respective homopolymers were also prepared under identical conditions and tested for VII and PPD properties in base oils by the standard ASTM methods. The biodegradability along with multifunctional additive performance showed potential for the copolymers for their industrial application as lube oil additives.     

Homo- and Copolymers of N-Acryloylpyrrolidine and N-Vinylpyrrolidone as Kinetic Inhibitors of Hydrate Formation

Two copolymers of N-acryloylpyrrolidine and N-vinylpyrrolidone with a different ratio of monomeric units and two homopolymers; poly-N-acryloylpyrrolidine and poly-N-vinylpyrrolidone, were synthesized to study the effect of the composition of macromolecular compounds (MMC) on their inhibiting power during formation of gas hydrates. The composition of the MMC was confirmed by ¹H and ¹³C NMR spectroscopy and the ratio of monomeric units in the copolymers was determined with the ¹H NMR spectra. The inhibiting power of the synthesized MMC was determined during hydrate formation.     

二甲基二烯丙基氯化铵的聚合与交联

本文报导了线型和交联聚二甲基二烯丙基氯化铵的制备和红外、核磁共振、热重分析结果。     

Performance evaluation of polymeric blend of vinyl acetate and acrylate-based copolymers in lubricating oil

Polymer modification processes like blending has attracted much attention as an easy, cost-effective and less time-consuming method for developing new polymeric materials enriched with versatile commercial application. Polymer blends are supposed to carry better thermal and mechanical properties compared to their parent polymers. In this view we have prepared a polymer blend of two copolymers– one of vinyl acetate and octyl acrylate and another of methyl methacrylate and dodecyl acrylate and characterized them by FT-IR and NMR spectroscopy. The molecular weight was determined by Gel Permeation Chromatography (GPC). We represented here a comparative study of their mechanical property as well as their performance as flow improver.     

聚α-蒎烯羟基化和聚α-蒎烯大分子单体的聚合性能

用ＨＣＢｒｏｗｎ硼氢化－氧化反应对聚α－蒎烯环内双键进行羟基化，获得了羟基化结构单元为３３％～５０％的产物。羟基化产物与丙烯酰氯反应，得到了带丙烯酸酯基的聚α－蒎烯大分子单体。大分子单体（平均每条分子链上丙烯酸酯基的数目为２．７）在偶氮二异丁腈引发下进行聚合时，生成交联聚合物，聚合转化率为２０％。在相同条件下与甲基丙烯酸甲酯共聚时，大分子单体的聚合转化率可达６０％。所得聚合物中８７．５％是以甲基丙烯酸甲酯为主链、大分子单体为侧链的接枝共聚物；１２．５％是体型共聚物。     

Influence of composition of Poly(meth)acrylate thickeners on the pour point of hydraulic oils

The influence of the characteristics (molecular weight, alkyl group composition, ratio of acrylate to methacrylate units) and dosage of poly(alkyl (meth)acrylate) thickening agents on the pour point of various base oils used for manufacturing hydraulic fluids has been studied. It has been shown that the effect of pour point elevation with the increasing additive concentration can be leveled by extending the range of alkyl groups and introducing methyl methacrylate units into the polymers.     

光敏性双亲性无规共聚物的自组装及其应用

甲基丙烯酸乙酯与肉桂酰氯反应合成光敏性单体甲基丙烯酰氧乙基肉桂酸酯(CEMA),加入阳离子性单体甲基丙烯酸二甲胺乙酯(DM)与疏水性单体甲基丙烯酸甲酯(MMA),在二氧六环介质中通过自由基溶液共聚合成了一系列具有光敏性双亲性无规共聚物 P(DM-co-CEMA-co-MMA)(简称 PDCM),加入乳酸中和,使其进行阳离子化得到了离子型双亲性无规共聚物P(IDM-co-CEMA-co-MMA)(简称 PIDCM,其中 IDM 表示离子化后的 DM 单元)。用傅里叶变换红外光谱、凝胶渗透色谱、核磁共振和示差扫描量热仪等对共聚物进行了表征。PDCM 和 PIDCM 均可在选择性溶剂(二氧六环/水)中进行自组装,形成稳定的聚合物胶束。胶束内部肉桂酰基单元在紫外光下可发生光交联反应,使胶束间定。聚合物组成及离子化程度对胶束粒径、表面荷电量及表面疏水性有影响。自组装形成的聚集体微粒用作乳液稳定剂具有良好效果。     

功能化嵌段共聚物负载铜配合物的制备及其催化氧化性能

利用可逆-加成-断裂链转移自由基聚合的方法合成3种不同嵌段比的双亲水性嵌段共聚物聚甲基丙烯酸二甲氨乙酯-b-聚甲基丙烯酸酯聚乙二醇单甲醚-b-聚甲基丙烯酸二甲氨乙酯(PDMAEMA-b-POEOMA-b-PDMAEMA),将该共聚物与CuSO4或CuCl2配合,采用FTIR,1H NMR,TG,XRD方法对所得配合物的结构和组成进行表征。表征结果显示,阴离子种类(SO24-或Cl-)对配合物的结构及配位都有一定影响,而共聚物的嵌段比影响配合物的铜含量。采用Cu(Ⅱ)/Polymer-3/SO4配合物(Polymer-3:PDMAEMA39-b-POEOMA11-b-PDMAEMA39)催化苯乙烯氧化反应,在80℃、H2O2为氧化剂、m(苯乙烯)∶m(配合物)=200∶1、6 h的条件下,苯乙烯转化率87.8%,苯甲醛选择性82.1%。该催化剂循环使用3次,催化性能几乎不变。     

二烯丙基胺类聚合物的研制和在石油开采中的应用

本文简介了二烯丙基胺类聚合物在国外石油开采中的应用概况,报道了此类聚合物的合成、产品物性和作为多功能油田化学剂的室内评价试验结果。     

Drag reduction and shear resistance properties of ionomer and hydrogen bond systems based on lauryl methacrylate

Based on molecular dynamics simulation results,a lauryl methacrylate polymer with drag reduction and shear resistance properties was designed,and synthesized by emulsion polymerization using 2-vinyl pyridine and methyl methacrylate as the polar polymerization monomer.After ionization of lauryl methacrylate polymer,an ion-dipole interaction based drag reduction agent (DRA) was obtained.The existence of ion-dipole interaction was proven through characterization of the drag-reducing agent from its infrared (IR) spectrum.The pilot-scale reaction yield of the DRA under optimum conditions was investigated,and the drag reduction and shear resistance properties were measured.The results show that:1) The ion-dipole or hydrogen bonding interaction can form ladder-shaped chains,therefore the synthesized DRA has shear resistance properties;2) The larger the molecular weight (MW) and more concentrated the distribution of MW,the better the drag reduction efficiency and the performance of the ionomer system was superior to that of the hydrogen bonding system;3) With increasing shear frequency,the drag-reduction rates of both the DRAs decreased,and the drag reduction rate of the ionomer system decreased more slowly than of the corresponding hydrogen bonding system.From the point of view of drag reduction rate and shear resistance property,the ionomer system is more promising than the hydrogen bonding system     

Synthesis and Evaluation of Some C14MC-MCNR2 Copolymers and C14MC-MA-MCNR2 Terpolymers as Cold Flow Improvers in the Diesel Fuels

In order to find efficient cold flow improvers for diesel fuels, a series of copolymers (C14MC-MCNR₂) derivated from long chain alkyl (i.e., tetradecyl) methacrylate C14MC and methacrylamide (MCNR₂) were prepared, and a series of terpolymers (C14MC-MA-MCNR₂) derivated from tetradecyl methacrylate C14MC, maleic anhydride (MA), and methacrylamide (MCNR₂) were also prepared. These copolymers and terpolymers were purified, and their structures were characterized by IR, ¹HNMR, and GPC. Their low temperature fluidities and filterability, such as solid point depression (ΔSP) and cold filter plugging point depression (ΔCFPP), used as cold flow improvers in two diesel fuels were evaluated. The results indicate that: (1) The C14MC-MCNR₂ copolymers possess good solid point depressing performance. (2) The C14MC-MA-MCNR₂ terpolymers exhibit dual function both as wax dispersants and flow improvers simultaneously, and they all possess very excellent solid point depressing performance, and can attain optimum effectiveness of CFPP depression when NR₂ is morpholine.     

紫外光聚合法合成有机硅改性苯丙微乳液

以丙烯酸丁酯和苯乙烯为单体、γ-甲基丙烯酰氧丙基三甲氧基硅烷为偶联剂和交联剂、十二烷基硫酸钠为表面活性剂、正戊醇为助表面活性剂、米氏酮和二苯甲酮为光引发剂,采用紫外光聚合法在室温下合成有机硅改性苯丙微乳液;考察了该微乳液的耐酸碱性能;采用傅里叶变换红外光谱、热重分析、透射电子显微镜、紫外-可见分光光度计等方法对该微乳液及其涂膜的结构、形貌、光学和热学性能进行了表征。实验结果表明,有机硅改性苯丙微乳液的耐酸性好于耐碱性;该微乳液为透明或半透明状,单体含量为20g(在100g水中)的微乳液在550nm处的透光率达55%,在760nm处的透光率可达87%;粒径为34～55nm,粒径分布指数为1.16～1.18。表征结果显示,所合成的产物为有机硅改性的苯乙烯与丙烯酸丁酯的共聚物。     

疏水性淀粉基阳离子共聚物的合成及堵水性能

通过胶束聚合法合成了疏水性淀粉基阳离子共聚物(HSCC)。以接枝效率为考察指标,确定了最佳合成条件,并用红外光谱对共聚物进行了表征。初步评价了该共聚物的堵水性能。结果表明,在淀粉/丙烯酰胺/二甲基二烯丙基氯化铵/丙烯酸十六酯的质量比为4∶8.3∶1.5∶0.2,体系pH值为6时,接枝共聚反应的最佳条件为:引发剂浓度2.2 mmol/L,表面活性剂含量(质量分数)3%,反应温度50℃,反应时间4 h。合成的共聚物具有良好的堵水效果。     

Synthesis and Evaluation of Some C14MC-MCNR2 Copolymers and C14MC-MA-MCNR2 Terpolymers as Cold Flow Improvers in the Diesel Fuels

Abstract

In order to find efficient cold flow improvers for diesel fuels, a series of copolymers (C14MC-MCNR₂) derivated from long chain alkyl (i.e., tetradecyl) methacrylate C14MC and methacrylamide (MCNR₂) were prepared, and a series of terpolymers (C14MC-MA-MCNR₂) derivated from tetradecyl methacrylate C14MC, maleic anhydride (MA), and methacrylamide (MCNR₂) were also prepared. These copolymers and terpolymers were purified, and their structures were characterized by IR, ¹HNMR, and GPC. Their low temperature fluidities and filterability, such as solid point depression (ΔSP) and cold filter plugging point depression (ΔCFPP), used as cold flow improvers in two diesel fuels were evaluated. The results indicate that: (1) The C14MC-MCNR₂ copolymers possess good solid point depressing performance. (2) The C14MC-MA-MCNR₂ terpolymers exhibit dual function both as wax dispersants and flow improvers simultaneously, and they all possess very excellent solid point depressing performance, and can attain optimum effectiveness of CFPP depression when NR₂ is morpholine.     

Polyacrylates and Acrylate-α-olefin Copolymers: Synthesis,Characterization, Viscosity Studies,and Performance Evaluation in Lube Oil

Homopolymer of isodecyl acrylate and dodecyl acrylate and their copolymers with different compositions of 1-decene were synthesized and characterized. Viscosity measurements of synthesized polymers in toluene solution at 313 K were performed. Six different equations, viz. Huggins, Kraemer, Martin, and Schulz-Blaschke (graphic extrapolation method) and Solomon-Ciuta, Deb-Chatterjee, and Schulz-Blaschke (by a single point determination method) were used to calculate intrinsic viscosity and viscometric constants of the polymer solutions. Molecular weight of the synthesized polymers was determined by the Mark Houwink-Sukurda equation. The pour point and viscosity index of the polymers were evaluated in lube oils.     

DMDAAC/AM絮凝剂的合成与性能评价

以二甲基二烯丙基氯化馆（DMDAAC）和丙烯酰胺（AM）为原料，采用反相悬浮聚合法合成了DMDAAC/AM絮凝剂（JHT絮凝剂），讨论其对聚合物驱产出污水的絮凝和破乳效果。结果表明，JHT有机絮凝剂具有良好的絮凝除浊，破乳除油和去除产出污水中有机污染物的能力。明显优于聚丙烯酰胺有机絮凝剂。