Synthesis and performance evaluation of vegetable oil polymer as a multifunctional lube oil additive

Abstract

The development and utilization of vegetable oils for polymeric materials are currently in the spotlight of the polymer and chemical industry. In this work homopolymer of palm oil and copolymer of it’s with decyl acrylate was prepared and their characterisation was carried out by spectral method, thermogravimitric analysis and gel permeation chromatography method. Performance of these polymers was evaluated by standard ASTM method in base oil. Biodegradability test of polymers was also carried out and shows excellent positive results. A comparison of their performances has also been evaluated and reported.     

Biodegradable multifunctional additives for lube oil: Synthesis and characterization

Homopolymers of isodecyl acrylate and isooctyl acrylate and copolymers of each of them with β-pinene (BP) were synthesized and characterized by spectral, thermogravimetric, and gel permeation chromatographic analysis. Pour point depressant (PPD) and viscosity index improver (VII) properties were tested with additive-doped base oil in terms of pour point (PP) and viscosity index (VI), respectively. Although the isodecyl acrylate polymers were thermally more stable than the isooctyl acrylate polymers, the latter showed higher VI and PPD efficiency. 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 VII. In addition, introduction of BP moiety in the acrylate backbone has induces excellent biodegradability in the above polymers.     

Biocompatible multifunctional lubricating oil additives

Six copolymers of different concentration of dodecyl acrylate and 1-decene with sunflower oil were prepared and their characterization was carried out by spectral, thermogravimetric, and viscometric analysis. Performance evaluation indicates that the polymers effectively act as pour point depressant and viscosity modifier. The viscosity index and pour point values depend on the nature of mineral base oils, polymer type, and also on the concentration of the additives in solution. Biodegradability test was also carried out and as anticipated, the sunflower oil copolymers showed a biodegradable nature in the additive.     

Multifunctional lube oil additives based on maleic anhydride

Copolymer of maleic anhydride with 1-decene was synthesized by using azobisisobutyronitrile as an initiator in toluene solvent and the prepared copolymer was reacted separately with different long chain amines (n-octyl amine, n-decyl amine, and n-dodecyl amine) to get three copolymers. The performance of the polymers in different base oils was evaluated as viscosity modifier (VM) also called viscosity index improver, pour point depressant (PPD), and dispersant by standard ASTM methods. The molecular weight of the polymers was determined by gel permeation chromatography. The TGA value was determined by the standard ASTM method. It was found that the efficiency of the polymers as a VM and dispersant increases with increasing the molecular weight of the polymers as well as with increasing the alkyl chain length. However, the efficiency as a PPD increases with decreasing molecular weight of the prepared polymers and with the decreasing the alkyl chain length.     

Dodecylmethacrylate – olive oil copolymers as potential biodegradable pour point depressant for lubricating oil

The application of greener additives based on vegetable oils has attracted considerable interest due to their biocompatibility and enhanced additive performances compared to conventional additives. Keeping this view in mind and in continuation of our explorative studies on lube oil additives, copolymer of dodecylmethacrylate with olive oil have been synthesized in a focused mono-mode microwave oven using BZP (benzoyl peroxide) as radical initiator. Characterization of the prepared polymers has been performed by spectral (NMR, IR), and SEC-GPC analysis. Performance evaluation of the polymers as pour point depressant (PPD), and viscosity modifier (VM) / viscosity index improver (VII) in different base oils (mineral) have been performed by standard ASTM methods. Biodegradability of the prepared additives was tested against fungal pathogens and microorganisms by disc diffusion (DD) method and by soil burial test (SBT) method respectively. Thermal stability of each of them has been evaluated and included. The multifunctional performances have been compared and reported. The copolymers showed excellent PPD performance along with VM properties and potential biodegradability.     

Multifunctional Additive Performance of Liquid Crystal Blended Polydecylacrylate in Lubricating Oil

A comparative study of additive performance (viscosity modifier [VM], pour point depressant [PPD], and anti wear [AW]) of homo polydecylacrylate (D) and its blend with three different types of liquid crystals (each containing three samples) has been performed. Very low concentrations (100 ppm) of liquid crystals are used in this study and processes include synthesis of D, characterization (FT-IR, NMR) and evaluation. A comparison based on performances has been made among the three different series of liquid crystals (LC) blended homo polydecylacrylate (D). The study indicates the LC blended additives are far better in AW performance compare to only D and their VM and PPD properties are comparable with D and amongst all the three series of liquid crystals, AW performance is better for long alkyl chain length sample. Multifunctional additive performance of this kind of LC blended polyacrylate is reporting for the first time.     

Synthesis and Performance Evaluation of Vinyl Acetate-Maleic Anhydride Based Polymeric Additives for Lubricating Oil

Copolymer of vinyl acetate with maleic anhydride was synthesised and the prepared copolymer was esterified with different long chain alcohols (octyl, decyl, and dodecyl alcohol). The performance of the polymeric additives in different base oils was evaluated as viscosity modifier (VM), also called viscosity index improver and pour point depressant by standard ASTM methods. Intrinsic viscosity and viscometric molecular weight of the polymers were determined by Huggins and Mark-Houwink equation, respectively. It was found that the efficiency of the polymers as a VM increases with increasing the alkyl chain length of the used alcohol. Whereas, the efficiency as a pour point depressant increases with decreasing alkyl chain length of the used alcohol of the polymers.     

新型胺解原油降凝剂PSMA的合成与性能评价

采用分散聚合法以聚乙烯吡咯烷酮(PVP)为分散剂,无水乙醇为分散介质,合成了马来酸酐和甲基丙烯酸十八酯为单体的二元共聚物(PSMA-a),并对聚合物用苯胺进行酰胺化处理,得到降凝剂PSMA。采用傅里叶红外光谱和热失重对聚合物的结构和热稳定性进行表征。以大庆油田原油为实验对象,采用差示扫描热分析、石油凝点试验仪和石油产品运动黏度计对其进行了降凝降黏性能的研究。通过正交试验确定了最佳的单体配比、反应温度、反应时间和引发剂用量。实验表明,当降凝剂质量浓度为750mg/L,PVP用量为单体总质量分数的8%时,具有最佳的降凝降黏效果。     

The effect of cationic surfactant additives on flow properties of crude oil

Pretreatment of the crude oil with flow improver or pour point depressants has received the greatest acceptance due to its simplicity and economy. Three cationic surfactants Bola form based on urea were prepared by quaternization reaction with alkyl dihalides of different chain length (hexayl, decyl-, and dodecyl-dibromide). The prepared compounds (U6, U10, and U12) were evaluated as surface active agents as well as pour point depressant for crude oil compared to monosurfactant (U12a) corresponding to (U12). The surface parameters of each synthesized surfactant were calculated from their surface tension profile including the critical micelle concentration, maximum surface excess (Γ_max), and the minimum surface area (A_min). The free energies of micellization (ΔG°_mic) and adsorption (ΔG°_ads) were also calculated. Its pour point and viscosity decreased significantly after adding surfactants. FTIR studies of crude-surfactant mixture showed remarkable decrease in concentration of viscosity enhancing groups such as alkanes, alcoholic, and acidic groups, indicating the effectiveness of both the surfactants.     

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.     

Homo- and Copolymers of Decyl Methacrylate as Performance Additives for Lube Oil

Homopolymer of decyl methacrylate and its copolymer with styrene at different concentrations using two types of initiators (benzoyl peroxide [BZP] and azobisisobutyronitrile [AIBN]) were synthesized. All the prepared polymers are characterized by FT-IR and NMR. The molecular weight was determined by gel permeation chromatography. The performance of the prepared polymers in different base oils were evaluated as viscosity modifier, also known as viscosity index improver and pour point depressant. The molecular weight of homopolymer prepared by using BZP initiator is higher than homopolymer prepared by using AIBN initiator but molecular weight of copolymers prepared by BZP are lower than copolymers prepared by AIBN initiator. The theromogravimetric analysis value of the prepared polymers was determined by standard ASTM method and it is found that the thermal stability of copolymers decrease with increasing the styrene content.     

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.     

潍北高凝点原油降凝降黏剂的研制

实验室自制的三元共聚物AMV-22与EVA复配,添加SLA-107作助剂,制备适用于胜利油田潍北区块高凝点原油的降凝剂AMVES。实验考察了该降凝剂对原油的降凝降黏效果。DSC热分析结果表明,AMVES加量为1000 mg/L时,可使原油凝点从48℃降低到37℃,析蜡点降低2℃。流变性曲线表明原油的剪切稀释作用随温度升高显著增强,当剪切速率大于100 s^-1后黏度基本不变,降凝剂可以大幅降低启动原油的屈服应力。偏光显微镜图显示原油温度越低,蜡晶网状结构越致密,交联度强,黏度大,流动性差;加AMVES之后原油中蜡晶变为团簇状颗粒,原油的流动性增强。由此可见降凝剂AMVES作用于蜡晶使其三维网状结构破坏,从而有效降低原油凝点和黏度。     

CHROMATOGRAPHIC SEPARATION AND CHARACTERIZATION OF MONO-, DI- AND TRIAROMATIC HYDROCARBONS IN GAS OIL

ABSTRACT

A simple procedure is described for separation of aromatic hydrocarbons into mono-, di- and trinuclear types in Iraqi gas oil. This is accomplished by elution through an alumina adsorption column under standardized conditions. Characterization is performed by UV-absorption and ratio matching method. The method can be used also for investigating aromatic hydrocarbon structures of other petroleum fractions.     

Synthesis of cyclohexanone-alcohol hemiketals and evaluation as flow improver for waxy crude oil

In this paper, four novel cyclohexanone-alcohol hemiketals (KL-1, KL-2, KL-3, KL-4) as waxy crude oil flow improver have been prepared by cyclohexanone and 1-pentanol, 1-Hexanol, 1-heptanol, 1-octanol. Evaluation results demonstrate the hemiketal compounds have obvious effect on the viscosity and pour point of Henan crude oil. DSC analysis showed that waxing point and waxing peak decreased to a certain degree in 0.05% hemiketal solutions. Wax crystal morphology analysis indicated the four hemiketals played a role of nucleation in the process of waxy crude oil decoagulation, and in that way acts as waxy crude oil flow improver.     

Liquid Crystal Blended Polyacrylate as a Potential Multifunctional Additive for Lube Oil

Polydecylacrylate (PDA) is synthesized, characterized (FT-IR and NMR), and evaluated for its performance as anti wear (AW), pour point depressant (PPD), viscosity modifier (VM), and thickening agent in lube oil of different compositions. In addition physical blend of it with liquid crystal (LC) of cholesteryl benzoate (CB) is also made and evaluated, and the data is compared. Molecular weight of the prepared polymer and that of it blends was determined by viscometric analysis. The blends showed better efficiency to act as multifunctional (AW, PPD, VM) additives compare to the pure homopolymer in lubricating oil.     

新型稠油流动性改进剂制备与评价

以脂肪酸和多胺为原料,制备了聚氨酰胺,将其作为稠油流动性改进剂评价了其对稠油凝点和粘度的影响。结果表明,所合成的聚氨酰胺型稠油流动性改进剂有一定的降凝作用,最高达4.1℃。所合成的聚氨酰胺型稠油流动性改进剂中胺的种类与结构对稠油的降粘效果影响较大,脂肪酸的种类与结构对稠油降粘效果影响小。聚氨酰胺分子中主链含氮数少时侧短链烷基结构的作用效果略好于侧长链烷基结构,然而,随着主链含氮数增多时侧长链烷基结构对稠油降粘效果增加。主链含氮原子数少且侧短烷基链的聚氨酰胺的降粘效果最高达23.1%。     

Synthesis of comb bipolymers and their pour point depressing properties

A bipolymer maleic anhydride-methyl acrylate(MAMA) was synthesized from maleic anhydride and methyl acrylate based on molecular design. MAMA further reacted with oleylamine or octadecyl alcohol to generate two comb polymers called Oleamide-MAMA(NMAMA) and OctadecanolMAMA(OMAMA), respectively. The structure of both the polymers was confirmed by their infrared spectral analysis(IR), gel permeation chromatography analysis(GPC) and differential scanning calorimeter(DSC). Moreover, the pour point depressing(PPD) properties of these comb polymers were examined experimentally. Experimental results showed that besides the molecular weight and concentration of the polymers, the length of side chains and the number of functional groups also had great influence on the pour point depressing performance. The π bonds and hydrogen bonds between depressants were the key factors for improving the pour point depressing properties. These results suggest that both OMAMA and NMAMA are potential pour point depressants for industry.     

树枝状长链酯的合成及其作为原油流动改性剂性能研究

以低代树状聚酰胺-胺和系列丙烯酸长链酯为原料,通过分子设计合成了6种具有树状结构的原油流动改性剂。采用傅里叶红外光谱、核磁共振氢谱和元素分析对其结构进行了表征,并研究了系列树枝状长链酯对原油流动性能的影响,主要分析了树状长链酯对原油凝点和流变性能的影响。结果表明,树枝状长链酯对原油流动性的影响不仅与其端基烷基链长度有关,而且与其代数也有关。端基烷基链越长,添加树状长链酯原油体系的凝点和表观粘度降低的越明显;含有8 个支化长链的1.5代树状长链酯对降低原油凝点和表观粘度的效率高于含有4个支化长链的0.5代树枝状长链酯。相同条件下,添加1.5代树状十八酯原油体系的原油凝点和表观粘度高于添加其它1.5代树枝状长链酯的原油体系。     

Synthesis and characterization of polymeric additives based on α-Olefin as pour point depressant for Egyptian waxy crude oil

Several strategies have been utilized to minimize the problems that causes losses of billions of dollars per year to the petroleum industry. Octadecene (OD) copolymerizes with styrene (S) at variable ratios of 1:1, 1:2, and its copolymers were obtained from alkylation by Friedel-Craft followed by esterification and amidation. Infrared spectra (IR), gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy were performed to characterize the end products. Waxy crude oil (Blank PPT = 27°C) from NQ7 well, Qarun Petroleum Company, Western Desert, Egypt, was studied, and the results indicate that crude oil treated with the prepared copolymers at dosage 2,000 ppm depresses PPT to 6°C and enhances the paraffin inhibition (PI) to 80% compared with blank. Good results are obtained by using the highest molecular weight copolymer compared with others.