Acrylics · Surfmer - kgk-rubberpoint.de

ELASTOMERE UND KUNSTSTOFFE ELASTOMERS AND PLASTICS

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Acrylics · Surfmer · Nanoemulsion · Reaction condition · Thickener

A novel series of water-soluble hydro-phobically associating terpolymer (WSHAT) nano particles with optimum thickening effect were successfully syn-thesized via free radical emulsion poly-merization using ethyl acrylate (EA), methyl acrylic acid (MAA), polymerizab-le surfactant (AS-25 MA) and N-methy-lol acrylamide (NMA).The terpolymers were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray dif-fraction analysis (XRD), Size Exclusion Chromatography (SEC), Zeta-sizer and Zeta-potential. The results obtained from various characterizations revealed that the molecular segments in amor-phous form with the particle sizes of 30-120 nm. The results showed that na-no modified WSHAT have better thicke-ning effect as compared with commer-cial samples and hence can be used as nano modified thickner.

Effekte einiger Parameter, die das Design von Nano-Wasser-Hydrophobie in Verbindung von Polymeren in wässriger Lösung beeinflussen Acrylate · Surfmer · Nano-Emulsion · Reaktionsbedingungen · Verdicker

Eine neue Serie von wasserlöslichen hy-drophob assoziierenden Terpolymeren (WSHAT) Nanopartikel mit einem Opti-mum im Verdickungseffekt wurden durch freie radikalische Polymerisation von Ethylacrylat (EA), Methylacrylsäure (MAA), polymerisierbarem Tensid (AS-25 MA) und N-Methylolacrylamid (NMA) synthetisiert. Das Terpolymer wurde durch FT-IR, XRD Gelpermeati-onschromatographie (GPC), Zeta-„Sizer“ und Zeta-Potenzial charakterisiert. Die erzielten Ergebnisse aus den verschie-denen Charakterisierungsmethoden of-fenbaren, dass die Molekülsegmente in amorpher Form mit den Partikelgrößen von 30 bis 120 nm vorliegen. Die Ergeb-nisse zeigten, dass nano-modifizierte WSHAT einen besseren Verdickungsef-fekt im Vergleich zu kommerziellen Pro-ben aufwiesen und dass diese somit als ein nanomodifizierter Verdicker einge-setzt werden können.

Figures and Tables: By a kind approval of the authors.

IntroductionHydrophobically associating water-solub-le polymers (HAWS) have recently become the subject of extensive research, due to their important applications in multiple industrial areas such as cosmetics, latex paints, pharmaceuticals, paper and petro-leum industrial, where they are used to increase viscosity in aqueous formulati-ons. The most advantage of HASE is might be less sensitive to effects of ionic strength of the fluid at varieties Salt concentra-tions, In addition, improved thermal sta-bility of product and mechanical proper-ties were observed [1-10] The hydropho-bically associating polymers rank high among the promising dispersion materi-als in formulations include solid compo-nents like inorganic clay, pigments and fillers or organic binder particles, droplets of immiscible fluids, and active ingre-dients due to their unique chemical and physical properties as well as their poten-tial applications as multifunctional it used as control agents in order to provide the desired processing and application properties, due to their additional cross linking formation with other different groups of polymer additives after applica-tion [11-12]. These hydrophobically modi-fied water-soluble polymers have achie-ved commercial acceptance as associative thickeners used in, for example, cosme-tics, paints, and enhanced oil recovery [13,14]. While regular polymers build vis-cosity through a combination of concent-ration and molecular weight, associating polymers depend on the formation of physical network via intermolecular asso-ciation of the hydrophobic groups leading to reversible formation of three dimensio-nal physical cross-links of polymer chains. [15] The Incorporation of small amounts of the hydrophobic monomer has drama-tically enhanced the viscosity values [16-20]. Surfactant plays an important role in emulsion polymerization Polymerizable extensive studies have been performed on hydrophobic acrylic derivatives to be obtained a whole comparison of their be-havior with conventional water soluble

polymers [21, 22]. The synthesized poly-meric associative thickeners include acry-lic-based polymers derived from acrylic acid or acrylate esters among others are the most common thickeners commonly found in paints [22-24] the associative system enhanced a network interaction which established by hydrophobic inter-action through intermolecular aggregates predominated and a three-dimensional network structure formed in latex formu-lation, print pastes and clay/mud leading to the increase in apparent viscosity of the aqueous composition and produces more favorable rheology profiles which provide the ability to hold the latex in well dis-persed state properties over comparable nonassociative systems [25-27]. Vinyl ac-rylic polymers are synthesized by copo-lymerization of acrylates with other materials, either monomers via direct po-lymerization [28] or with natural materi-als via graft copolymerization [29,30] using different polymerization tech-niques. to prepare associating polymers There are many methods , such as micel-lar homogeneous and heterogeneous me-thod the most applied is micellar copoly-merization method. due to it allows to the preparation of associating polymers with high thickening effect , high solid content

Effects of Some Parameters Affecting Designing of Nano-Water Hydrophobically Associating Polymers in Aqueous Solution

AuthorsMagdy A-H Zahran, Waseam A. Hassan, Moneer M. Basuni, Cairo, Egypt

Corresponding author:Moneer Moneer BasuniEBCA R&D Petroleum center Cairo, EgyptPhone: +202 38331682 Fax: +202 38333026 Ext.: 130 Mobile +0201096717177E-Mail: [email protected]

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and good water solubility in addition to homogenous particle size for the polymer obtained, Recently, our research group re-ported [5] the synthesis and aqueous so-lution properties of a series hydrophobic alkali-swellable modified emulsions (HA-SE) with optimum thickening effect via the variation of polymerizable surfactant (AS-25 MA) ratio, ethyl acrylate (EA) and meth acrylic acid (MAA) ratio and ratio in monomer mixture with varying amount of hydrophobic N-methylol acrylamide (NMA) as co-monomers. Our present stu-dy, reports the synthesis, solution proper-ties and thickening efficiency of a series of hydrophobic alkali-swellable modified emulsions (HASE) in Nano scale with vary-ing amount of monomers. The study also examines the impact of some important parameter for preparation of water hydro-phobically associating Polymers such as polymer concentration, initiator concen-tration, polymerization temperature, and reaction time on the percentage of preci-pitate and thickening efficiency of the so-lution were determined.

Experimental

MaterialMethacrylic acid and Ethyl acrylate were obtained from Elf Chem. Co., ATO, France. EMULDAC-AS-25-SC product of Elf Chem. (ATO) company (France). Galaxy les70 Sodium lauryl ether sulfate, Conc. 70 % was obtained from Galaxy Co., India. Two commercial synthetic thickeners, namely Rheovis 112 (HASE thickener 30 % conc., Ciba, Germany) and ACRYSOL™ RM-7 (HASE thickener conc. 30 %, Dow Co., USA), were used throughout this work. All other chemicals used are of laborato-ry reagent grade.

Synthesis of surfmer (EMULDAC-AS-25-SC-Methacrylate)The EMULDAC-AS-25-SC-Methacrylate can be prepared by direct reaction bet-ween EMULDAC-AS-25-SC and Methac-rylic acid in the presence of concentrated H2OS4 or solid Paratoluene sulphonic acid as catalyst and hydroquinone as in-hibitor. The reaction Emuldac AS-25-SC (1532 g, 1 mole) was charged into a 250 ml 3-necked flask settled with a magnet, condenser and thermometer. The tempe-rature was raised to 110 ºC by using a hot plate equipped with a stirrer adjusted at 100 rpm, into which a mixture of me-thacrylic acid (MAA) (111.8 g, 1.3 mole) and hydroquinone (HQ) (3 g, 0.0277 mo-le) was added. The latter was used to

prevent polymerization of MAA at the high temperatures of esterification. Af-terward, p-toluene sulfonic acid (PTS) as a catalyst was added over 3 hrs to remo-ve the water during the course of esteri-fication. Then, the temperature was raised gradually to 120 ºC and hold at this temperature for 2 hrs. A stream of nitrogen air is purged through the flask to prevent polymerization of monomer via oxidation of hydroquinone to quino-ne. The liberation of water was stopped after 2 hrs and the reaction product was cooled, discharged and filtered [5].

Synthesis of acrylic thickenerIn 2 liter three neck flask equipped with magnetic stirrer, condenser, N2 inlet thermometer and heater, a mixture of 29.9 g (1.66 mole) distilled water and 0.1 % of Galaxy les70 was charged and the temperature was adjusted to polymeri-zation temperature (85 ºC). Then the pre-emulsion was prepared by mixing 30 g monomer mixture of ethyl acrylate (EA),the pre-emulsion is stirred well by magnetic stirrer at 500 rpm methacrylic acid (MAA) and visiomer EMULDAC-AS-25-SC, 0.9 gm of Galaxy les70 and 29.1 gm (1.61 mole) distilled water into the flask, the pre-emulsion is stirred well by

magnetic stirrer at 500rpm for 1hr. The initiator solution is prepared by dissol-ving 0.2g of sodium persulfate (0.0008 mole) in 9.8 g distilled water (0.54 mole).Then the temperature of flask contents is raised to 85˚C and the stirring rate was adjusted at 200 rpm. The pre-emulsion and initiator solution were added conti-nuously over 4hrs, the temperature re-mains constant at 85±2° C. After the ad-dition was finished the reaction tempe-rature was hold for 2 h. To ensure a high percentage of monomer conversion, then the flask charge was cooled, filtered and the precipitate was weighted and the viscosity of 1 % solid. the formulas of thickener at different concentration of initiator at constant concentration of vi-siomer AS-25 MA as well as the variation of EA and MAA ratios at constant C18PM are given in Tables 1 respectively. The Structure of synthesis modified water-soluble hydrophobically associating po-lymer (HASE) is represented by the fol-lowing general scheme (Scheme.2):

Thickener Viscosity PropertiesThe polymer solution viscosity is measu-red according to Standard Test Methods for Rheological Properties of Non-New-tonian Materials (ASTM-D2196-99) using

Scheme 1: Synthesis of surfmer (Emuldac AS-25-Methacrylate)

Scheme 2: Structure of the water-soluble hydrophobically associating polymer. From left to right, the structure contains methacrylic acid (MAA), ethyl acrylate (EA), and the surfmer EMULDAC AS-25-Methacrylate (A25M). Its molar monomer ratio (MAA: EA: A25M) is 25:67:10. x, y, and z represent relative molar monomer quantities.



Fig. 3: Effect of initiator concentration on the thickening effect and precipitate

3

LVD V-II Brookfield viscometer with spindle 63 and speed 3 at 24 ºC. The po-lymer solution was measured in distilled water at different concentration of poly-mer solid (solid content range 20-30) af-ter adjusting the pH at 7.5-8 with aque-ous ammonium hydroxide solution (25 %). All samples are adjusted at solid content 20 % by thinning with water and thus 1 % solid = 5 % polymer emulsion.

Solid contentThis test is used to evaluate the solid ma-terial in the polymer emulsion (nearly

equal polymer content). A sample of 1.2±0.1g was weighted into a flat-botto-med glass dish. The sample was gently tilted and spread for 3hrs, in ventilated oven maintained at 105±2 ºC. The film was cooled and weighted, the nonvolatile matter was calculated as follows this equation:

Solid content % =

Where, A: weight of empty dish in gram, B: grams of sample used, C: weight of dish

and content after heating in grams. All sample are adjusted at solid content 20 % by thinning with water and thus 1 % solid = 5 % polymer emulsion.

Rheological study The Rheological study were carried out on a DV-III + CP Programmerable Rheo-meter Brookfield Model LVDV-III + Cp R p 66336 LVD V-3Cp115 Brookfield visco-meter with spindle 52 at controlled tem-perature 25.0 +- 0.1 ºC. The polymer sample was rested for 24 h before measuring by the Rheometer to guaran-tee no were present in polymer solution. Before the measurement, all the polymer samples were rested for 20 min after the cylinder reached the measuring position to eliminate the shear influences.

Electrolyte tolerance This test is used to evaluate the resis-tance efficiency of thickener to electroly-te, where in this test different conc. of NaCl solution is mixed with a polymer solution (1 % solid) of then the viscosity is measured.

Mud properties testEach batch of base mud used in each ex-periment was prepared by adding 80 g bentonite together with 4 g of sodium carbonate into 1000 ml of water before aging it for more than 24 hrs [31].

pH measurementpH measured directly by using MV.temp-PL-700 PV to measure pH of samples af-ter dilution of polymer 3 % deionized water, with periodic calibration with known accurate standards Using diluted buffers pH 4.01 and pH7.00 to calibrate is recommended for best results there would be three time points.

Result and discussion

Synthesis of hydrophpically associative acrylics and their viscosity studiesHydrophpically associative acrylic as thi-ckening agent was prepared in this study by emulsion polymerization technique. The study was aimed to determine the optimum condition for the production of hydrophpically associative acrylics in na-no-scale with high thickening effect and lower precipitate. To achieve this aim va-rious Parameters (surfmer type, stirring rate, polymerization temperatures, addi-tion time, initiator concentration and monomer ratios to each other) were stu-died.

Fig. 1: Effect of polymerization temperature on the thickening effect and precipitate

1

Fig. 2: Effect of addition time on the thickening effect and precipitate

2



Fig. 4: Effect of surfmer EMULDAC-AS-25-SC-Methacrylate concentration on the thickening effect and precipitate

4

Fig. 5: Effect of EMUL-DAC-AS-25-SC-Meth-acrylate concentration on the precipitate percentage

5

Effect of polymerization temperature The emulsion polymerization reactions were contacted at various temperatures ranging from 75 to 98 ºC. The data listed in Fig. 1 indicate that, the thickening ef-fect of polymer obtained increased from 75 to 85 ºC ,but decrease thereafter .The increase thickening efficiency of polymer before 85 could be attributed to the incre-ase in decomposition rate of initiator so-dium per sulphate and it contributed to the polymerization reaction [32]. On the other hand, when the polymerization temperature was high, the decomposition of initiator sodium per sulphate could be too fast and the possibility formation of radical transfer could be greatly enhanced [33].Therefore when polymerization tem-perature exceeded 85 ºC, the thickening efficiency of the product polymer decrea-se due to the shorter life time of initiator sodium persulphate at high temperatu-res, The preferred polymerization tempe-rature which gives hydrophpically associ-ative acrylic in nano size with lower preci-pitate and higher thickening efficiency was between 75 ºC and 85 ºC. So The ideal polymerization temperature is 85 ºC.

Fig. 1 Effect of polymerization tempe-rature on the thickening effect and preci-pitate

Effect of addition time To study The impacts of reaction time on the percentage of precipitate and thicke-ning effect the emulsion polymerization was carry out by addition reaction under predetermined condition for a variety of reaction time ranging from 1 to 6 h, Fig. 2, indicate that, the weight of precipitate decrease with increase the addition time and the viscosity also increase but to cer-tain limit 3 hrs. and then thickening effici-ency return to decrease again, when the addition time exceeded 3 hrs. the thicke-ning efficiency decrease and the precipi-tate percentage become relatively cons-tant. The reason may be attributed to the decline in the number of acrylic mono-mers and the initiator as time increase [34], and the low molleculer weight thick-ner was obtained. the advantage to avoid coagulation, and rubbery past formation at high molecular weight polymer. The ideal reaction time that gives Hydrophpi-cally associative acrylic in nano size with higher thickening effect and low precipi-tate amount was 3 hrs.

Effect of initiator concentrationTo study the effect of initiator concentra-tion on the amount of precipitate and

thickening effect of hydrophobically as-sociating polymers, the range of initiator concentration was varied from 0.05 to 0.27 % of total batch. The data which are presented in Fig. 3, indicated that a small change in initiator concentration lead to dramatic change in precipitate percenta-ge and thickening properties. The initia-tor concentration of 0.15 % was preferred where it gives lower precipitate amount (0.3 %) and give optimum thickening ef-fect at viscosity (26000 cps).on the other hand, the high concentration of the initi-ator stimulated the increase of particle size and molecular weight, the perfor-mance of Water Hydrophobically Associa-

ting Polymers has been shown to be strongly dependent upon the molecular weight .thus 0.15 % initiator concentrati-on is preferred and used as an ideal initi-ator percentage in the next experiment.

Effect of surfmer typeThe selection of the (surfmer) visiomer EMULDAC-AS-25-SC-Methacrylate con-centration is more important where the surfmer is the responsible about the hydrophobic association that is respon-sible for thickening effect and thus the concentration of it affect largely on the thickening effect and precipitate per-centage Fig. 4 shows that, the thicke-

1 Effect of Et.A to MAA ratio on the thickening effect and precipitateMAA Et.A initiator AS-25 NMA ppt.% Viscosity

24 64 0.05 12 1.2 10 1400026 62 0.1 12 1.2 5 2000028 60 0.15 12 1.2 0.3 27000030 58 0.2 12 1.2 0.07 32000032 56 0.25 12 1.2 0.1 3800034 54 0.3 12 1.2 0.25 35000



ning effect and precipitate amount are depended on carbon and ethoxylate number in the structure of surfmer, where the increase in carbon number of alkyl group and ethoxylation number (EO) in parent ethoxylated fatty alcohol enhance the increase in thickening ef-fect and in precipitate percentage that is appear in change of surfmer type from Lutensol TO3 (T3M) to EMULDAC-AS-25-SC (T25M) the viscosity will change from 200 to 9000 and precipitate per-

centage from 0.5 to 7 respectively. The increase of ethoxylation number at con-stant carbon number increase the thi-ckening effect and precipitate percenta-ge. The surfmer based on ethoxylated nonyl phenol give higher thickening 3000 cps TERGITOL NP-30 (N30M) than that is based on ethoxylated fatty alco-hol TO3 (T3M) 100 cps and TO8 (T8M) 200 cps.the visiomer - EMULDAC-AS-25-SC (A25M) give higher thickening ef-fect (8000 cps).

Effect of surfmer (EMULDAC-AS-25-SC-Methacrylate) concentration The surfmer is the responsible about the repulsion and a hydrophobic inter-action that is responsible for thickening effect and thus the concentration of it affect largely on the thickening effect and precipitate percentage .via electro-static mutual repulsion between negati-ve charges on carboxylic groups on me-thacrylic acid which rise after neutrali-zation with alkali causing entanglement in molecule which increase viscosity of the solution [35]. On the other, the surf-mer enhance the increase the mutual repulsion which lead to the largely of the thickening effect Fig. 5 Indicate that increasing of EMULDAC-AS-25-SC-me-thacrylate concentration increase the viscosity but to certain limit (10 %) and also increase the precipitate percentage but to certain limit (10 %) due to the increase of mutual repulsion and hydro-phobic content. high surfmer concent-ration give higher precipitate percenta-ge and lower solution viscosity , thus 10 % EMULDAC-AS-25-SC-Methacrylate concentration was used as an ideal surf-mer percentage.

Effect of different ratios of ethyl acrylate (Et.A) and methacrylic acid (MAA)To study the effect of monomers ratio, the other reaction conditions, such as surfmer type, stirring rate, polymeriza-tion temperatures, addition time, and initiator concentration were kept con-stant. The data shown in Table (1) indi-cate that, the thickening effect change from 14000 cp at (MAA: Et.A=24:64) to 38000 cp. at (MAA: Et.A=32:56) Largely increasing of The MAA concentration in-creases the precipitate.in addition to,the increasing dosage of monomer, lead to the increasing viscosity of the polymer obtained, due to the increased molecu-lar weight of the polymer leading to the increasing viscosity of the polymer ob-tained [22, 23]. At higher monomer con-centration the polymerization solution becomes very viscous, so the stirring be-comes too difficult and the distribution of reactants may be insufficient and hence the conversion of monomer to polymer decreases [24-25]. The opti-mum Et.A: MAA ratio that give higher viscosity and lower precipitate was 32:56, thus the modified polymer from this series namely (EBCA EM 501) is in-volved in the comparative study with another type of thickener.

Fig. 6: Comparison between different thickener samples

Fig. 7: Effect of electrolyte on thickening effect of different sample

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7

2 Effect of Share rate on polymer solutionSpeed (Rpm)

Viscosity (cp)

Share stress (1/sec)

Share rate (D/Cm3)

Torque (%)

1 7486 150.1 2 80.742 3599 160.2 4 84.05 1330 132.1 10 74.9

10 650 142.8 20 76.820 314 140 40 7730 220 125 60 67.2

40 193 155.4 80 84.250 180 175 100 94.160 156 184.3 120 97.3



Comparison between thickening effect of modified polymer (EBCA EM 501) and commercial sample The thickening effect of different type of thickener EBCA EM 501, Rheovise 112 and Acrysol RM7 in distilled water at different concentration are presented in Fig. 6, respectively the (EBCA EM 501) thickener have higher thickening effec-ting in water than Rheovise and acrysol RM7 thickeners at all concentration. Thus can be used for thickening of aque-ous base medium (such as water-base- drilling mud/fluid, aqueous paint, texti-le printing, liquid detergents and cosme-tics) in place of these types of thickener and at lower concentration than them

Comparison between resistances to electrolyte different types of thicke-nersThe resistances of different types of thi-ckeners electrolyte at different dosage are depicted in Fig. 7, respectively. the re-sults clearly indicate that the electrolyte tolerance is more in case of (EBCA EM 501) than in case of Rheovise 112 or Acry-sol RM7 either at high or low concentrati-on of electrolyte, thus can be used in place of them in practical applications such oil field chemicals (enhanced oil re-covery (EOR), drilling fluid /drilling mud, brine), dyeing and coating. the prepared nano hydrophobically associating copoly-mers exhibit a relatively high salt toleran-ce, typical of non-ionic polymers [36-38].

Rheology of polymer solutionThe rheological properties of a hydropho-bically associating water-based copoly-mer solution containing hydrophobically groups were measured by using Program-merable DV-III + CP Rheometer Brook-field. These chemically modified polymer improved properties of have an impor-tant role to use in practical industrial such as oilfield, painting and dyeing. The key success in practical industrial may de-pend on maintaining proper flow and fluids viscosity under certain conditions. The effect of share rate on viscosity of the selected EBCA EM-510 sample was stud-ied at 1-60 rpm using spindle52 at 25 °C, the data are listed in table 2. Both table and figure show decrease in viscosity val-ues with increase share rate that is mean share thinning or in other words Pseudo-plastic behavior, this drop in viscosity may be due to destroying the networks formed by the association between the hydrophobic chains presented in thicken-er molecules leading to drop in viscosity.

Application of Nano-modified acrylic thickener EBCA EM 501The application of (EBCA EM 501) in paint formulation is performed by labo-ratory of Mas Egypt for paints & Chemi-cals Company and proper formula for this company is used. The modified thi-

ckener (EBCA EM 501) is examined ver-sus Acrysol RM-7 that is used in paint formulas. The two thickeners are inser-ted in the same formula of paint and then the viscosity of two formula is mea-sured with Brookfield Viscometer (model: KU-1+), (ASTM-D562) and the glossity

Fig. 8: FTIR spectra of the modified polymer (EBCA EM 501)

Fig. 9: X-Ray spectra of modified thickner (EBCA EM 501) sample

8

9

4 Effect of EBCA EM 501 on ph. properties of water base mud at different temperature and dosageMud formulation T(°C) pHBase mud + 0.1 % EBCA EM 510 12.05 Base mud + 0.5 % EBCA EM 510 50 11.74 Base mud + 0.7 % EBCA EM 510 11.63 Base mud + 0.1 % EBCA EM 510 12.08 Base mud + 0.5 % EBCA EM 510 70 11.76Base mud + 0.7 % EBCA EM 510 11.68Base mud + 0.1 % EBCA EM 510 12.08Base mud + 0.5 % EBCA EM 510 90 11.94Base mud + 0.7 % EBCA EM 510 10.80

3 Viscosity and gloss measurements of Acrysol RM-7 and EBCA EM 501Thickener Acrysol RM-7 EBCA EM 501

solid content 30 30Dosage 0,5 % 0.5 %

Viscosity (KU) 132 133gloss at 60º 52.8 54.8



of two films with thickness 200 micron was measured with, PICOGLOSS 560 MC, (ASTM D523 ). Table (3) shows the results of viscosity and gloss for two formulas. The modified acrylic thickeners (EBCA EM 501) give better glossity and viscosity at lower dosage comparing with commer-cial thickner type Acrysol RM-7 thickener.

Effect of EBCA EM 501 on mud formulation The addition different dosage of nono-modified polymer to mud formulation, under the aging process at different tem-peratures from (30 to 90 ºC) was studied, the results showed that the newly for-mulated has multifunctional properties, it is may be employed as pH controlling in addition to their application as viscosi-ty modifier for water base drilling mud at low and high-temperature degree wi-thout further additives which added to

control pH of the water base drilling mud. The data listed in a table (4) shows the new formulated EBCA EM 501 main-tained the pH of the drilling mud within the desired drilling pH range and showed that, the pH value was slightly deviated after the aging at high temperature. This also reveals the thermal stability of the polymers. The thermal stability may de-scribe to unique chemical structure of new formulated EBCA EM 501 which comprised different functional groups [39] such as ester in poly ethyl acrylate (EA) unit, ethoxylated in prepared surf-mer (Emuldac AS-25-Methacrylate) unit, carboxyls in poly meth acrylic acid (MAA) unit in addition to amides groups in N-methylol acrylamide (NMA) unit. The la-ter groups and their derivatives molecu-les play an important role in long term long term storage and increase antimi-crobial activity [40].

CharacterizationFTIR spectra of modified polymer (EBCA EM 501) FTIR spectroscopy was used as an analyti-cal technique for the estimation of the functional groups presented in modified Polymers [41]. The chemical composition of the modified thickner can for instance be determined by Fourier transform infra-red (FTIR) spectroscopy Fig. 9. FTIR spec-trum in the region from 4000 to 500 cm-1 were recorded with a sample prepared by making a film of the latex on the surface of a glass and drying it, and then remov-ing the film from the glass using TENSOR 27 Mid FT-IR spectrophotometer made by BRUKER Optics Ettlengen-Germany [42]. IR spectra of the modified polymer (EBCA EM 501) sample give band at 3420 cm-1 that is characteristic of carboxyl [OH] group of methacrylic acid, band at 1638cm-1 that is characteristic of ester or carboxyl [C=O] group of ethyl acrylate or methacrylic acid, band at 1129 cm-1 that is characteristic of ether [C-O] group of eth-oxylate groups and give band at 2992 cm-1 that is characteristic of aliphatic [CH] groups and 1170 cm−1 were associ-ated with C–H of alkane, C=O, and C=C stretching frequencies of the ethoxylated fatty alcohol methacrylate surfmer, re-spectively. Water of crystallization stretch-ing vibrations with appearing a σ CH de-formation at 1457.86 cm-1 .and OH out of plan at 1097.23 cm-1 [43].

X-ray diffraction of modified polymer (EBCA EM 501) sampleX-ray diffraction analysis was performed at room temperature for the polymer sam-ple on a Bruker D8 Avance using CuKa as the target with secondary monochomator to operate at 40 kV and 40 mA. The scans were performed within the range of 48, 2u, 608 with scanning step of 0.028 in the reflection geometry. The X-ray diffraction analysis of Non-modified polymer Fig. 18 shows distinct peaks around 12◦ and 20◦. This is attributed to the plenty of carbox-ylic and ethoxilate groups in (MAA and EMULDAC-AS-25-SC-Methacrylate), which can form strong inter-molecular and intra-molecular hydrogen bonds, and hence, the structure of Modified Polymers molecules has certain regularity. The results from X-ray diffraction analysis Fig. 9 show that the modified polymer (EBCA EM 501) sam-ple is amorphous.

Zeta Size and zeta potentialThe behavior of the colloid the particle size of the modified hydrophobically as-

Fig. 10: Zeta size of EBCA EM 501

Fig. 11: Zeta potential of modified thickner (EBCA EM 501) sample

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11

5 Size Exclusion Chromatography (SEC) data for acrysol (RM 7) and modified thickner EBCA EM501Sample Retention

TimeMn(g/mol) Mw(g/mol) MP MZ

(Daltons)MZ+1

(Daltons)Mw/Mn

(polydisper-sity)

Acryzol 23.700 19383 65040 34249 160971 261947 3.355EBCA EM501

26.283 2424 9609 5363 27598 47922 3.963



sociating water-soluble polymers EBCA EM 501 was measured by the malvern instrument in the polymer laboratory of the National Institute of Measurement and Calibration, Egypt. The zeta potential is a key indicator of the stability of collo-idal dispersions the magnitude of the zeta potential indicates the degree of electrostatic repulsion between adjacent Zeta potential [mV] Stability relationship and particle size can be showed in Fig. 10 and Fig. 11 the results of the EBCA EM 501 thickeners which show that the mo-dified polymer in nano particle sizes (30-120 nm) with high emulsion stability.

Size Exclusion Chromatography (SEC) analysis SEC spectra of modified water-soluble hy-drophobically associating terpolymer (WSHAT) namely EBCA EM 501the weight average (Mw), number average (Mn), and polydispersity compared with commercial sample Acrysol (RM 7) are given in table (5).

ConclusionThe nano-associative acrylic thickener na-mely EBCA EM-501 with higher thicke-ning effect and lower precipitate percen-tage (EBCA EM 501) was successfully syn-thesized by emulsion polymerization technique in the presence of 1.2 percen-tage of Galaxy les70 as anionic emulsifier using 0.15 percentage of sodium persulfa-te as initiator at polymerization at tempe-rature 75-85 ºC for 3 hrs reaction time and at monomer ratio 32:56:12 for MAA:EA: EM (EMULDAC-AS-25-SC-Methacrylate).The results showed that nano modified polymer showed multifunctional proper-ties it is give better thickening perfor-mance at high salt concentration compa-red to commercial sample. Furthermore, the newly synthesized Nano-copolymer has a remarkable rheology and pH control properties at both room temperature and high aging temperatures.

AcknowledgmentsThe authors are deeply grateful to the support from EBCA R&D Petroleum cen-ter (Egyptian British co. for chemical and auxiliaries), EGYPT.

Reference[1] Wanli Kang, Xianzhong Wang, Xiaoyan Wu,

Lingwei Meng, Shuren Liu, Bin Xu, and Xiuhua Shan. Designing water-soluble poly-mers for enhanced oil recovery, society of plastics Engineer (SPE)., (2012)

[2] Lai, N., Dong, W., Ye, Z., Dong, J., Qin, X., Chen, W. and Chen, K.,. Journal of Applied Polymer

Science, 129(4), 2013,pp.1888-1896.[3] Bai, Y., Xiong, C., Wei, F., Li, J., Shu, Y. and Liu,

D., 2015. Energy & Fuels, 29(2), pp.447-458.[4] Yap, R.K.L., Whittaker, M., Diao, M., Stuetz,

R.M., Jefferson, B., Bulmus, V., Peirson, W.L., Nguyen, A.V. and Henderson, R.K.,. Water research, 61, 2014, pp.253-262.

[5] Yahiya. A. Youssef, Waseam. A. Hassan, Mohammed A. Tawila, and Moneer M. Basu-ni., Salah. M. El-Kousya, RJPBCS 7(5) 2016, pp. 2650-2664

[6] Ye, Z., Jiang, J., Zhang, X., Chen, H., Han, L., Song, J., Xian, J. and Chen, W., Journal of Applied Polymer Science, 133(11), 2016.

[7] Abidin, A.Z., Puspasari, T. and Nugroho, W.A.,. Polymers for enhanced oil recovery technol-ogy. Procedia Chemistry, 4, 2012,pp.11-16.

[8] A. Kowalczyk1, C. Oelschlaeger, S. Neser, N. Willenbacher, Progr Colloid Polym Sci DOI 10.1007/2882_2008_083

[9] Braun DB, Rosen: MR (2000) Rheology modi-fiers handbook,practical use & application. William Andrew, Norwich,NY, US

[10] Glass JE, editor. Associating polymers in aqueous solution.ACS symposium series 765. Washington, DC: American Chemical Society;2000.

[11] Saeid Kheirandish shat Guy baidullin·Wendel Wohlleben Norbert Willenbacher, Rheol Acta, 2008, DOI 10.1007/s00397-008-0292-1

[12] Otakar Quadrat, Jiˇr´Horský, Libuše Mrkviˇcková, Jana Mikešová, Jarom´ırŠˇnupárek Progress in Organic Coatings 42 (2001) 110–115

[13] Deng, Quanhua, et al. Australian Journal of Chemistry 67.10 (2014): 1396-1402.

[14] Deng, Q., Li, H., Li, Y., Cao, X., Yang, Y. and Song, X.,. Australian Journal of Chemistry, 67(10), 2014, pp.1396-1402.

[15] Hussein, I.A., Ali, S.A., Suleiman, M.A. and Umar, Y.,. European Polymer Journal, 46(5), 2010, pp.1063-1073.

[16] Quadrat, O., Horský, J. and Šňupárek, J.,. Progress in organic coatings, 50(3), 2004,pp.166-171.

[17] Biggs, S., Hill, A., Selb, J. and Candau, F.,. Journal of physical chemistry, 96(3), 1992,pp.1505-1511.

[18] Horský, J., Mikešová, J., Quadrat, O. and Šňupárek, J.,. Journal of Rheology, 48(1), 2004, pp.23-38.

[19] Ma J, Cui P, Zhao L, Huang EurPolym J 38, R (2002), 1627

[20] Taylor, K.C. and NASR-EL-DIN, H.A.,. Rheology of Hydrophobically Associating Polymers for Oilfield Applications. ANNUAL TRANSACTIONS-NORDIC RHEOLOGY SOCIETY, 11, 2003, pp.13-20.

[21] Al-Sabagh, A.M., Kandile, N.G., El-Ghazawy, R.A., Noor El-Din, M.R. and El-Sharaky, E.A., Journal of Dispersion Science and Technol-

ogy, 33(10), 2012.,pp.1458-1469.[22] Glass, J.E., Journal of Coatings Technology,

73(913), 2001, pp.79-98.[23] Zhang, L.M.,. Carbohydrate Polymers, 45(1),

2001, pp.1-10.[24] Kostansek, E.,. Journal of Coatings Technol-

ogy and Research, 4(4), 2007, pp.375-388.[25] Hongping Quan, Zhuoke Liab and Zhiyu

Huang, RSC Adv., 2016, 6, 49281–49288 [26] Kostansek, E., Journal of Coatings Technol-

ogy and Research, 3(3), 2006, pp.165-171.[27] Sperry, P.R., Thibeault, J.C. and Kastanek, E.C.,.

Adv. Org. Coatings Sci. Technol, 9, 1987, pp.1-11.[28] Dupont,Francois,mongoin,Jacques,Sua.,Je

an-Marc,. U.S.patent /0311888 A1, 2010[29] Abdel, M., Zahran, H. and Basuni, M.M.,.

Kautschuk Gummi Kunstst. 68(9), 2015, pp.35-40.

[30] LI Jian-fa1, 2, SONG Zhan-qian1 , SHANG Sh-i bin1, LU Jin-hong: Study on Graft- Copolymerization of Crude Lignosulfonates with Acrylic-Monomers monomers Chemistry and Industry of Forest Products Vol. 24 No. 3 pp1-6. 2004.

[31] M. Ibrahim, M. Nazlina, A. Fauzana, S. Chuah, J. Phys. Sci. 24 (2003) 114-115.

[32] Zahran, M.A., Abd El-Mawgood, W.A. and Basuni, M.M., Kautschuk Gummi Kunstst. 69(7-8), 2016. pp.53-58.

[33] Fang, R., Cheng, X.S., Fu, J. and Zheng, Z.B.,. Natural Science, 1(01), 2009, p.17.

[34] Ibrahim, M.N.M., Lim, S.L., Ahmed-Haras, M.R. and Fayyadh, F.S., BioResources, 9(1), 2014, pp.1472-1487.

[35] Tonge, S.R. and Tighe, B.J., Advanced drug delivery reviews, 53(1), 2001.,pp.109-122.

[36] W. Xue, I. W. Hamley, and M. B. Huglin Polymer 43 (19), (2002) pp 5181–5186.

[37] Y. Bai, C. Xiong, F. Wei, et al., Energy Fuels, 29(2), 2015,, 447–458.

[38] Ye, Z., Jiang, J., Zhang, X., Chen, H., Han, L., Song, J., Xian, J. and Chen, W.,. Journal of Applied Polymer Science, 133(11), 2016.

[39] Liang, L.S. and Ibrahim, M.N.M.,. Journal of Engineering Science, 9, 2013,pp.39-49.

[40] Magdy A-H Zahran, Mohamed M. Mohammady, Moneer M. Basuni: .Design, Synthesis, Aqueous Properties and Investi-gation of Novel Cationic Surfactants as A Long Term Green Corrosion Inhibitors Expo-sure, RJPBCS 7(6) 2016, pp. 1809-1822

[41] Mohamed Rashid Ahmed-Haras, Mohamad Nasir Mohamad Ibrahim, Abdussalam Salhin Mohamed Ali, Coswald Stephen Sipaut, Ashraf Ahmed Ali Abdalsalam, American Journal of Engineering Research (AJER), V(2), Issue-(11), 2013., pp-230-241

[42] NAGHASH, H.J., Karimzadeh, A., Momeni, A.R., Massah, A.R. and Alian, H., Turkish Jour-nal of Chemistry, 31(3), 2007, pp.257-269.

[43] Mallya, P. and Plamthottam, S.S., Polymer Bulletin, 21(5), 1989, pp.497-504

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