Preparation and Characterization of Polymeric Surfactants Based on

University of Michigan—Flint, Flint, Michigan 48502, United States. J. Agric. Food Chem. , 2015, 63 (41), pp 9062–9068. DOI: 10.1021/acs.jafc...
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Preparation and Characterization of Polymeric Surfactants Based on Epoxidized Soybean Oil Grafted Hydroxyethyl Cellulose Xujuan Huang, He Liu, Shibin Shang, Xiaoping Rao, and Jie Song J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.5b03765 • Publication Date (Web): 29 Sep 2015 Downloaded from http://pubs.acs.org on October 3, 2015

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Preparation and Characterization of Polymeric Surfactants Based on Epoxidized Soybean Oil Grafted Hydroxyethyl Cellulose Xujuan Huang†, He Liu†*, Shibin Shang†‡*, Xiaoping Rao†‡and Jie Song§ †

Institute of Chemical Industry of Forestry Products, Chinese Academy of Forestry, Key

Laboratory of Biomass Energy and Material, National Engineering Laboratory for Biomass Chemical Utilization, Key and Laboratory on Forest Chemical Engineering, State Forestry Administration, Nanjing 210042, Jiangsu Province, China ‡

Institute of New Technology of Forestry, Chinese Academy of Forestry, Beijing 100091,

China §

Department of Chemistry and Biochemistry, University of Michigan-Flint, Flint,

Michigan 48502, United States AUTHOR INFORMATION *Corresponding author: He Liu & Shibin Shang Email: [email protected] & [email protected]. Phone: 086-25-85482452. Fax: 086-25-85482499.

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ABSTRACT: Epoxidized soybean oil (ESO) grafted hydroxyethyl cellulose (HEC)

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was prepared via ring-opening polymerization, in which the hydroxyl groups of HEC

3

acted as initiators, and the polymeric ESO were covalently bonded to the HEC.

4

Hydrolysis of ESO grafted HEC (ESO-HEC) was performed with sodium hydroxide,

5

and the hydrolyzed ESO-HEC (H-ESO-HEC) products were characterized via Fourier

6

transform infrared (FT-IR),

7

spectroscopies, high-temperature gel permeation chromatography (HT-GPC), and

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differential scanning calorimetry (DSC). The results indicated that ring-opening

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polymerization of ESO occurred with the hydroxyl groups of HEC as initiators. The

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molecular weights of the H-ESO-HEC products were varied by adjusting the mass

11

ratio of HEC and ESO. Through neutralizing the carboxylic acid of H-ESO-HEC with

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sodium hydroxide, novel polymeric surfactants (H-ESO-HEC-Na) were obtained, and

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the effects of polymeric surfactants on the surface tension of water were investigated

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as a function of concentration of H-ESO-HEC-Na. The H-ESO-HEC-Na was effective

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at lowering the surface tension of water to 26.33 mN/m, and the critical micelle

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concentration (CMC) value decreased from 1.053 to 0.157 g/L with increases in

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molecular weights of the polymeric surfactants. Rheological measurements indicated

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that the H-ESO-HEC-Na solutions changed from pseudoplastic property to Newtonian

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with increasing shear rate.

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KEYWORDS: hydroxyethyl cellulose; epoxidized soybean oil; polymeric

21

surfactants

1

H and

13

C nuclear magnetic resonance (NMR)

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INTRODUCTION

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Polymeric surfactants are important for a variety of industrial applications. The

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increasing interest in natural, renewable and biodegradable materials makes natural

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polymers like cellulose and its derivatives attractive raw materials for the preparation

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of bio-polymeric surfactants.1 Cellulose-based polymeric surfactants have drawn

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much attention in the last decades because they present many novel performances

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such as low cost, biodegradation, associative properties in water, rheological

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properties, and surface-active properties that can control foaming or emulsion

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stability.2-7

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Landoll did pioneering work on cellulose-based polymeric surfactants in

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1980s.8,9 Since then, various cellulose-based polymeric surfactants have been

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synthesized

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Cellulose-based polymeric surfactants were generally synthesized by the modification

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of hydrophilic cellulose backbones with hydrophobic long alkyl chains. Hydroxyl

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groups always have chemical handles that can react with hydrophobic chains

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containing epoxide, halide, acyl halide, isocyanate or anhydride for the preparation of

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amphiphilic cellulose. Polymeric surfactants based on hydroxyethyl cellulose (HEC)

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were prepared by the reaction of a long-chain terminal epoxide with the hydroxyl

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groups of HEC in an alkaline slurry.9 Partial hydrophobization of carboxymethyl

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cellulose with C12–C18 alkyl halides was carried out in the presence of sodium

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hydroxide as a catalyst in DMF/H2O (1:1).16 The HEC-based copolymer was prepared

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via ultraviolet irradiation by copolymerizing HEC with hexadecyl acrylate and

including

nonionic,

ionic,

fluorocarbon,

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amphoteric.10-15

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co-monomer styrene (St) in aqueous solution.12 The C10–C14 alkyl cellulose ester

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sulfate surfactants were prepared by hydrophilic sulfonation and hydrophobic

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esterification.17 Further attempts to substitute the environmentally dangerous

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petrochemical products as well as schemes to increase the hydrophobicity of cellulose

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derivatives with fatty acids to synthesize cellulose-based surfactants have been

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investigated.18,19 Grafting fatty acid chains to cellulose increases the hydrophobicity

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of the ester derivatives even at a low degree of esterification.

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Although fatty acid esters are found in nature as triglycerides and inexpensive as

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acylation reagents, the improvement of surface-active properties of fatty

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acid-esterified cellulose derivatives is limited.1 According to the literature, the surface

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tension of water was decreased from 72.8 mN/m to 46 - 65 mN/m by fatty

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acid-esterified cellulose derivatives.18 However, it is well known that saponified fatty

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acid esters are an important surfactant and are effective at lowering the surface tension

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of water from 20 to 40 mN/m.20,21 In addition, the surface tension of polymerized

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saponified fatty acid ester is 20.5 to 39.6 mN/m.22 This study suggests that, versus

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saponified fatty acid esters, polymerized saponified fatty acid esters have similar

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utility at lowering the surface tension of water. Saponified fatty acid-grafted cellulose

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surfactants formed via cellulose derivatives as backbones are polymerized saponified

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fatty acid surfactants. Therefore, cellulose chains grafting saponified fatty acid esters

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to form ionic surfactants—instead of fatty acid-esterified cellulose surfactants—may

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become an effective method for synthesis of cellulose-based surfactants with highly

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surface-active properties. Fortunately, the chemical reactivities of some fatty acids 4

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isolated from vegetable oils can achieve this vision.

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Soybean oil is one of the most abundant renewable vegetable oils in the world.23

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It possesses three unsaturated fatty acids, oleic (23%), linoleic (54%) and linolenic

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(8%). It contains 1, 2, and 3 double bonds, respectively.24 The double bonds can be

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used in many reactions including addition reaction25, oxidation reaction26, and

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polymerization reaction27. More significantly, the expoxidation reaction makes the

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soybean oil become epoxidized soybean oil (ESO). A ring-opening reaction of ESO

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with different alcohols was carried out in presence of Amberlyst 15 (Dry) as a

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catalyst.28 Furthermore, the ring-opening polymerization of ESO can be catalyzed by

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boron trifluoride diethyl etherate (BF3·OEt2) in liquid carbon dioxide and methylene

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chloride, respectively.26,29 The ESO-based polymeric surfactants in particular were

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prepared by hydrolysis of polymerized ESO with a base.22 These interesting works

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suggest that hydroxyl groups of cellulose can initiate ring-opening polymerization of

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ESO in the presence of catalysts. Moreover, novel saponified fatty acid-modified

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cellulose-based polymeric surfactants are obtained by saponification of the ESO

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grafted cellulose products in which fatty acid chain are combined with cellulose by an

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ether linkage at the middle site of a fatty acid molecular chain.

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To prove this assumption, the modification of HEC by grafting ESO was

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investigated and hydrolysis of ESO grafted HEC (ESO-HEC) was performed with

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sodium hydroxide (Figure 1). The hydrolyzed ESO-HEC (H-ESO-HEC) products

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were characterized with Fourier transform infrared (FT-IR), 1H and

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magnetic resonance (NMR) spectroscopies, high-temperature gel permeation 5

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chromatography (HT-GPC), and differential scanning calorimetry (DSC). After

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neutralizing the carboxylic acid of the H-ESO-HEC with sodium hydroxide, novel

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polymeric surfactants (H-ESO-HEC-Na) were obtained and the effects of polymeric

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surfactants on the surface tension of water were investigated as a function of

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concentration of H-ESO-HEC-Na. In addition, the rheological behaviors of the

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H-ESO-HEC were investigated.

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MATERIALS AND METHODS

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Materials. Hydroxyethyl cellulose (HEC), epoxidized soybean oil (ESO) and

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stannic chloride (SnCl4) were purchased from Aladdin Industrial Co., Ltd. Dimethyl

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sulfoxide (DMSO) was purchased from Sinopharm Chemical Reagent Co., Ltd.

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Sodium hydroxide (NaOH), hydrochloric acid (HCl) and ethyl acetate were obtained

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from Nanjing Chemical Reagent Co., Ltd. Deionized water was purified to a

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conductivity of 18.3 MΩ·cm on a Hitech-Sciencetool Master-Q laboratory water

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purification system (Shanghai Hetai Reagent Co., Ltd). All chemicals were used

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without further purification.

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Synthesis of ESO-grafted HEC Derivatives (ESO-HEC). HEC (1.0 g) was

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dissolved in 40 mL DMSO under stirring at room temperature for 2 h and then

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transferred into a three-necked round-bottomed flask. ESO (1.0 g) was added to the

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HEC solution. The mixture was stirred by mechanical agitation at room temperature.

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A mixture of 10 µL SnCl4 and 10 mL DMSO were then added dropwise into the

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reactor, and the reaction was maintained for 30 min. The resulting products were

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washed sequentially with deionized water to remove DMSO and dried under vacuum 6

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at 50 °C. Finally, the ESO-grafted HEC derivatives (ESO-HEC) were obtained.

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Hydrolysis of ESO-HEC (H-ESO-HEC). The ESO-HEC (2.0 g) was added to a

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flask with 50 mL of 0.6 M NaOH solution. The reactor was heated to 100 °C with

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agitation for 12 h under a condensing condition. After reaction, the solution was

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separated by filtration and the aqueous solution was removed by reduced pressure

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distillation. The solid product was washed with ethyl acetate three times to remove the

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glycerin. The solid product was then re-dispersed in aqueous solution and the solution

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was adjusted to pH 5~6 by 0.1 M HCl. The solution became turbid, and the product

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appeared as a floating oil. The product was extracted by ethyl acetate, and the organic

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phase was washed with hot distilled water three times. Finally, the H-ESO-HEC

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product was purified by reduced pressure distillation. The H-ESO-HEC-Na was

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obtained by neutralizing the carboxylic acid of H-ESO-HEC with sodium hydroxide.

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FT-IR. Fourier transform infrared (FT-IR) spectra was used to confirm the

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structure of the H-ESO-HEC. These spectra were obtained on the Thermo Scientific

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Nicolet IS10 spectrometer with the attenuated total reflectance (ATR) method. The

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spectra were recorded over the range 4000-500 cm-1 at 4 cm-1 resolution and averaged

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over 16 scans per sample.

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NMR. 1H NMR and 13C NMR spectra for H-ESO-HEC were recorded at 40 °C

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on a BRUKER AV400 spectrometer (Bruker, Rheinstetten, Germany) operating at a

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frequency of 400.13 and 100.61 MHz, respectively. Deuterated dimethyl sulfoxide

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(DMSO-d6) and tetramethylsilicane (TMS) were used as the solvent and the internal

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standard, respectively. The chemical shift values were referenced to the signals of 7

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DMSO-d6 and TMS.

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HT-GPC. Molecular weight distribution curves and relative values of number

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average (Mn) and weight average (Mw) molecular weight of H-ESO-HEC were

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determined by HT-GPC (HT-GPC Module 350A, Viscotek; GPC equipped with

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I-MBHMW-3078 HT-GPC column) at 60 °C. The HT-GPC instrument was equipped

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with refractive index detector, viscosity detector and small-angle light scattering

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detector. The flow rate of the carrier solvent (HPLC-grade DMSO) was 1.0 mL/min.

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Samples were filtered over microfilters with a pore size of 0.2 µm (Nylon, Millex-HN

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13 mm Syringes Filters, Millipore). The results were obtained from OmniSEC

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software.

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Conductimetry. The carboxyl content of H-ESO-HEC was determined by

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conductometric titrations.30 The H-ESO-HEC (30-40 mg) was suspended into 15 mL

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of 0.01 M hydrochloric acid solution. After 2 h of stirring, the suspensions were

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titrated with 0.01 M NaOH. The carboxyl content of the sample was determined from

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the conductivity and VNaOH curve. The carboxyl content is calculated by the following

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equation:

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Carboxyl Content (mmol/g) =

c (V2 − V1 ) m

(1)

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Here, V1 and V2 are the volumes of NaOH (mL) in the first and second inflection point

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of titration curves, respectively. The c is the concentration of NaOH (mmol/L), and m

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is the weight of oven-dried sample (mg). To minimize errors, titrations were

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duplicated at least three times, and the average value was retained for the discussion.

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DSC. To determine the ring-opening polymerization of ESO, the DSC 8

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measurements of the H-ESO-HEC were performed on a Diamond DSC at 40 mL/min

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dry nitrogen as the purge gas. Typically, ~4 mg of the H-ESO-HEC was accurately

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weighed in an aluminum pan and sealed with pin-perforated lids. The sample was

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cooled to -50 °C at a rate of 10 °C/min and a refrigerated cooling system was used to

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equilibrate the sample at -50 °C for 5 min. Data were recorded while the oven

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temperature was raised from -50 °C to 0 °C at 10°C /min.

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Surface Tension. The surface tension of H-ESO-HEC-Na was measured at

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25 °C using the Wilhelmy plate T107 (width: 19.44 mm; thickness: 0.1 mm; height:

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65 mm; circumference: 39.08) on a Sigma 701 Automatic Surface Tensiometer. The

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instrument was calibrated against pure water before measurements were made. The

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concentration of H-ESO-HEC-Na surfactant was gradually increased by dispersing

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stock solution into the measurement cell. The software automatically determined the

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surface tension as a function of the bulk concentration. The surface tension data were

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plotted against the H-ESO-HEC-Na concentration in water from 0.0003 to 2.0 g/L.

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Each concentration of aqueous H-ESO-HEC-Na solution was tested in triplicate—this

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was done automatically by the instrument. The concentration at which the equilibrium

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surface tension of the polymeric surfactants stopped decreasing with concentration

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and plateaued is the critical micelle concentration (CMC).22 From the inflection point

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of the plot, the critical micelle concentration (CMC) and minimum surface tension

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(γcmc) were derived. All data were obtained from the OneAttention software.

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Krafft Point (KP). 20 mL 0.5 wt% surfactant aqueous solution (at least

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quintuplicate the CMC of studied surfactant) was prepared in an alkaline solution and 9

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added to a beaker. The beaker was then heated and the particular temperature was

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recorded as KP when the solution transformed from turbid to pellucid.31

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Hydrophile Lipophile Balance (HLB) Value. The emulsions were prepared

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using a mixture of the nonionic surfactants Tween 60 and Span 80 to satisfy the

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proper HLB values for optimum emulsification conditions. The mixed HLB values

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were calculated with the following equation:

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HLBmix = HLBT × T % + HLBS × S %

(2)

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Here, HLBmix, HLBT and HLBS are the HLB values of the mixed surfactants, Tween 60

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(14.9) and Span 80 (4.3), respectively. The T% and S% are the mass percentages of

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Tween 60 and Span 80 in the mixed surfactants, respectively.32 All the HLB values

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used were measured at 25 °C.

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Rheology. Rheological measurements were performed at a rotational rheometer

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HAAKE MARS II equipped with a measuring geometry named PP60 Ti (diameter d=

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50 mm). The H-ESO-HEC-Na-III was selected to evaluate the rheological properties.

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H-ESO-HEC-Na-III solutions at three different concentrations (0.1 g/L, 1 g/L, 5 g/L)

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were prepared to measure the shear viscosity that changed with the shear rate ranging

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from 0.01 to 100 s-1.15 The rheological measurements were carried out at 40 °C. All

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data were obtained using the HAKKE RheoWin data manager software.

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Statistical Method. Origin Pro 9.0 was used to calculate the standard deviation of

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carboxyl content and the surface tension of H-ESO-HEC. The standard deviation was

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calculated with the following equation:

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n

∑(X 198

S=

i

− X )2

i =1

n −1

(3)

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Here, S is the standard deviation of a sample. X i is the ith value in a sample, X is

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the average number of a sample, n is the total number of a sample.

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RESULTS AND DISCUSSION

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Figure 1 outlines a simplified mechanism for the entire reaction. The ESO-HEC

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was prepared via ring-opening polymerization, in which the hydroxyl groups of HEC

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acted as initiators. In addition, the ring-opening polymerization generated new

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hydroxyl groups that can also act as initiators via the SnCl4 catalyst. The polymeric

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ESO were covalently bound to the HEC, and hydrolysis of ESO-HEC (H-ESO-HEC)

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was obtained with sodium hydroxide. As shown in Table 1, H-ESO-HEC products

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with different molecular weights were obtained by adjusting the mass ratio of HEC

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and ESO in graft reaction. The graft reaction occurred at room temperature with a

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short reaction time because of the high-activity of the SnCl4 catalyst. The yields of the

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H-ESO-HEC were measured and ranged from 1.2 to 2.7 g per g HEC as the amount of

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ESO increased in graft polymerization reaction. In addition, H-ESO-HEC-Na samples

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with different molecular weights were obtained by neutralizing carboxylic acid of

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H-ESO-HEC with sodium hydroxide.

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Spectroscopic Identification of the Structures of H-ESO-HEC. In Figure 2,

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the FT-IR spectrum of H-ESO-HEC-III attested to the presence of ESO chains onto

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the HEC by appearance of the characteristic absorption bands assigned to the carbonyl

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functions at 1710 cm-1 versus the HEC. The spectral peak at 2920 cm-1 was attributed 11

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to the –CH3 group of the alkane chains of ESO. Also, peaks at 716 cm-1 indicate the

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vibration of –(CH2)n– (n ≥ 4).33 No significant change in hydroxyl group signal at

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3360 cm-1 was noticed because the hydroxyl groups of the HEC acted as initiators and

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were consumed in the grafting reaction. The ring-opening polymerization generated

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new hydroxyl groups simultaneously—these are obvious from Figure 1. These results

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indicated that the H-ESO-HEC was prepared successfully. The introduction of the ESO on HEC chains is further confirmed by the 1H and

225 226

13

C NMR spectra of the H-ESO-HEC-III in Figure 3. In 1H NMR spectrum, the

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clusters of signal peaks ranged from δ0.8 to δ1.6. These were related to the protons of

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the alkane chains of ESO on HEC. The peaks at δ2.1 corresponded to the side groups

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–OH of the HEC. The alkane chains were produced by the ring-open reaction. The

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clusters of signal peaks in the range of δ3.2 to δ5.0 were attributed to the chemical

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shifts of anhydroglucose unit (AGU) protons. In the 13C NMR spectrum, the possible

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assignments of the peaks were found according to the previous literature.34,35 The

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inserted region at δ176 correspond to carbonyl signals of the carboxylate groups.36

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The C-1 carbon resonance in AGU was poor at δ101. The clusters of signal peaks in

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the range of δ62 to δ76 contributed to the chemical shifts of AGU carbons. Table 2

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offers detailed information. Distinct peaks were observed at δ62. There are attributed

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to the C-6 substituted by the hydroxyethylation and connected to the ether bond that is

238

obtained by the graft polymerization. The clusters of peaks in the range from δ10 to

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δ35 corresponding to the carbon signals of ESO chains demonstrated that the graft

240

reaction was successful. The 1H NMR and

13

C NMR spectroscopy confirmed the

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characteristic groups of H-ESO-HEC-III.

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Molecular Weight and Carboxyl Content of H-ESO-HEC. The molecular

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weight value of H-ESO-HEC was determined by HT-GPC. The HT-GPC profile

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signals of the refractive index detector are shown in Figure 4. This shows that the

245

H-ESO-HEC with different molecular weights had a similar tendency of distribution

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and moved towards the higher molecular weight regions as the amount of ESO

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increased in the graft reaction. As listed in Table 1, the Mn of H-ESO-HEC (I-V)

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ranged from 1.48 × 105 to 4.58 × 105 Da and the Mw of H-ESO-HEC (I-V) ranged

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from 2.71 × 105 to 8.28 × 105 Da along with the mass ratio of HEC and ESO ranged

250

from 1:1 to 1:5, respectively. The conductometric titration curve to determine

251

carboxyl content of H-ESO-HEC-III was divided into three parts in Figure 5. The first

252

part showed the presence of a strong acid corresponding to excess of HCl. The second

253

part where the conductivity remains constant showed a weak acid corresponding to

254

the carboxyl content. The last part showed that strong base corresponded to an excess

255

of sodium hydroxide. The V1 and V2 are volumes of NaOH (mL) in the first and

256

second inflection points of the titration curves, respectively. Finally, the carboxyl

257

content can be calculated by the equation (1). The carboxyl contents of H-ESO-HEC

258

(I-V) were 1.89-2.80 mmol/g (Table 1). We concluded that the carboxyl content were

259

closely associated with the molecular weight. As the amount of ESO increased in

260

graft reaction, the carboxyl content increased according to the Mn of H-ESO-HEC. In

261

addition, the polydispersity indexes (PDI) of H-ESO-HEC (I-V) ranged from 1.46 to

262

2.1. This indicates that the H-ESO-HEC samples had a wide distribution (figure 4). 13

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DSC Analysis. The ring-opening polymerization of ESO grafting on HEC was

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confirmed by DSC in which the glass transition temperature (Tg) was determined to

265

be the temperature at the inflection point. Figure 6 clearly illustrates that there was no

266

Tg in HEC and H-ESO-HEC-I because the HEC did not exhibit glass transition, and

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there was no polymerization of ESO on HEC in H-ESO-HEC-I. Previous literature

268

reported that the products obtained by ring-opening polymerization of ESO existed

269

Tg.26

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H-ESO-HEC-V were -25.81 oC, -23.74 oC, -22.24 oC and -21.48 oC, respectively. As

271

expected, increasing the amount of ESO in the graft reaction resulted in more ESO

272

being grafted on HEC. The ring-opening polymerization reaction took place in the

273

graft reaction—this was in consistent with the GPC results. Furthermore, the Tg of

274

H-ESO-HEC samples became higher as the molecular weights of H-ESO-HEC

275

increased.

The

Tg

of

H-ESO-HEC-II,

H-ESO-HEC-III,

H-ESO-HEC-IV

and

276

Surface Tension of Aqueous H-ESO-HEC Polymeric Surfactants. The

277

H-ESO-HEC products were added to a beaker containing the required amount of

278

NaOH to neutralize all of the acidic protons from carboxylic acid groups. This was

279

then placed in a 60oC water bath and stirred with a glass rod until the samples were

280

dissolved.28, 29 A series of aqueous solutions of the H-ESO-HEC-Na were prepared,

281

and their surface tensions were investigated at room temperature. It is well known that

282

amphiphilic polymers with a suitable hydrophilic-hydrophobic balance can form a

283

micelle structure when exposed to a selective solvent.37 As shown in Figure 7, the

284

surface tension of H-ESO-HEC-Na in water decreased markedly in the low 14

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concentration at first. When the concentration was higher, the surface tension reduced

286

slightly. Finally, the surface tension was held nearly constant because its

287

concentration was sufficiently high.

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As shown in Table 3, the minimum surface tensions of H-ESO-HEC-Na (I-V)

289

were almost same and ranged from 26.33 mN/m to 28.88 mN/m. The

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H-ESO-HEC-Na displayed efficient surface properties versus HEC and the

291

hydrolyzed ESO at 54.68 mN/m and 34.28 mN/m, respectively. In addition, the

292

previous studies reported that the surface tension of fatty acid-esterified cellulose

293

derivatives ranged between 46 mN/m and 65 mN/m.17, 18 Different efficiency of these

294

fatty acid modified cellulose polymeric surfactants in lowering surface tensions of

295

water was attributed to the status of fatty acid in polymeric surfactants. In our study,

296

hydroxyl groups of HEC acted as initiators for ring-opening polymerization of ESO.

297

The fatty acid chains were combined with HEC by ether linkage at the middle site of

298

the fatty acid molecular chain. In this structure, both the hydrophobic alkanes and the

299

hydrophilic carboxyl were introduced into HEC. The simultaneous introduction of

300

hydrophobic

301

hydrophilic-hydrophobic balance of HEC and provided an opportunity to form

302

micelles in water. The CMC values of H-ESO-HEC-Na were decreased from 1.053

303

g/L to 0.157 g/L along with the obviously increasing molecular weight of

304

H-ESO-HEC-Na. As the molecular weights increased, the H-ESO-HEC-Na displayed

305

greater propensity to form micelles because of the flexible molecular chains. This

306

indicated that the efficiency in reducing surface tension was significantly enhanced

alkanes

and

hydrophilic

carboxyl

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groups

improved

the

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307

when the molecular weight of H-ESO-HEC-Na increased. The KP of the

308

H-ESO-HEC-Na ranged from 39 °C to 68 °C. It increased as a function of molecular

309

weight accordingly. The HLB values of the samples ranged from 9.6 to 10.6.

310

Surface

Rheological

Properties.

The

apparent

viscosities

of

the

311

H-ESO-HEC-Na aqueous solution as a function of shear rate at different

312

concentrations were investigated. The results of H-ESO-HEC-Na-III displayed the

313

same properties as the other products (Figure 8). The curves were not smooth at the

314

low shear rate because of instrument error and the complete minor viscosity.

315

Therefore, the curve of the 0.1 g/L H-ESO-HEC-Na-III can largely be considered a

316

straight line. The curve of the 0.1 g/L H-ESO-HEC-Na-III below the CMC

317

demonstrated that the solution behaved like water due to the low number of species

318

H-ESO-HEC-Na-III in solution. The curves of the 1.0 g/L and 5.0 g/L

319

H-ESO-HEC-Na-III above the CMC that formed micelles in aqueous solution can be

320

divided into two parts. First, the viscosity of the H-ESO-HEC-Na-III solution

321

decreased as the shear rate increased, and the H-ESO-HEC-Na-III solution exhibited a

322

pseudoplastic property at the low shear rate.38 This was because micelles in aqueous

323

solution were damaged, and the macromolecules experienced conformational

324

change.39 Its winding structure was separated under the action of shearing force and

325

arranged along the flow direction along with the increasing shear rate.40 Sequentially,

326

the viscosity remained constant when the shear rate reached a certain level. It behaved

327

like a Newtonian property.41 This is because the winding structure was completely

328

destroyed, and the molecular orientation reached at limiting condition. 16

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329

In summary, ESO-grafted HEC were prepared via ring-opening polymerization

330

and five novel polymeric surfactants H-ESO-HEC-Na (I-V) were obtained by

331

neutralization of H-ESO-HEC with sodium hydroxide. The molecular weights of

332

H-ESO-HEC products were varied by adjusting the mass ratio of HEC and ESO in the

333

grafting reaction. The synthesized polymeric surfactants H-ESO-HEC-Na exhibited

334

higher activities in reducing water surface tension. These ranged from 26.33 mN/m to

335

28.88 mN/m in comparison to 34.28 mN/m for hydrolyzed ESO and 54.68 mN/m for

336

HEC. In addition, the efficiency in reducing water surface tension was definitely

337

enhanced when the molecular weights of H-ESO-HEC increased. Rheological

338

measurements indicated that the H-ESO-HEC-Na solutions changed from a

339

pseudoplastic state to Newtonian with increasing shear rate. This study may facilitate

340

an increase in the use of renewable and biodegradable materials with improved

341

properties as polymeric surfactants.

342 343 344

Funding

345

The authors express their gratitude for the financial support From Natural Science

346

Foundation of Jiangsu Province of China (BK2012063 and BK20140973); Special

347

Fund for Basic Scientific Research Business of Central Public Research Institutes

348

(CAFINT2012C05); National Natural Science Foundation of China (31200446).

349 350

Notes 17

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351

The authors declare no competing financial interest.

352

REFERENCES (1) Tomanova, V.; Srokova, I.; Ebringerova, A.; Sasinkova, V., Surface-Active and Associative Properties of Ionic Polymeric Surfactants Based on Carboxymethylcellulose. Polym. Eng. Sci. 2011, 51, 1476-1483. (2) Nikfarjam, N.; Qazvini, N. T.; Deng, Y. L., Surfactant free Pickering emulsion polymerization of styrene in w/o/w system using cellulose nanofibrils. Eur. Polym. J. 2015, 64, 179-188. (3) Hu, Z.; Ballinger, S.; Pelton, R.; Cranston, E. D., Surfactant-enhanced cellulose nanocrystal Pickering emulsions. J. Colloid. Interf. Sci. 2015, 439, 139-148. (4) Khuman, P.; Singh, W. B. K.; Devi, S. D.; Naorem, H., Viscosity-Temperature Behavior of Hydroxypropyl Cellulose Solution in Presence of an Electrolyte or a Surfactant: A Convenient Method to Determine the Cloud Point of Polymer Solutions. J. Macromol. Sci. A. 2014, 51, 924-930. (5) Durand, A., Synthesis of amphiphilic polysaccharides by micellar catalysis. J. Mol. Catal. a-Chem. 2006, 256, 284-289. (6) Zhang, L. M., Cellulosic associative thickeners. Carbohyd. Polym. 2001, 45, 1-10. (7) Karlberg, M.; Thuresson, K.; Lindman, B., Hydrophobically modified ethyl (hydroxyethyl) cellulose as stabilizer and emulsifying agent in macroemulsions. Colloid. Surface. A. 2005, 262, 158-167. (8) M.L. Landoll, US Patent No. 4,228,277 (1980). (9) Landol, L. M., Nonionic polymer surfactants. J. Polym. Sci. 1982, 20, 443-455. (10) Yang F.; Liu Y.N.; Yu J.L.; Li H.P.; Gang Li, Synthesis, micellization behavior and alcohol induced amphipathic cellulose film of cellulose-based amphiphilic surfactant. Appl. Surf. Sci. 2015, 345, 187-193. (11) S. Evani, US Patent No. 4,432,881 (1984). (12) Li, Z. X.; Wang, L. G.; Huang, Y., Photoinduced graft copolymerization of polymer surfactants based on hydroxyethyl cellulose. J. Photoch. Photobio. A. 2007, 190, 9-14. (13) Sardar, N.; Ali, M. S.; Kamil, M.; Kabir-ud-Din, Phase Behavior of Nonionic Polymer Hydroxypropylmethyl Cellulose: Effect of Gemini and Single-Chain Surfactants on the Energetics at the Cloud Point. J. Chem. Eng. Data. 2010, 55, 4990-4994. (14) Thongngam, M.; McClements, D. J., Characterization of interactions between chitosan and an anionic surfactant. J. Agr. Food. Chem. 2004, 52, 987-991. (15) Wei, Y. P.; Cheng, F.; Hou, G.; Sun, S. F., Amphiphilic cellulose: Surface activity and aqueous self-assembly into nano-sized polymeric micelles. React. Funct. Polym. 2008, 68, 981-989. (16) Srokova, I.; Talaba, P.; Hodul, P.; Balazova, A., Emulsifying agents based on 18

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O-(carboxymethyl)cellulose. Tenside. Surfact. Det. 1998, 35, 342-344. (17) Yu, J. L.; Yang, F.; Liu, Z. H.; Liu, Y. N.; Li, G., Preparation and Characterization of C-10-C-14 Alkyl Cellulose Ester Sulfate Surfactant. J. Surfactants. Deterg. 2014, 17, 647-653. (18) Tomanova, V.; Pielichowski, K.; Srokova, I.; Zoldakova, A.; Sasinkova, V.; Ebringerova, A., Microwave-assisted synthesis of carboxymethylcellulose based polymeric surfactants. Polym. Bull. 2008, 60, 15-25. (19) Peydecastaing, J.; Girardeau, S.; Vaca-Garcia, C.; Borredon, M. E., Long chain cellulose esters with very low DS obtained with non-acidic catalysts. Cellulose 2006, 13, 95-103. (20) Chumpitaz, L. D. A.; Coutinho, L. F.; Meirelles, A. J. A., Surface tension of fatty acids and triglycerides. J. Am. Oi.l Chem. Soc. 1999, 76, 379-382. (21) Osipow, L.; Snell, F. D.; Marra, D.; York, W. C., Surface Activity of Monoesters - Fatty Acid Esters of Sucrose. Ind. Eng. Chem. 1956, 48, 1462-1464. (22) Liu, Z. S.; Biresaw, G., Synthesis of Soybean Oil-Based Polymeric Surfactants in Supercritical Carbon Dioxide and Investigation of Their Surface Properties. J. Agr. Food. Chem. 2011, 59, 1909-1917. (23) Meier, M. A. R.; Metzger, J. r. O.; Schäfer, H. J., Oils and Fats as Renewable Raw Materials in Chemistry. Angew. Chem. Int. Edit. 2011, 50, 3854-3871. (24) Lawate, S. S.; Lal, K.; Huang, C., Vegetable oils-structure and performance. CRC Press: New York, 1997; p 103. (25) Bantchev, G. B.; Kenar, J. A.; Biresaw, G.; Han, M. G., Free Radical Addition of Butanethiol to Vegetable Oil Double Bonds. J. Agr. Food. Chem. 2009, 57, 1282-1290. (26) Lowe, A. B., Thiol-ene "click" reactions and recent applications in polymer and materials synthesis: a first update. Polym. Chem-Uk. 2014, 5, 4820-4870. (27) Liu, Z. S.; Doll, K. M.; Holser, R. A., Boron trifluoride catalyzed ring-opening polymerization of epoxidized soybean oil in liquid carbon dioxide. Green. Chem. 2009, 11, 1774-1780. (28) Lathi, P. S.; Mattiasson, B., Green approach for the preparation of biodegradable lubricant base stock from epoxidized vegetable oil. Appl. Catal. B-Environ. 2007, 69, 207-212. (29) Biresaw, G.; Liu, Z. S.; Erhan, S. Z., Investigation of the surface properties of polymeric soaps obtained by ring-opening polymerization of epoxidized soybean oil. J. Appl. Polym. Sci. 2008, 108, 1976-1985. (30) Perez, D. D.; Montanari, S.; Vignon, M. R., TEMPO-mediated oxidation of cellulose III. Biomacromolecules 2003, 4, 1417-1425. (31) Wang, X. G.; Yan, F.; Li, Z. Q.; Zhang, L.; Zhao, S.; An, J. Y.; Yu, J. Y., Synthesis and surface properties of several nonionic-anionic surfactants with straight chain alkyl-benzyl hydrophobic group. Colloid. Surface. A. 2007, 302, 532-539. (32) Liu, W. R.; Sun, D. J.; Li, C. F.; Liu, Q.; Xu, H., Formation and stability of paraffin oil-in-water nano-emulsions prepared by the emulsion inversion point method. J. Colloid. Interf. Sci. 2006, 303, 557-563. (33) Wei, Y. P.; Cheng, F.; Zheng, H., Synthesis and flocculating properties of 19

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cationic starch derivatives. Carbohyd. Polym. 2008, 74, 673-679. (34) Zhou, J. P.; Xu, Y. L.; Wang, X. L.; Qin, Y.; Zhang, L. N., Microstructure and aggregation behavior of methylcelluloses prepared in NaOH/urea aqueous solutions. Carbohyd. Polym. 2008, 74, 901-906. (35) Tezuka, Y.; Imai, K.; Oshima, M.; Chiba, T., Determination of Substituent Distribution in Cellulose Ethers by Means of a C-13 Nmr-Study on Their Acetylated Derivatives .4. O-Methyl-O-Hydroxyalkylcelluloses. Makromol. Chem. 1990, 191, 681-690. (36) Reuben, J.; Conner, H., Analysis of the carbon-13 NMR spectrum of hydrolyzed O-(carboxymethyl) cellulose: Monomer composition and substitution patterns. Carbohyd. Res. 1983, 115, 1-13. (37) Eastoe, J.; J.S.Dalton, Dynamic surface tension and adsorption mechanisms of surfactants at the air-water interface. Adv. Colloid. Interfac. 2000, 85, 103-144. (38) Hong, P.; Fa, C.; Wei, Y. P.; Sen, Z., Surface properties and synthesis of the cellulose-based amphoteric polymeric surfactant. Carbohyd. Polym. 2007, 69, 625-630. (39) Tam, K. C.; Jenkins, R. D.; Winnik, M. A.; Bassett, D. R., A structural model of hydrophobically modified urethane-ethoxylate (HEUR) associative polymers in shear flows. Macromolecules 1998, 31, 4149-4159. (40) Ji, Y. Q.; Wang, W. S.; Li, G. Z.; Zheng, L. Q., Rheological properties of wormlike micelles formed in the sodium oleate/trisodium phosphate aqueous solution. Chinese. Chem. Lett. 2008, 19, 483-487. (41) Kfistner, U.; Hoffmann, H.; Dönges, R.; Ehrler, R., Interactions between modified hydroxyethyl cellulose (HEC) and surfactants. Colloid. Surface. A. 1996, 209-225.

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Figure captions Figure 1. Synthetic route of H-ESO-HEC polymeric surfactants Figure 2. FT-IR spectra of HEC and H-ESO-HEC-III Figure 3. 1H NMR and 13C NMR spectrum of H-ESO-HEC-III sample in DMSO-d6 Figure 4. GPC profile signal of the refractive index of H-ESO-HEC samples Figure 5. Conductometric titration curve of H-ESO-HEC-III Figure 6. The DSC curves of HEC and H-ESO-HEC samples Figure 7. Effect of H-ESO-HEC-Na concentration in water on equilibrium surface tension of water Figure 8. Apparent viscosity of the H-ESO-HEC-Na-III solution as a function of shear rate

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Tables Table 1. Effect of reaction condition on yield and carboxyl content and the HT-GPC data of H-ESO-HEC HEC:ESO

Samples

Yielda

Carboxyl Content

(mass ratio)

(g/g)

(mmol/g)





0

HEC

b

HT-GPC data Mn×10 (Daltons)

Mw×105(Daltons)

PDIc

0.7

2.28

3.20

5

H-ESO-HEC-I

1:1

1.2

1.89±0.13

1.48

2.71

1.80

H-ESO-HEC-II

1:2

1.6

2.12±0.06

1.55

3.31

2.10

H-ESO-HEC-III

1:3

1.9

2.35±0.10

3.77

5.50

1.46

H-ESO-HEC-IV

1:4

2.1

2.72±0.03

4.19

6.61

1.57

H-ESO-HEC-V

1:5

2.7

2.80±0.11

4.58

8.28

1.80

a

Expressed as g of the H-ESO-HEC per g HEC (on dry mass basis)

b

Expressed as mmol of carboxyl per g H-ESO-HEC (on dry mass basis)

c

Determined by Mw/Mn

Table 2. 1H and 13C NMR signals of H-ESO-HEC 1

13

H NMR

Signal

C NMR

δ (ppm)

Signal

δ (ppm)

-OH

2.10

-COOH

176

-(CH2)n-CH3

0.90

-CH3

15

-(CH2)n-CH3

1.30-1.50

-CH2-

27-35

CH2-O-CH2

2.80

CH2-O-CH2

83

CH-OH

3.20

CH-OH

80

AGU-H1

4.75

AGU-C1

101

AGU-H2

3.50

AGU-C2

74

AGU-H3

3.55

AGU-C3

70

AGU-H4

3.30

AGU-C4

76

AGU-H5

3.65

AGU-C5

73

AGU-H6

3.45

AGU-C6

62

Table 3. CMC, γcmc, KP and HLB value of samples Samples

CMC (g/L)

γcmc (mN/m)

KP (oC)

HLB value

HEC



54.68±1.20





H-ESO-Na

1.105

34.28±0.93

18

9.6-10.6

H-ESO-HEC-Na-I

1.053

26.33±0.56

39

9.6-10.6

H-ESO-HEC-Na-II

0.702

28.88±0.99

42

9.6-10.6

H-ESO-HEC-Na-III

0.514

27.83±0.61

45

9.6-10.6

H-ESO-HEC-Na-IV

0.402

26.37±0.50

52

9.6-10.6

H-ESO-HEC-Na-V

0.157

26.94±1.26

68

9.6-10.6

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Figure graphics Figure 1.

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Figure 2.

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Figure 3.

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Figure 4.

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Figure 5.

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Figure 6.

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Figure 7.

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Figure 8.

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Table of Contents Graphics (For Table of Contents only)

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