Research Article Rheological Properties of Hydrophobically...

Research ArticleRheological Properties of HydrophobicallyAssociative Copolymers Prepared in a Mixed Micellar MethodBased on Methacryloxyethyl-dimethyl Cetyl AmmoniumChloride as Surfmer

Rui Liu12 WanFen Pu12 Hu Jia12 XiaoPei Shang2 Yue Pan3 and ZhaoPeng Yan2

1 State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation Southwest Petroleum University Chengdu 610500 China2 School of Petroleum and Gas Engineering Southwest Petroleum University Chengdu 610500 China3 CNOOC Research Institute CNOOC Building Beijing 100027 China

Correspondence should be addressed to Rui Liu breakthroughliu163com

Received 18 January 2014 Accepted 11 April 2014 Published 15 May 2014

Academic Editor Peng He

Copyright copy 2014 Rui Liu et al This is an open access article distributed under the Creative Commons Attribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

A novel cationic surfmer methacryloxyethyl-dimethyl cetyl ammonium chloride (DMDCC) is synthesized The micellarproperties including critical micelle concentration and aggregation number of DMDCC-SDS mixed micelle system are studiedusing conductivity measurement and a steady-state fluorescence technique A series of water-soluble associative copolymerswith acrylamide and DMDCC are prepared using the mixed micellar polymerization Compared to conventional micellarpolymerization this new method could not only reasonably adjust the length of the hydrophobic microblock that is 119873

119867 but

also sharply reduce the amount of surfactant Their rheological properties related to hydrophobic microblock and stickers arestudied by the combination of steady flow and linear viscoelasticity experiments The results indicate that both the hydrophobiccontent and especially the length of the hydrophobic microblock are the dominating factors effecting the intermolecularhydrophobic association The presence of salt influences the dynamics of copolymers resulting in the variation of solutioncharacters Viscosity measurement indicates that mixed micelles between the copolymer chain and SDS molecules serving asjunction bridges for transitional network remarkably enhance the viscosity Moreover the microscopic structures of copolymersat different experimental conditions are conducted by ESEM This method gives us an insight into the preparation ofhydrophobically associative water-soluble copolymers by cationic surfmer-anionic surfactant mixed micellar polymerization withgood performance

1 Introduction

The incorporation of a few hydrophobic units into a hydro-philic backbone results in hydrophobically associative water-soluble polymers In aqueous solution above a certain poly-mer concentration the hydrophobic moieties associate andbuild a transitory three-dimensional cross-links leading tounique rheological properties such as dramatic viscosityenhancement [1 2] gelation [3] time-dependent effects [4]and marked elasticity [5 6] Such salient features result fromthe reversible association processes of the physical networksoccurring under shear compared to that of polymers with-out associative groups These polymers have triggered great

attention in various applications including petrochemicalscosmetics and pharmaceuticals [7ndash9]

There have been substantial efforts with regard to thesynthesis and properties of hydrophobically modified water-soluble polyacrylamides Following Strauss et al [10 11] in the1960s who developed the original hydrophobically modifiedwater-soluble polymers called polysoaps by using n-dodecylbromide and decyl vinyl ether as hydrophobic monomersMcCormick et al [12] Morishima et al [13] and Winniket al [14] launched an extensive research on such polymersfrom photophysical and rheological viewpoints Notably oneof the most classical and well-studied methods to copoly-merize acrylamide (AM) with a hydrophobic comonomer

Hindawi Publishing CorporationInternational Journal of Polymer ScienceVolume 2014 Article ID 875637 14 pageshttpdxdoiorg1011552014875637

2 International Journal of Polymer Science

is a free radical micellar copolymerization technique [1]However the addition of well amount surfactant (above thecritical micelle concentration CMC) caused some negativeinfluences such as low-molecular weight caused by thechain transfer effects of surfactants [5] impurity withinthe surfactant and the complicated treatment to removethe surfactants to obtain pure products [15] An additionalproblem originates from the difficulty to prepare copolymerswith both high associativity and good water compatibilitybecause the microblocky hydrophobe of the copolymers isvery limited to maintain solubility in water [16]

To overcome these drawbacks the conventional micellarcopolymerizationmethod ismodified by using polymerizablesurfactants that is surfmers to substitute the traditionalones Surfmers are a family of unique surfactants which notonly have amphiphilic structures that is cationic or anioniclong-chain alkyl structure but also contain polymerizablevinyl double bonds [17ndash19] Surfmer molecules formmicellesat concentration above the CMC Both micellar aggrega-tion (119873agg) and CMC of such micellar systems could bemediated by adding either cosurfactants such as electrolytesand medium chain-length alcohols or surfactants [20ndash23]Therefore the hydrophobic microblock length that is 119873

119867

of the copolymers chains was controlled Mixing behaviorof surfmer and cosurfactant has been widely investigated[24 25] On the other hand due to an amazing interactionbetween the surfactants that are mixed mixed micelles com-posed of binary surfactants have received increasing atten-tion Properties of binary mixed micelles upon hydrocarbon-hydrocarbon hydrocarbon-fluorocarbon surfactants includ-ing nonionic-nonionic anionic-nonionic anionic-cationicand zwitterionic-anionic mixtures were extensively inves-tigated by advanced analytical techniques such as lightscattering small angle neutron scattering and fluorescenceprobingmeasurement [26 27] Based on these experiments aregular solution theory that accountswell for the characters ofbinarymixedmicelles has been established inwhich theCMCvalues and 119873agg values involved in different compositionalmixtures depended on an interaction parameter (120573) [22]Apparently the regular solution theory is also applied wellin the surfactant-surfmer mixed micelle system Chang andMcCormick [28] firstly suggested that the microblock lengthof the cationic polymerizable surfactant dimethyl-dodecyl (2-acrylamidoethyl) ammonium bromide could be controlledby addition of cetyltrimethyl-ammonium bromide (CTAB)as a cationic cosurfactant Direct experimental evidence ofthis behavior is reported by Zhang and Wu [23] from con-ductivity and fluorescence studies on the samemixed micellesystem Stahler et al [29] found that cationic fluorocarbon-hydrocarbon surfmer pairs that bear the same hydrophobiccompoundmayhave the partial compatibility in single type ofmixed micelles despite the repulsive headgroup interactions

It is thought that only the surfmer-surfactant mixedmicellar system corresponds to the same charge either posi-tive or negative the microblock of length could be adjustedCan the cationic surfmer-anionic surfactant binary systemshare the same capacity in the preparation of hydropho-bically associative polyacrylamide with good performanceThis paper just addressed this issue Firstly a long-chain

alkyl cationic surfmer of methacryloxy-ethyl-dimethyl cetylammonium chloride (DMDCC) was synthesized and theproperties of DMDCC-SDS (sodium dodecyl sulfate) mixedmicelles are determined by conductivity measurement and asteady-state fluorescence technique We discuss the synthe-sis and characterization of cationic associating copolymersprepared by DMDCC-SDS mixed micellar copolymerizationwith DMDCC as cationic hydrophobic comonomer Particu-larly we focus on the effect of the length and number of thehydrophobic microstructures on the rheological propertiesIn addition we look at the effect of salt and surfactant on theapparent viscosity of copolymers

2 Experimental Section

21 Materials Acrylamide (Chengdu KeLong Chemical Re-agent Co Ltd) was recrystallized twice from acetone andvacuum dried at room temperature prior to use The azo-initiator V-50 (221015840-azobis(2-amidinopropane)dihydrochlo-ride) (UA Alfa Aesar 99) was used without further purifi-cation NN-Dimethyl-ethylamine methacrylate and cetylchloride purchased from Aldrich chemicals (purity 99)were used as received Water was double deionized with aMillipore Milli-Q system Other reagents were analyticallypure and used as received

22 Synthesis of Cationic Polymerizable Surfactant (DMDCC)Scheme 1 illustrates the synthesis of the cationic surfmermethacryloxyethyl-dimethyl cetyl ammonium chloride(DMDCC) NN-Dimethylethylamine methacrylate (282 g02mol) was added into a 250mL three-necked round-bottom flask and placed in an oil bath and agitated by amagnetic stirrer under a nitrogen atmosphere Cetyl chloride(469 g 0180mol) was subsequently added to the additionalfunnel When the temperature increased to 85∘C cetylchloride was added to the flask dropwise over a period of6 h After 42 h the yellow viscous gel was obtained Theexcess crude product was dissolved in a small amount ofacetone at 45∘C and cooled to minus10∘C and the yellow semisolidproduct was obtained Further purification of the productwas accomplished by recrystallization from a 1 1 (wtwt)mixture of acetone and ether yield of 618 g (85)

23 Properties of DMDCC-SDS Binary Surfactant System

231 CMC Values CMC values of DMDCC and mixtureof DMDCC-SDS were determined by conductivity on adigit conductivity meter The conductivity 120581 of aqueoussurfactant solutions was measured against the surfactantmolar concentration at 50∘CThe difference in themagnitudeof the gradients above or below the inflection points in eachsample results in a concomitant increase in the uncertaintyof the CMC values Thus the CMC values of DMDCC andDMDCC-SDS were measured from the break points of the 120581to 119888 plots

232 Aggregation Number Using pyrene as a probe theaggregation numbers (119873agg) of DMDCC as well as mixture

International Journal of Polymer Science 3

C CO

O CCl

ClC NC C

OO C C N

H2H2 H2 H2 H2C

H2CH3C H3CCH2

CH3 CH3 CH3

CH3

CH3CH2CH3+ minus

(CH2)14

(CH2)14

85∘C

Scheme 1 Synthesis of the cationic surfmer (DMDCC)

of DMDCC-SDS surfactants at different bulk mole fractions1205721were determined by a steady-state fluorescence technique

Samples solutions with 01mM of pyrene were prepared byadding a small amount of concentrated pyrene dissolved inacetone All the samples were heated at 50∘C for 12 h and thenfiltered with a 02 120583m membrane filter before measurementThe quenching of pyrene monomer fluorescence originatingfrom excimer formation was used to determine 119873agg Fluo-rescence decay data corresponded to the following equation

ln(1198680

119868) = 119873

[119876]

(119862119905minus CMC)

(1)

where 1198680and 119868 are the fluorescence intensities in the absence

and presence of quencher of the purebinary surfactant sys-tems [119876]119862

119905 and CMC are the quencher concentration total

surfactant concentration and critical micelle concentrationrespectively The ln(119868

0119868) to [119876] at different compositions is

pseudo-first-order Therefore values of Nagg were calculatedfrom the slope of the pseudolinear fits In each case the totalsurfactant concentration was constant

24 Synthesis of the Copolymers A 250mL three-neckedround-bottom flask is equipped with a mechanical stir-rer nitrogen inlet and a thermometer Acrylamide (AM)and methacryloxyethyl-dimethyl cetyl ammonium chloride(DMDCC) and sodium dodecyl sulfate (SDS) in the desiredratio are dissolved in 100mL of deionized water and thenplaced in the flask The total concentration of the monomersis kept constant at 10M The flask is purged with a smallN2stream for half an hour prior to being heated to 50∘C

Polymerization is then initiated by addition of 035mL of V-50 (1 wtpreferentially dissolved in the deionizedwater) via apipette scaled to 1mL under slow stirring In this case insteadof potassim persulfate v-50 was used as initiator to avoidthe redox side reaction between mercaptan and persulfatePolymerization is conducted continuously for 8 h at 50∘CThe reaction mixture is diluted with five volumes of distilledwater and two volumes of acetone are then added with stir-ring to precipitate the polymers The precipitated polymersare further washed twice with acetone and extracted withethanol to remove all traces of water surfactant residualmonomers and initiator The polymers are recovered byfreeze-drying after vacuum-drying at 50∘C for three daysFor reference PAM is prepared under identical experimentalconditions and purification method mentioned above

25 Characterization

251 Spectroscopic Measurement IR was carried out usingShimadzu-1800S spectrometer on KBr pellets in the range

of 4000ndash400 cmminus1 The peak intensities are characterized asfollows vs = very strong s = strong w = weak ] correspondsto stretching elongation and 120575 corresponds to bendingelongation 1H NMR spectra were measured with a BrukerAVanceII-400NMR spectrometer using D

2O as a solvent at

room temperature Chemical shifts were determined by usingTMS as an internal standard The peaks multiplicities arecharacterized as follows s = singlet d = doublet t = triplet q =quartet and m = multiplet

252Molecular Weights The intrinsic viscosities [120578] of thepolymers were determined by an automatic capillary vis-cometer (Ubbelohde type) in 01MNaCl aqueous solutionat room temperature The molecular weight of each polymersample was determined in watermethanol mixture (37 VV)containing 01MNaCl by classical light scattering using amultiangle spectrometer (AMTEC model MM1) at 633 nmThe refractive index increment (119889119899119889119888) was measured at thesame wavelength on a differential refractometer The 119889119899119889119888value for PAM sample was equal to 016mL gminus1 [2]

253 Rheological Measurements Polymer solutions wereprepared by dissolution of a known amount of the polymerpowder in water and NaCl solutionThe apparent viscosity ofsamples solution at low concentrations was determined by aBrookfield DV-III rheometer equipped with different sizes ofspindles (different diameter depending on solution viscosity)at 25∘C Rheological experiments were carried out with aRS100 controlled-stress rheometer equippedwith a cone plategeometry (angle 1∘ diameter 35mm) We measured flowcurves by increasing the shear stress in regular steps andwaiting at each step until equilibrium was attained Theshear rate 120574 ranged from 01ndash10 to 1000 sminus1 according tothe viscosity behavior of samples To overcome the problemthat a slight increase in stress caused a large jump in shearrate we used controlled-rate mode of the rheometer whichpermits us to scan the whole shear rate range without largegaps In all cases we checked that the curves measuredin controlled-stress and controlled-rate mode were wellsuperposed Dynamic measurements were conducted understrains and at frequencies of 001ndash100Hz to lead to a linearresponse All the experiments were conducted with a solventtrap to avoid any evaporation

254 Morphology The microstructure of polymers in bothaqueous and salt solutions was observed by environmentscanning electron microscope (ESEM XL 30) The samplesolutions were maintained at minus35∘C and the pressure wascontrolled below 5Torr to keep samples solution state duringthe whole observation


255 Fluorescence Fluorescence spectra were measured ona Lengguang 970CRT fluorescence spectrometer All mea-surements were conducted at ambient temperature The slitwidth of excitation and emission was kept at 5 nm duringexperimentsThe excitationwavelength (120582) was set at 339 nmThe ration of the intensities of the third 119868

3(385 nm) to first 119868

1

(375 nm) vibronic peak of fluorescence spectrum of pyreneprobe was used as an estimate of micropolarity of pyrenemicroenvironment

3 Result and Discussion

31 Characterization of DMDCC-SDS Mixed Micelles SDSwas chosen to study the micellar behavior of DMDCC-SDSbinary mixed system because it bears the same hydrophobiclong chain asDMDCCand themost common surfactant usedin radical micellar copolymerization and most importantlymixture of cationic (DMDCC) and anionic (SDS) surfactantshas a net interaction (120573 lt 0) In the case of binary mixedmicelles composed of cationic-anionic pairs the CMC of thesurfactant mixture can be calculated as follows

1

CMC119898

=1205721

119891119898

1CMC1

+1205722

119891119898

2CMC2

(2)

where CMC119898is the critical micelle concentration of binary

mixed surfactants the subscripts 1 2 represent DMDCCand SDS respectively CMC

1 CMC

2are the critical micelle

concentration of single surfactant species 1205721and 120572

2are

the bulk mole fractions of the respective surfactants in thesystem and 119891119898

1 1198911198982

are the activity coefficients that can befound by using the regular solution theory

ln1198911198981= (120572119898

2)2120573

ln1198911198982= (120572119898

1)2120573

(3)

where 120573 is an interaction parameter quantifying the netinteraction between the surfactant species in the mixedmicelle 120572119898

1and 120572119898

2are the mole fractions of the single

surfactant in mixed system which are written as follows

120572119898

1=

1205721119891119898

2CMC2

1205721119891119898

2CMC2+ 1205722119891119898

1CMC1

120572119898

2= 1 minus 120572

119898

1

(4)

Figure 1 shows the CMC119898of DMDCC-SDS binarymixed

system as a function of DMDCC mole fraction in solutionWe can see that the CMC values of single SDS and DMDCCin aqueous solution are 8mM 082mM respectively For theDMDCC-SDSmixed system the CMC values of anionic sur-factant SDS significantly decrease by adding a small amountof DMDCC without causing any precipitation Interestinglythe CMC values of the binary surfactant remain almostconstant with the increase in DMDCC molar fraction inaqueous solution

The CMC of mixed surfactants strongly depends onparameter values 120573 Positive 120573 values imply a net repulsiveforce between the surfactant components whereas negative 120573

00 02 04 06 08 10

001

01

1

10

CMC

DMDCC composition in binary solution

CMC

(mM

)

55

60

65

70

75

80

85

90

95

Nagg

Nag

g

Figure 1 Variation of critical micelle concentration of DMDCC-SDS binary mixture system as a function of DMDCC mole fraction(119879 = 50∘C)

00 02 04 06 08 100

10

20

30

40

50

CMC

(mM

)

DTAB composition in binary solution

SDS + DTAB120573 = minus132

Figure 2 Variation of critical micelle concentration of DTAB-SDSbinary mixture system as a function of DTAB mole fraction [22]reproduced from [22] with permission from John Wiley amp Sons

values imply a net attractive forceThemore negative120573 valuesare the stronger the net interaction between the surfactantsin the mixed system will become thus the CMC of mixedsurfactants is much lower For reference the CMC of DTAB-SDS mixed system as the function of CTAB mole fraction isdepicted in Figure 2The strong synergetic effect (120573 = minus132)indicated that there was a large net attraction between thesurfactants

The much lower CMC values of SDS are obtained byadding cationic surfactant DTAB We note that DMDCCbears almost the same structure as DTAB Therefore we candraw a conclusion that the CMC behavior of DMDCC-SDSmixed system as shown in Figure 3 has the same dynamiccharacter as that of DTAB-SDS However the aggregation


+

+

++

+++

+

+

+

+

+

++ + + +

+

++

+

+

++

+

+

+

++

+

Pure SDS micelles

Pure DMDCC micelles

Mixed DMDCC-SDS micelles

minus

minus

minus

minus

minus

minus

minus

minus

minusminusminusminus

minus

minus

minus

minus

minus

minus

minusminus minus

minus

minus

Figure 3 Schematic representation of the mixed DMDCC-SDS micelles compared to pure DMDCC micelles and pure SDS micelles

morphology of DMDCC-SDS mixed system as the molefraction of DMDCC has unique dynamic character whichis shown in Figure 1 The 119873agg value of anionic surfactantSDS significantly increases by adding a small amount ofDMDCC and then remains almost constant with the increasein DMDCCmolar fraction in aqueous solution which couldbe written as follows

119873119898

agg = 120572119898

1119873agg1 + 120572

119898

2119873agg2 (5)

where119873agg1 and119873agg2 are the respective aggregation numbervalues of DMDCC and SDS in aqueous solution The lengthof hydrophobic microblock in hydrophobically modifiedpolyacrylamide prepared by conventional radical micellecopolymerization is determined by

119873119867=

[119867]119873agg

[119878] minus CMC (6)

where [119867] [119878] and CMC are the mole concentration of thehydrophobicmonomer themole concentration of surfactantand critical concentration of surfactant whereas the length ofhydrophobic microblock from mixed micelle copolymeriza-tion should be rewritten as

119873119867=

([119867] minus CMC119867)119873119898

agg

[119867 + 119878] minus CMC(119867+119878)

(7)

In the DMDCCSDS mixed system CMC119867is the CMC

of surfmer and CMC119867+119878

is the critical micelle concentrationof DMDCC-SDS binary mixed micelles and 119873119898agg which

is determined by steady-state fluorescence quenching tech-nique Therefore the length of microblock could be tunedreasonably by the mixed micelle technique

32 Synthesis and Characterization The copolymers poly(AMDMDCC) with low amounts of cationic hydrophobewere obtained in water using a DMDCC-SDS binary mixedmicellar polymerization (Scheme 2)The characteristic of thecopolymer is depicted in Table 1 For DMDCC IR (KBr]cmminus1) 3432 (s ](C=O)) 2919 (vs ]as(CndashH)) 2844 (s]s(CndashH)) 1633 (w ](C=C)) 1299 (s ](CndashN)) 1167 (vs ](CndashC)) 1028 (w ](CndashO)) For copolymer 075DM128 IR (KBr]cmminus1) 3450 (vs ]s(NH2) ](C=O)) 2925 (w ](CndashH)) 1025(w ](CndashO)) 628 (s 120575(CndashH)) 1H NMR (400MHz D

2O

120575ppm) 111 (q 2Hg CH2) 158 (d 2Ha CH2) 216 (d 1HbCH) 236 (t 3Hc CH3) 248 (s 3Hf CH3) 359 (m 2HeCH2) 372 (q 2Hd CH2) (Figures 4 and 5)

33 Rheological Behavior

331 Viscometric Behavior in Dilute Solution The effect ofthe hydrophobic microblock length that is 119873

119867value and

the concentration of hydrophobic monomer on intra- andintermolecular interaction is depicted in Figure 6 Apparentviscosity is plotted as a function of polymer concentration forthree copolymers (05DM45 05DM93 and 075DM93) andfor the corresponding polyacrylamide

All the samples are well measured at a constantshear rate of 734 sminus1 In extremely dilute solution regime


Table 1 Structural parameters of the copolymers

Samplea Polymer composition mol 119873119867

b Polymer characterization

AM DMDCC SDS 119878c 10

minus6times119872119908

gmolminus1[120578]

mL gminus1[120578]calc

d

mL gminus1Solubility in watere

PAM 100 0 0 0 0 350 610 755 ++

05DM45

995 05

175 45 25 315 586 697 ++

05DM93 08 93 124 329 540 720 +05DM127 05 127 9 325 520 714 +05DM92 0 92 06 164 299 428 plusmn

075DM46

9925 075

55 46 25 222 335 536 ++

075DM93 21 93 17 306 470 683 +075DM128 135 128 13 335 418 730 +075DM92 0 92 0 minus

aThe first number indicated the mole frication of hydrophobic monomer and the final number indicated the rounded value of119873119867 (eg 05DM5 stands for apolymer that contains 05mol of DMDCC with 119873119867 asymp 45)

bNumber of hydrophobes per micelle asymp hydrophobic block length cNumber of hydrophobicblocks per chain (ie stickers)30 calculated using the relationship 119878 = (1198721198822119898)[119867]119873119867 where119898 is themolecular weight of themonomer unit (acrylamide119898= 71) and1198721198822119898 corresponds to the number average degree of polymerization N dIntrinsic viscosity calculated using relationship [120578] = 933 times 10minus3119872119882075established for PAM31 e++ easily soluble + soluble plusmn cloudy solution minus difficult to dissolve

H2N

H2H2 H

C

H2CH3C

H2C

H2C

H3CH2C

O O OO

OO

C

C

C C CC

Cl

NN

C

CH2

CH2

CH2

CH3

CH3

CH2

CH3

NH2

CH3

CH3

CH3

CH2

14

14

+

+

+

minus

Clminus

Scheme 2 Copolymerization of AM and DMDCC

4000 3500 3000 2500 2000 1500 1000 500

68210251117

1319

14172925

2919

3450

1028

9611299

T (

)

DMDCC P(AM-DMDCC)

3432 23601633

1464

1641

1167

2844 1719

Wavenumbers (cmminus1)

Figure 4 IR spectra of the DMDCC and copolymer 075DM128

(119888119875lt 005 g dLminus1) the apparent viscosity of copolymers is

lower than that of PAM due to intramolecular associationwhich leads to the coil of chain This effect is enhancedby increasing either the 119873

119867or the hydrophobe concen-

tration And it is well explained that the [120578] of all thepoly(AMDMDCC) is reduced compared to that of PAM andinverse to the 119873

119867value Because the [120578] of the polymer was

determined by automatic capillary viscometer at low poly-mer concentration intermolecular interaction was graduallyenhanced with the increase in polymer concentration Abovea critical concentration that is CAC an upward curvaturein the apparent viscosity can be observed The apparentviscosity increases more markedly and shows up at lowerconcentration with increasing the hydrophobic length atthe same hydrophobe concentration The CAC of 05DM45and 05DM93 is 015 g dLminus1 and 013 g dLminus1 respectively Onthe other hand 075DM93 and 05DM93 have the samehydrophobic microblock length the increase in hydrophobealso enhances thickening efficiency This behavior can be


55 50 45 40 35 30 25 20 15 10(ppm)

+

minus

CH2

NH2

CH3

CH 3CH2

CH3

CH2

H H2

H2C

H2C

H3C

d

d

f f

f

g

ge

e

e

c

bC C C

C

cCl

N

C O OO

baa

a

372

359

248

236

216

158

111

14

Figure 5 1HNMR spectra of copolymer 075DM128

00 01 02 03 04 050

100

200

300

400

500

600

700

800

CAC

CAC

075DM12805DM127

05DM93PAM

CAC

0025 0050 0075 0100 01251

10

Polymer concentration (g dLminus1)

120578ap

p(m

Pamiddots)

clowast

Figure 6 Apparent viscosity as a function of polymer concentrationfor copolymers 075DM128 05DM127 and 05DM93 samples andfor a PAM sample (119879 = 25∘C the inlet of apparent viscosity ispartially enlarged for purpose of smart understanding)

explained by the increase in sticker reported in Table 1which makes the intermolecular interactions much strongerand the CAC of 075DM93 is 011 g dLminus1 The upturn ofapparent viscosity in case of the PAM is due to the onset ofchain overlap that is 119888lowast and related to the chain size Theviscosity upturn observed for poly(AMDMDCC) cannotbe attributed to a chain overlap since poly(AMDMDCC)had the similar range of molecular weight Moreover thechain overlap behavior was long-term effect which occurredat high polymer concentration Therefore the remarkableviscosity onset is a result of the formation of hydropho-bic microdomain caused by hydrophobic intermolecularinteraction The hydrophobic microblock length directly

influences the thickening efficiency However when the 119873119867

goes beyond a certain value negative impact such as lowrate polymer conversion and the poor solubility would occurwhich accorded with the general law of the water-solubleassociating polymer prepared by conventional radical micellecopolymerization [4 16 30]

332 Steady Flow Experiments Apparent viscosity as a func-tion of shear rate is conducted for three copolymers modifiedby 05mol DMDCC and for PAM The viscosityshearrate curves of the copolymers and PAM at concentration of10 g dLminus1 and 20 g dLminus1 are shown in Figures 7 and 8 It isinteresting to figure out that the rheological properties ofthe copolymers are strongly dependent on 119873

119867and polymer

concentrationPAM exhibits the classic rheological behavior that is

a slight shear thinning effect after Newtonian plateau Allthe copolymers present the same type of behavior Forpoly(AMDMDCC) at 10 g dLminus1 concentration a shearthickening domain reaches first followed by shear thinningThe shear thickening is interpreted in terms of the balancebetween intra- and intermolecular associations At a certainshear rate the shear forces are strong enough to extend thepolymer coils and disrupt the intramolecular hydrophobicinteractions The intramolecular hydrophobic microdomainis released and favors forming intermolecular hydrophobicinteractions resulting in an increase in viscosity Furtherincreasing shear rate these interactions are gradually brokenand shear thinning behavior is observed This behaviorwas general agreement with the nonionic hydrophobicallymodified polyacrylamides [31]

To determine the role of the 119873119867

in the apparent vis-cosity for all polymers the values of viscosity (120578

0) which

corresponded to the shear rate ( 120574lowast) and shear stress (120590lowast)on the onset of Newtonian plateau were reported in Table 2Apparent viscosity increases with the increasing of shear rate


Table 2 Rheological values of 120590lowast 120574lowast and 1205780for poly(AMDMDCC) and PAM at concentration of 10 g dLminus1 and 20 g dLminus1

Polymer 119888119901= 10 g dLminus1 119888

119901= 20 g dLminus1

120590lowast (Pa) 120574

lowast (sminus1) 1205780(mPasdots) 120590

lowast (Pa) 120574lowast (sminus1) 120578

0(mPasdots)

PAM 093 103 90 36 10 35705DM45 109 166 658 82 056 1465005DM93 155 123 1264 978 036 2716005DM127 207 076 2723 1315 025 62600

01 1 10 100 100010

100

1000

10000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)

Shear rate (sminus1)

Figure 7 Variation of apparent viscosity as a function of shear ratefor PAM 05DM127 and 05DM45 (119888

119901= 10 g dLminus1 119879 = 25∘C)

at such shear rate ( 120574lowast) this plateau is attainable as shownin Figures 7 and 8 and beyond which the fluid presents ashear thinning behavior the values of the stress threshold120590lowast= 120574lowast1205780

In case of PAM a higher 120574lowast is presented compared tothat of copolymers With the increase in shear rate shearforce is strong enough to disrupt the gauss coils structuredby the macromolecular chains overlap and entanglementand the original chain orientation is released to form orderlyorientation resulting in a decrease in viscosity As for copoly-mers the length of hydrophobic microblock 45 (05DM45)is enough to induce an increase in the solution viscos-ity Lengthening of hydrophobic microblock enhanced thedegree of association facilitating shear thickening behaviorAt a certain shear rate the shear forces are strong enoughto extend the copolymer coils and disrupt the intramolecularhydrophobic interactions resulting in the decrease of viscos-ity

The stress threshold values 120590lowastshow that the longer the119873119867 the higher the 120590lowast This indicates that more stress

force is required to disrupt the molecular interactions withincrease in the length of hydrophobic microblock whichresults in a stronger transitory three-dimensional networkAt the identical polymer concentration the increase in119873

119867is

accompanied by a decrease of 120574lowast shortening the Newtonian

001 01 101 100 1000

100

1000

10000

100000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 20 g dLminus1 119879 = 25∘C)

zone The solution became more sensitive to shear rateFor example at a concentration of 10 g dLminus1 the shearrate 120574lowast of copolymers 05DM127 and 05DM93 is 076 sminus1and 123 sminus1 respectively compared to 166 sminus1 of copolymer05DM45 Higher viscosity at low shear rate indicates amore pronounced shear thickening domain and a longershear thinning plateau At higher shear rate the copolymerviscosity trends towards that of PAM but even at 1000 sminus1the value is mainly greater indicating that intermolecularinteraction also existed

We should figure out that even at a higher concentration(20 g dLminus1) shear thickening domain is also observed andboth copolymers show classical shear thickening subsequentshear thinning behavior within the range of shear rateThis owning to the fact that beside molecular weight andpolymer concentration the nature of hydrophobic monomeralso influences shear thickening efficiency The apparentviscosityshear rate curves at the characteristic values at theNewtonian plateau are also given in Table 2 We also observethat increasing the concentration shortens the shear thick-ening plateau while the magnitude of the 120578

0increases with

increasing polymer concentration The values reported inTable 2 confirmed that for cationic hydrophobic associativepolyacrylamides concentration especially 119873

119867 had great

effects on steady flow rheological properties


333 Linear Viscoelasticity Figures 9 and 10 present illus-tration of the oscillatory response for poly(AMDMDCC)and PAM at 10 g dLminus1 in aqueous solution The variationsof the storage (1198661015840) and loss (11986610158401015840) modulus are curved versusfrequency (119891) The slopes of 1198661015840 and 11986610158401015840 in the terminal zonefor polyacrylamide are 22 and 098 Note that the slopes of1198661015840 and 11986610158401015840 will not keep constant which are dependent on

the PAM concentration [4]However for copolymers modified by hydrophobic

groups at low frequencies the behavior of the shear modulusis Maxwellian indicating the variations of 1198661015840(119891) and 11986610158401015840(119891)that scaled as 1198912 and 119891 respectively The curves obtained forthe different series of copolymers have a profile similar to thatfor solutions whose viscoelastic properties are governed bychain entanglementsThese solutions are characterized at lowfrequency by a slope of 1198661015840 and 11986610158401015840 where the values of 1198661015840were below that of 11986610158401015840 Above the frequency at which curves1198661015840(119891) and 11986610158401015840(119891) cross each other (119866

119888) the shape of these

curves deviates from Maxwellian behavior indicating thepresence of faster relaxation processes which superimposeeach other on themain slow relaxation processThis behaviorcan be interpreted in terms of the copolymers polydispersityand imperfections in the macromolecular microstructurewhich should inevitably broaden the relaxation spectra Thedynamics of the system are scaled by the slope of 1198661015840 and 11986610158401015840in the terminal zone 119866

119888 and characteristic time 119905

119888(1119891) at a

frequency corresponding to the crossing point119866119888 According

to the sticky reputation theory of Leibler et al [32] the valueof 119905119888indicated the disentanglement time of polymer chain

limited outside the tube The values obtained are reported inTable 3

The presence of the hydrophobic group intomacromolec-ular chain increased both moduli and the terminal zoneis shifted toward low frequencies due to the transitionalnetwork junctions by hydrophobic associations 05 DM45exhibits a slight increase in the modulus at Hz comparedto that of PAM while copolymer 05 DM93 shows a moremarked enhancement with 119866

119888= 227 Pa at 117Hz Increasing

the microblock length of the hydrophobe or its hydrophobicmolar proportion in the polymer is accompanied by theincrease in the modulus and the slower relaxation timeBoth the storage (1198661015840) and loss (11986610158401015840) modulus reflected thestrength of the intermolecular interactions At the identicalhydrophobic proportion 119866

119888(1198661015840 = 11986610158401015840) of 075DM93 is

278 Pa compared to 179 Pa of 075DM46 Also in consid-eration of the similar 119873

119867the value of 119866

119888was respectively

245 Pa and 356 Pa for 05DM127 and 075DM128 Note thatthe storage (1198661015840) and loss (11986610158401015840)modulus exhibit uncoordinatedvariation over the frequency considered 1198661015840 becomes largerthan 11986610158401015840 after the cross-point indicating the domination ofelastic part

On the other hand time 119905119888also increased significantly

with the strength of the intermolecular associations that iswith the lifetime of the hydrophobic groups in interactionform For copolymers 05DM45 and 075DM46 the relax-ation time is respectively 32 and 82 times the values forPAM We also find the longer 119873

119867with less hydrophobic

proportion had the equivalent 119905119888to that shorter 119873

119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400

Figure 9 Storage (1198661015840) and loss (11986610158401015840) modulus as a function offrequency for copolymers 05DM127 05DM93 and 05DM45 andfor PAM (119888

119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc

Figure 10 Storage (1198661015840) and loss (11986610158401015840) modulus as a function offrequency for copolymers 075DM128 075DM93 and 075DM46and for PAM (119888

119901= 20 g dLminus1 119879 = 25∘C)

more hydrophobic proportion The relaxation time is 082 sfor 075DM46 to 085 s for 05DM93 Moreover at the samehydrophobic proportion the increase in 119905

119888was even more

pronounced when119873119867increases The second relaxation time

is not observed and it will probably be located at higherfrequencies which is experimentally inaccessible since theresponse is no longer linear


Table 3 Values of the slopes of the storage modulus 1198661015840 and the loss modulus 11986610158401015840 in the terminal zone and values of the crossing time 119905119888for

the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866

10158401015840 (Pa)PAM 22 098 lt00105DM45 16 117 151 03205DM93 135 105 227 08605DM127 127 086 245 285075DM46 146 115 179 082075DM93 125 093 278 192075DM128 132 096 356 625

34 Additives Influence

341 Influence of Salt The apparent viscosity as a functionof NaCl concentration for 075DM128 and PAM at polymerconcentration of 015 g dLminus1 and 075 g dLminus1 was representedin Figure 11 The values of the curves are expressed in termsof a relative viscosity that is the ratio of the viscosity in thepresence of salt to the viscosity in salt-free solution

The behavior of PAM exhibits almost the same trend attwo different concentrations in the whole salt concentrationrange At low salt concentration the viscosity decreasessmoothly upon the increase in salt content and above thecertain salt concentration relative constant apparent viscosityis exhibited For PAM increasing the concentration slightlyshifts the constant apparent viscosity towards the lowersalt concentration At the highest salt level the viscosityof PAM at 075 g dLminus1 is about 85 of its initial valuein pure water This can be explained that the polarity ofsolvent is changed in the presence of salt resulting in theoppression of macromolecular chain accompanied by slightdecrease of the apparent viscosity However for copolymer075DM128 in salt solution the variation of the viscositydepends significantly on the polymer concentration Forcopolymer 075DM128 dilute solution (015 g dLminus1) slightlyhigher than critical concentration (011 g dLminus1) apparentviscosity increases with increasing of NaCl concentrationAt NaCl concentration of 080 g dLminus1 apparent viscosityreaches the maximum value (3 times that value in saltfree solution) subsequently decreases steeply and it finallybecomes close to that of PAM Solution polarity induced bythe presence of NaCl enhances intermolecular interactionbetween hydrophobic groups of the chains and the good salt-thickening behavior is observed On the other hand withfurther increasing the salt concentration the hydrophobicmicrostructures turn compact and isolated macromoleculesresulting in the disappearance of intermolecular interactionand the decrease of the apparent viscosity This behaviorsupports the conclusion that below the chain overlap regimethe thickening efficiency arises from the intermolecular inter-action between the hydrophobic segments of the chainsOncethe transient network is disrupted into small clusters theviscosity is significantly lowered Conversely over the chainoverlap regime (075 g dLminus1) apparent viscosity of copoly-mer 075DM127 almost keeps constant after attaining the

001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128

075 gdL PAM015 gdL PAM

NaCl concentration (g dLminus1)

120578N

aCl120578

wat

er

Figure 11 Relative variation of the viscosity with NaCl con-centration for copolymer 075DM128 and PAM at two differentconcentrations (shear rate 734 sminus1 119879 = 25∘C)

maximum value (35 times that value in salt-free solution)This can be ascribed to the high degree of chain overlapand even entanglement at this concentration prevents thenetwork from disruption For copolymer 075DM127 whenthe salt concentration is above 10 g dLminus1 either clouding orseparation is observed

342 Influence of Surfactant Figure 12 depicts the depen-dence of the variation viscosity for copolymers 075DM127and 075DM93 on the SDS concentration SDS and hydro-phobic monomer DMDCC bear the opposite charges thusinteraction between copolymer chain and SDS occurs Sur-factant molecules first absorb at the hydrophobic units atlow surfactant concentrations to form hydrophobic clustersWith continuously increasing concentration of SDS themicrodomain is reinforced by mixed micelles formed byhydrophobic groups and surfactant expanding the clusterssize resulting in the increase in viscosity Near the CMCof SDS significantly cooperative interaction between thecopolymer chain and surfactant molecule is constructed dueto mixed micelles serving as junction points for transitional


0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800

Surfactant concentration (mM)

075 DM93075 DM128

120578ap

p (m

Pamiddots)

Figure 12 Variation of apparent viscosity of as a function ofSDS concentration for copolymers 075DM128 and 075DM93 at05 g dLminus1 (shear rate 734 sminus1 119879 = 25∘C)

network And the maximum value of viscosity for copolymer075DM128 is observed (2 times that of value in SDS-freesolution) Beyond the CMCof SDS hydrophobic segments ofcopolymer chains are dissolved intomicelles formed bymuchnumbers of surfactant molecules disrupting junction pointsresulting in the decrease of viscosity

It is noteworthy that the increasing of 119873119867

shifts themaximum viscosity toward the higher SDS concentrationand more remarkable viscosity is observed For copolymer075DM128 the maximum viscosity 1750mPasdots is exhibitedat the SDS concentration of 85mM compared to 1530mPasdotsfor 075DM93 at the SDS concentration of 67mM Coop-eratively as the SDS concentration is raised above CMC alarge viscosity for 075DM128 is still observed Two pointscan be used to interpret that the viscosity for 075DM128 inthe presence of surfactant is much higher than that of valuefor 075DM93 that is hydrophobic association and ionicattraction Hydrophobic associations reduce the contactsof the hydrophobic segments of polymer chain with waterleading to lowering the free energy of the system [3] It isdiscussed above that the longer the hydrophobic microblockthe stronger the intermolecular association and thus less freeenergy of the system Ionic attraction between SDSmoleculesand copolymer chains is obviously enhanced with prolongingthe length of cationic hydrophobic groups per chain Inthe case of cationic nonionic and zwitterionic surfactantswhether the length of hydrophobic microblock plays a role inthe rheological behavior should be further studied

35 Fluorescence Investigation The intensity ratio 11986831198681of

the third (385 nm) to the first (375 nm) vibronic peak in thefluorescence emission spectrum of pyrene is sensitive to thepolarity of the local microenvironment of the pyrene probe[12 14] This ratio is directly proportional to polarity Thus

360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)

Aqueous solution 8 mM SDS solution

I1

I1

I1

I3

I3

I3

585 g dLminus1 NaCl solution

Figure 13 Fluorescence spectra of pyrene in 025 g dLminus1 075DM128solutions at different conditions

the values of 11986831198681provide significant evidence for the for-

mation of hydrophobic microdomains at salt concentrationsand the development of bridge points ormixedmicelles whensurfactant is added Figure 13 depicts the fluorescence spectraof 02 g dLminus1 075DM128 for pyrene at different conditionsThe 11986831198681value is 0706 in aqueous solution which increases

to 0835 in 8mM SDS solution where the pyrene probeis located in the mixed micelles constructed by surfac-tant molecules and hydrophobic segments of 075DM128Additionally the 119868

31198681value in 585 g dLminus1 solution is 0883

higher than that in aqueous solution indicating that thehydrophobic microdomains became more compact in thehigh salt concentration These results agree favorably withthat obtained from viscosity

36 Morphology of Networks The microscopic structuresof poly(AMDMDCC) at different experimental conditionsare observed through ESEM at room temperature and themorphological images are shown in Figure 14 In extremelydilute solution of copolymer 05DM127 intramolecular asso-ciations of hydrophobic segments compact polymers chainsand an irregularmicrostructure is observed which of courselowers viscosity At the critical association concentrationshown in Figure 14(b) three-dimensional network formedby intermolecular association results in a regular morphol-ogy and dramatically enhances solution viscosity Thesethree-dimensional networks are disrupted in the presenceof higher concentration salt and broke into small clus-ters As shown in Figure 14(c) for copolymer 075DM128morphology of salt aggregation is observed due to highconcentration of salt At higher polymer concentration asexhibited in Figure 14(d) high degree of chain entanglementprotects three-dimensional networks from disruption andkeeps viscosity relatively stable Adding SDS a significantlycooperative interaction between the copolymer chain and


(a) (b) (c)

(d) (e) (f)

Figure 14 ESEM images of poly(AMDMDCC) at different experimental conditions (a) 05DM127 with 0075 g dLminus1 (b) 05DM127 with015 g dLminus1 (c) 075DM128 with 015 g dLminus1 in 2 g dLminus1 salt solution (d) 075DM128 with 075 g dLminus1 in 2 g dLminus1 salt solution (e) 05DM127with 05 g dLminus1 in 8mM SDS solution (f) 075DM128 with 05 g dLminus1 in 8mM SDS solution

surfactant leads to more regular microstructures than theseof copolymer solution Moreover for copolymer 075DM128with the longest119873

119867 at the CMC of SDS both intermolecular

hydrophobic interactions and ionic attractions are coopera-tive to promote the aggregation behavior of copolymer thusthe most regular microstructures are observed

4 Conclusion

A novel cationic surfmer methacryloxyethyl-dimethyl cetylammonium chloride (DMDCC) was synthesized in theexperiment For DMDCC-SDS binary mixed surfactantssystem conductivity measurement and a steady-state fluo-rescence technique indicated that synergetic mixed micelleswere obtained due to strong net attraction between cationic(DMDCC) and anionic (SDS) surfactants which dramat-ically reduce the CMC and keep the Nagg almost stableTherefore this new method could not only reasonably adjustthe length of the hydrophobic microblock (119873

119867) but also

sharply reduce the amount of SDS Utilizing a DMDCC-SDSmixed micellar copolymerization method a series of water-soluble associative copolymers with acrylamide (AM) andDMDCC are synthesized

The incorporation of hydrophobic segments into polymerchains induces a strong enhancement of apparent viscosity

Rheological measurements including steady flow and linearviscoelasticity experiments are used to study the associationprocess in the semidilute regime of copolymers In the wholeshear rate range of steady flow experiments a shear thicken-ing behavior of copolymers is exhibited and followed by shearthinning Increasing hydrophobic microblock enhances thedegree of association and results in shear thickening behaviortowards lower share rate The presence of the hydrophobicgroup into macromolecular chain increased both storage(1198661015840) and loss (1198661015840) modulus At low frequencies solutionbehaves as a Newtonian liquid and at high frequenciesoriginating from strong intermolecular association solutionexhibits as an elastic solid with storage modulus higherthan loss modulus Relaxation time (119905

119888) is also calculated to

interpret the degree of intermolecular association formed byhydrophobic segments And the results indicate that boththe hydrophobe content and especially the length of thehydrophobicmicroblock are found to be the twomain factorsinducing an increase in the final relaxation time

In the vicinity of the critical associative concentrationthe presence of salt influences the dynamics transformationbetween intramolecular and intermolecular junctions result-ing in changing the solution viscosity However at highercopolymer concentration governed by chains entanglementand intermolecular associations viscosity enhancement is


observed in the whole salt concentration range Apparent vis-cosity measurement performed on the copolymer indicatesthat both ionic attraction and intermolecular interactionsplay a great role At the CMC of SDS the formation ofmixed micelles between the copolymer chain and surfactantwhich serve as junction bridges for transitional networkremarkably enhances the viscosity What is more the micro-scopic structures for copolymers at different experimentalconditions conducted by ESEM confirm the results discussedabove

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

The authors are grateful to theMajor Special Project of China(Grant no 20082X05049-05-03) for financial support of thiswork

References

[1] A Hill F Candau and J Selb ldquoProperties of hydrophobicallyassociating polyacrylamides influence of themethod of synthe-sisrdquoMacromolecules vol 26 no 17 pp 4521ndash4532 1993

[2] E Volpert J Selb and F Candau ldquoAssociating behaviour ofpolyacrylamides hydrophobically modified with dihexylacry-lamiderdquo Polymer vol 39 no 5 pp 1025ndash1033 1998

[3] S Wu R A Shanks and G Bryant ldquoProperties of hydropho-bically modified polyacrylamide with low molecular weightand interaction with surfactant in aqueous solutionrdquo Journal ofApplied Polymer Science vol 100 no 6 pp 4348ndash4360 2006

[4] M Camail A Margaillan and I Martin ldquoCopolymers of N-alkyl-and N-arylalkylacrylamides with acrylamide influenceof hydrophobic structure on associative properties Part Iviscometric behaviour in dilute solution and drag reductionperformancerdquo Polymer International vol 58 no 2 pp 149ndash1542009

[5] Q Yang C Song Q Chen P Zhang and P Wang ldquoSynthesisand aqueous solution properties of hydrophobically modifiedanionic acrylamide copolymersrdquo Journal of Polymer Science BPolymer Physics vol 46 no 22 pp 2465ndash2474 2008

[6] M S Kamal I A Hussien A S Sultan and M Han ldquoRhe-ological study on ATBS-AM copolymer-surfactant system inhigh-temperature and high-salinity environmentrdquo Journal ofChemistry vol 2013 Article ID 801570 9 pages 2013

[7] P Zhang Y Wang W Chen H Yu Z Qi and K Li ldquoPrepa-ration and solution characteristics of a novel hydrophobicallyassociating terpolymer for enhanced oil recoveryrdquo Journal ofSolution Chemistry vol 40 no 3 pp 447ndash457 2011

[8] C Zhong P Luo Z Ye and H Chen ldquoCharacterization andsolution properties of a novel water-soluble terpolymer forenhanced oil recoveryrdquo Polymer Bulletin vol 62 no 1 pp 79ndash89 2009

[9] F Liu M Yao and M T Run ldquoSynthesis and characterizationsof poly (trimethylene terephthalate)-b-poly (tetramethyleneglycol) copolymersrdquo International Journal of Polymer Sciencevol 2013 Article ID 156289 10 pages 2013

[10] U P Strauss and B L Williams ldquoThe transition from typicalpolyelectrolyte to polysoap III Light scattering and viscositystudies of poly-4-vinylpyridine derivativesrdquo The Journal ofPhysical Chemistry vol 65 no 8 pp 1390ndash1395 1961

[11] R Varoqui and U P Strauss ldquoComparison of electrical trans-port properties of anionic polyelectrolytes and polysoapsrdquo TheJournal of Physical Chemistry vol 72 no 7 pp 2507ndash2511 1968

[12] C L McCormick C E Hoyle andM D Clark ldquoWater-solublecopolymers 35 Photophysical and rheological studies of thecopolymer of methacrylic acid with 2-(1-naphthylacetyl)ethylacrylaterdquoMacromolecules vol 23 no 12 pp 3124ndash3129 1990

[13] Y Morishima T Kobayashi T Furui and S-I NozakuraldquoIntramolecular compartmentalization of photoredox centersin functionalized amphiphilic polyelectrolytes a model forcollisionless electron transfer systemsrdquoMacromolecules vol 20no 7 pp 1707ndash1712 1987

[14] M A Winnik S M Bystryak and J Siddiqui ldquoInteractionof pyrene-labeled poly(ethylene imine) with sodium dodecylsulfate in aqueous solutionrdquo Macromolecules vol 32 no 3 pp624ndash632 1999

[15] B Gao H Guo J Wang and Y Zhang ldquoPreparation ofhydrophobic association polyacrylamide in a new micellarcopolymerization system and its hydrophobically associativepropertyrdquoMacromolecules vol 41 no 8 pp 2890ndash2897 2008

[16] E Volpert J Selb and F Candau ldquoInfluence of the hydrophobestructure on composition microstructure and rheology inassociating polyacrylamides prepared by micellar copolymer-izationrdquoMacromolecules vol 29 no 5 pp 1452ndash1463 1996

[17] A Samakande P CHartmann andRD Sanderson ldquoSynthesisand characterization of new cationic quaternary ammoniumpolymerizable surfactantsrdquo Journal of Colloid and InterfaceScience vol 296 no 1 pp 316ndash323 2006

[18] T Noda A Hashidzume and Y Morishima ldquoSolution proper-ties ofmicelle networks formed by nonionic surfactantmoietiescovalently bound to a polyelectrolyte salt effects on rheologicalbehaviorrdquo Langmuir vol 16 no 12 pp 5324ndash5332 2000

[19] A B Lowe and C L McCormick ldquoSynthesis and solutionproperties of zwitterionic polymersrdquoChemical Reviews vol 102no 11 pp 4177ndash4189 2002

[20] C Thevenot B Grassl G Bastiat and W Binana ldquoAggregationnumber and critical micellar concentration of surfactant deter-mined by Time-Dependent Static Light Scattering (TDSLS)and conductivityrdquo Colloids and Surfaces A Physicochemical andEngineering Aspects vol 252 no 2-3 pp 105ndash111 2005

[21] A A Dar G M Rather and A R Das ldquoMixed micelleformation and solubilization behavior toward polycyclic aro-matic hydrocarbons of binary and ternary cationicmdashnonionicsurfactant mixturesrdquo The Journal of Physical Chemistry B vol111 no 12 pp 3122ndash3132 2007

[22] B Jonsson B Kronberg and B Lindman Surfactants andPolymers in Aqueous Solution John Wiley amp Sons 2003

[23] X F Zhang and W H Wu ldquoNovel hydrophobically associativepolyacrylamide with tunable viscosityrdquo Chinese Chemical Let-ters vol 20 no 11 pp 1361ndash1365 2009

[24] D Attwood V Mosquera J Rodriguez M Garcia and M JSuarez ldquoEffect of alcohols on themicellar properties in aqueoussolution of alkyltrimethylammonium bromidesrdquo Colloid ampPolymer Science vol 272 no 5 pp 584ndash591 1994

[25] J X Liu Y J Guo Y W Zhu et al ldquoPolymerization of micro-block associative polymer with alcohol-surfmer mixed micellarmethod and their rheological propertiesrdquoActa Physico-ChimicaSinica vol 28 no 7 pp 1757ndash1763 2012


[26] W Jaeger J Bohrisch and A Laschewsky ldquoSynthetic polymerswith quaternary nitrogen atomsmdashsynthesis and structure of themost used type of cationic polyelectrolytesrdquo Progress in PolymerScience vol 35 no 5 pp 511ndash577 2010

[27] A Kotzev A Laschewsky P Adriaensens and J Gelan ldquoMicel-lar polymers with hydrocarbon and fluorocarbon hydrophobicchains A strategy to multicompartment micellesrdquo Macro-molecules vol 35 no 3 pp 1091ndash1101 2002

[28] Y Chang and C LMcCormick ldquoWater-soluble copolymers 49Effect of the distribution of the hydrophobic cationic monomerdimethyldodecyl(2-acrylamidoethyl)ammonium bromide onthe solution behavior of associating acrylamide copolymersrdquoMacromolecules vol 26 no 22 pp 6121ndash6126 1993

[29] K Stahler J Selb and F Candau ldquoMulticompartment poly-meric micelles based on hydrocarbon and fluorocarbon poly-merizable surfactantsrdquo Langmuir vol 15 no 22 pp 7565ndash75761999

[30] E J Regalado J Selb and F Candau ldquoViscoelastic behaviorof semidilute solutions of multisticker polymer chainsrdquoMacro-molecules vol 32 no 25 pp 8580ndash8588 1999

[31] C Zhong R Huang L Ye and H Dai ldquoStudy on the mor-phology of the novel hydrophobically associative acrylamide-based terpolymer in aqueous solution by AFMmeasurementsrdquoJournal of Applied Polymer Science vol 101 no 6 pp 3996ndash4002 2006

[32] L Leibler M Rubinstein and R H Colby ldquoDynamics ofreversible networksrdquo Macromolecules vol 24 no 16 pp 4701ndash4707 1991

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


is a free radical micellar copolymerization technique [1]However the addition of well amount surfactant (above thecritical micelle concentration CMC) caused some negativeinfluences such as low-molecular weight caused by thechain transfer effects of surfactants [5] impurity withinthe surfactant and the complicated treatment to removethe surfactants to obtain pure products [15] An additionalproblem originates from the difficulty to prepare copolymerswith both high associativity and good water compatibilitybecause the microblocky hydrophobe of the copolymers isvery limited to maintain solubility in water [16]

To overcome these drawbacks the conventional micellarcopolymerizationmethod ismodified by using polymerizablesurfactants that is surfmers to substitute the traditionalones Surfmers are a family of unique surfactants which notonly have amphiphilic structures that is cationic or anioniclong-chain alkyl structure but also contain polymerizablevinyl double bonds [17ndash19] Surfmer molecules formmicellesat concentration above the CMC Both micellar aggrega-tion (119873agg) and CMC of such micellar systems could bemediated by adding either cosurfactants such as electrolytesand medium chain-length alcohols or surfactants [20ndash23]Therefore the hydrophobic microblock length that is 119873

119867

of the copolymers chains was controlled Mixing behaviorof surfmer and cosurfactant has been widely investigated[24 25] On the other hand due to an amazing interactionbetween the surfactants that are mixed mixed micelles com-posed of binary surfactants have received increasing atten-tion Properties of binary mixed micelles upon hydrocarbon-hydrocarbon hydrocarbon-fluorocarbon surfactants includ-ing nonionic-nonionic anionic-nonionic anionic-cationicand zwitterionic-anionic mixtures were extensively inves-tigated by advanced analytical techniques such as lightscattering small angle neutron scattering and fluorescenceprobingmeasurement [26 27] Based on these experiments aregular solution theory that accountswell for the characters ofbinarymixedmicelles has been established inwhich theCMCvalues and 119873agg values involved in different compositionalmixtures depended on an interaction parameter (120573) [22]Apparently the regular solution theory is also applied wellin the surfactant-surfmer mixed micelle system Chang andMcCormick [28] firstly suggested that the microblock lengthof the cationic polymerizable surfactant dimethyl-dodecyl (2-acrylamidoethyl) ammonium bromide could be controlledby addition of cetyltrimethyl-ammonium bromide (CTAB)as a cationic cosurfactant Direct experimental evidence ofthis behavior is reported by Zhang and Wu [23] from con-ductivity and fluorescence studies on the samemixed micellesystem Stahler et al [29] found that cationic fluorocarbon-hydrocarbon surfmer pairs that bear the same hydrophobiccompoundmayhave the partial compatibility in single type ofmixed micelles despite the repulsive headgroup interactions

It is thought that only the surfmer-surfactant mixedmicellar system corresponds to the same charge either posi-tive or negative the microblock of length could be adjustedCan the cationic surfmer-anionic surfactant binary systemshare the same capacity in the preparation of hydropho-bically associative polyacrylamide with good performanceThis paper just addressed this issue Firstly a long-chain

alkyl cationic surfmer of methacryloxy-ethyl-dimethyl cetylammonium chloride (DMDCC) was synthesized and theproperties of DMDCC-SDS (sodium dodecyl sulfate) mixedmicelles are determined by conductivity measurement and asteady-state fluorescence technique We discuss the synthe-sis and characterization of cationic associating copolymersprepared by DMDCC-SDS mixed micellar copolymerizationwith DMDCC as cationic hydrophobic comonomer Particu-larly we focus on the effect of the length and number of thehydrophobic microstructures on the rheological propertiesIn addition we look at the effect of salt and surfactant on theapparent viscosity of copolymers

2 Experimental Section

21 Materials Acrylamide (Chengdu KeLong Chemical Re-agent Co Ltd) was recrystallized twice from acetone andvacuum dried at room temperature prior to use The azo-initiator V-50 (221015840-azobis(2-amidinopropane)dihydrochlo-ride) (UA Alfa Aesar 99) was used without further purifi-cation NN-Dimethyl-ethylamine methacrylate and cetylchloride purchased from Aldrich chemicals (purity 99)were used as received Water was double deionized with aMillipore Milli-Q system Other reagents were analyticallypure and used as received

22 Synthesis of Cationic Polymerizable Surfactant (DMDCC)Scheme 1 illustrates the synthesis of the cationic surfmermethacryloxyethyl-dimethyl cetyl ammonium chloride(DMDCC) NN-Dimethylethylamine methacrylate (282 g02mol) was added into a 250mL three-necked round-bottom flask and placed in an oil bath and agitated by amagnetic stirrer under a nitrogen atmosphere Cetyl chloride(469 g 0180mol) was subsequently added to the additionalfunnel When the temperature increased to 85∘C cetylchloride was added to the flask dropwise over a period of6 h After 42 h the yellow viscous gel was obtained Theexcess crude product was dissolved in a small amount ofacetone at 45∘C and cooled to minus10∘C and the yellow semisolidproduct was obtained Further purification of the productwas accomplished by recrystallization from a 1 1 (wtwt)mixture of acetone and ether yield of 618 g (85)

23 Properties of DMDCC-SDS Binary Surfactant System

231 CMC Values CMC values of DMDCC and mixtureof DMDCC-SDS were determined by conductivity on adigit conductivity meter The conductivity 120581 of aqueoussurfactant solutions was measured against the surfactantmolar concentration at 50∘CThe difference in themagnitudeof the gradients above or below the inflection points in eachsample results in a concomitant increase in the uncertaintyof the CMC values Thus the CMC values of DMDCC andDMDCC-SDS were measured from the break points of the 120581to 119888 plots

232 Aggregation Number Using pyrene as a probe theaggregation numbers (119873agg) of DMDCC as well as mixture


C CO

O CCl

ClC NC C

OO C C N

H2H2 H2 H2 H2C

H2CH3C H3CCH2

CH3 CH3 CH3

CH3

CH3CH2CH3+ minus

(CH2)14

(CH2)14

85∘C




ln(1198680

119868) = 119873

[119876]

(119862119905minus CMC)

(1)









25 Characterization



2O as a solvent at







3(385 nm) to first 119868

1




1

CMC119898

=1205721

119891119898

1CMC1

+1205722

119891119898

2CMC2

(2)



1 CMC



2are


1 1198911198982


ln1198911198981= (120572119898

2)2120573

ln1198911198982= (120572119898

1)2120573

(3)


1and 120572119898



120572119898

1=

1205721119891119898

2CMC2

1205721119891119898

2CMC2+ 1205722119891119898

1CMC1

120572119898

2= 1 minus 120572

119898

1

(4)




00 02 04 06 08 10

001

01

1

10

CMC


CMC

(mM

)

55

60

65

70

75

80

85

90

95

Nagg

Nag

g


00 02 04 06 08 100

10

20

30

40

50

CMC

(mM

)







+

+

++

+++

+

+

+

+

+

++ + + +

+

++

+

+

++

+

+

+

++

+

Pure SDS micelles

Pure DMDCC micelles


minus

minus

minus

minus

minus

minus

minus

minus


minus

minus

minus

minus

minus

minus

minusminus minus

minus

minus



119873119898

agg = 120572119898

1119873agg1 + 120572

119898

2119873agg2 (5)


119873119867=

[119867]119873agg

[119878] minus CMC (6)


119873119867=

([119867] minus CMC119867)119873119898

agg

[119867 + 119878] minus CMC(119867+119878)

(7)






2O




119867value and









gmolminus1[120578]


d


PAM 100 0 0 0 0 350 610 755 ++

05DM45

995 05

175 45 25 315 586 697 ++

05DM93 08 93 124 329 540 720 +05DM127 05 127 9 325 520 714 +05DM92 0 92 06 164 299 428 plusmn

075DM46

9925 075

55 46 25 222 335 536 ++

075DM93 21 93 17 306 470 683 +075DM128 135 128 13 335 418 730 +075DM92 0 92 0 minus



H2N

H2H2 H

C

H2CH3C

H2C

H2C

H3CH2C

O O OO

OO

C

C

C C CC

Cl

NN

C

CH2

CH2

CH2

CH3

CH3

CH2

CH3

NH2

CH3

CH3

CH3

CH2

14

14

+

+

+

minus

Clminus


4000 3500 3000 2500 2000 1500 1000 500

68210251117

1319

14172925

2919

3450

1028

9611299

T (

)

DMDCC P(AM-DMDCC)

3432 23601633

1464

1641

1167

2844 1719










55 50 45 40 35 30 25 20 15 10(ppm)

+

minus

CH2

NH2

CH3

CH 3CH2

CH3

CH2

H H2

H2C

H2C

H3C

d

d

f f

f

g

ge

e

e

c

bC C C

C

cCl

N

C O OO

baa

a

372

359

248

236

216

158

111

14


00 01 02 03 04 050

100

200

300

400

500

600

700

800

CAC

CAC

075DM12805DM127

05DM93PAM

CAC

0025 0050 0075 0100 01251

10


120578ap

p(m

Pamiddots)

clowast






119867and polymer





0) which





119901= 20 g dLminus1

120590lowast (Pa) 120574



0(mPasdots)

PAM 093 103 90 36 10 35705DM45 109 166 658 82 056 1465005DM93 155 123 1264 978 036 2716005DM127 207 076 2723 1315 025 62600

01 1 10 100 100010

100

1000

10000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 10 g dLminus1 119879 = 25∘C)





119867is


001 01 101 100 1000

100

1000

10000

100000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 20 g dLminus1 119879 = 25∘C)



0increases with


119867 had great









119888(1119891) at a







119888(1198661015840 = 11986610158401015840) of 075DM93 is









119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400


119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc


119901= 20 g dLminus1 119879 = 25∘C)


119888was even more





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




C CO

O CCl

ClC NC C

OO C C N

H2H2 H2 H2 H2C

H2CH3C H3CCH2

CH3 CH3 CH3

CH3

CH3CH2CH3+ minus

(CH2)14

(CH2)14

85∘C




ln(1198680

119868) = 119873

[119876]

(119862119905minus CMC)

(1)









25 Characterization



2O as a solvent at







3(385 nm) to first 119868

1




1

CMC119898

=1205721

119891119898

1CMC1

+1205722

119891119898

2CMC2

(2)



1 CMC



2are


1 1198911198982


ln1198911198981= (120572119898

2)2120573

ln1198911198982= (120572119898

1)2120573

(3)


1and 120572119898



120572119898

1=

1205721119891119898

2CMC2

1205721119891119898

2CMC2+ 1205722119891119898

1CMC1

120572119898

2= 1 minus 120572

119898

1

(4)




00 02 04 06 08 10

001

01

1

10

CMC


CMC

(mM

)

55

60

65

70

75

80

85

90

95

Nagg

Nag

g


00 02 04 06 08 100

10

20

30

40

50

CMC

(mM

)







+

+

++

+++

+

+

+

+

+

++ + + +

+

++

+

+

++

+

+

+

++

+

Pure SDS micelles

Pure DMDCC micelles


minus

minus

minus

minus

minus

minus

minus

minus


minus

minus

minus

minus

minus

minus

minusminus minus

minus

minus



119873119898

agg = 120572119898

1119873agg1 + 120572

119898

2119873agg2 (5)


119873119867=

[119867]119873agg

[119878] minus CMC (6)


119873119867=

([119867] minus CMC119867)119873119898

agg

[119867 + 119878] minus CMC(119867+119878)

(7)






2O




119867value and









gmolminus1[120578]


d


PAM 100 0 0 0 0 350 610 755 ++

05DM45

995 05

175 45 25 315 586 697 ++

05DM93 08 93 124 329 540 720 +05DM127 05 127 9 325 520 714 +05DM92 0 92 06 164 299 428 plusmn

075DM46

9925 075

55 46 25 222 335 536 ++

075DM93 21 93 17 306 470 683 +075DM128 135 128 13 335 418 730 +075DM92 0 92 0 minus



H2N

H2H2 H

C

H2CH3C

H2C

H2C

H3CH2C

O O OO

OO

C

C

C C CC

Cl

NN

C

CH2

CH2

CH2

CH3

CH3

CH2

CH3

NH2

CH3

CH3

CH3

CH2

14

14

+

+

+

minus

Clminus


4000 3500 3000 2500 2000 1500 1000 500

68210251117

1319

14172925

2919

3450

1028

9611299

T (

)

DMDCC P(AM-DMDCC)

3432 23601633

1464

1641

1167

2844 1719










55 50 45 40 35 30 25 20 15 10(ppm)

+

minus

CH2

NH2

CH3

CH 3CH2

CH3

CH2

H H2

H2C

H2C

H3C

d

d

f f

f

g

ge

e

e

c

bC C C

C

cCl

N

C O OO

baa

a

372

359

248

236

216

158

111

14


00 01 02 03 04 050

100

200

300

400

500

600

700

800

CAC

CAC

075DM12805DM127

05DM93PAM

CAC

0025 0050 0075 0100 01251

10


120578ap

p(m

Pamiddots)

clowast






119867and polymer





0) which





119901= 20 g dLminus1

120590lowast (Pa) 120574



0(mPasdots)

PAM 093 103 90 36 10 35705DM45 109 166 658 82 056 1465005DM93 155 123 1264 978 036 2716005DM127 207 076 2723 1315 025 62600

01 1 10 100 100010

100

1000

10000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 10 g dLminus1 119879 = 25∘C)





119867is


001 01 101 100 1000

100

1000

10000

100000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 20 g dLminus1 119879 = 25∘C)



0increases with


119867 had great









119888(1119891) at a







119888(1198661015840 = 11986610158401015840) of 075DM93 is









119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400


119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc


119901= 20 g dLminus1 119879 = 25∘C)


119888was even more





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





3(385 nm) to first 119868

1




1

CMC119898

=1205721

119891119898

1CMC1

+1205722

119891119898

2CMC2

(2)



1 CMC



2are


1 1198911198982


ln1198911198981= (120572119898

2)2120573

ln1198911198982= (120572119898

1)2120573

(3)


1and 120572119898



120572119898

1=

1205721119891119898

2CMC2

1205721119891119898

2CMC2+ 1205722119891119898

1CMC1

120572119898

2= 1 minus 120572

119898

1

(4)




00 02 04 06 08 10

001

01

1

10

CMC


CMC

(mM

)

55

60

65

70

75

80

85

90

95

Nagg

Nag

g


00 02 04 06 08 100

10

20

30

40

50

CMC

(mM

)







+

+

++

+++

+

+

+

+

+

++ + + +

+

++

+

+

++

+

+

+

++

+

Pure SDS micelles

Pure DMDCC micelles


minus

minus

minus

minus

minus

minus

minus

minus


minus

minus

minus

minus

minus

minus

minusminus minus

minus

minus



119873119898

agg = 120572119898

1119873agg1 + 120572

119898

2119873agg2 (5)


119873119867=

[119867]119873agg

[119878] minus CMC (6)


119873119867=

([119867] minus CMC119867)119873119898

agg

[119867 + 119878] minus CMC(119867+119878)

(7)






2O




119867value and









gmolminus1[120578]


d


PAM 100 0 0 0 0 350 610 755 ++

05DM45

995 05

175 45 25 315 586 697 ++

05DM93 08 93 124 329 540 720 +05DM127 05 127 9 325 520 714 +05DM92 0 92 06 164 299 428 plusmn

075DM46

9925 075

55 46 25 222 335 536 ++

075DM93 21 93 17 306 470 683 +075DM128 135 128 13 335 418 730 +075DM92 0 92 0 minus



H2N

H2H2 H

C

H2CH3C

H2C

H2C

H3CH2C

O O OO

OO

C

C

C C CC

Cl

NN

C

CH2

CH2

CH2

CH3

CH3

CH2

CH3

NH2

CH3

CH3

CH3

CH2

14

14

+

+

+

minus

Clminus


4000 3500 3000 2500 2000 1500 1000 500

68210251117

1319

14172925

2919

3450

1028

9611299

T (

)

DMDCC P(AM-DMDCC)

3432 23601633

1464

1641

1167

2844 1719










55 50 45 40 35 30 25 20 15 10(ppm)

+

minus

CH2

NH2

CH3

CH 3CH2

CH3

CH2

H H2

H2C

H2C

H3C

d

d

f f

f

g

ge

e

e

c

bC C C

C

cCl

N

C O OO

baa

a

372

359

248

236

216

158

111

14


00 01 02 03 04 050

100

200

300

400

500

600

700

800

CAC

CAC

075DM12805DM127

05DM93PAM

CAC

0025 0050 0075 0100 01251

10


120578ap

p(m

Pamiddots)

clowast






119867and polymer





0) which





119901= 20 g dLminus1

120590lowast (Pa) 120574



0(mPasdots)

PAM 093 103 90 36 10 35705DM45 109 166 658 82 056 1465005DM93 155 123 1264 978 036 2716005DM127 207 076 2723 1315 025 62600

01 1 10 100 100010

100

1000

10000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 10 g dLminus1 119879 = 25∘C)





119867is


001 01 101 100 1000

100

1000

10000

100000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 20 g dLminus1 119879 = 25∘C)



0increases with


119867 had great









119888(1119891) at a







119888(1198661015840 = 11986610158401015840) of 075DM93 is









119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400


119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc


119901= 20 g dLminus1 119879 = 25∘C)


119888was even more





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




+

+

++

+++

+

+

+

+

+

++ + + +

+

++

+

+

++

+

+

+

++

+

Pure SDS micelles

Pure DMDCC micelles


minus

minus

minus

minus

minus

minus

minus

minus


minus

minus

minus

minus

minus

minus

minusminus minus

minus

minus



119873119898

agg = 120572119898

1119873agg1 + 120572

119898

2119873agg2 (5)


119873119867=

[119867]119873agg

[119878] minus CMC (6)


119873119867=

([119867] minus CMC119867)119873119898

agg

[119867 + 119878] minus CMC(119867+119878)

(7)






2O




119867value and









gmolminus1[120578]


d


PAM 100 0 0 0 0 350 610 755 ++

05DM45

995 05

175 45 25 315 586 697 ++

05DM93 08 93 124 329 540 720 +05DM127 05 127 9 325 520 714 +05DM92 0 92 06 164 299 428 plusmn

075DM46

9925 075

55 46 25 222 335 536 ++

075DM93 21 93 17 306 470 683 +075DM128 135 128 13 335 418 730 +075DM92 0 92 0 minus



H2N

H2H2 H

C

H2CH3C

H2C

H2C

H3CH2C

O O OO

OO

C

C

C C CC

Cl

NN

C

CH2

CH2

CH2

CH3

CH3

CH2

CH3

NH2

CH3

CH3

CH3

CH2

14

14

+

+

+

minus

Clminus


4000 3500 3000 2500 2000 1500 1000 500

68210251117

1319

14172925

2919

3450

1028

9611299

T (

)

DMDCC P(AM-DMDCC)

3432 23601633

1464

1641

1167

2844 1719










55 50 45 40 35 30 25 20 15 10(ppm)

+

minus

CH2

NH2

CH3

CH 3CH2

CH3

CH2

H H2

H2C

H2C

H3C

d

d

f f

f

g

ge

e

e

c

bC C C

C

cCl

N

C O OO

baa

a

372

359

248

236

216

158

111

14


00 01 02 03 04 050

100

200

300

400

500

600

700

800

CAC

CAC

075DM12805DM127

05DM93PAM

CAC

0025 0050 0075 0100 01251

10


120578ap

p(m

Pamiddots)

clowast






119867and polymer





0) which





119901= 20 g dLminus1

120590lowast (Pa) 120574



0(mPasdots)

PAM 093 103 90 36 10 35705DM45 109 166 658 82 056 1465005DM93 155 123 1264 978 036 2716005DM127 207 076 2723 1315 025 62600

01 1 10 100 100010

100

1000

10000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 10 g dLminus1 119879 = 25∘C)





119867is


001 01 101 100 1000

100

1000

10000

100000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 20 g dLminus1 119879 = 25∘C)



0increases with


119867 had great









119888(1119891) at a







119888(1198661015840 = 11986610158401015840) of 075DM93 is









119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400


119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc


119901= 20 g dLminus1 119879 = 25∘C)


119888was even more





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials









gmolminus1[120578]


d


PAM 100 0 0 0 0 350 610 755 ++

05DM45

995 05

175 45 25 315 586 697 ++

05DM93 08 93 124 329 540 720 +05DM127 05 127 9 325 520 714 +05DM92 0 92 06 164 299 428 plusmn

075DM46

9925 075

55 46 25 222 335 536 ++

075DM93 21 93 17 306 470 683 +075DM128 135 128 13 335 418 730 +075DM92 0 92 0 minus



H2N

H2H2 H

C

H2CH3C

H2C

H2C

H3CH2C

O O OO

OO

C

C

C C CC

Cl

NN

C

CH2

CH2

CH2

CH3

CH3

CH2

CH3

NH2

CH3

CH3

CH3

CH2

14

14

+

+

+

minus

Clminus


4000 3500 3000 2500 2000 1500 1000 500

68210251117

1319

14172925

2919

3450

1028

9611299

T (

)

DMDCC P(AM-DMDCC)

3432 23601633

1464

1641

1167

2844 1719










55 50 45 40 35 30 25 20 15 10(ppm)

+

minus

CH2

NH2

CH3

CH 3CH2

CH3

CH2

H H2

H2C

H2C

H3C

d

d

f f

f

g

ge

e

e

c

bC C C

C

cCl

N

C O OO

baa

a

372

359

248

236

216

158

111

14


00 01 02 03 04 050

100

200

300

400

500

600

700

800

CAC

CAC

075DM12805DM127

05DM93PAM

CAC

0025 0050 0075 0100 01251

10


120578ap

p(m

Pamiddots)

clowast






119867and polymer





0) which





119901= 20 g dLminus1

120590lowast (Pa) 120574



0(mPasdots)

PAM 093 103 90 36 10 35705DM45 109 166 658 82 056 1465005DM93 155 123 1264 978 036 2716005DM127 207 076 2723 1315 025 62600

01 1 10 100 100010

100

1000

10000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 10 g dLminus1 119879 = 25∘C)





119867is


001 01 101 100 1000

100

1000

10000

100000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 20 g dLminus1 119879 = 25∘C)



0increases with


119867 had great









119888(1119891) at a







119888(1198661015840 = 11986610158401015840) of 075DM93 is









119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400


119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc


119901= 20 g dLminus1 119879 = 25∘C)


119888was even more





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




55 50 45 40 35 30 25 20 15 10(ppm)

+

minus

CH2

NH2

CH3

CH 3CH2

CH3

CH2

H H2

H2C

H2C

H3C

d

d

f f

f

g

ge

e

e

c

bC C C

C

cCl

N

C O OO

baa

a

372

359

248

236

216

158

111

14


00 01 02 03 04 050

100

200

300

400

500

600

700

800

CAC

CAC

075DM12805DM127

05DM93PAM

CAC

0025 0050 0075 0100 01251

10


120578ap

p(m

Pamiddots)

clowast






119867and polymer





0) which





119901= 20 g dLminus1

120590lowast (Pa) 120574



0(mPasdots)

PAM 093 103 90 36 10 35705DM45 109 166 658 82 056 1465005DM93 155 123 1264 978 036 2716005DM127 207 076 2723 1315 025 62600

01 1 10 100 100010

100

1000

10000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 10 g dLminus1 119879 = 25∘C)





119867is


001 01 101 100 1000

100

1000

10000

100000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 20 g dLminus1 119879 = 25∘C)



0increases with


119867 had great









119888(1119891) at a







119888(1198661015840 = 11986610158401015840) of 075DM93 is









119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400


119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc


119901= 20 g dLminus1 119879 = 25∘C)


119888was even more





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






119901= 20 g dLminus1

120590lowast (Pa) 120574



0(mPasdots)

PAM 093 103 90 36 10 35705DM45 109 166 658 82 056 1465005DM93 155 123 1264 978 036 2716005DM127 207 076 2723 1315 025 62600

01 1 10 100 100010

100

1000

10000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 10 g dLminus1 119879 = 25∘C)





119867is


001 01 101 100 1000

100

1000

10000

100000

PAM05DM127

05DM9305DM45

120578ap

p(m

Pamiddots)



119901= 20 g dLminus1 119879 = 25∘C)



0increases with


119867 had great









119888(1119891) at a







119888(1198661015840 = 11986610158401015840) of 075DM93 is









119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400


119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc


119901= 20 g dLminus1 119879 = 25∘C)


119888was even more





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










119888(1119891) at a







119888(1198661015840 = 11986610158401015840) of 075DM93 is









119867with

001 01 1 10 100

001

01

1

10

05D

Frequency (Hz)

Gc

GcGc

05DM127 G998400

127 05DM G998400998400

05D 05D

05D

998400 PAM G 998400 PAM G998400

G998400 G998400998400

(Pa)

M93 G998400

M93 G998400998400

M45 G998400

M45 G998400998400


119901= 10 g dLminus1 119879 = 25∘C)

001 01 1 25 50 75 100001

01

1

10

100

Frequency (Hz)

075DM128 G998400998400 075DM93 G998400998400

075DM46 G998400998400

075DM128 G998400

075DM93 G998400 075DM46 G998400

G998400 G998400998400

(Pa)

GcGc

Gc


119901= 20 g dLminus1 119879 = 25∘C)


119888was even more





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





the polymers

Polymer Slope119866119888(Pa) 119905

119888(s)

1198661015840 (Pa) 119866





001 01 1 10025

05

1

2

4

075 gdL 075DM128015 gdL 075DM128



120578N

aCl120578

wat

er





0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




0 2 4 6 8 10 12 140

200

400

600

800

1000

1200

1400

1600

1800


075 DM93075 DM128

120578ap

p (m

Pamiddots)







360 380 400 420 440 460 480 500 520 5400

2

4

6

8

10

Inte

nsity

(au

)

Wavelength (nm)


I1

I1

I1

I3

I3

I3










(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b) (c)

(d) (e) (f)





4 Conclusion


119867) but also











Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials







Acknowledgment


References









































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials


















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



Research Article Rheological Properties of Hydrophobically...

Documents

Transcript of Research Article Rheological Properties of Hydrophobically...