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N,N-Dimethylacetamide

Institute of Macromolecular Compounds, RAS, Bolshoy pr ., 31, Saint Petersburg 199004, Russia

ABSTRACT

PAN, as an engineering material with increasing technological interest. The

methods of translational diffusion, velocity sedimentation and viscometry are

employed . At first time, optical anisotropy of the PAN molecule was

determined with flow birefringence technique which is very sensitive to

intramolecular structure . The PAN sample with molecular weight of 9x105 and

low stereoregularity was studied in dilute solution in N,N-dimethylacetamide.

Intrinsic viscosity was calculated according to Huggins equation from the

dependence of reduced viscosity on concentration of solution . Molecular

mass was determined with Svedberg's equation . The heterogeneity

parameter was evaluated by the absolute method of analytical ultra-

centrifugation . Translation diffusion was Investigated using a gradient method

in a cell Teflon in the Tsvetkov's interferometric diffusometer . The flow

birefringence measurements were made in titanium dynamooptimeter and the

Hg-lamp was used as a light source. The sign of the effect and the stress

optical coefficient were determined . The role of the micro and macro form

effects in flow birefringence is discussed . The intrinsic optical anisotropy

-25)

(-3 .3x10 cm3 of the chain unit of the PAN molecule is attributed to

structural features of the polymer molecule and anisotropy of the cyano-

groupS.

Key Words : polyacrylonitrile, flow birefringence, hydrodynamic properties, macromolecule . optical anisotropy

the PAN molecular characterization.

Polyacrylonitrile (PAN) is a widely used and com- Classical light scattering [4-9], diffusion-

mercially important polymer because of its unique sedimentation [10], equilibrium ultracentrifugation

properties and chemical resistance [1, 2] . Polymeriz- (and Archibald method) [11, 12], sedimentation-

235

Optical Properties of Polyacrylonitrile Molecules in N.N.Dimethylacetamide

methods have been successfully employed . As a Solution viscosity, rl, was measured by using an

result, the molecular-weight dependence of hydro- ordinary capillary viscometer of the Ostwald type

dynamic properties is already determined, and the with average shear rate <--100 s-' . The kinetic energy

coiling of the PAN macromolecules in dilute solution correction was negligible.

is characterized . The stereoregularity effects on Sedimentation velocity measurements were

solubility and molecular parameters of PAN are also made on a MOM model 3180 analytical ultracentri-

studied [5, 6, 14]. fuge (Hungary) in a double-sector polyamide cell 1 .2

Experimental results of these works show cm in height, h, with a synthetic boundary at a

clearly that insertion of a cyano-group as a side rotation frequency of n=50 .103 rpm . The accuracy in

substituent to a vinyl molecule brings about, unexp- n was not lower than 0 .2%.

ectedly, large stiffness in the polymer chain (the steric Fluctuations in temperature did not exceed

factor a from 2 .2 to 2 .8 [6]) which cannot be ±0 .05 K . A high sensitive polarizing-interferometric

explained by a simple steric hindrance due to the recording system [18] with spar twinning of a=0 .020

molar volume of the side cyano-groups. cm and interferometric fringes period of b=0 .094 cm

The intramolecular electronic interactions of was used.

the CN-groups are supposed to be mainly responsible Free diffusion of the polymer molecules in

for the chain stiffness observed for PAN . The similar solution was investigated using a gradient method in

effect was observed for cyano-derivatives of other which a sharp boundary was formed between solvent

polymers, for example, for cyanoethylated cellulose and solution in a Teflon cell [19] of 2 .0 cm in height

ethers [15]. in the Tsvetkov' s interferometric diffusometer [18].

The cyanoethylation of cellulose ethers leads The flow birefringence (FB) measurements

also to higher optical anisotropy of the macro- were made at 21 'C in temperature controlled titanium

molecule [16]. dynamooptimeter with an internal rotor 8 .08 cm in

To study origins of the effect, in the present height and a rotor-stator gap of 0 .059 cm . The double

work, dynamo-optical (the Maxwell effect) and refraction (birefringence), An, induced in the polymer

hydrodynamic properties of PAN in dilute solution in solution by shear flow (the Maxwell effect) was

N,N-dimethylacetamide (DMAA) have been invest- measured by the visual compensation technique [18].

igated, and optical anisotropy of the PAN molecule is Two mica plates with the optical retardation of 0 .019

estimated. ? and 0.0389 at wavelength 2i. were used as the

elliptic compensatories . The Hg-lamp (X =546 .1 nm)

was used as a light source.

EXPERIMENTAL All data were evaluated via non-weighted

linear regression analysis.

Sample and Solutions

Sample of PAN with low stereoregularity of the

molecules was synthesized by anionic polymerization RESULTS AND DISCUSSION

and purified as early described [17] . DMAA of

chemically pure grade with density pq' .943 g/cm 3, Hydrodynamic Properties

-2

viscosity r)o'=1 .04x 10 gcm 's ', and a refractive Intrinsic viscosity, [fl], was obtained from extra-

index of nn=1 .4365 was used as a solvent . Solutions polation of relative viscosity increment, rl i mi,plc=tl-

were prepared with magnetic stirring at ambient tlolrloc, to vanishing solute concentration [11]-

temperature . They were stable during, at least, two lim(rl,/c) made according to Huggins' equation

weeks . Intrinsic viscosity, sedimentation velocity and tl sy/c=[rl]+[tl]'kHe, where c is the solute concentration

free diffusion measurements were made at 26 °C . (g/em 3 ) and kH the Huggins ' constant. Figure 1 shows

SneIiru L A . et W.

rotor. Sedimentation coefficient, s, was determined

from the time dependence of x m (shown in Figure 2)

by s—w2 (dlnxm/dt) . Here, co is the angular rotor rate,

w=21tn/60, and n is the frequency of the rotor rota-

tion . Pressure (P) effect was evaluated by st=sp(1+p.P)

with Is the DMAA compressibility parameter

-9

(0.8x10 cm s2lg) and si,, sedimentation coefficient

determined at pressure P, where:

0.1 02

c (g/dL)

The effect does not exceed the experimental

The solid linea represent linear approximation In the ranee estl[ti]. uncertainty (3%) and it is, therefore, ignored.

Figure 1 . Concentration dependence of (1) relative visco- Points on curve to 2 in Figure 1 represent the s

sity increment and (2) reciprocal sedimentation coefficient values, thus obtained at various concentrations, as 11s

for PAN in DMAA at 28 °C (points). versus c . At c5l/[r)], this dependence was

approximated by a linear function (solid curve 2)

tbr,/c versus c (points on curve 1). Experimental data described by expression so=s(l+k,c) where so=lim

are well approximated by a linear function with the scyo and k, is the concentration parameter. The result

intercept [11] equal 6 .4 g/dL and the slope which is so=5 .0x10-13 s, k,= I3 dL/g, and k,/[fl] a 2. The last

yields kr —0.3. value is typical for the coiled molecules of many

A series of experiments with a freely sediment- flexible polymers [20].

ing boundary between the solvent and the solution The sedimentation curve area, Q, was used to

was performed at several different dilutions (with estimate the specific refractive index increment by

decreasing value of c down to the minimum possible dn/dc=(Q1c)(a,labh) . The result is (dn/dc) 5, 6 =0 .07

value) and under identical experimental conditions cm3 /g. This value agrees well with those known for

(frequency, temperature and cell) . The first moment PAN in other solvents [8] if we take into account the

of the sedimentation curve was used as the boundary difference in solvent refractive indices . Hence, we

1 .90

may conclude that the PAN molecules dissolve

3 molecularly in DMAA.

Figure 3 shows time dependence of the diff-

///

c/c// usion curve dispersion, 62, which was calculated by

E ~ the height-area method . Diffusion coefficient, D, was

= 1 .88 evaluated from the slope of this dependence by

D=(1/2) C3&I .t . A correction to the concentration

effect (14%) . was made using expression D=

Do(l+koc) with ko= 3 .9 dUg [7] . Here, Do—lim Dc ,o.

1 .88 The result is Do=0 .6x 10-7 cm 2/s.

50 100 The experimental [q], D, and so values were

Time (min) used to evaluate the hydrodynamic parameter Ao

Figure 2. Semi-logarithmic plot of the sedimentation bound- defined by [21] : Ao=(Dr1o1T)"3([rl][s]RI100) in. Here,

ary position xm versus tine at a rotor rotation frequency of [s]nso>lol(1 — vpo), R is the gas constant, T is the

n=50x109 rpm . Solute concentration is c(x102)=(1) 0.0687, Kelvin temperature, v is the partial specific volume

(2) 0.107, (3) 0 .148, and (4) 0.193 glcm3 . of PAN in solution (t=0.83 cm 3/g (8, 10]), and other

a

the change in 2 with t . This dependence is obviously

not linear, the rate of change being profoundly

10 affected by solute concentration.

sr-

The concentration effect as well as the diffu-

a sion effect were, therefore, taken into account with

X the aid of a recently proposed method [22] . In this

way, the standard deviation, a, of the x-spectrum is

plotted in Figure 5 against the boundary position, xm.

The slope at the origin, dal8x m, was determined

and then extrapolated to vanishing concentration in

5 15 coordinate axes f3a/dx,a–ds, where A.imsa s. The

Time (h)

result is (8cr/8x91 )0= 1im(7alax,,) 0 .33 . Time

The sold line represents linear approximation. dependence of was, first, approximated in terms

Figure 3 . Time dependence of dispersion ts 2 (second of displacements x by:

central moment) of the x-spectrum of the macromolecules in

the region of diffusion boundary in DMAA solution of PAN at aL° (aa18xm }i (xn,–x0)2 ( 1)

solute concentration c 1 .07x10-2 glans (points).

where x° is equal to xm at the initial time, t=0 . By

quantities as defined above . The result is A °=3 .4x using definition of sedimentation coefficient, s, given

10-10 erg•K 1 •mol-1" which coincides with those of by x m=x° exp(w2st) with s=5x10-13 , s function (1)

many vinyl polymers [21]. was, rewritten in terms of the sedimentation time

Molecular mass was determined with the (in s) as:

Svedberg's equation M,D=RT(so1Do)/(1 – vp0). The

(

application of2) the experimental so and Do values a ~~o = 4 .46[exp(1 .37x10-5t)–1] 2

yields M ,,D–9x 10 5 . For the PAN molecule in solution,

the length, A, of the random link is close to 30 A[6, 8,

10] with mass per this link is being 636 Dalton [6]. 20

Hence, the chain of the investigated PAN

sample consists of near 10 3 random links, and the coil

conformation may be obviously accepted as a good

model in a treatment of the polymer solution

properties.

The M,,D and [TI] values obtained are in

agreement with Mark-Kuhn equation [ri]--M a found in

refs . [5, 6 and 11] for PAN in solution with average

a=0 .67±0 .07 . We may assume, therefore, that scaling 50 100

Time (mitt)

exponent b in equation sb--MI-b is close to 0 .561-0 .02

as evaluated by b=( 1 +a)/3 valid for the coiled chains. Solid curves 1-3 connect smoothly the data pants . Curve Al represents

diffusion spreading es calculated by a 2 =201.

Polydispersity Figure 4. Time dependence of sedimentation curve disper-

Heterogeneity was evaluated by the absolute method sion u 2 in DMAA solution of PAN at a rotor rotation

of analytical ultracentrifugation . Dispersion ii 2 (the frequency of n=50x103 rpm and solute concentration

second central moment) of the x-spectrum was c(x102.)=(1) 0.0687, (2) 0 .107, (3) 0.148, and (4) 0 .193

calculated at different time t using the boundary glcm3 (points).

Sttellna L A . el al.

with An being the excess FB of the solution . The

4 intrinsic FB [n]l[t)] was thus obtained to be

-(1 .7±03)10-'0 cros Z.g-'.

For PAN in DMAA, dn/dcx0, and intrinsic FB

n is provided by proper optical anisotropy of the

2 macromolecule (i) as well as by the macroform (f)

and microform (fs) effects [18]:

6 .5 6 .6 6.7

X,n (cm)

The form effects are caused by the form

Figure 5. Standard deviation a of the sedimentation curve asymmetry of the macromolecule and the Kuhn

versus the boundary abscissa x,,, in DMAA solution of PAN segment, respectively, and the difference in refractive

at c(x102)=(1) 0 .148, (2) 0 .107, (3) 0 .0687 glcm3 . indices of PAN and DMAA . The macroform effect

was estimated by:

On the other hand, during concentration-independent

sedimentation, the dispersion of the x-spectrum is [n]r = (0 .23011NART)[(no+2) 2/na](dn/dc) 2M/[rl]

known [23] to satisfy equation:

where 4) is Flory coefficient, NA is Avogadro's

a2 = 2Dt + xo,ta4 a;t2 (3) number, R is the gas constant, and no is refractive

index of the solvent. The application of X2 .1 x 10 23

where a; is the dispersion of the s-spectrum (distri- mol-', T=294 K and the experimental dn/dc value

bution of the macromolecules with respect to sedi- (0 .07 cm31g) yields [n]f/[rl]=0.6x 10-10 cm s eg-'.

mentation coefficients). Hence, we have to find a In the random coil limit (in the Gaussian

power series which approaches to eqn (3) at starting approximation), intrinsic FB does not depend on M

time (mainly, diffusion spreading) and, in turn, to eqn and may be related to optical anisotropy Aa, of the

(2) at large time when the boundary spreading is random link by [n]/[sl]–[n]j/[q]=B Aa, where B is the

mainly provided by heterogeneity of the sample . The optical constant, B=(4n/45k$T)(no+2)2/n 0, and k$ is

least mean-square treatment of sedimentation data

yields:

0

ation heterogeneity parameter ( )1f2/so=0 .27 . Further,

the polydispersity parameter M,1 Mw was evaluated

by MYIM,,=[(a,/so)/(1–b)]2 + 1 with (1–b~0.44 as 0.2

estimated above . The result is Ma/ Mw=1 .4±03.

Flow Birefringence 2 4

gid 0-3 (s-l)

Figure 6 shows the dependence of the FB, An, on the

shear rate, g, for PAN sample in DMAA . Experi- Figure 6. Shear rate (g) dependence of flow birefringence

mental points are well approximated by a linear en observed in DMAA solution of PAN at c(x10 2 )=(1) 0.175,

function with the slope `giving the dynamo-optical and (2) 0 .109 glcm 3 .

Optical Properties of Polyacryloaenlle Molecules in N,N-Dimeaiylacetamide

The application of B=7 .8x10' 3 yields Aa,=

–(30±5)x10 —25 cm 3 , The microform effect caused by The authors thank Dr A.V. Novoselova for providing

the form asymmetry of the segment was evaluated us with the PAN sample and useful discussions.

from: Partial financial support from the RFFI, grant No . 96–

15–97335, and from the FSPS program "Integration"

Aat, = ([nlf/[1i])1B = (dn/dc) 2(Mos/iN A')c (No. 326 .38) is gratefully acknowledged.

monomer units in the segment, and the form factor s. REFERENCES

The application of Mas=636[6], v =0.83 cm 3/g

[8], and a=112 yields Aa f,=10x10-23 cm 3 . Thus, the 1. Peng F .M ., In: Encyclopedia of Polymer Science and

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chain axis) polarizabilities of the PAN monomer unit, Macromolecules, 30, 6398, 1997.

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chain anisotropy may be assumed to be equal to (Kobunshi Kagaku), 19, 73, 81, 1962.

anisotropy of the polyethylene chain unit, (a lba3 )pE= 5. Kamide K., Miyazaki Y., and Kobayashi H., Polymer J., 17,

7x 10-25 cm3 [24]. 607, 1985.

Hence, the contribution of the CN-group to the 6. Kamide K., Yamazaki H ., and Miyazaki Y ., Polymer J., 18.

optical anisotropy of the PAN monomer unit may be 819, 1049, 1986.

estimated by (a ll–a,)a,=(a ll–a3)pA –(all –al)pE to be 7. Kobayashi H ., J. Polym. Sci., 26, 230, 1975 ; 39, 369, 1959.

-10 .3x10-25 cm 3 . 8. Krigbaum W.R . and Kotliar A .M., J. Polym . Sci ., 29, 399,

1958; 32, 323, 1958.

9. Peebles L.H ., J. Polym. See, A3, 361, 1965.

CONCLUSION 10. Bisscllops J., J. Polym . Sci ., 17, 81, 1955.

11. Inagaki H ., Hayashi K., and Matsui) T., Makromol. Chem.,

Negative in sign the Maxwell effect was observed in 84, 80, 1965.

DMAA dilute solution of PAN sample with low 12, Scholtan W. and Marzolph H ., Makromol. Chem., 57, 52,

stereoregularity . The effect is referred to negative 1962.

optical anisotropy of the PAN monomer unit which is 13. Linow K.-J . and Philipp B., Faserforch u . Textillechn., 21,

estimated by the value -3 .3x10—25 cm 3 . 483, 1970; 22, 444, 1971.

Negative sign of this quantity agrees well with 14. Minagawa M ., Miyano K., Morita T ., and Yoshii F.,

the fact that, in the PAN monomer unit structure, the Macromolecules, 22, 2054, 1989.

main axis of the –C=N group is oriented in the direc- 15. Lavrenko P.N ., Okatova O.V ., Strelina I.A ., and Kutsenko

tion normal to the contour axis of the macromolecule. L .I ., Polym . See. (Engl. Trawl), A37, 811, 1995.

The different orientation of the cyano-group is 16. Lavrenko P.N ., Strelina LA., Magarik S.Y ., and Kutsenko

predicted for PAN with higher stereoregularity of the LI ., Polym . See (Engl. Transl.J, A37, 1221, 1995.

chain [6] . We may expect, therefore, that the FB 17. Korotkov A .A ., Krasulina V .N., and Novoselova A-V., Auth.

method may be used as the instrument sensitive to the Certificate No . 274356 ; Bull. !eobret., 21, 1970.

PAN chain tacticity as well as to other changes in 18. Tsvetkov V .N., Rigid-Chain Polymer Molecules, Plenum,

internal structure of the PAN macromolecule [25] . New York, 1989.

Medina], A, et al

19. 1 .avrcnko P .N . and Okatova QV ., Poltiwe. Set. USSR (Engl. 23. Baidw•in R .I . . and Williams ] .W., J. Am . Chem Soc ., 72.

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1991. Khim ., 22, 4, 72, 1962.

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Sri., Polym Chem., 22 . 3447, 1984 113, 1997.

22. Lavrenko P .N ., Polymer, 35, 2133, 1994 .

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