As discussed previously, PA and PB represent the fractions of the original A and B

functional groups that have reacted. Similar1 y, r is the ratio of the initial number of
A groups to the initial number of B groups. The term p is the fraction of original
A groups that are contained in the tri- (or higher) functional monomer. It can be
shown 1 that (xc can be attained only when 1/(1 + p) < r < 1 + p.
There are three interesting special cases of (64).

1. No bifunctional monomer that contains A groups is present. In this case p = 1

and (64) simpJifies to

α=rpi=lp§ (65)
r

2. The initial numbers of A and B groups are equal. In this case r = 1 and
PA = P B = P and (64) simpJifies to
p 2p

。
α=-一一一一-一- (6
1 - P2(1 - p)
3. If the initial number of A and B groups are equal and no bifunctional monomer
that contains A groups is present, (64) simpJifies to
α = p2

As an example, let us apply the expressions above to predict the gel points
the hypothetical systems mentiçmed ear1ier:
For system X, with 2 mol of gly∞ rol and 3 mol of bifunctional aeìd, r = 1
p = 1. The critical branching coe且 cient for this trifunctional system is (x c = 吉.
from (67), the gel point will 0 ∞ ur at a degree of reaction of
P =.jf = 0.707
or a conversion of 70.7%.
For system Y with 2 mol of glycerol, 1 mol of diol , and 4 mol of
and p = 1. Again 血c= 告， so that from (66) the gel point will occur at
P= 品= 0.756
or at a conversion of 75.6%.

STUDY QUESTIONS

1. Three samples of monodisperse poly(I ， 10-d凹 anediol adipate) are mixed

lows: 10 g of A, having a molecular weight of 40,000; 5 g of B, having a
of 100,000; and 3 g of C, having a molecular weight of 200,000
(a) The number-average molecular weight of the polymer mixture.
(b) The weight-average molecular weight of the polymer mixture

1
P. J. Flory, J. Am. Chem. Soc且， 63， 3083 (1 941).
278 Part 11 Thermodynamics and Kinetics of Polymerization
 l(?-m

2. A sample of a condensation polymer has the following experimental distribution of molec-

ular weigh的;

Range of M x 10-' Weight (mg) Range of M x 10- 3 Weight (mg)

。一20 。 35 120-140 14.4 3

20-40 2.52 140-160 14.70
4。一60 5.70 160-180 13.77
60-80 8.75 180-200 12.1 6
80-100 11. 52 200-220 8.40
100-120 13.31 220-240 5.75

Determine the weight-average and number-average molecular weights of the polymer.

3. The hydroxy acid HO-CH 2 CH 2 CH 2 CH 2 COOH undergoes a condensation polymeri-
zation to form the polymer
101
I 11 I
H十 OCH 2 CH 2 CH 2 CH 2 C汁n OH

It is found in a certain polymerization the product has a weight-average molecular weight

of 18,400 gjmo l. Calculate:
(a) The percentage of carboxyl groups that have esterified. [Ans.: 98.9%.]
(b) The number-average molecular weight of the polymer. [Anι: 9250 gjmo l.]
(c) The average numb訂 of structural un恥 in the polymer molecules. [Ans.: 92.5.]
(d) The probability that a polymer molecule chosen at random wi1l contain twice the
av它rage number of structural uni紹 • [Ans.: 1.44 x 10- 3.]
4. It has been reported [Zhubanov et 泣 ， Izv. A切d. Nauk Kaz. SSR Ser. Khim. , 17, 69 (1967)]
that aminoheptanoic ac泊， H 2 N-CH 2 一 (CH 2 );CH 2 COOH， in m-cresol ,s olution under- /
goes condensation polym位 ization to a polyamide. The reaction was found to be sec沿nd-
order in the ami n,o acid conce祖tration， with the following rate constants:
t(OC) I 150 187
k (kgjmol叩i吋 |ω ×叮 3 2.74 xω-3
(a) Write a balanced chemical reaction that describes the conversion of monomer to a
polyamide of molecular weight equal to 12,718 gjmo l.
X (b) Calculate the activation energy of the reaction and the pree法ponential factor of the
Arrhenius expression for the rat冶 constant
(c) What percent conversion of monomer is n臼 ~ssary to produce a polyamide with a
number-average molecular weight of 4.24 x 103 gjmol?
(d) What p前cent conversion is necessary to produce a polyamide with a weight-average
moleωlar w自 ght of 2.22 x 10 4 gjmol? ~:.

5. A solution of aminoheptanoic acid (see Problem 4) in m-cresol , having a concentration of

3.3 mol of amino acid per k iJ ogram of solution, is prepared and quickly brought to a
0
temperature of 187 C
(a) Derive an expression for the degree of polymerization (i.e., the average number of
structural units p叮 polymer molecule) as a function of reaction time. Modify your
expression to apply to a system in which caproic acid is present at a level of 0.65% of
the amino acid
(b) Calc叫late the time required to form polyamide with a number-average molecular
we司ght of 6340 gjmol. [Ans.: 541 min.]

Chap. 11 Kinetics of Condensation (Step-Growth) Polymerization 279

一I
 (c) If the polymerization is carried out in a solution weighing 1 kg and for the reaction
time calculated in (b) , what would be the weight of polyamide formed that has a molec-
ular weight of 12,718 gjmol? [Ans.: 5.4 1 g.]
6. Derive expressions that relate the mole fraction of x-mer to the reaction rate constant,
initial concentration of carboxyl groups , and reaction time for (a) an uncatalyzed poly-
esterification, and (b) an acid-catalyzed polyesterification. Plot the mole fractions ofpoly-
mer with x = 10 and x = 100 as a function of reaction time.
7. The following data we凹 obtained by Hamann, Solomon, and Swift [J. Macromo l. S仇，
Chem. , A2 , 153 (1968); reproduced by permission of Marcel Dekker, Inc.] for the poly-
esterification of an equal molar mixture of

HO-(CH 2 )j 。一 OH+HOOC一 (CH2)4-COOH

The kinetics were studied by taking time zero to correspond to 82% esterification of the
original COOH groups (e.g. , see Figure 1 1.2). [COOH]o may be taken as 1. 25 equivjkg
of mixture.

FURTHER POLYMERIZATION OF
POLY(1 ,1 O-DECANEDIOL ADIPATE)

個) (b) (c)
Temp. 161 C,
0

Catalyzed by p-Toluene
Sulfonic Acid (0.004 mol
Temp.190 C 0
Temp.161 C 0
Per Mole of Polymer)

Time % Time % Time %

(min) Reaction (mi吋 Reaction (min) Reaction/'"

。
30 20.6
。 。
20
。9.1 。5 。
34.6
60 39.0 40 16.0 10 54.7
90 50.2 100 31.6 15 65 .5
150 61.2 150 41.1 20 70.8
225 66.8 210 47.9 30 77.9
300 71.5 270 52.5 40 82.9
370 74.4 330 57.0 50 85.7
465 77.2 390 60.0 60 87.9
510 78.2 ,450 62.6 75 90.1
550 78.8 510 64.6 90 91. 5
600 79.6 550 65.5 105 92.6
660 80.6 700 69.2 120 93.6
730 81.7 840 71.9
800 82.5 880 72 .4
1060 74.8
1200 76.2
1320 77.2

(a) Determine the rate constants and the activation energy for the uncatalyzed reaction
[Ans: k3 (190o C) = 1. 55 x 10- 2 kg 2 jequiv-min; 仇 (161 0 C) = 5.48 x 10• kg 2jequiv-
min; E叫= 14.3 'kcaljmol.]
(b) Determine the rate constant for the catalyzed polymerization. [Ans: 0 .1 08 kgjequiv-
min.]

280 Part 11 Thermodynamics and Kinetics of Polymerization

 8. From the rate constant obtained in Problem 7 for the catalyzed polyesterification of
1,10-decanediol and adipic acid , calculate and plot the mole fraction and weight fraction
distribution of x-mer [N.JN versus x , and 夙 versus xJ at 120 min and at 240 min.
9. Suppose that in the polyesterfication reaction in Problem 7, the adipic acid has an impurity
of 0.85 mol %, of which you were unaware. What are the maximum values of the number-
average and weight-average molecular weights that you cOllld obtain in the reaction?
[Ans.: (M，九ax = 33,246; (Mw)max = 66,492 (both in gramjmol).J
10. The fo!lowi時 data were obtained [P.J. Flory, J. Am. Chem. Soc. , 61 , 3334(1939日 for the
polyesteri且cation of diethylene glycol with adipic acid at 166 C:
0

Time (min) % Conversion Time (min) % Conversion

6 13. 79 321 86.72

12 24.70 398 88.37
23 36.75 488 89.74
37 49.75 596 90.84
59 60.80 690 91.63
88 68.65 793 92 .20
170 78.94 900 92.73
203 81.61 1008 93.03
235 83 .49 II47 93.54
270 85.00 1370 94.05

(a) Determine the order of the reaction with respect to the concentr的ion of carboxyl
grollps
(b) Determine the rate constant of the reaction in appropriate lI nits. (Hint: Take the
concentratIon umts to be moles ofCOOH per kilogram ofreactant mixture and reqFEre
that [OHJo = [COOHJo')
的 Calculate and plot the weight-fraction distribution of molecular weights obtained at
reaction times of 270 and 1370 min.
11. Calculate the % conversion of acid at which gelation will occllr in a mixtllre of 50 mol %
adipic ac泊， 40 mol % ethylene glycol , and 10 mol % gly臼rol. [Ans.: 93.0%.J

SUGGESTIONS FOR FURTHER READING

ALLEN, P. E. M. , and C. R. PATRICK, Kinetics ànd Mechanisms of Polymerization Reactions.

New York: Wiley, 1974, Chap. 5.
BILLMEYER, F. W.，鼠 ， Textbook of Polymel' Science , 3rd ed. New York: Wil呵， 1984, Chaps.
1, 2.
FLORY, P. J. , Principles of polymer Chemist l' y. Ithaca , N.Y.: Corne!l University Press, 1953,
Chap.3
HIEMENZ, P. c., Polymel' Chemist l'Y. New York: Dekker, 1984, Chaps. 1, 5.
LENZ , R. W. , Organic Chemistry of Synthetic Hi gh Polymel's. New York: Wiley-Interscience,
1967, Chap. 3
ODlAN，缸， P l' inciples of Polyme l' ization. New York: McGraw-Hill , 1970, Chap. 2.
SEYMOUR, R 且， and C. E. CARRAHER, JR. , Polymel' Chemistry, 2nd ed. New York: Dekker,
1988, Chap. 7

Chap. 11 Kinetics of Condensation (Step-Growth) Polymerization 281

 7. Derive the number distribution function for DP analogous to that in Problem 4 when
chain transfer is operating and k" = O.
8. Show that the weight-fraction distribution of DP, ，吭， is equal to the number-fraction
distribution , X ,,, multiplied by Il jDP.
0
9. Vinyl acetate at a concentration of 4 M in benzene is polymerized at 60 C using benzoyl
peroxide (0.05 M) as an initiator. The rate constant for benzoyl.peroxide decomposition
is given by kd = 3.0 x 1013e-29.600，al/肘's - 1, and you may assume an initiation efficiency
of 0.75. You may also assume that k" = 0 (see Table 3.5). Using data from this chapter,

of po1ymerization; “)
calculate (a) the rate of polymerization; (b) the kinetic chain 1ength; (c) the average degree
the distribution function for DP, including an appropriate plot; (e)
the lifetime of the kinetic chain;σ) the lifetime of the propagating radical of DP = 15.
The densities ofvinyl acetate and benzene are 0.93 and 0.87 gjcm" respectively. [Alls . (a)
1.5 X 10- 4 mol月即r-s; (b) v = 1. 8 X 10 3; (c) 8.4 x 10月 (e) 0.4泊; (f) 2.5 x 10 、]
10. A reaction mixture containing 8.6 molfliter of styrene an址。 1 moljliter carbon tetrachlo-
ride is po1ymerized at OOC using photosensitization. The average kinetic chain length is
observed to be 1000. Calcu1ate, using data given in this chapter: (a) the rate of initiation;
0
(b) the average degree ofpolymerization; (c) the average degree ofpolymerization at 100 C
if the initiation rate remains the same.
[Ans . (a) 7.7 x 10- 10 molfliter-s; (b) 1. 8 x 10 3; (c) 2.8 X 10 3.]
11. A sample of polystyrene prepared by a free-radical polymerization was separated into 21
fractions of d臨rent molecular weight [G. V. Schulz, A. Scholz, and R. V. Figini , Makro-
mo l. Chem. , 57, 220 (1962) , published by Hiithig and Wepf Verlag, Basel]. The data
obtained were as follows:

Weight of Fraction (mg) DP of Fraction Weight of Fraction (mg) DP of Fraction

25.60 138 23.05 885

51.65 274 47.55 960
55.95 365 51.1 5 1050
37.40 428 52.65 1160
45.05 480 50.10 1260
52.85 535 47.70 1420
31.30 605 44.75 1600
33.75 673 36.25 1890
40.10 740 27.00 2100
38.75 795 28.90 2030
42.60 835

(a) From these data construct the weight distribution and number distribution curves of
the molecular weigh t. (Hi nt: First construct the integral distribution curves by plot-
ting the weight fraction of molecules with M less than a given M versus the given
M. Then differentiate the curve obtained. A similar procedure is used to determine
the number distribution curve.)
(b) Compare the experimental distribution points obtained in (a) with the theoretical curve
calculated by equation (6乃-
12. A benzene solution contains vinyl acetate at 3.5 M and vinyl chloride at 1. 5 M. A free-
radical polymerizati凹的 initiated by adding 0.1 M azobisisobutyronitrile and heating the
solution to 60 oC. Calculate:
(a) Composition of the copolymer first formed.
(b) Average sequence lengths of vinyl acetate and vinyl chloride in the copolymer first
formed.

Chap. 12 Kinetics of Free-Radical Polymerization 315