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88 89 90 91 10 9 8 7 6 5
Chapter 1
Μ
I
(β) « - C H 2- C H ; (b) -f-CMj-c-^
C-0 CH,
OCH3
Η Η
( C ) - H C H 2- C 4 ; ( d ) H - C H j - C -»7
1
0 CH.
1 | *
C-0 O-C-CH. 3
1 II
CM3 0
Μ
(e) -t- C H J - C - ^

Μ Η
1-2. (a) «- c 4 - C M 2- ^ c - N H - C M 2v N - > r
ο ο

(b) - H O - C H 2- C H 2- C H 2- C H 2- 0 - C - @ - C - * y
0.

51' " Ν - C —0 - C M j — C M 2— C H 2- 0 -fr;

(c) V 0
N-M
I
-K-0

Η Μ
( d ) - t - C H 2- C — C H 2 — C 4 ;
CN

(e) -i-o-CHj-CMj-CHj-CHj-o-c-^^-c-)-,
ο ο

1-3. (a) 100.000 . c flfl

113 8 8 5

( b ) 12^20-521

(d) ^ 0 - 6 1 7

1t4. (a) (i) 2 (ii) 2 (lii) 0 (iv) 4

(b) same as In (a)
 Μ CM. 3
I I

6
«4- c m 2 - c - c m 2 - c - h
I
c-o
/
OCH,

CH,

Η Μ
+ N ^ C M 2^ N - C 4 . C M 2^ C ^
Ο Ο

+ 0 - C H -r C H . O2- C -(oV-C4r 1
II w II
0 0

polyisobutene (polyisobutylene)

poly(vinyl chloride) (PVC)

poly(tetramethylene terephthclate) (poly(butylene terephthalate))

poly(ethyl methacrylate)

poly(vinyl acetate)

poly(methyl aerylate)

polycaprolactam ( n y l o n 6)

poly(phenylene oxide)

poly(para-bromostyrene)

poly(ethylene-2,5-toluene-urethane)

poly (ethy l e n e - 2 , 5 - t o l y l - u r e t h a t i e )

l s t o o weak mechanically;

i s too d i f f i c u l t t o shape i n t o p i p e form. The c o r r e c t answer

is (b).

The f u n c t i o n a l i t y of g l y c e r o l i s 3 i n e v e r y c a s e listed.

CH 3
Ν
(a) R e a c t 1 mole of HOCl^CHjOH w i t h 2 m o l e s Γ θ Τ ° ° as in

NCO

reaction (1-12). Then r e a c t t h e p r o d u c t of t h i s reaction with

H«OCH 2CH 2CH 2CH 2-O^H a s i n r e a c t i o n (1-13).

 3

1-10. (a) +- c h 2 - C H j - t r
(g) + C H 2 - C ^
(b) 0 - t - C H 2^ 0 - C - { O ) - C 4 ;

(c) Η- CM - C (h) ^ - C F ^
I
c«o
I
OCMjCMj^
(i) « ^ C M 2- C - H t
(d) •O-0-C-0-O-CT c-o
I
CM, OCM.
CM,
(e) + o - c - c h j - o - c - c +t
I II II (j) 4 - C H 2- C - H
Μ 0 0
CMj I
0
(f) H-O-S.-* I
/ C-0
CM3 I
CM,

1-11. The polyisobutene requires a f a i r l y high molecular weight for use

in inner tubes and cable coatings, in order to ensure good mech­

anical strength. Reasonably low viscosity is needed in adhesive

and o i l additive applications and this calls for lower molecular

polymers.

1-12. (a) 4 (b) 2 (c) 1

1-13. (a) 2

(b) The functionality of 2 is 5 since there are 5 active hydrogens

on the nitrogens.

(c) Yes.

(C) +C-N-H 0
II
0
Chapter 2

2-1. ν - w · 0.5.
A ο

f
For t h e m i x t u r e :
-1
1 0.5 0.5
Μ
1.35,000 150,000J

Μ · 57,000
η
Mw - i « i ( M w ) i - (0.5(90,000) + 0.5(300,000))

Μ - 195,000.
w

2-2. Molecular w e i g h t of c a l c i u m s c e a r a c e - 6 0 7 .

0.02 0.98 i - l
Μ 25,000 - +
607
Μ
11
5 5
( 3 . 2 9 χ ΙΟ" ) Μ + 0 . 9 8 - (4.00 χ 1θ" ) Μ
η η
Μ (of b a l a n c e of PVC compound) « 1 3 8 , 0 0 0 .
η

2
U' Σν Μ
ν 2 i ι
2 3 M
~ · z " u f - i w V
w 1 i i3 2 4 2
0.5(5 χ 1 0 ) + 0.5(5 χ 1 0 )
45,900.
3 4
0.5(5 χ 10 ) + 0.5(5 χ 10 )

2-4. DP « Lw.,(DP),
v
w i 'i
( s i n c e Μ - Σν.Μ. (2-13)
w i i
and Μ (DP) Μ (1-1)).

DP w - ( 0 . 3 H 20) + 0 . 2 ( 2 5 ) + 0 . 1 5 ( 3 0 ) + 0 . 1 1 ( 3 5 ) + 0 . 0 8 ( 4 0 )

+ 0.06(45) + 0.04(50) + 0.03(60) + 0.03(80) - 31.45

The formula w e i g h t of t h e r e p e a t i n g u n i t « MQ - 1 0 4 .

Λ Μ - 104(DP ) - 3270.
w w
 5

2-4. (Cont'd)

Similarly: DP n -

L· (DP).

and Μ - 2880.
η
V a r i a n c e of t h e number distribution
2 2
ϋ - s - ΜΜ - Μ (2-32)
η 2 η w η η
• 1 . 1 2 χ 10 (standard d e v i a t i o n - 1060)

2-5. (a) see Section 3.3.1

(b) i f Mv " MQ t h e polymer sample i s m o n o d i s p e r s e and

Μ «Μ - Μ - Μ etc.
ζ ν η w

2-6. Number Diameter Weight of Weight of a l l Weight

(cm) 1 Sphere* Spheres of Fraction
this Size w
i
1 1 ID 2p 0.0076
3 2 8c 24o 0.0916
4 3 27o 108o 0.4122
_2 4 64o 1280 0.4886
11 2620 1.0000

density

2(1) + 3(2) + 4(3) + 2(4)

2.6
2 + 3 + 4 + 2

D - Zw.D, - 0 . 0 0 7 6 + ( 0 . 0 9 1 6 ) 2 + ( 0 . 4 1 2 2 ) 3 + (0.4886)4 3.4

V 1 1

2-7. Fraction Weight ( g ) Weight F r a c t i o n (w^ Μ

η
1 1.5 0,03
2,000
2 5.5 0.12
50,000
3 22.0 0.47
100,000
2-7. (Cont'd)

Fraction Weight ( g ) Weight F r a c t i o n (w.) Μ

ι η

4 12.0 0.255 200,000

5 4.5 0.095 500,000

6 1.5 0.03 1,000,000

47.0 g 1.00
0 . 0 3 Ί "!
η ^ wA |_2000 50,000 l.OOO.OOOj

- 41,000

Mw - Σ ν ^ - (0.03)2,000 + (0.12)50,000 + . . . + 0.03 (1,000,000) - 185,000

Alternatively:

Fraction Weight (g) Μ Number of M o l e s ,

η
3
1 1.5 2,000 0.75 χ 1 0 "
4
2 5.5 50,000 1.1 χ 10~
5
3 22.0 100,000 22 χ 10"
5
4 12.0 200,000 6 χ 10"
5
5 4.5 500,000 0.9 χ 10"
6
6 1.5 1,000,000 1.5 χ 10"

* n c M w h e r c w e i
i " i^ i i " 8ht in grams, in t h i s case (eq. (2-9)).

- Σ η
Λ 47
Μn - - = J Z- ±n - — r -
- 4
41,000
i 11.505 χ 10

2 1 2
S t a n d a r d d e v i a t i o n of t h e number d i s t r i b u t i o n - s • (MM - M ) ^ « 7 7 , 00 9
η w η η -
\ . 184,000 m
k> , :
g 41,000
2-8. By definition

lv i - 1

10 -
J
Iw 1 - 1 - I k(l - 1 + 1 ) • 2560k (in this case)
i-1
4
/. k - 1/2560 - 3.906 χ 1 0 " .

(a) I η - ^- ~v. - 7.95

u; iw -i 2

( b) s ( ( f ar o
w * V*v " <2-35) and (1-1))

iw - Ζν±.ί - 8.45

2 1 72
Λ s u - ((8.76)(8.45) - ( 8 . 4 5 ) ) - 1.64.
W

(d) From equation ( 1 - 1 ) :

i 2 - 8.76

Μ - lOOi - 876.
ζ ζ
Chapter 3

3-1. w • w • 0.5
A ο

(3-54)

74 7 4 1 / 0 74
- (0.5(39,000)°' + 0.5(292,000)°' ) '

1 , 35
- (1248 + 5 5 3 8 ) - 149,000.

a 5 0 , 74
[η] - K M v - 9.18 χ 1 0 " (dl/g) (148.000)

- 0.62 dl/g

alternatively: [n] - I ( i w M ^ ) - 0.62.

3-2. h cm HCC1 3(100 ml)

8 h (cm HCC1 3)
[100 mlj c g
0.57 2.829 4-96
0.28 1.008 3.60
0.17 0.521 3.06
0.10 0.260 2.60
:
cm HCC1 3(100 cm
p l o t ( h / c ) against c. The i n t e r c e p t at c - 0 · (h/c) - 2.30

pressure exerted by a column of HCCl^ 2.30 cm long - hog

3 2
- (2.30 cm) (1.48 g/cm ) (980 cm s e c " )
-1 -2
- 3263 g cm sec .
-1 - 2
Dimensions of π • mi t - pressure
2 -2
Dimensions of f / c • I t
3 2
100 cm cm
3263 326.300
cm sec se' "

2 —2 τ
if π/c is i n caTsec R should be i n ergs/molK to y i e l d Μ i n g mol"

RT
Μ
 9

3-2. (Cont'd)

7
(8.344 χ 1 0 £ J L - ) ( 2 9 3 Κ)
Μ - . , " , - 75,000 - * r -
η , ι * · , ι η5 2 -2 mole
3.263 χ 10 cm sec

3-3. c (dl/g) ^inh

0.20 1.290 0.270 1.27

0.40 1.632 0.632 1.22

0.60 2.026 1.026 1.18

plot data as in Figure ( 3 - 8 ) to o b t a i n [n] - 1.32 dl/g.

5 0 , 08
1.32 - 3.4 χ Ι Ο " Μ
V
Μ - 545,000.
ν

3-4. See the discussion connected w i t h equation (3-70) i n the text,

6
3-5. M w - I w M j - ( 0 . 9 7 ) ( 1 0 ) + 0.03(30,000) - 971,000

-1
0.97 0.03
δη - 1

v. 430,000 30,000
- 307,000

Light s c a t t e r i n g measures M^. The r e s u l t s of such determinations

w i l l not be affected to w i t h i n experimental u n c e r t a i n t y . Membrane

osmometry measures M^« These r e s u l t s w i l l be s i g n i f i c a n t l y affected.

3-6. for Μ : sample A - vapor phase osmometry

η

sample Β - membrane osmometry,

for M^: use l i g h t s c a t t e r i n g i n both cases.

Gel permeation chromatography could be used for M n and M w for both

samples with a s u i t a b l e calibration.

3-7. No. See Section 3 . 3 . 2 .

 10

3-8. (a) vapor phase osmometry

(b) l i g h t s c a t t e r i n g or gel permeation chromatography (with

calibration)

(c) membrane osmometry.

3-9. (a) No. Osmometry y i e l d s (eq. (3-2)) and l i g h t scattering

gives Μ ( e q . ( 3 - 2 9 ) ) . The two averages are the same w i t h i n

w

experimental e r r o r only for polymers with very narrow

molecular weight d i s t r i b u t i o n s ,

(b) No. The slope of the l i g h t s c a t t e r i n g zero concentration

l i n e w i l l be i d e a l l y twice that in the osmometry p l o t

(compare equations (2-76) and ( 3 - 2 6 ) ) .

3-10. (a) If each polymer molecule contained 2 terminal-COOH groups there

4 χ io"" 3
-3
are = - 2 χ 10 moles i n the sample. Μ is
2 η

« 2130 g mol -1
4 ,6 2 r mS
then given by , 8 f
3 m 0e l
2 χ IO"

(b) It is assumed that there are 2 c a r b o x y l i c acid groups per

molecule.

--
3 u R
9 " rk -
(3 24)

Re " - - 5 (3-18)
I o( l + cos* Θ)

R Is defined per '.nic volume (see text In connection w i t h eq. ( 3 - 2 0 ) )

X 2
e 3 τ(1 + c o s 90') .
·=— "mr r *, ' x volume
Io 16k 2 r

3 2 6
- * ^ * - 3 χ IO"
16* χ ( 2 0 ) Z
 11

3-12. η - π.
In] + k H hlc (3-62)

1
[η] - 1.50 c m V

yn] 2
- 0.9 cm Υ 2

0.9
• Huggins' constant • 0.40
(1.50)'

Huggins' constant is dimensionless.

3-13. Standard d e v i a t i o n of the weight d i s t r i b u t i o n "

- - - 2 1/2
s - (MM - Μ ) (2-35)
W 2 W W '

• 4.69 χ 10

By extension from equation (2-39) measure of skevness of the

weight d i s t r i b u t i o n is:

U,/s
w 3 w 3 w
2 3
Μ ·Μ ·Μ - 3M M + 2M
J
U,/s 2+1 Ζ W W 2 w
w3 w 3 w 2 3 /2
(Μ ·Μ - Μ )
2 W W

2.66.

3-14, - 1 2.5

1 2
JL
- 1 *^* (c · concentration i n 4r
1 J
c c -
100 cm
c 3

c grams solute has volume • — cm

( p - apparent density of solute).

·*. volume f r a c t i o n solute at concentration of

c g/100 ml s o l u t i o n - $L - .
 12

3-14. (Cont'd)

1 2.5Φ m 2J5 [ c 0 , 0 52
- 0.025 ν ( v - s p e c i f i c volume)
1
c c " c [lOOc,
η
ο

lim - - 1 » 0.025 ν
eO C
 13

Chapter 4

4-1. (a) (1,2-polybutadiene)

(b)
CH-z
II
Μ CH, Η H-C Η CH- Η
1 1 1 1
4 2 ( ) ' ι
H-C
H-C Η CH3 II
»·
CH, CH.2

Μ
j

Η
• Η
j

C-CH- Η
Η
|
Η
I

C-CH2 Ν
Η
I
Η
I

C-CM 2 Η
Η
I

1 *
CM, CH3 CH 3

4-3. Polyethylene c r y s t a l l i z e s very r a p i d l y because i t s structure is

regular and symmetrical and the chain c a r r i e s no bulky substituents

(see also Sect. 4 . 5 . 1 ) . Polyisobutene i s amorphous ( S e c t . 4.3)

and can therefore e x h i b i t recovery from high extensions.

Η η
4-4. (a) K H , - C-f • CH.OH —
5 — «hCH- — C-f- • % C H - C -OCH.3 3 Z
I * I II
0 OH 0
I
C«0
CH3

(b) There are a few head-to-head linkages in t h e p o l y ( v i n y l a c e t a t e )

which produce 1 , 2 - d i o l s t r u c t u r e s on a l c o h o l y s i s to poly(vinyl

alcohol). There are i n s u f f i c i e n t head-to-head placements to

register in terms of HIO^ consumption but i t only takes an

average of one such linkage per macromdlecule to r e s u l t in

a halving of the molecular w e i g h t , as shown. I n t h i s case

the average number of v i n y l alcohol repeating u n i t s in the

i n i t i a l macromolecule i s (250,000)/44 - 5700 (where the formula

weight of the repeating u n i t i s 44 g m o l " ^ ) . It only requires

 14

4-4. (Cont'd)

about 1 head-to-head linkage out of an average of 2300 such bonds

to r e s u l t i n the observed reduction i n molecular weight.

4-5. The g l y c o l should be 1,3-propane d i o l . T h i s molecule is symmetrical

and would produce polyester s t r u c t u r e s like

- f O — C H 1- - C H - -1C H - 10 - C — < N 0 } — O f -
ο — ^ δ

which w i l l c r y s t a l l i z e . Polymers from 1,2-propane d i o l have the

following s t r u c t u r e s :

„ Η
— ί Ο - C - C H . - O - C — { o V - C*- and —(O-CH - C - O - C — / o > - - C - ) - »
CH3 0 0 CH3 0 0

A mixture of such s t r u c t u r e s i n the polymer chains would i n h i b i t

c r y s t a l l i z a t i o n because of the d i f f e r e n t s t e r i c requirements of the

two p o s i t i o n a l isomers.

4-6. There are 150 C atoms between c r o s s - l i n k s on the average. This

corresponds to ^ ~ « 37 monomer u n i t s between c r o s s - l i n k s (see

structure 1^13).

Formula weight of an isoprene monomer · 68 g m o l " * .

Λ molecular weight between c r o s s - l i n k s

Μ - 68 χ 37 - 2516
c
3oRT
Y - (4-43)
c

• Young's modulus.

7
γ . 3(0.98)(8.3 χ 10 )(298) β 7 dynes
Αυ x
2516 2
cm
 15

4-7. pRT

t-i>]
(4-41)
Μ

mol'V" .
7 1
Τ - 298 Κ, R - 8.37 χ Ι Ο ergs

For 100% elongation Λ - 2 ( e q . (4-37)).

7
. ( 0 - 9 8 ) ( 8 . 3 7 χ 1 0 ) ( 2 9 8 ) L _ 1_]
(a)
10,000

6 dynes
τ - 4.2 χ 10
2
cm

dyne
since 1 - 1.02 χ 10- 6 M . o . l ^
cm

τ - 0.42 MN/in .

(b) I f Μ - 5000 the stress is doubled from i t s value i n (a)

c

(O 3oRT
(4-43)
Μ

3(0.98)(8.3 χ 1θ')(298)
Y -
10,000
6 2 2
- 7.3 χ 1 0 dynes/cm - 0.73 MN/m .

4-8. Formula weight f o r propylene - 42.

5
10

Degree of polymerization • ^ y - - 2376.

Number of C-C bonds - 2 χ 2376 - 4752

(there are 2 bonds i n the main chain per repeating unit)
2 2 c 8
<d >-ot ; ^ ° ;> (4-11)

(1 - cos Θ)

θ - 180 - 109.5 - 70.5*

cos θ - 0.33
2 8 2 1 + 0.33
<d > - 4753(1.54 χ 1 0 ~ )
1 - 0.33
 16

4-8. (Cont'd)

2 1/2 —8
<d > « rms end-to-end distance - 150 χ 10 cm.

(b) The most h i g h l y extended form involves the a l l - t r a n s conformation

of the polymer backbone:

35.25·

The p r o j e c t i o n of the bond length on the chain length direction

8 8
is (1.54 χ 10~ ) cos 35.25° - 1.26 χ 1 0 ~ cm.

For σ » 4753 the end-to-end distance of the f u l l y extended

8 8
chain - 4753(1.26 χ 10~ ) - 5989 χ 1Ό~ cm.

5 99 8 1 50
Extensibility - ^ q - 39 times.

(c) Because of the lack of r o t a t i o n a l freedom of the r e a l chain

and because two segments of the chain cannot occupy the same

space (excluded volume e f f e c t ) the r e a l macromolecule w i l l

have a longer rms end-to-end distance than that calculated in

part (a) ( c f . equation ( 4 - 1 2 ) ) . The r a t i o c a l c u l a t e d in

part (b) w i l l therefore be lower. Conclusion: the r e a l chain

i s less extensible.

2 1 /2 2 2 1 /2
4-9. <d > - (x*a + y* b )

This is a straightforward extension of the ideas behind equation

(4-11).
 17

Chapter 5

5-1. Two NH^ groups react w i t h one C00<f> group and the number of NH 2

groups i s twice that of COOφ, so f of each monomer « f « 2 .

av
Since η · 200 X - 400 here,
η

X β i n t h i s case.
n 2 - pf 1 - Ρ
av

(Χ Γ -
1
1 - Ρ -- <X n)
1/400; ρ - 0.9975.

5-2. The number of molecules cannot change and the number of repeating

u n i t s cannot change i n t h i s closed system. Therefore Μ does not

η
change.

-1
-1 0.5 0.5
Μ ( I w i / M ±) 72,000.
i60,000 ' 90,000J

The molecular weight d i s t r i b u t i o n of the mixture of polyamides

becomes randomized however. Then

Μ - (1 + p)M ( e q . ( 5 - 3 6 ) ) .
w η
Since these are presumably high conversion commercial polymers ρ

i s close to 1 and Μ i s close to 144,000.

w

5-3. moles ι equivalents

pentaerythritol 1.21 4 4.84

phthalic anhydride 0.50 2 1.00

tricarballylic acid 0.49 3 1.47

2.20 7.31

T o t a l OH equivalents - 4.84

T o t a l acid equivalents « ( 1 . 0 0 * 1.47) - 2 . 4 7 .

Since the acid equivalents are i n d e f i c i e n t supply:

. 2(2.47? .
av 2.20
 18

5-3. (Cont'd)

When the mixture gels X q i s i n f i n i t e and 2 - 2.25p - 0.

.'. ρ at the gel point - 0 . 8 9 .

5-4. ρ - 0.99

2 1 -1
νΑ - i d - ρ) ρ

2
w1 00 - 1 0 0 ( 0 . 0 1 ) ( 0 . 9 9 ) " - 0.0037.

5-5. t o t a l acid equivalents - 1.0 + ( 2 ) ( 1 . 3 1 ) » 3.62

t o t a l OH equivalents - 3 ( 1 . 3 0 ) + 2 ( 0 . 5 0 ) - 4.90

2
£ - <3·62) . 1 76
av 4.11

(a) X. - 8.33
2 - pf 2 - 1.76
av

(b) moles f equivalents

oleic acid 1.0 1 1.0

phthalic acid 1.31 2 2.62

glycerol 1.30 3 3.90

t o t a l acid equivalents * 3.62

t o t a l OH equivalents - 3.90

2(3.62)
av 1 + 1.31 + 1.30 3.61

c 2 when the mixture g e l s .

η 2 - p(2.006)

2 - 2.01p - 0

The mixture w i l l g e l at 99.72 per cent conversion.

2 1 1
5-6. (a) wA - i ( l - p) ? "

with i - 1 and ρ - 0.9

 19
2 1 1 2
χ - 1(1 - 0 . 9 ) ( 0 . 9 ) " - (0.1) - 0.01

» 1 per cent by weight,

w 1 - ρ 0.1

X
u; u:
z " wU 2
! 2

w 2 *
U £
V'
2 1 -1
but v± » i(l - ρ) ρ

Λ
3
ϋ! - Z i ( l - ρ ) ρ
2 1 _1
- (1 - p^riV" 1

using Che summation i n eq. (5-31c):

u- . ι + *p + p 2

w 2
(l - p ) 2

+ 2
• χ - 1 P . 1 + 3.6 + 0.81 m 2 78 - A
·· ζ (1 + p M l - p ) (1.9X0.1)

Μ - 10(183) - 1830
η

M y · 19(183) - 3477

M z - 28.47(183) - 5210.

p
( f o r l a t e r use: X - * * · χ4 - 4 . 0 )
w 1 - ρ 0.4

2 2
(b) w p - 2p - p - 1.2 - (0.6) - 0.84

• weight f r a c t i o n of polymer i n r e a c t i o n mixture.

(c) mixture consists of monomer w^ - 0.16

polymer w^ • 0.84
 20

5-7. (Cont'd)

Χ - Σ ν , · 1 - 0 . 1 6 ( 1 ) + 0.84Χ - 4.0
w 1 wp
monomer polymer

0.84X - 4.0 - 0.16 - 3.84

vp
X^p - 4.6 - weight average degree of p o l y m e r i z a t i r u of the

polymer.

5-8. Formula weight of - f O C H , C H , 0 - < 0 > C + - - 164.

2 2 > ι
0

^tgSl
164
. 305 - Xη
Need to make sure X does not exceed 305 at ρ 1.
η
add a monofunctional Impurity l i k e

*^T>-C-OCH 3 or ζθ^-C-OH.
0 0

How much to add?

V T^pT-
av
r

2
lim Ϊ - , . - 305
η 2 - t

2 f 0 0 6 57 5
" av - i f e - ° '

£ - 2 - 0.006557 - 1.993443

moles _f equivalents

C H O C H C H OH
3°j~C^" 2 2 1 2 2
0

CH,-Q-C-^T> ζ 1 ζ
0
1 + ζ 2 + ζ
 21

5-8. (Cont'd)

. Σ equivalents . j_+_z . 1 < 9 9 33 A 4

av Σ moles 1 + ζ

2 + ζ « 1.993443 + 1.993443z

0.993443z - 2 - 1.99 344 3

ζ - 0.0066. Add 0.0066 moles monofunctional ingredient for every

mole of monomer.

i _1
5-9. x± - (1 - p)p

(a) χχ - (1 - p)p° - 0.005

2 i _1
(b) v. - i ( l - p) p

2 2
νχ - 1(1 - p ) p ° - (0.005) - 0.00025.

5-10. X w - (1 + p ) X R (5-36)

Assuming ρ - 0.9999

X , - 1.9999X - 199.99 - 200

w η

U 1 1
- w 2 \
2
v i U
^
2 1 1
v. - id - p) ? "

1+4 +

*z · "(ΐ + ρ) ( χ ^ « )
p ( s o l u t i o n to problem 5-6)

A
Xz - 3 χ 10 .

5-11. Compare Figure 5-4

Moles Functionality Equivalents

HOCH2CH2OH 1 2 2

HOOC—^TS-COOH 0.99 2 1.98

ζ]Γ>—COOH 0.01 1 0.01

(Cont'd)

T o t a l OH equivalents - 2

T o t a l acid equivalents - 1.99

£ mno* useful equivalents m 2(1.99) m

av t o t a l no. moles 2

r
av

In the absence of the benzoic acid impurity f

ρ ·+ 1 i s very large ( e q . ( 5 - 1 9 ) ) .
 23

Chapter 6

k R 14 0 8 7
° t p (10 )(1.5 χ I O " )
2
k « j.9,900 k - 144 1/nole sec.
Ρ Ρ

T
" 2k"R Γ - Α
· 7 S e C O n d s
'
" t p 2(10°)(1.5 χ 10)

6-2. - i — + £flftl . 7 9 b)
Jl
DP (DP ) "
η no

104 104 3.7fTal

85,000 * 138,000 (1)

3
[ T ] - 0.13 χ 1 0 " moles.

6 -3. dp - 1 m
9 32
η 104

_ . . . . g monomer 0.011 moles monomer

κρ - u . u n ^ £ - 1 0 .4 ae t £

_ 0.011 . χ 763
, w
χ ιο~^ " « Ι * * monomer
104 χ 60 " " ί sec

tM]k .
"TIT? - ( D
VV <- >
6 66

t
_ 6 1 /2
- [(1923)(1.763 χ 1 0 )]

2
- 5.823 χ 1 0 ~ .

For polymerization by thermal decomposition of an i n i t i a t o r :

KM 1/7
R
p -ii72 C f t dI i »
1 /2

t
2 4 1 /2
- (5.823 χ 1 0 " ) [ ( 0 . 8 ) ( 1 0 " ) ( 0 . 1 ) ]

4 _ 1 1
- 1.647 χ 1 0 " moles £ e e c "
 24

6-3. (Cont'd)
Total rate of polymerization - R + R'
Ρ Ρ

R + R* - 1.763
Ρ Ρ
χ 10" 6
+ 1.647 χ 10
_A

-4 -1 -1
- 1.665 χ 10 moles monomer £ s
- 0.017 grams polymer/litre/second.

6-4. In a droplet of monomer:

(a) [M] - 22° - 15.09

R
P ""lTI [ M l ( f k
d [ I ] ) 1 / 2

t k

1 9 06 6 1 /2
- (15.09)(0.4 χ 3 χ Ι Ο " χ 0.01)
A /
(780) *
m o es 1,
0 1157 ^- "οηο"»* m 6.13 g polymer
2- G ΖS

In one litre of reaction mixture, however:

» - m < ·»> • ·
P
6 2 4 5
"τι ^ 3 2

(b) (DP ) • n e g l e c t i n g chain

β t r a n s f e r to monomer
no R k °
Ρ t

2 2
. (1960? (15.09) m

6.13 χ 780 iBJ.uuu.

(Note that [M] and are taken per u n i t volume of monomer

droplets since t h i s is the locus where Μ is determined.)

η

M
DP (DP )
η n'o

183,000
+ 0.3 χ 10"
4

DP n - 3.33
η
χ 10 A
; Μ - 1.77
η
χ ΙΟ ,
6
 25

ilS=§S2H.
4+
6-5. k [ R C H 5O H ] [ C e ]
at Γ i

d[RCHOH]
rate of i n i t i a t i o n * f
dt
4+,
- f k r ( R C H 2O H ] [ C e ] - ^

4+
rate of termination - k ^ [ M . ] [ C e ] - R£

d[M-1
steady state assumption:
dt

4 + 4 +
i.e. R t - R t - k r [ R C H 2O H ] f [ C e ] - k ^ [ M - ] [ C e ]

k r [ R C H 2O H ] f

k k [M][RCH 90H]f
- d[M]
rate of polymerization k p[ M ] [ M . ] — £
dt

0
6-6. (a) [ M l - i - - ^ M Q - 7 1 for acrylamide

• 1 . 4 1 molar

£n 2
t, /0• 9.0 hours · 9 χ 3600 sec - —
1/2 kd
N
u
k
* 2 -
2 X
,
10 Λ
- 5
8c e
-1
d · 9 χ 3600 '

k [M]
1/2
( f k m )
V : i 7 r d
t

1 / 2 5 1 1 /2
- (22) (1.41)[(0.3)(2 χ 10~ )(10* )]

- 5.1 χ 10 moles monomer/I/sec

3
- (5.1 χ 10* ) ( 7 6 ) - 0 . 36 g polymer11/sec.

|l/2
(b) - in f[M] I 2k
[M t[I
1 - - 2.17
J
ι
l oj
lM]
L
k<i

1/2 ^5,
1/2 0.3(0.1) . e x p ( - 2 χ 10 " ) ( 6 0 ) ( 1 0 ) - 2.17
- 2(22) 1
-5 " 2
2 χ 10
 26

6-6. (Cont'd)

la - g f - - - 2.17

Μ- - Γ " 2 1 7
- 0.114
[MJ0

[M] - 0.114 [M]

[M] Q - [M] · 0 . 8 8 6 [ M ] o

0.886(100) • 88.6 g r a m s / l i t r e - amount polymer made i n 10 minutes.

_3
6-7. density of MMA « 0.94 g cm

.·. [M]J - 0.94

1 - i - · ^ · . - 9.4
3 1 litre 100 g/mole £
cm

10 2
[I] - ±jjg=- - 0.102 moles/*
5
t1 /0 - 50 hours - ^-2. - 1.8 χ 1 0 sec
d
6 1
Λ k. - 3.85 χ 1 0 ~ sec" ,
α

k [Μ]
(a) ν - - ϊ-ττ" - k i n e t i c chain length •
i /Z
2 ( f k dk t [ I ] )

5-5(9.4) . l i9 t

2[0.3(3.85 χ 10 °)(25.5 χ 1 0 ° ) 0 . 1 0 2 ] '

djMj
(b) 8p - k p[ M ] (1)
dt

[I] - [ I ] 0e (2)

Solve as for problem 6-6 to obtain f**j · 0.99.

[MJo
 27

6-7. (Cont'd)

Amount monomer consumed - [Μ] - [M]

ο

- (9.40 - 9.31)100 - 9 moles and

amount of monomer made · 9 χ 100 " 900 grams.

2 +
6-8. R^, - f k [ H 20 2] [ F e ]

2
Rt - 2 k t[ M - ]

At the steady s t a t e :

R R
i " t

2 + 2
f k [ H 20 2] [ F e ] - 2 k t[ M - ]

2 + ,| 1 2/
a[H,0.)[Fe ]

R_ - k [ Μ ] [ Μ · ]
Ρ Ρ
2 11 2
k [Μ] f k [ H 20 2] [ F e ^ ] " ]
1 2 1,

6-9 (a) (1) R l s Increased 10 f o l d

Ρ
(11) DP i s Increased 10 f o l d
1
(b) (i) R is decreased by a f a c t o r · ( ^ 2 )f '
Ρ

(ii) DP n i s increased by a f a c t o r - /2.

6-10. See Section 6 . 8 ( v ) .

6-11. " - k t r[ M . ) [ T H ] (6-70)

= - ^ p - " k p[ M ] [ M . ] (6-13)
 28

6-11. (Cont'd)
k
d[TH ] t r ™
d[M] " k [Μ]

d[TH] tr dfM] c d£Ml

C
[TH] ' kp [M] [M]

i n t e g r a t e between [ T H ] - [ T H ] o at t 0

[M] - [M]Q at t 0

and [ Τ Η ] , [M] at t:

in IULL
[TH]
C in
[Ml

[0.007]
0.01
- 2.18
0.85
In
I 1 J
6-12. The parameters which p e r t a i n to the i n i t i a l polymerization (which

i s to be modified) are subscripted z e r o . For i n i t i a t i o n by thermal

decomposition of an i n i t i a t o r :

k
1/2
S> - Γ Ϊ 7 2 I « H £ k d [ i ] ) (6-29)
ο kt

1^ - 2 f k d[ I ] (6-9)
ο

"P0
OP - - — and i s to be unchanged when the r e a c t i o n conditions are
η
ο

modified. If R i s doubled then R. must also be doubled to keep

P i
DP constant, i.e.
η

R.1 • R. i n
1
f i n a l p o l y m e r i z a t i o n mixture
f
- 2Rt - 2 f k d[ 2 I ] .
ο
 29

F i r s t , then, double the i n i t i a t o r concentration. A t t h i s stage

1/2
X / 1/2
To increase 2 * R to 2R multiply [M] by 2 ' then
p P
o o

R 'f - ~i72
k
(V ) 1 / 2 [ 2 1 / 2 M H 2 I I 1 / 2
" '2R

Conclusion: double [ I ] and m u l t i p l y the i n i t i a l [M] by /l.

 30

Chapter 7

-χ. Z * i M l . 0. 3 7 ( a S ) -
0 6
[1 ' ,0 4
" (7-14)
<lt - - Χ - , - / y

(a) If the sodium l a u r y l s u l f a t e concentration i s doubled the

rate of polymerization i s increased by a f a c t o r of

0 6
2 · · 152 ( s u r f a c t a n t « S i n the above e q u a t i o n ) .

(b) Ζ - 2 L k d[ I ] (7-4)

from equations ( 7 - 4 ) and (7-14) the rate of polymerization

0 4
K S i n c r e sa s e
is p r o p o r t i o n a l to [ I ] * . Λ doubling [ 2 2°8^
0 4

the rate of polymerization by a f a c t o r of 2 - 1.32.

0 # 6 0 - 4
(c) Ihe rate i s increased by a f a c t o r of (2 )(2 ) - 2.

(d) No e f f e c t . The mercaptan reduces the molecular weight of

the product polymer without a f f e c t i n g the rate of p o l y m e r i z a t i o n .

2. (a) no change

(b) no change.

3. (a) There are r e l a t i v e l y few termination events i n i n t e r v a l I and

the effects of slow termination would therefore be s l i g h t .

(b) In interval I I the average polymer p a r t i c l e could contain

more than one r a d i c a l i f termination reactions were slow. The

average number of r a d i c a l s would be > 0.5 and would increase

w i t h reaction time as the p a r t i c l e s grew i n s i z e . The conver­

sion rate would increase with time and the conversion-time plot

would not be l i n e a r i n i n t e r v a l I I ( F i g . 7-1) but would curve

away from the time a x i s .

(c) The conversion time p l o t would e x h i b i t autoacceleration

effects (Section 6.13 ( i i ) ) i n i n t e r v a l I I I . The rate of

 31

(Cont'd)

polymerization would probably increase i n some region instead

of decreasing s t e a d i l y as i n Figure 7 - 1 .

(See r e f . ( 8 ) f o r a q u a n t i t a t i v e d e s c r i p t i o n of the effects

of slow termination rates.)

i0.4
0.6 2
Ν - 0.37(a S) (7-7)
s

Molecular weight of sodium l a u r y l s u l f a t e * 288

a * area occupied by u n i t weight of emulsifier

5

16 2 23
50 χ 1 0 " cm ^ 6.023 χ 1 0 molecules 1 mole
molecule mole 288 g J
7 2 -1
a - 1.05 χ 1 0 cm g
s
S « weight concentration of emulsifier

3
3.5 g 1000 cm 19.44 grams
3
180 cm 1 l i t r e I aqueous phase
0.6
0.6
(a S)
5
1.05 x l O * ? -
g
7
lUiU
ί H^O phase

r 0.6
(a S )
0 ,6
- 9.7 χ 1 0
5
cm
s £ H 20 phase

1.2
(a S ) -
0 6
- 9.7 χ 1 0
5
cm
0.6
U H 20 )

0 1 7
5 ΐ Μ k S
f I , 0,85 1000 , ° · °° 2 2°8
1 x
270 180 " l i t r e of aqueous phase

Ζ - 2 k d[ I ] L (7-4)

*-8, *23,
. 2(600 χ 10 " ) 0.0175 moles (6.023 χ 1 0 ^ )
s £. H 20 phase mole

15
z « 126.5 χ 10
s χ I H 20
 32

(Cont'd)
0.4
2.0.4 15
126.5 χ 1 0 s
u 2 0 3
( s ) ( i H 20 ) ( 5 χ 1 0 " ) cm

0.4 14
3.6 χ 10
3 0 ,4
t ( i H 20 ) ( c m ) ]

14
3.6 χ 10
Α 1 ,2
( Ζ Η 20 ) ° · ( α η )

0.4
0.6
Ν - 0.37(a S) (7-10)
s

1.2 U
J
cm (3.6 χ 1 0 )
(0.37)(9.7 χ 10 )
0 ,6 0 , 4 1 ,2
( £ H 20 ) ( £ U 20 ) (ca)

19 particles
Ν - 12.9 χ 10
2. aqueous phase

- d[Ml
rate of polymerization -
dt

C n (7-12)
dt L M

,19
200 £ mole 5 mole 12.9 χ 10 particles 0.5 1
|moles J 23 I H 20 [particlej
6.022 χ 10

- d[M] 0.1 moles

dc ( l i t r e aqueous phase)s

Add more i n i t i a t o r i n i n t e r v a l I I so [ I ] i s doubled (equation (7-17))·

The rate of polymerization ( e q . ( 7 - 1 4 ) ) and number of p a r t i c l e s per

u n i t volume of aqueous phase ( e q . ( 7 - 1 0 ) ) w i l l not be a l t e r e d because

the [ I ] value which i s operative i n these r e l a t i o n s i s that in

interval I (see text f o r d e t a i l s ) . An a l t e r n a t i v e procedure would

involve a d d i t i o n of chain t r a n s f e r agents but the d e t a i l s of such

 33

7-5. (Cont'd)

procedures cannot be q u a n t i f i e d without knowledge of the nature of

the polymerizing monomer and reaction temperature. Since this

information was not provided the only way the question can be

answered i n general i s as o u t l i n e d .

7-6. The enhanced polymerization rate probably r e f l e c t s the existence of

more than one r a d i c a l per p a r t i c l e because of the large particle

size. The rate of mutual termination of such macro-radicals is

also decreased by the autoacceleration e f f e c t ( S e c t i o n 6 . 1 3 (ii)).

 3A

Chapter 8

d [ M]
~ l 5 (0.4)5 + 1
8-1. (a) (8-13)
d [ M 2] " 1 5 + 0 . 6 9 ( 1 )

- 2.64. The copolymer contains 2.64 moles methyl

methacrylate f o r every mole of 5 - e t h y l - 2 - v i n y l pyridine.

[ M 1]
1 - 0.69
(b) - 0.52 .
[ M 2] 1 - 0.40
J
^ azeotrope

8-2. Using equations (8-44) and ( 8 - 4 5 )

dMj dM.
- 2.867 2.608
dj£

if dM^ • 1 for every mole of M^ i n the copolymer dM^ 2.867

and dM 2 - 2.608.

2.867
:. f 0.443
1 1 + 2.867 + 2.608

2.608
r - 0.403
2 * 1 + 2.867 + 2.608

F3 - 1 - F2 - ΐ - 0.154.

8-3. Use r e a c t i v i t y r a t i o from problem 8-2

[Mj]
n
i - —
12
-
r
i [ϊςι + 1
eqs. ( 8 - 4 9 ) and (8-57)

When · mole f r a c t i o n of methacrylonitrile:

[ Μ χ]
- 0.3
[Mj] +[Mj]

f2 " mole f r a c t i o n styrene i n copolymer

[ M 2]
- 0.7 -
[Mj] + [ M 2]
 35

8-3. (Cont'd)

0.43
0.7 " [ M 2]

1^ - average sequence length of m e t h a c r y l o n i t r i l e • 0 . 4 4 ( 0 . 4 3 ) + 1 * 1.19,

9
$2 average sequence length of styrene units

[ M 1]

ΤΐζΤ + 2 r
0.43 + 0.37
eqs. (8-58) and (8-50)
0.43
21

1.86.

8-4. £ ϋ Remarks

Butadiene -1.05 2.39 negative e, high Q: i . e .

e l e c t r o n - r i c h double bond
( r e l a t i v e l y n u c l e o p h i l i c ) and
resonance s t a b i l i z e d

V i n y l acetate -0.22 0.03 low Q - no resonance s t a b i l i z a ­

t i o n , probably won't copolymerize
w i t h butadiene by free r a d i c a l means

Styrene -0.80 1.00 similar to butadiene

Acrylonitrile 1.20 0.60 positive e: i . e . relatively

e l e c t r o p h i l i c double bond

Methyl 0.40 0.74 l i k e a c r y l o n i t r i l e has p o s i t i v e

methacrylate e and i s an e l e c t r o n acceptor.

Use r^rj as a measure of a l t e r n a t i o n . A l t e r n a t i o n Increases as

r^rj 0 provided both and r 2 are < 1.

2
r xr 2 - exp[- - e 2) ] (8-72)

(a) butadiene/vinyl acetate:

r x r 2 - e x p [ - ( - 1.05 • 0 . 2 2 Γ ] - 0.5
 36

8-4. (Cont'd)

check:

r β χ ρ ί( β ( β e ) J 33
l " " 1 1 · 2 " (butadiene - ^ ) (8-70)

Q
2
r e x e e 0 # 20
2 " Q~ P t * 2^ 2 ~ * (v *?
1 1
acetate) (8-71)

Conclusion: This i s probably not a p r a c t i c a l copolymerization.

(b) butadieneIstyrene:

2
r x r 2 - e x p [ - ( - 1.05 + 0 . 8 0 ) ] - 0.94

(c) butadiene/acrylonitrile:

2
r x r 2 - e x p [ - ( - 1.05 - 1 . 2 0 ) ] - 0.01

(d) butadiene/methyl methacrylate:

2
r r 2 - e x p [ - ( - 1.05 - 0 . 4 0 ) ] - 0.12

Λ order of increasing a l t e r n a t i o n - styrene < methyl

methacrylate < a c r y l o n i t r i l e ; v i n y l acetate does not

copolymerize.

η -1

8-5. Ν(Μ^,η^) - P ^ (1 - ? n ) (8-53)

1 1 _ rf + f
* l r
ll l 2
f

β
- (8-49)
Ρ 0.9(0.75) . ο 73
U ,J /
11 0 . 9 ( 0 . 7 5 ) + 0.25

NiMj.l) - - P u ) - I d - 0 . 7 3 ) - 0.27 - f r a c t i o n of

acrylonitrile sequences w i t h one a c r y l o n i t r i l e unit.

N(M 2) - - P u ) - ( 0 . 7 3 ) (1 - 0.73) - 0.20 - f r a c t i o n of

 37

8-5. (Cont'd)

a c r y l o n i t r i l e sequences containing 2 a c r y l o n i t r i l e units.

F r a c t i o n of a c r y l o n i t r i l e sequences with 3 or more a c r y l o n i t r i l e

units « 1 - N ( M 1, 1 ) - N C ^ 2 ) - 1 - 0.27 - 0.20 - 0 . 5 3 .

1 - r2

l azeotrope ζ - r^ -

1 - 0 4
• ο r> η * A / * 0.86 • mole f r a c t i o n acrylonitrile.
2 - 0.9 - 0.4

8-6. ρ - (8-68)
Ρo y
y
w°

m
ρ » extent of reaction at which g e l a t i o n occurs. ° 0 f r a c t i o n of

reactive groups which are p a r t of a m u l t i f u n c t i o n a l cross-linking

agent and y° is the weight average degree of polymerization which

w
the polymer would have had i f a l l monomers were b i f u n c t i o n a l .

Increase of i n i t i a t o r concentration r e s u l t s i n a decrease i n y °

•'w
(Chapter 6 ) .

8-7. To avoid having the c r o s s - l i n k a b l e u n i t s bunched together the

r e a c t i v i t y r a t i o of the a c i d - c o n t a i n i n g v i n y l monomer should be

close to zero i n i t s reaction w i t h v i n y l toluene. A l s o , the

r e a c t i v i t y r a t i o f o r v i n y l toluene should be < 1 to ensure that

the polymerization w i l l not j u s t y i e l d p o l y ( v i n y l toluene) without

incorporating the acid v i n y l comonomer.

Conclusions: r ( a c i d v i n y l monomer) » 0

r ( v i n y l toluene) < 1.

8-8. Take a l l y l acetate as monomer 1:

Γ
1 " (ζ
e x
P(~ V i " V
]
" ΊΐΤ^Γ 1
«Φΐ ·!^- Ι · " - 0 . 4 0 ) ] - 0.007
 38

8-8. (Cont'd)

r2 - ^ exp[- e 2( e 2 - β χ) ] - e x p [ - 0 . 4 0 ( 0 . 4 0 + 1 . 1 3 ) ] - 14.3

T
A + l 2 f f

1 4) ( 8
χ ' 2 2 "
Vl + 2 f
2 2 l 2 f + r f

0.007(0.25) + ( 0 . 2 5 )
0.007(0.25) + 2 ( 0 . 2 5 ) + 1 4 . 3 ( 0 . 2 5 )

- 0.06.

It I s not a good I d e a . The reaction w i l l not y i e l d copolymers w i t h

appreciable concentrations of both monomers.

8-9. For a random copolymerization r ^ r 2 - 1. Here r^ · 5 (ethylene » Mj)

A l s o , i n a random copolymerization the simple copolymer equation

reduces t o :

dlMj] rjtMj]
(8-18)
d[M 2] [Mj]

r f
i i
or: F, »
1 γ Λ + £ 2

( r e q u i r e d ) - 0.70

5 f
l
1
F, - 0.7 ~ 5 f x + (1 - f x)

Solving: f^ - 0.32 • mole f r a c t i o n of ethylene i n the gas phase.

Gas phase composition • 32 mole Ζ ethylene and 68 mole Ζ propylene,

2
r f • f f
8-10. F - ^-t - (8-14)
+ 2 ff + r f
VI l 2 2 2

2
1.4f + £,(1 - £,)
F, - 0.95 -
— 2 ^w
β — — —
2
l.Af* + 2 f x( l - fj) + 0.65(1 - f x)
 39

8-10. (Cont'd)

0.4f* + £
0.95 -
0.05f* + 0 . 7 0 f 1 + 0.65

- 0.3525f^ + 0 . 3 3 5 ^ + 0.6175 - 0 .

- 0.931 ( p o s i t i v e root).

Conclusion: need 0.931 mole f r a c t i o n v i n y l c h l o r i d e (0.069 mole

f r a c t i o n v i n y l acetate) i n the feed.

8-11. The best product contains i s o l a t e d acrylamide residues so that

the eventual c r o s s - l i n k s formed at these s i t e s are spaced apart and

not bunched together. That i s to say, the average sequence length

(N^) of acrylamide (monomer 2) i s i d e a l l y - 1 i n these polymers.

f r f
rr 1 l + 2 2
N eqs. (8-58) and (8-52)
2 " F ~ " f
Δ r l
21 l
^ 0.85, f 2 - 0.15.
Here i}

For the methyl methacrylate case:

tt m 0.85 + 0 . 5 ( 0 . 1 5 ) m ςβ
N 0 9 1
2 O s · ·

There w i l l be l i t t l e difference i n the styrene case ( r 2 " 0 . 6 ) .

Conclusion: There i s nothing to choose between the two cases i n

terms of i s o l a t e d , useful c r o s s - l i n k i n g s i t e s . (There w i l l be other

differences i n costs and p r o p e r t i e s which may be i m p o r t a n t . )

8-12. moles f u n c t i o n a l i t y equivalents

f

ethylene g l y c o l 2 2 4

a d i p i c acid 1.90 2 3.80

tricarballylic acid 0.051 3 0.153

3.951 7.953
 40

8-12. (Cont'd)

There are a t o t a l of 3 . 9 5 3 acid e q u i v a l e n t s . Λ only 3 . 9 5 3

alcohol equivalents are a v a i l a b l e for reaction ( b a r r i n g side

reactions)·

ρ - ~ - (8-68)
ο 7y°
ow

ρ - extent of conversion at the gel p o i n t .

P q · f r a c t i o n of r e a c t i v e groups which are part of a multifunctional

c r o s s - l i n k i n g agent.

y° · weight average degree of polymerization which the polymer

would have i f a l l monomers were bifunctional

At high conversions the weight average degree of polymerization

of the reaction mixture w i l l be close to that of the polymer,

as a good approximation we w i l l set

Κ " f^H; < f r o m

(5-35))
W X — ρ

( T h i s c a l c u l a t i o n of 0Q uses only the useful e q u i v a l e n t s . Calcu­

l a t i o n with the t o t a l number of equivalents (7.953) yields

OQ • 0.01924. T h i s makes no difference i n t h i s case.)

S u b s t i t u t i n g i n eq. (8-68):

P
. 1 - Ρ
* 0.01935(1 + p)

2
0.01935p + 1.01935p - 1 - 0

ρ - 0.9633.
 Al

8-12. (Cont'd)

(b) Carothers equation:

τ, _ . 2
(5-19)
= 2-pf a v

(you could put X • y f o r the sake of consistency of

η η
symbols i n t h i s c a s e ) .

^ no. useful equivalents

m
av no. moles

2 χ 3.953 , n .n
0 01
" 3.951 " 2·

at the gel point X R - · and 2 - p f f lv - 2 - ρ(2.001) « 0

ρ - 0-9995.

The difference i n the c a l c u l a t i o n s r e f l e c t s the fact that

one estimate assumes that g e l a t i o n occurs when is infinite

whereas the other assumes that y is i n f i n i t e when the

^n
reaction gels* We know from Chapter 2 that y > y and
w η

so the former c a l c u l a t i o n indicates the occurrence of massive

c r o s s - l i n k i n g at an e a r l i e r stage of the p o l y m e r i z a t i o n .

(Note that these c a l c u l a t i o n s r e q u i r e the c a r r y i n g of

r e l a t i v e l y many decimal p l a c e s . )
 42

Chapter 9

9-1. Isobutene i s c a t i o n i c a l l y a c t i v e because of the i n d u c t i v e effects

of the two e l e c t r o n - r e l e a s i n g methyl groups attached to one of the

doubly bonded carbons ( F i g u r e 9 - 2 ) . For t h i s reason i t does not

respond to anionic i n i t i a t o r s . Free r a d i c a l s do not produce high

polymers because chain t r a n s f e r reactions on the methyls produce

relatively stable r a d i c a l species which do not propagate r e a d i l y

( c f . reaction ( 6 - 8 5 ) ) . The e l e c t r o n e g a t i v e -CN group i n

acrylonitrile decreases the e l e c t r o n density on the double bond.

T h i s f a c i l i t a t e s attack by anionic i n i t i a t o r s and discourages

reactivity towards c a t i o n s . I n a d d i t i o n , anionic a c t i v e centres

can be s t a b i l i z e d to some extent by d e r e a l i z a t i o n of the charge

across the cyanide group:

Μ Η

ι ι
* A A C H2, — C '© • wvCH, —C 2
I II
c c
III II
Ν Ν
Θ
9-2. (a) NaOCH^ i n tetrahydrofuran or an alkane or a mixture of these

solvents i s an example. Almost any anionic i n i t i a t o r is

strong enough to effect the p o l y m e r i z a t i o n of t h i s monomer,

(b) l i t h i u m metal or l i t h i u m a l k y I s i n hydrocarbon s o l v e n t s .

A l k a l i metal complexes of alpha-methylstyrene ( S e c t . 9.2b-5)

i n tetrahydrofuran would also probably i n i t i a t e t h i s polymer­

i z a t i o n but the product polymers would not be stereoregular

and t h i s would therefore not be a p r a c t i c a l process.

 43

9-2. (Cont'd)

(c) A Levis acid or Levis acid s a l t i s a s u i t a b l e i n i t i a t o r for

tetrahydrofuran. See reactions (9-60) and ( 9 - 6 1 ) , for example.

Polymerization can be c a r r i e d out i n the b u l k , l i q u i d monomer

or i n an i n e r t d i l u e n t l i k e methylene c h l o r i d e . Incidentally,

the polymerization of t h i s monomer i s u s u a l l y performed at

room temperature. The c e i l i n g temperature ( S e c t i o n 6 . 1 5 ( i i ) )

e
of polytetrahydrofuran i s 85 C.

(d) Table 9-2 l i s t s examples of conditions for the production of

isotactic and s y n d i o t a c t i c polypropylene.

(e) Protonlc a c i d s . A l C l ^ , e t c . are a l l suitable (Section 9 . 3 b - l ) .

Polymerizations can be c a r r i e d out i n concentrated solutions

i n aromatic hydrocarbons.

9-3. (a) See Section 9 . 2 f - 2 a - 3 . I n i t i a t e styrene polymerization v i t h

butyl lithium i n tetrahydrofuran. Add methyl methacrylate

monomer and use a coupling agent l i k e I 2 to complete the process.

(b) See Sections 9.2b-2 and 9 . 2 f - 2 a - l . I n i t i a t e alpha-methylstyrene

polymerization v i t h b u t y l l i t h i u m i n benzene s o l u t i o n . Form

a polylsoprene block by a d d i t i o n of t h i s monomer to the l i v i n g

alpha-methylstyrene ends and then add styrene to the i s o p r e n y l

ends. A l i t t l e tetrahydrofuran v i l l accelerate the attack of

the d l e n y l ends on styrene monomer.

(c) See Table 9-1. Any process that forms l i v i n g p o l y s t y r y l ends

can be used to i n i t i a t e m e t h a c r y l o n i t r i l e blocks.

9-4. P o l y t e t r a h y d r o f u r a n . l M O C H ^ H ^ H j C ^ - ^ H can be made by methods

sketched i n the answer to problem 9 - 2 ( c ) : T h i s hydroxy1-ended

 44

(Cont'd)

polymer i s then reacted w i t h 2 moles of 2,4-toluene diisocyanate

to produce an isocyanate-ended prepolymer ( c f . reaction (1-12)).

Polybutadiene i s polymerized i n hydrocarbon solvent .with a l i t h i u m

alkyl initiator ( F i g u r e 9-1) and then capped w i t h ethylene oxide

( r e a c t i o n (9-22)) to y i e l d a hydroxy1-ended polybutadiene which

can be made to react w i t h 0.5 moles of the isocyanate-ended

prepolymer described above

Η Μ
27
C 4H f L ι • CH2 - C C4M -CM2 -C © Li*

6 6
(a)

AlCl, HCI • M® AlCiP

(b) © θ v> C M

Η AlCl4 • CHj — C — CM. - C © A l C l /

/
CM*

(c) See (9-57).

(d) See (9-10) and (9-11).
(e) See (9-64) and (9-65).

See Section 9 . 2 c - 2 .

for i n i t i a t i o n s by e l e c t r o n t r a n s f e r (eq. (9-11)) followed by

d i m e r i z a t i o n of the monomeric r a d i c a l anions ( e q . (9-12)). Since

the r e a c t i o n was complete i n t h i s case d[M] · [M] and d [ I ] - [I].

molecular weight of styrene • 104 Μ

[Μ] - 1000 mL
[104 g m o l " !
1 11 50 ml}

No. moles Na 1.0 g

0.043 moles.
23 g mol- 1

No. moles naphthalene - — & . ο.047 moles.

128 g mol
 45

(Cont'd)

Since the napthalene is i n excess the t o t a l no. moles i n i t i a t o r

i n 50 ml tetrahydrofuran i s 0.043 moles. The no. moles i n i t i a t o r

0 043 -4
transferred i n 1 Μ of dark green s o l u t i o n - *^ - 8.6 χ 10

moles.

T o t a l volume of the polymerization mixture « 50 mi + 1 mi. • 51 a * .

8.6 χ 10 mol 1000 mL

[I] - χ - 0.0169 Μ.
51 ml 1 I

From eq. ( 9 - 6 - 1 ) above:

2(0.96)
DP « - 113.6
η 0.0169

Μ - (DP ) Μ (1-2)
η n o

- ( 1 1 3 . 6 ) ( 1 0 4 ) - 11,800

(9-14)

1
- 1 + - 1.01
113.6

Mw - ( 1 . 0 1 ) ( 1 1 , 8 0 0 ) - 11,900.
 46

Chapter 10

d U n Κ) ΔΗ
10-1.
d(l/T) R

I n t e g r a t i n g between temperatures and T ^ :

In K ( T 2 ) - In Κ ( Τ χ) - | ^
T T
2 l

K ( T 2)
ΔΗ 1 l_
In
Κ ( Τ χ) R T,

.-1
mol deg

(a) e q u i l i b r i u m constant f o r polymerization:

Κ χ( 2 5 0 ) >3
6.5 χ 10' 1 1
In 0.34
^(280) 1.987 523 " 553

0.34,
Κ χ( 2 5 0 ) - · -"^(280) - ( 1 . 4 0 ) (300) - 422.

(b) e q u i l i b r i u m E^O c o n c e n t r a t i o n :

H 20 ( n y l o n ) • HjO (vapor)

-1
ΔΗ - 8 k c a l mol
vap

K 2( 2 5 0 )
8 χ 10' U-__iJ
£n - - 0.42
K 2( 2 8 0 ) 1.987 (523 553,

0 # 4 2
K 2( 2 5 0 ) - e " K 2( 2 8 0 ) - 0 . 6 6 K 2( 2 8 0 ) .

The volume of che head space i n the p o l y m e r i z a t i o n reactor

above the polymer melt i s independent of temperature. The

vapor pressure (1 atm steam) also does noc vary w i t h

temperature. L e t [H_0 ] ~ - concentration of water in

·& # vap ZDU
the head space at 250 C.
 47

10-1. (Cont'd)

IH j
2°vap 250 273 + 280
Η 2 73 + 2 50
Ι 2°ν.ρ1 280 " "

assuming that the H^O vapor behaves as an i d e a l gas.

H
Let t 2°nylon^ "
e <
l m
u D r i u a
concentration of water i n the polymer melt:

( H 20 J(250)
2 v a r
ΓΗ
l t l
0 1(250)
J U 3 ;U
- — P °
2 nylon K 2( 2 5 0 )
H ] ( 2 5) 0
t 2°vanor
0.66K 2(280)

1.06 Η,Οv a 2 r
(280)
1 1(250) P°
2 nylon J U J ;U
0.66K 2(280)

1/2
C K.
o 1
(c) X Q - (10-8)
[ H 20 ]

Compare X (250) and X (280)

α η
1/2
X n( 2 5 0 ) C (250) Κ.(250) [ Η , Ο . 1(280)

1
ο . __l ι ny ion
f^"l_Ce(280) h< 2S0) H
t 2°nylonJ
( 2 5 )0

C Q i s the same i n both cases. Substituting the calculated values:

X (250)
η 422 . 0 . 6 6 Ί 1 7 2
.
υ

X (280) 300 1.06J ***

η

The molecular weight decreases as the f i n a l r e a c t i o n temperature

i s lowered at f i x e d water vapor pressure.

10-2. The suspension polymerization process could be modified by any o r all

of the following techniques:

(a) add e l e c t r o l y t e ( e q . NaCl) to the aqueous phase to s a l t out the

acrylonitrile;
 48

10-2. (Cont'd)

(b) add small amounts of w a t e r - s o l u b l e I n h i b i t o r s (e.g. thio-

sulfates or thiocyanates) to the aqueous phase to prevent

polymerization i n t h i s phase;

(c) use an i n i t i a t o r w i t h n e g l i g i b l e water solubility;

(d) add a w a t e r - i n s o l u b l e solvent that acts as an extraction

agent (an a l k y l a r y l ether could be used i f its costs were

acceptable and i t could be l e f t i n the f i n a l copolymer

product).

10-3. The three temperature/time stages a r e :

#
(a) 8 0 C / 6 hours
e
(b) 9 0 C / 5 hours
e
(c) 110 C/12 hours.

_ *n 2 _ 0.6931
(6-33)
•1/2 Ι/2

The required k rf values are then:

( e) k 3 2x 1 0 5 8 ( 8 0
c )
d ' ΤΤχδδ ' · ~ *

6 9 1
3 5
(b) k °' - 3.85 χ 10~ β <90*C)
d 5 χ 3600

(c) k 0.6931 5
- 1.60 χ 1 0 " s (110'C)
12 χ 3600

kd - (6-116)

k d at Τ χ -E/RT,
Ae

T T
2" 1
k. at T , » ( k . at T . ) exp
T T
1 2
 49

10-3. (Cont'd)

ΤA - Τ
30,000 c a l A
» ( k . at T , ) exp 2 l
1 1 ΤX τ
A
[1.98 c a l m o l " d e g " 1 2

The f o l l o w i n g table gives the calculated values f o r some of

the p o t e n t i a l i n i t i a t o r s l i s t e d i n Table 6-1.

Initiator Temp. (°C) k rf

5
dibenzoyl peroxide 73 1.93 χ 10~
5
dibenzoyl peroxide 80 4.60 χ 1 θ "
5
dibenzoyl peroxide 90 15.0 χ 1 θ "
5
t - b u t y l peracetate 102 1.93 χ 10~
5
t - b u t y l peracetate 110 4.49 χ 10~
5
dicumyl peroxide 115 1.93 χ 1 θ "
5
dicumyl peroxide 110 1.16 χ 10~

From these c a l c u l a t i o n s benzoyl peroxide is reasonably close to

the requirements f o r stage ( b ) and dicumyl peroxide i s the best

of the l i s t for stage ( c ) .

10-4. Since the e f f e c t i v e monomer concentration i n the polymerizing

p a r t i c l e s l s reduced i n ( b ) and ( c ) compared to ( a ) the molecular

weights of the polymers made by the Μ ADD and Ε ADD processes w i l l

be lower than i n the batch (B) process. (Refer to eq. (7-16).)

The p a r t i c l e s i z e d i s t r i b u t i o n i n the Ε ADD process w i l l be very

broad because soap i s being added and p a r t i c l e s are being formed

through the course of the whole p o l y m e r i z a t i o n . Some p a r t i c l e s

which are formed near the end of the p o l y m e r i z a t i o n w i l l not have

had much time to grow w h i l e those formed i n the beginning w i l l

have become very l a r g e . Particles grow f a s t e r i n the Β process

10-4. (Cont'd)

than i n the Μ ADD or Ε ADD v e r s i o n s . Thus the time for disappearance

of soap micelles w i l l be greater i n the Μ ADD than the Β process.

Since the rate of r a d i c a l generation i s the same i n a l l cases more

micelles w i l l be " s t u n g " and more p a r t i c l e s w i l l be generated i n

the Μ ADD than Β process. The average s i z e of the p a r t i c l e s w i l l

therefore be smaller i n the Μ ADD v e r s i o n than i n the batch process

and the p a r t i c l e s i z e d i s t r i b u t i o n w i l l also be somewhat broader

because the formation of p a r t i c l e s extended over a greater time

interval.

10-5 . \ U M ] o - [M]> - R p (10-16)

[M]
1 - 6 Μ
ο

[M] - 3 Μ at 50% conversion w i t h no volume shrinkage.

3 3
In an i n i t i a l volume of 50 m there w i l l be 16.67 m H^O and
3
33.33 m monomers. When the r e a c t i o n has gone to 50 per cent

conversion the volume of the same mixture w i l l have shrunk to a

t o t a l of 16.67 (H^O) + 16.67 (unreacted monomer) + ^ ' 2 7 (polymer)

3
• 46.47 m . Then the true monomer concentration i n the effluent

R - 50%/hour

moles
- 0.05
l i t r e min

[ M 0] - [M]
6 - 3.23 min
» 55.40 min
0,05

V reactor volume 50 m
θ - mean residence time • — •
—— m m •
v flow rate ν
 51

10-5· (Cont'd)

3 3
. 50 m m0.90 m
V
·· * 55.40 min " min

(b) F ( t ) • f r a c t i o n of e x i t i n g m a t e r i a l which i s i n the reactor

f o r a time < t. ( t • β i n this question.)

For a p e r f e c t l y s t i r r e d CSTR

t /6
F(t) - 1 - e ~ (10-22)

1
F(t) - 1 - e" - 0.63

10-6. The volume of the l a r g e r vessel i s 8 times that of the smaller

vessel. Thus the rate of generation of heat w i l l be 8 times

greater. But the w a l l area i s only 4 times as great i n the

larger vessel. T r a n s f e r through the reactor w a l l s can remove

heat 4 times as fast as i n the smaller v e s s e l . The rate of

heat removal i n the smaller vessel was l / 8 t h the r a t e of heat

generation i n the l a r g e r vessel and 80% of t h i s heat was

taken out through the r e a c t o r w a l l s . Thus the rate of heat

removal through the w a l l s i n the l a r g e r vessel i s (4(0.8)(Q/8)

* 0.4Q, where Q i s the rate of heat generated i n the l a r g e r

reactor. By d i f f e r e n c e . 602 of the process heat i n the l a r g e r

reactor must be removed by taking off and condensing propylene

vapor ( c f . eq. (10-14)).

 52

Chapter 11

11-1* Nylon 6,6 is a c r y s t a l l i z a b l e polymer. It can be oriented at

temperatures between Τ and Τ to ehance i t s tensile strength.

g m

Release of the o r i e n t i n g stress does not r e s u l t i n loss of

o r i e n t a t i o n because the f i b r e s t r u c t u r e is anchored by c r y s t a l l i t e s

formed during the drawing process. Polyisobutene is elastomeric

and normally not c r y s t a l l i n e . O r i e n t a t i o n at any temperature

above the low of t h i s polymer has no permanent e f f e c t . The

structure r e t r a c t s when the drawing load i s removed.

11-2. C r o s s - l i n k or copolymerize w i t h comonomers whose homopolymers

have higher T g ' s than p o l y s t y r e n e . Alpha-methylstyrene, metha-

c r y l o n i t r i l e , maleic anhydride or a c r y l o n i t r i l e could be used as

comonomers.

11-3. (b) has a higher T ^ and higher T g because the phenyl group s t i f f e n s

the macromolecular c h a i n .

11-4. Y - 2G(1 + β) (11-7)

7 2
G » 10 dynes/cm

β · 0.49

7 7
Λ Υ - 2(10 )(1.49) & ψ - 2.98 χ 1 0 & ψ .
cm cm
2 2
C r o s s - s e c t i o n a l area of the specimen - (0.5)(0.25) cm - 0.125 cm .

load - 5,000 g

6
force - (5,000 g) 980 ^ 4.9 χ 10 dynes
I sec j

cm cm
 53

11-4. (Cotrt'd)

2 , 89 x 1 0
e - strain - Υ/τ - ^ - 0.76

3.92 χ 10

O r i g i n a l length of specimen - 10 cm.

the specimen w i l l elongate

0.76(10) cm • 7.6 cm.

W W
1 A B
11-5. + .4)
g gA gB
T 1 e
gA ( P o i y ^ i n y chloride)) - 8 7 C ; w A - 0.9

e
T g B ( p o l y ( v i n y l acetate)) - 32 C; w B - 0.1

- 3
i_ . 0-9 + + 0-1 . 22 828
, 88 2χ
x I 1O
0
T 273 + 87 273 + 3 2
g

T g - 354 Κ - 81°C.

11-6. Refer to Section 1 1 - 6 .

Units fo force •

units of elongation - 1
,2
units of area under f o r c e - e l o n g a t i o n curve • ~ (1) » · u n i t s of work.
t t

11-7. From Table 11-11 f o r polyisobutene

e
Τ - - 73 C - 200 K.
g
17.44 χ 73 1273 n i ,
l o 8 a 1 0 2
10 273 * " 51.6 • 73 uCl " " '

Ue >.ave to c a l c u l a t e a temperature ( T ) change corresponding to a

s h i f t f a c t o r of 10.

f.a
273
i.e. l o g 1 (} 1 - - 10.2 - log a T
 54

11-7. (Cont'd)

17.44(T - Τ )
log a T - - 11.2 - - 5 .
1 6 + (T . T )g

- 598.6 - 1 1 . 2 ( T - Τ ) - - 17.44 ( Τ - Τ )
8 8
Τ - Τ - 20.9
8
e e e
Τ - - 73 C + 21 C - - 52 C.

do
11-8. "rf - ΐ °- - C (11-28)
dt G dt η

do
Cn - σ n

Boundary c o n d i t i o n s :

t - 0; σ - 0

t - t; σ · o(t)

ro(t)
do
dt
Cn - σ

o(t)
G
- £n(Cn - σ) c
" η
0

Gt
o ( t ) - Cn 1 - exp

b u t , Y ( t ) - Ct i n t h i s case and so:

2 L
o ( t ) - C n [ l - exp [ - ^

11-9. Cut t e n s i l e specimens at r i g h t angles to each other from the

film. The more h i g h l y oriented samples w i l l have higher moduli

and l o v e r elongations to break. These w i l l be machine direction

specimens i n films w i t h unbalanced p r o p e r t i e s . (As a check,

the shrinkage of the samples can be measured, e . g . , a f t e r immersion

i n b o i l i n g water f o r a given time. The more h i g h l y oriented

d i r e c t i o n w i l l e x h i b i t greater s h r i n k a g e . )
 55

Chapter 12

ΔΗ - RT
Ζ
12-1. δ - — ~ : ο (12-12)

T f e - 273 + 110.6 - 383.6

2
A H 2 5. C - 23.7(383.6) + 0 . 0 2 0 ( 3 8 3 . 6 ) - 2950

- 9091 + 2943 - 2950 - 9,084 cal/mole

1 1
RT - ( 1 . 9 8 7 ) ( 2 7 3 + 25) cal m o l " - 592 c a l m o l "

.2 (9.084 - 592)0.87 cal g mole

6
" 92 mol 3 g

CIS

2 3
δ - 80.30 c a l c m "

3 1 / 2
6 - 9.0 ( c a l cm" ) .
12-2. For a s t a t i s t i c a l copolymer

δ - Σν δ ±

where δ^ i s the s o l u b i l i t y parameter of the polymer of monomer i.

and w^ i s the weight f r a c t i o n of monomer i i n the copolymer.

Μ (butadiene) - 54

Μ (methyl methacrylate) - 100

There are 3 butadiene units i n the copolymer for every methyl

methacrylate residue. Λ f o r every 100 g (1 mole) methyl

methacrylate the copolymer contains 3(54) * 162 g butadiene.

Weight f r a c t i o n of methyl methacrylate

01 0
- . 0 38
3 8
100 * 162 °· ·

From Table 1 2 - I I I ( b )

δ(ΡΜΜΑ) - 9.3

δ(ΡΒϋ) - 8.4
 56

12-2. (Cont'd)

then 6 (copolymer ) - 0 . 3 8 ( 9 . 3 ) + (1 - 0.38)(8.4)

3 1 / 2
- 3.53 + 5.21 - 8.7 ( c a l c m " ) .

12-3. Η

0
?2

?2
CH3

From Table 12-11:

Group No. Groups

fi

-CH2 131.5 4 526.0

>CH- 85.99 1 85.99

-O(ether) 114.98 1 114.98

-CH3 148.3 1 148.3

875.27

-3 -1
density - 1 g cm Μ - 108 g mol
r

12-4. (a) The copolymer i s soluble i n poorly hydrogen-bonded solvent

3 1/2

mixtures w i t h 8 . 5 < 6 < 9 . 5 (cal/cm ) . Take 6 • 9.0 as

a target v a l u e . From the b r i e f l i s t of s o l u b i l i t y parameters

i n Table 1 2 - I I I methylene c h l o r i d e (δ - 9.7) and nitromethane

(6 - 12.7) are possible cosolvents.

Let Varsol be solvent a, and the other l i q u i d be solvent b.

' Va Vb " -
+ ( 1 2 1 5 )
'mixture
γ
where the φ 8 are volume fractions.
 57

12-4. (Cont'd)

With solvent b • methylene c h l o r i d e , 6 fc • 9.7 and:

9.0 - (7.6)φ + 9.7(1 - φ )

a a
φ • 0.33 - volume f r a c t i o n of Varsol 2 i n a mixture v i t h
a

methylene c h l o r i d e . Similarly, the volume f r a c t i o n of Varsol

required i n a mixture v i t h nitromethane « 0.73.

(The s p e c i f i c g r a v i t i e s of these solvents are approximately

as follows: Varsol 0 . 7 , methylene c h l o r i d e 1.33, nitromethane

1.14). As a r e s u l t , the f i r s t mixture vould be only about

21% by v e i g h t of Varsol v h i l e the second blend v o u l d contain

622.)

(b) The copolymer vould probably form stable mixtures v i t h

polyethylene, depending on i t s v i n y l acetate content. If

there vere any appreciable lengths of ethylene segments i n

the copolymer these vould c o - c r y s t a l l i z e v i t h polyethylene

( 2 ( b ) , Table 1 2 - V ) .

12-5. (a) Solvent £ Η-bonding Three-Dimensional S o l . Paramete:

(Table 12-111) " (Table 12-IV)
6 6 δ
d Η
Ρ
tetrahydrofuran 9.1 mod. 8.2 2.8 3.9

n-hexane 7.2 poor 7.2 0 0

1-butanol 11.4 strong 7.8 2.8 7.7

d l o c t y l phthalate 7.9 mod. 8.1 3.4 1.5

The 6 d values of the d i f f e r e n t solvents do not d i f f e r enough to

v a r r a n t concern. It i s then necessary only to match the 6 and

6 values of the solvent mixture and t e t r a h y d r o f u r a n .

 58

12-5. (Cont'd)

(a) Let φ^ « volume f r a c t i o n of n-hexane i n the mixture

φj • volume f r a c t i o n of 1-butanol i n the mixture

• volume f r a c t i o n of d i o c t y l phthalate

φ^ * 1 · Φ^ · $2 d e f i n i t i o n of volume f r a c t i o n s .

With equation (12-15):

6 p (tetrahydrofuran) - 2.8 » φ χ( 0 ) + Φ 2 ( 2 . 8 ) + (1 - φχ - Φ 2) 3 . 4 (1)

6 Η ( t e t r a h y d r o f u r a n ) - 3.9 - φ χ( 0 ) • Φ 2 ( 7 · 7 ) + (1 - φ χ - Φ 2>1.5 (2)

0.6 - 0.6Φ 2 + 3 . 4 Φ 1 (1)

2.4 - 0.2Φ 2 + 1.5Φ 1 (2)

Simultaneous s o l u t i o n of these two equations y i e l d s :

φ^ • volume f r a c t i o n n-hexane • 0.10

Φ 2 « volume f r a c t i o n 1-butanol « 0.43

Φ^ · volume f r a c t i o n d i o c t y l phthalate • 0.47

Check on 6^ of the mixture

0 . 1 0 ( 7 . 2 ) + 0 . 4 3 ( 7 . 8 ) + 0 . 4 7 ( 8 . 1 ) - 7.9

δ^ ( t e t r a h y d r o f u r a n ) - 8 . 2 .

(b) An a l t e r n a t i v e route can be t r i e d using equation (12-30) to

calculate 6^ and matching the δ^ and δ β of the blend to the

corresponding values of t e t r a h y d r o f u r a n . I n t h i s instance

negative volume f r a c t i o n s are calculated I n d i c a t i n g that t h i s

blend cannot match the solvency of t e t r a h y d r o f u r a n . The

c o n t r a d i c t i o n between the c a l c u l a t i o n s of s o l u t i o n s (a) and

(b) to t h i s problem emphasize the e m p i r i c a l nature of subparameter

s o l u b i l i t y parameter models. An e m p i r i c a l model can be very

useful but i t w i l l e v e n t u a l l y f a i l to match some n a t u r a l

phenomenon.
 59

12-6. Block copolymers are prime choices as v i s c o s i t y reducing a d d i t i v e s .

Examples are ethylene-propylene block copolymers admixed w i t h

polyethylene ( A . Rudin, Polym. Eng. S c i . f 10. 94 (1970)) and

styrene-butadiene block copolymers i n SBR ( C . K. S h i h , i n "Science

and Technology of Polymer P r o c e s s i n g , " N. P. Suh and N-H. Sung, e d . ,

MIT Press, Cambridge, Mass., 1979). Graft copolymers could also

be used i n some instances but the s t r u c t u r e of block copolymers i s

more accurately known and c o n t r o l l e d . The blocks which are s i m i l a r

i n s t r u c t u r e to the host polymer ensure good interphase adhesion

while the second blocks provide the required c o n t r o l l e d immiscibility

i n the melt phase.

12-7. From Table 12-111:

Solvent Volume F r a c t i o n

toluene 8.9 0.50

1-butanol 11.4 0.13

methyl e t h y l ketone 8.4 0.12 ( - 0.32 χ 0.37)

methyl i s o b u t y l ketone 8.4 0.20

diethylene g l y c o l
monomethyl ether 10.2 0.05

δ · Σφ f (12-15)
mixture i i

- 0 . 5 0 ( 8 . 9 ) + 0 . 1 3 ( 1 1 . 4 ) + 0 . 1 2 ( 8 . 4 ) -Ι­

Ο.20(8.4) + 0.05(10-2) - 9.1.

The bulk of the solvents are medium or p o o r l y hydrogen bonding

according to the t a b l e . By i n s p e c t i o n , tetrahydrofuran should be

as good a solvent f o r n i t r o c e l l u l o s e as the mixture listed.