The Kinetics of Copolymerization of Various Acrylate Systems

COPYRIGHTED
by
JOHN W. VANDERHOFF
1951
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
THE KINETICS OF COPOLYMERIZATION CF
VARIOUS ACRYLATE SYSTEMS
by
John W illiam V anderhoff
A d is s e r ta tio n subm itted to th e F a c u lty o f th e Graduate
School o f A rts and Sciences o f th e U n iv e rsity
o f B uffalo in p a r t i a l f u lf illm e n t o f th e
requirem ents f o r th e degree o f
Doctor o f Philosophy
F ebruary 1951
ACKNOWLEDGMENT
The a u th o r w ishes to express h is g ra titu d e to
Dr. George G o ldfinger whose i n t e r e s t , encouragement and
a s s is ta n c e made t h i s in v e s tig a tio n p o s s ib le .
The a u th o r a lso w ishes to express h is a p p re c ia
tio n to th e Rohm & Haas Company who su p p lied th e monomers
f o r t h i s in v e s tig a tio n .
TABUS OF COHTENES
C hapter Page
• I. Synopsis------------------------------------------------------------------------- 1
II. In tro d u c tio n
A. H is to r ic a l Review — 2
B. Statem ent of th e Problem— —----------------------------------- — - 4
III. E xperim ental Procedure
A. P re p a ra tio n o f Monomers----------------------------- 7
B. C a lib ra tio n o f Method------------ :---------------------------------------- 7
C. E xperim ental D eterm inatio n s-— ------ 9
IV. C a lib ra tio n Data
A. TheStyrene-M ethyl A c ry la te System —------------------ 11
B. TheS ty ren e-E th y l A cry late System------------------------- 23
C. The Styrene-M ethyl M ethacrylate System ------------- 15
D. The S ty ren e-E th y l M ethacry late System -------------------- — 17
E. The S tyrene-B utyl M ethacrylate System------------------ - 19
F. The M ethyl A c ry la te -E th y l A cry late System-------------- 21
G. The Methyl A crylate-M ethyl M ethacrylate System------ 23
H. The M ethyl A c ry la te -E th y l M ethacrylate System------- 25
I. The M ethyl A c ry la te-B u ty l M ethacrylate System------- 27
J. The E th y l A crylate-M ethyl M ethacrylate System— —-----29
K. The E th y l A c ry la te -E th y l M ethacrylate System - 31
L. The E th y l A c ry la te-B u ty l M ethacrylate System-— --- 33
M. The Methyl M eth acry late-E th y l M ethacrylate System- 35
N. TheMethyl M ethacrylate-B u ty l M ethacrylate System——— 37
0. The E th y l M ethacrylate-B u ty l M ethacrylate System— — - 39
TABLE OF CONTENTS (Continued)
C hapter Page
P. V a lid ity of th e Method o f C a lib ra tio n —— -------------------- 41
V. E xperim ental Data
A. D iscussion ----------------------------- —-------------------------------- 43
B. The Styrene-M ethyl A cry late System- --------- 44
C. The S ty ren e-E th y l A c ry la te System------------- ----- ,— . 45
D. The Styrene-M ethyl M ethacrylate System----------------------— 47
E. The S ty ren e-E th y l M ethacrylate System ----------------- 49
F. The S tyrene-B utyl M ethacry late System---— — —— — — 50
G. Summary o f Q and e V alues— --------------- — -------------------- 51
H. The Methyl A c ry la te -E th y l A cry late System-------------------- 53
I. The Methyl A crylate-M ethyl M ethacrylate System --- 56
J. The Methyl A c ry la te -E th y l M ethacrylate System --------------------59
K. The E th y l A crylate-M ethyl M ethacrylate System——-------------- 62
L. The E th y l A c ry la te -E th y l M ethacrylate System-------------- — 65
M. The E th y l A c ry la te -B u ty l M ethacrylate System--------------- 68
N. The Methyl M eth acry late-E th y l M ethacrylate System 71
0. The Methyl M eth acry late-B u ty l M etriacrylate System—— 74
P. The E th y l M eth acry late-B u ty l M ethacrylate System----------------77
Q. Summary o f r-j_ and r 2 V alues—--------------------------------------- 80
V I. Conclusion— ———----------— —--------------------------------— — 83
V II. B ibliography— — -------------------- — --------------- 84
with permission of the copyright owner. Further reproduction prohibited without permission.
I, SYNOPSIS
This in v e s tig a tio n *ra.s undertaken to add th e p re v io u s ly u n rep o rted
v a lu e s f o r th e r a t i o s of th e r a te c o n sta n ts f o r v a rio u s two-component
a c r y la te and m e th a cry late copolym erization systems t o th e c o n sid e ra b le
amount o f d a ta a lre a d y re p o rte d f o r o th e r systems and to determ ine i f
p o s s ib le th e e f f e c t o f a homologous s e r ie s o f s u b s titu e n ts on th e r a t i o s
o f th e ra te c o n s ta n ts .
S ix monomers were chosen f o r t h i s stu d y : s ty re n e , m ethyl a c r y la te ,
e th y l a c r y la te , m ethyl m e th a c ry la te , e th y l m e th a cry late , and b u ty l
m e th a c ry la te . A ll but one o f th e f i f t e e n p o s sib le system s were m easurable
by th e method used.
From t h i s in v e s tig a tio n i t was determ ined t h a t th e presence o f a
s u b s titu e n t lias a v e ry d e f in ite e f f e c t on th e r a ti o s o f th e r a te c o n sta n ts
and t h a t th e n a tu re o f th e s u b s titu e n t has a sm all but m easurable e f f e c t
on th e r a tio s o f th e r a te c o n sta n ts .
- 3 -
t r a t i o n s o f th e monomers in th e i n i t i a l polymer form , m^ and mg, and th e
r a t i o s o f th e r a t e c o n s ta n ts , r^ and r g , was developed in d ep en d en tly by
A lfre y and G oldfinger 12 ) , Mayo and Lewis ( 3 ) , and W all (4)*
mi Mx rjM ! + Mg
mg Mg rgt'Ig + M i
L a te r an atte m p t to d escrib e th e b eh av io r o f monomers in
copolym erization on a q u a n tita tiv e b a s is was made by A lfre y and P ric e ( 5 ) .
These au th o rs a s s ig n a r e a c t i v i t y "Q" and a p o l a r i ty "e" t o every monomer.
For a given copolym erization system th e s e re la tio n s h ip s a re :
The sty re n e monomer i s used a s a b a s is o f th e a r b i t r a r y s c a le o f "Q"
and "e" v a lu e s and a v alu e o f Q = 1.00 and e = - 0 .8 have been a ssig n e d to

i t ( 6) .
NOTE: A more d e ta ile d h i s t o r i c a l review and d is c u s s io n wi l l be found in th e

t h e s i s "The Temperature Depeuuence o f th e C opolym erization R e a c tiv ity R atio s
i n th e Systems: A c ry lo n itrile - S ty re n e ; D ic h lo ro s ty re n e -A c ry lo n itrile ; and
D ich lo ro sty ren e-S ty ren e" subm itted by Mark S t e i d l i t z to th e F a c u lty o f th e
Graduate School o f A rts and S cien ces o f th e U n iv e rs ity o f B u ffalo in
February 1943,
- 2 -
ii. imoiycTiON
A. H is to r ic a l Review
There a re th r e e main s te p s in a l l a d d itio n po ly m erizatio n re a c tio n s :
1. The i n i t i a t i o n s te p in which a fr e e r a d ic a l i s formed by such processes
a s a c o llis io n of a monomer m olecule w ith a n o th e r monomer m olecule, a
c o llis io n o f a monomer m olecule w ith a so lv en t m olecule, by a b so rp tio n
o f a l ig h t quantum, e t c .
2. The p ro p ag atio n s te p in which a molecule o f monomer adds on t o a chain
ending in a f r e e r a d ic a l and th e fre e r a d ic a l i s th u s tr a n s f e r r e d to th e
end o f th e c h a in .
3. The te rm in a tio n s te p in which th e fre e r a d ic a l i s destro y ed by some
process such a s ch ain t r a n s f e r , d is p ro p o rtio n a tio n , e t c . ( l )
In a system c o n ta in in g two d if f e r e n t monomers, th e re a re fo u r p o ssib le
p ro p ag atio n re a c tio n s :
+ Mx *11 > M-j*
M]* + m2 *12 , Mg*
M2* + Ml - k21 , Mj*

A
m2* + *2-
Using th e assum ption o f a stea d y s t a t e w herein th e t o t a l c o n c e n tra tio n
o f f r e e ra d ic a ls rem ains co n stan t and th e re fo re th e r a te o f conversion o f
M3# to must be e q u a l to th e r a te o f conversion o f fit,# t o Mj*, an
e x p re ssio n in v o lv in g i n i t i a l monomer c o n c e n tra tio n s , Mj_ and M2 , th e concen-
- 4 -
B, Statem ent o f th e Problem
T his in v e s tig a tio n was undertaken w ith a tw o -fo ld purpose in mind:
1, To add to th e c o n sid e ra b le amount o f d ata a lre a d y e x is tin g f o r o th e r
system s, th e p re v io u s ly unrep o rted v a lu e s f o r th e r a t i o s o f th e rate,
c o n s ta n ts , r^ and r 2> f o r v a rio u s a c r y la te and m eth acry late system s,
2. To determ ine i f p o s s ib le th e e f f e c t o f a homologous s e r ie s o f s u b s titu e n ts
on th e r a t i o s o f th e r a t e c o n s ta n ts .
S ix monomers were chosen f o r t h i s study: s ty re n e , m ethyl a c r y la te ,
e th y l a c r y la te , m ethyl m e th a c ry la te , e th y l m e th a c ry la te , and b u ty l m ethacry
la te . Styrene was chosen because i t i s more o r l e s s a "stan d ard " o r
"re fe re n ce " monomer and th e v a rio u s a c r y la te s and m e th a ciy la te s were chosen
t o show th e e f f e c t o f in c re a s in g s iz e o f s u b s titu e n t i n th e a c r y la te and
m eth acry late s e r i e s . There a re f i f t e e n d if f e r e n t copolym erization systems
p o s sib le from th e s e s i x monomers. A ll b u t one o f th e f i f t e e n system s were
m easurable by th e method u sed .
From th e "copolym erization e q u a tio n ",
“L % +
m2 M2 ^ 2 +
i t i s evident t h a t th e problem i s e s s e n tia l ly one o f analyzing th e
copolymer i n i t i a l l y formed. T his can be accom plished by allow ing th e
sample to polym erize t o a conversion o f about 5$ , th e n stopping th e re a c
t i o n , and reco v erin g th e copolymer f o r a n a ly s is . I f th e r e a c tio n i s
allow ed to proceed to a conversion o f more th a n 10$ th e i n i t i a l monomer
c o n c e n tra tio n cannot be assumed to be c o n stan t d u rin g th e course o f th e
r e a c tio n and th e e q u atio n w i l l not h o ld .
- 5-
For most o f th e system s in volved, o rd in a ry chem ical a n a ly s is i s
t h e o r e t i c a l l y p o s s ib le b u t i s im p rac tic ab le because o f th e com paratively
sm all d iffe re n c e in percentag e com positions. T h erefo re th e measurement
o f a p h y s ic a l c o n sta n t o f th e copolymer and polymer samples was re s o rte d
to . Of th e p h y s ic a l c o n sta n ts th e r e f r a c tiv e in d ex seemed th e most
prom ising and con seq u en tly was used a s a method o f copolymer a n a ly se s.
A f a c t o r o f g re a t importance in th e measurement o f th e p h y sica l
co n sta n ts o f a polymer i s th e "apparent second-order t r a n s i t i o n p o in t" . ( 7 )
Many supercooled o rg a n ic liq u id s possess d e f i n ite sh o rt tem perature
ranges i n which th e y change to " v itre o u s s o lid s " o r " g la s s e s " . This
t r a n s i t i o n i s e n t i r e l y d i s t i n c t from c r y s t a l l i z a t i o n i n t h a t th e re i s
no d is c o n tin u ity in th e prim ary thermodynamic v a ria b le s and no sudden
s tr u c tu r a l change i s in v o lv e d . On th e o th e r hand such v a ria b le s as
s p e c ific h e a t, c o e f f ic ie n t o f expansion, r a t e o f change o f r e f r a c tiv e
index, e tc . - undergo marked changes in th e course o f a v e ry few d eg rees.
In th e case o f polymer samples t h i s t r a n s i t i o n may be regarded as tk « t
from a g la s s y to a ru b b ery s ta te and i t o ccu rs i n th e same g e n eral
tem perature range a s t h a t in which th e m echanical "so fte n in g p o in t"
occu rs. Above th e "ap p aren t second-order t r a n s i t i o n p o in t" , th e re fra c
tiv e index o f a polymer sample i s a fu n c tio n o f th e tem p eratu re, w hile
below th e "apparent second-o rd er t r a n s i t i o n p o in t" , th e r e f r a c tiv e index
i s a fu n c tio n o f both th e tem perature and th e th erm al h is to r y o f th a t
p a r tic u la r polymer sample. Therefore i t was n e ce ssa ry to ta k e th e r e fra c
t i v e index measurements a t a tem perature which was above th e h ig h e st
"apparent second-order t r a n s i t i o n point" o f th e polymers in volved.
The "apparent second-order t r a n s i t i o n p o in t" o f s ty re n e , about 8CPC., was
th e h ig h e st and consequently th e r e f r a c tiv e in d ex measurements were made
a t 85°C. At t h i s tem peratu re some o f th e polymers and copolymers (th o se
w ith low er "apparent second-order t r a n s i t i o n p o in ts " ) were q u ite s o ft and
gave c le a r d i s t i n c t l i n e s in th e re fra c to m e te r f i e l d w h ile o th e rs (polym ers
and copolymers o f sty re n e and methyl m e th acry late) so ften ed o n ly s l i g h t l y
and gave r a th e r hazy and in d is tin c t l in e s in th e re fra c to m e te r f i e l d .
in . EXPERIMENTAL PROCEDURE
A. P re p a ra tio n o f Monomers
A ll o f th e monomers used in t h i s in v e s tig a tio n were re c e iv e d from
th e Rohm & Haas Company. The monomers were p u r if ie d by d i s t i l l a t i o n
under vacuum a t l e a s t fo u r tim es in a sm all Hickman vacuum s t i l l .
The p u rif ie d monomers were sto re d u n t i l used in a r e f r i g e r a to r
a t -5°C.
B. C a lib ra tio n o f Method
For each of th e f i f t e e n systems in v o lv ed , samples o f th e pure
monomers, a 25-75 mol p e rc e n t m ix tu re, a 50-50 mol p ercen t m ix tu re,
and a 75-25 mol percen t m ixture were p rep ared . These samples were
prepared by p ip e ttin g th e monomer in to an empty g la s s re a c tio n tube
which had been cleaned and weighed p re v io u sly . The tube was th en
rew eighed. This p ro cess was rep eated f o r samples co n tain in g more th a n
one monomer. The f i l l e d re a c tio n tu b es were th en cooled to th e tem pera
tu r e o f liq u id n itro g e n , evacuated and s e a le d . The po ly m erizatio n was
th e n c a r rie d out in a b a th a t 84°C. * 0.5°C . A fte r two weeks th e samples
were removed and in some cases where a d d itio n a l po ly m erizatio n seemed
w arranted, were placed in an oven f o r th re e days a t 120°C. T h is t r e a t
ment seemed s u f f ic ie n t to in s u re p r a c tic a l ly complete p o ly m erizatio n .
The sample tu b e s were th en broken open, th e sample recovered and d rie d
under vacuum a t about 71°C <t The vacuum achieved in drying th e polymer and
copolymer samples by a mercury j e t pump was probably o f th e o rd e r o f 0 .0 1
mm. although no p re ssu re measurements were made. W hile th e samples were
being d rie d th e y were weighed d a ily and when th e w eights f o r th re e succes
s iv e days were id e n tic a l to w ith in 0 .1 mg., th e samples were assumed t o be
- 3 -
o f co n stan t weight* A fte r th e samples had been d rie d to c o n sta n t w eight,
th e y were p ressed in to film s between th e p la te n s of„a h eated h y d ra u lic
p re ss a t about 100°C.
The r e f r a c tiv e in d ic e s o f th e se film s were th e n measured a t 85° 0 .
An Abbe re fra c to m e te r was used. The p ressed film s were placed between
th e prism s of th e re fra c to m e te r so t h a t th e sample made c o n ta c t w ith th e
m easuring prism . Then th e m etal prism housings o r "jaws" were tig h te n e d
c a r e f u lly and th e sample was allow ed to remain in th e re fra c to m e te r u n t i l
tem perature e q u ilib riu m could be assumed and th e sample "w etted" th e prism .
The tim e re q u ire d f o r t h i s was g e n e ra lly tw enty to s ix ty m in u te s. A fte r
t h i s p erio d o f tim e th e r e f r a c tiv e index was measured. The tem perature
was c o n tro lle d to ± 0.2°C .
For each o f th e r e f r a c t iv e index measurements, many re a d in g s were
ta k e n (9 -6 0 ), and th e average v alu e c a lc u la te d . From th e average v alue
th e average e r r o r and th e probable e r r o r were c a lc u la te d acco rd in g to th e

follow ing form ulae ( 8) :
average e r r o r = ± ^ d
n
probable e r r o r = ± 0.6745 *
where i d = th e sum o f th e d e v ia tio n s from th e average v alu e

n = th e number o f re a d in g s.
For each o f th e f i f t e e n system s, r e f r a c tiv e index was p lo tte d
a g a in s t mol f r a c tio n o f copolymer. In a l l o f th e se p lo ts "bands" o f
average e r r o r and o f probable e r r o r were p lo tte d r a th e r th a n a s in g le l i n e .
From th e s e p lo ts i t was p o s sib le to determ ine th e com position o f any copoly
mer sample by measuring i t s re f r a c tiv e index and reading o f f a sm all range
o f com position v alu es from th e cu rv e.
- 9 -
C. E xperim ental D eterm inations
For each o f th e f i f t e e n system s involved (w ith th e ex cep tio n o f th e
m ethyl a c r y la te - b u ty l m eth a cry late system which liras n o t m easurable by
th e method u s e d ), samples o f a 25-75 mol p ercen t m ix tu re , a 50-50 mol
p e rc en t m ixture and a 75-25 mol p ercen t m ixture were p rep ared . These
samples were p rep ared in th e same manner a s were th e c a li b r a tio n sam ples.
D eteim inations o f th e r a t i o s o f th e r a t e c o n s ta n ts were c a r rie d out
a t two d if f e r e n t te m p e ra tu re s, 50°C. and 70°C. In bo th d eterm in atio n s
th e samples were p laced i n co n stan t tem perature b a th s which were con
t r o l l e d to ± 0 .2 ° C . They were allow ed to rem ain i n th e b a th s u n t i l an
in c re a s e in th e ir v i s c o s i t y could be n o tic e d v i s u a l ly . When t h i s had
o ccu rred th e tu b e s were removed, weighed, and broken open. The co n ten ts
o f each tu b e was poured in to a t e s t tu b e c o n tain in g enough methanol t o
in s u re complete p r e c ip ita tio n o f th e copolymer form ed. In some cases th e
m ethanol was d ilu te d w ith a sm all amount o f d i s t i l l e d w a te r to give more
ra p id p r e c ip ita tio n and a b e t te r form o f th e p r e c ip ita te d polymer. The
polymer was th e n re c o v ere d , d rie d to c o n sta n t w eight u sin g th e same method
a s was used w ith th e c a li b r a t io n sam ples, p ressed in to a film a t about
100°C. and i t s r e f r a c tiv e index measured.
Again as in th e case o f th e c a lib r a tio n sam ples, many read in g s were
tak en and from th e se th e average value was c a lc u la te d . From th e average
•'Value th e average e r r o r and th e probable e r r o r were c a lc u la te d . Using th e
probable e r r o r “band" ( th e probable e r r o r was always g r e a te r th a n th e
average e r r o r ) a sm all range o f copolymer com position was re a d o f f from
th e c a lib r a tio n curve. S u b s titu tio n o f th e s e v a lu e s and o f th e v alu es fo r
- 10 -
t.he i n i t i a l com position o f th e monomer m ixture in th e "copolym erization
equation" gave th re e eq u atio n s in two unknowns, r^_ and r 2, f o r each
system a t both te m p e ratu res. These th r e e eq u atio n s when solved gave
th e r-^ and r^ v a lu e s. From th e s e r ^ and r 2 v a lu e s th e "Q" and "e" v alu es
were c a lc u la te d f o r each monomer.
For th e fiv e systems in v o lv in g sty ren e and an o th er monomer th e "Q"
and "e" v alu es were c a lc u la te d u sin g th e a r b i t r a r y v alu es f o r sty re n e o f
Q s 1.00 and e = - 0 .8 ( 6) . S ince th e s e v a lu es a r e a r b i t r a r y any number
o f s ig n if ic a n t fig u r e s n e ce ssa ry can be assumed. The "Q" and "e" v alu es
th u s o b tain ed were used in c ro ss checking th e rem aining a c r y la te and
m eth acry late system s.
- 11 -
IT . CALIBRATION DATA
A. The Styrene-M ethyl A c ry la te System
Table 1 ,
fiampla No. Mol F ra c tio n o f Monomers in I n i t i a l M ixture

Styrene Methyl A c ry la te
11 1.000 0.000
12-3 0.721 0.279

12-2C 0 .4 8 0 0 .5 2 0
12-2 0.477 0.523
12-1 0.240 0.760
12-10 0.2 1 4 0.786
22 0.000 1.000
Sample Mb. R e fra c tiv e Index Average B rro r Probable E rro r
11 1.5897 ± 0.0 0 0 3 4 ± 0 .0 0 1 0 9
12-3 1.5582 ± 0.00020 ± 0.00087
12- 2C 1.5304 ±0.00008 ± 0.00027
12-2 1.5298 ± 0.00007 ± 0.00025
12-1 1.4987 ±0.00009 ± 0.00031
12-1C 1.4949 ± 0.00007 ± 0.00022
22 1.4622 ± 0.00005 ± 0.00017
12
F ig u re 1.
A p lo t o f r e f r a c tiv e index v e rsu s mol f r a c tio n o f th e copolymer
samples f o r th e sty ren e-m eth y l a c r y la te system a s determ ined in Table 1 .
The sty re n e monomer i s denoted by (1) and th e m ethyl a c r y la te monomer i s
denoted by (2)*
I n t h i s f ig u r e and i n a l l o th e r fig u r e s which fo llo w , th e "p o in ts"
on th e curve a re re p re se n te d by c i r c l e s . The magnitude o f th e diam etera
o f th e s e c i r c l e s i n th e d ir e c tio n o f th e o rd in a te (th e v e r t i c a l d ire c tio n )
i s in d ic a tiv e o f th e m agnitude o f th e p ro b ab le e r r o r and o f th e average
e r r o r o f th e measurement o f t h a t p a r ti c u la r sam ple. The magnitude o f th e
diam eters o f th e c i r c l e s in th e d ir e c tio n o f th e a b c is s a (th e h o riz o n ta l
d ire c tio n ) i s o f no s ig n ific a n c e . T his method o f n o ta tio n was used to
emphasize th e r e la tiv e m agnitudes o f th e probable e r r o r s and o f th e
average e r r o r s o f th e v a rio u s sam ples.
- 13 -
B. The Styrene-E thyl A crylate System
T able 2.
Sample Mo. Mol F r a c tio n o f Monomers i n I n i t i a l M ixture

St.yrene E th y l A c ry la te
11 1.000 0.000
13-3 0.732 0 . 26S
13-2 0.503 0.497
13-2C 0.445 0.555
13-1C 0.245 0.755
13-1 0.239 0.761
33 0.000 1.000
Sample No. R e f ra c tiv e Index Average E r r o r P ro b ab le E rro r
11 1.5897 ± 0.00034 ± 0.00109

13-3 1.5511 ± 0.00006 ± 0.00016
13-2 1.5226 ± 0.00006 ± 0.00021
13-2C 1.5121 ± 0.00003 ± 0.00010
13-10 1.4860 ± 0.00005 ± 0.00016
13-1 1.4843 ± 0.00008 ± 0.0002s
33 1.44-88 i 0.00005 ± 0.00016
- 14 -
F ig u re , 2t .
A p lo t o f r e f r a c t i v e ind ex v e rs u s mol f r a c t i o n o f th e copolym er
sam ples f o r th e s ty r e n e - e th y l a c r y la te system a s determ ined i n T able 2.
The s ty re n e monomer i s denoted by ( l ) and th e e th y l a c r y la te monomer i s
denoted by (3)*
- 1 5 -
0. The Styrene-M ethyl M ethacrylate System
T able 3 .
Samplft Tfr>. Mol F r a c tio n o f Monomers i n I n i t i a l M ixture

S ty re n e M ethyl M eth acry late
11 1.000 0.000
14-3 0 .7 1 8 0.282
14-2 0.485 0.515
H -l 0.230 0.770
44 0.000 1.000
Sample No. R e f r a c tiv e Index Average E r ro r P ro b ab le E rro r
11 1.5897 ± 0.00034 ± 0.00109
14-3 1.5548 ± 0.00019 ± 0.00065
14-2 1.5310 ± 0.00006 ± 0.00020

14-1 1.5071 * 0.00015 ± 0.00054
44 1.4894 ± 0.00028 ± 0.00158
Figure 3«
A p l o t o f r e f r a c t i v e in d ex v e rs u s mol f r a c t i o n o f th e copolymer
samples f o r th e sty re n e -m e th y l m e th a c ry la te system a s d eterm ined i n T ab le 3*
The s ty re n e monomer i s denoted by (1 ) and t h e m ethyl m e th a c ry la te monomer i s
denoted b y (4) •
- 17 -
The Styrene-E thyl M ethacrylate System
Table 4 .
Sample No. Mol F r a c tio n o f Monomers i n I n i t i a l M ixture

S ty ren e Efthyl M eth a c ry la te
11 1.000 0.000
15-3 0.713 0.287
15-2 0.465 0.535
15-1 0.23 8 0.762
55 0 .0 0 0 1 .0 0 0
Sample Mo. R e fra c tiv e Index Average E rro r P ro b ab le E r r o r
11 1.5897 ± 0.00034 ± 0.00109
15-3 1.5459 ± 0.00007 ± 0.00026
15-2 1.5170 ± 0.00011 ± 0.00050

15-1 1.4931 ± 0.00008 ± 0.00028
55 1.4717 ± 0.00008 ± 0.00022
- IS -
F ig u re 4«
A p lo t o f r e f r a c t i v e in d ex v e rs u s mol f r a c t i o n o f th e copolymer
sam ples f o r th e s ty r e n e - e th y l m e th a c ry la te system a s determ ined i n T ab le 4»
The s ty re n e monomer i s denoted by ( l ) and th e e th y l m e th a c ry la te monomer i s
denoted by (5)*
- 19 -
E. The St.yrene-Butyl M ethacrylate System
T able 5.
Mol F r a c t i o n o f Monomers I n I n i t i a l M ix tu re
S ty ren e B u ty l M eth a c ry la te
11 1 .0 0 0 0.0 0 0
16-3 0.7 3 4 0.2 6 6
16-2 0.476 0 .5 2 4
16-1 0.2 5 1 0 .7 4 9
16-1C 0 .2 3 8 0 .7 6 2
66 0.0 0 0 1.000
Sample No. R e f r a c tiv e Index Average E r r o r P ro b a b le E r r o r
11 1 .5 8 9 7 ± 0 .0 0 0 3 4 ± 0 .0 0 1 0 9
16-3 1.5 4 3 4 * 0 .0 0 0 0 7 ± 0.00023
1 6 -2 1.5119 ± 0 .0 0 0 0 7 ± 0.00020
16-1 1 .4 8 7 5 ± 0 .0 0 0 0 5 ± 0.00017
16-1C 1 .4 8 6 2 ± 0 .0 0 0 0 5 ± 0.00017
66 1 .4638 ± 0.00005 ± 0.00016
- 21
F. The Methyl A crylate-E th yl A crylate System
T able 6 .
Sample Mo. Mol F r a c tio n o f Monomers in I n i t i a l M ixture

M ethyl A c ry la te E th y l A c ry la te
22 1.000 0.000
23-3 0.7 3 6 0.2 6 4
23-2 0.469 0.531
23-1 0.235 0.765
33 0.000 1.000
Sample Kb. R e fra c tiv e Index Average E rro r P ro b ab le E rro r
22 1.4622 ± 0.00005 ± 0.00017
23-3 1.4572 * 0.00003 ±0.00009

23-2 1.4540 ± 0.00003 ± 0 .0 0 0 0 8
23-1 1.4510 ± 0.00005 ± 0.00013
33 1.4488 ± 0.00005 ± 0.00016
Figure 5»
A p l o t o f r e f r a c t i v e in d e x v e rs u s m ol f r a c t i o n o f th e copolymer
sam ples f o r th e s ty r e n e - b u ty l m e th a c ry la te system a s determ in ed i n T a b le 5*
The s ty re n e monomer i s d en o ted b y ( l ) and th e b u ty l m e th a c ry la te monomer i s
denoted b y ( 6 ) ,
- 22 -
F ig u re 6.
A p lo t o f r e f r a c tiv e in d ex v ersu s mol f r a c t i o n o f th e copolymer
samples f o r th e m ethyl a c r y la te - e th y l a c r y la te system a s determ ined i n
Table 6. The m ethyl a c r y la te monomer i s denoted by (2) and th e e th y l
a c r y la te monomer i s denoted by ( 3 ) .
- 23 -
G. The Methyl A crylate-M ethyl M ethacrylate System
Table 7 .

M ethyl A c ry la te M ethyl M eth acry late
22 1.000 0 .0 0 0
24-3 0.690 0.3 1 0
24-2 0.471 0.529
24-1 0.223 0.777
44 0 .0 0 0 1.000
Sample Ho. R e fra c tiv e Ihdex Average E r ro r Probable E r r o r
22 1.4622 ± 0 .0 0 0 0 5 ± 0.00017
24-3 1.4678 ± 0.00003 ± 0.00009

24-2 1.4732 ± 0.00005 ± 0.00013
24-1 1.4811 ± 0.00007 ± 0.00018
44 1.4894 ± 0.00028 ± 0.00158
— 2 4 «■
F ig u re 7«
A p lo t o f r e f r a c t i v e index v e rsu s mol f r a c t i o n o f th e copolymer
samples f o r t h e m ethyl a c ry la te -m e th y l m e th a c ry la te system a s determ ined
i n T able 7 . The m ethyl a c r y la te monomer i s denoted by (2 ) and th e m ethyl
m e th a cry late monomer i s denoted by (4)*'
- 25 -
H. T h e M e th y l A c r y l a t e - E t h y l M e t h a c r y l a t e S y s te m
T able 8 .
Sample No. Mol F r a c tio n o f Monomers in I n i t i a l M ixture

M ethyl A cry late E th y l M eth acry late
22 1.000 0 .0 0 0
25-3 0.732 0.268
25-2 0.463 0.5 3 7
25-1 0.223 0.777
55 0.000 1.000
Sample Mo. R e fra c tiv e Index Average E r r o r P ro b ab le E rro r
22 1.4622 ± 0.00005 ± 0.00017
25-3 1.4622 ± 0.00004 ± 0.00011
25-2 1.4650 i 0.00000 ± 0.00000
25-1 1.4683 ± 0.00007 ± 0.00020
55 1.4717 ± 0.00008 ± 0.00022
- 26 -
F ig u re 8,
A p lo t o f r e f r a c t i v e in d ex v e rsu s mol f r a c t i o n o f th e copolymer
sam ples f o r t h e m ethyl a c r y la te - e th y l m e th a c ry la te system a s determ ined
i n Table 8 . The m ethyl a c r y la te monomer i s denoted by (2 ) and th e e th y l
m e th a c ry la te monomer i s denoted by (5)»
I. T h e M e th y l A c r y l a t e - B u t y l M e t h a c r y l a t e S y ste m
Table 9 .
Sample No. Mol F r a c tio n o f Monomers in I n i t i a l M ixture

M ethyl A c ry la te B u ty l M eth acry late
22 1.000 0.0 0 0
26-3 0.707 0.293
26-2 0.489 0.511
26-1 0.219 0 .7 8 1
66 0.000 1.000
Sample No. R e f ra c tiv e Index Av e ra g e E rro r P ro b ab le E rro r
22 1.4622 t 0.00005 ± 0.00017
26-3 1.4605 ± 0.00006 ± 0.00016
26-2 1.4605 ± 0.00005 ± 0.00014
26-1 1.4616 ± 0.00011 ± 0.00029
66 1.4638 ± 0.00005 ± 0.00016
- 28 -
F ig u re 9»
A p lo t o f r e f r a c t i v e index v e rs u s mol f r a c t i o n o f th e copolymer
sam ples f o r th e m ethyl a c r y la te - b u ty l m e th a cry late system a s determ ined
i n T able 9« The m ethyl a c r y la te monomer i s denoted by (2) and th e b u ty l
m e th a c ry la te monomer i s denoted by ( 6 ) ,
T h is system i s n o t m easurable u sin g t h i s method o f a n a ly s is because
th e r e f r a c t i v e in d ic e s o f m ethyl a c r y la te and b u ty l m e th a c ry la te a re to o
c lo se to g e th e r to g iv e th e accu racy req u ired #
- 29 -
J* The E th y l A cr.vlate-M ethyl M eth acry late System
Table 10.
Sample ho. Mol F r a c tio n o f Monomers i n I n i t i a l M ixture

E th y l A c ry la te M ethyl M eth acry late
33 1.000 0.000
34-3 0.702 0.298
3 4 -2 0.473 0.527
34-1 0.225 0.775
44 0.000 1.000
Sample No. R e f ra c tiv e Index Average E rro r P ro b ab le E rro r
33 1 .4488 ± 0.00005 ± 0.00016
34-3 1.4578 ± 0.00007 ± 0.00018
34-2 1 .4664 ± 0 .0 0 0 0 6 ± 0.00016
34-1 1.4775 ± 0.00005 ± 0.00017
44 1.4894 ± 0.00028 ± 0.00158
- 30 -
F ig u re 10»
A p lo t o f r e f r a c t i v e in d e x v e rsu s mol f r a c t i o n o f th e copolymer
samples f o r th e e th y l a c ry la te -m e th y l m e th a c ry la te system a s determ ined
i n T able 10. The e th y l a c r y la te monomer i s d enoted by (3 ) and th e m ethyl
m e th a cry late monomer i s denoted by (4)«
- 31 -
K. T h e E t h y l A c r v l a t e - E t h y l M e t h a c r y l a t e S y s te m
Table 11.

E th y l A c ry la te E th y l M eth a c ry la te
33 1.000 0.000
35-3 0.724 0.276

3 5 -2 0.475 0.525
3 5 -1 0.235 0.765
55 0 .0 0 0 1 .0 0 0
Sample No. R e fra c tiv e Index Average E r ro r P ro b ab le E rro r
33 1.4488 ± 0.00005 ± 0.00016
35-3 1.4536 ± 0.00007 ± 0..00018
3 5-2 1.4590 * 0.00006 ± 0.00016
35-1 1.4649 ± 0.00005 * 0.00014
55 1.4717 * 0.00008 * 0.00022
- 32 -
F ig u re 11,
A p lo t o f r e f r a c t i v e in d e x v e rs u s mol f r a c t i o n o f th e copolymer
sam ples f o r th e e th y l a c r y la te - e t h y l m e th a c ry la te system a s determ ined
i n T able 11, The e th y l a c r y la te monomer i s denoted by (3) and th e e th y l
m e th a c ry la te monomer i s denoted by ( 5 ) .
~ 33 -
L. T h e E t h y l A c r y l a t e - B u t y l M e t h a c r y l a t e S y ste m
Table 12.
Sample Mb. Mol F r a c tio n o f Monomers i n I n i t i a l M ixture

E th y l A c ry la te B u ty l M eth acry late
33 1.000 0.000
36-3 0.648 0.3 5 2
3 6 -2 0.442 0.558
3 6 -1 0.234 0.7 6 6
66 0.000 1.000
Sample No. R e f ra c tiv e Index Average E r ro r P ro b ab le E r ro r
33 1.4488 ± 0.00005 ± 0.00016
36-3 1.4527 ± 0.00008 ± 0.00023
36-2 1.4563 * 0.00001 ± 0.00005
36-1 1.4594 ± 0.00009 ± 0.00025

66 1.4638 * 0.00005 ± 0.00016
- 34 -
F ig u re 12.
A p lo t of r e f r a c t i v e index v e rsu s mol f r a c t i o n o f th e copolymer
sam ples f o r th e e th y l a c r y la te - b u ty l m e th a c ry la te system a s determ ined
i n T able 12. The e th y l a c r y la te monomer i s denoted by (3 ) and th e b u ty l
m e th a c ry la te monomer i s denoted by (6)*
- 35 -
M. T h e M e th y l M e t h a c r y l a t e - E t h y l M e t h a c r y l a t e S y s te m
T able 13.
Sample Nr>. Mol F r a c tio n o f tfcnomers i n I n i t i a l M ixture

M ethyl M eth acry late E th y l M eth acry late
44 1.000 0.000
45-3 0.674 0.326
4 5 -2 0.438 0.5 1 2
45-1 0.230 0.770
55 0.000 1.000
Sample No. R e fra c tiv e Index Average E r r o r P ro b ab le E r r o r
44 1.4894 ± 0.00023 ± 0.00158
45-3 1.4820 ± 0.00009 ± 0.00023
4 5 -2 1.4781 ± 0.00009 ± 0.00023
45-1 1.4738 ± 0.00006 ± 0.00018
55 1.4717 ± 0.00008 ± 0.00022
- 36 -
P.jflSg...3ay.
A p lo t o f r e f r a c t i v e in d ex v e rsu s mol f r a c t i o n o f th e copolymer
samples f o r th e m ethyl m e th a c ry la te -e th y l m e th a c ry la te system a s determ ined
i n T able 13. The m ethyl m e th a cry late monomer i s denoted by (4 ) and the
e th y l m e th a c ry la te monomer i s denoted by (5 )*
- 37 -
N. T h e M e th y l M eth ac r y l a t e - B u t y l M e t h a c r y l a t e S y s te m
T able 1 4 .
Sample Mo. Mol F r a c tio n o f Monomers in I n i t i a l M ixture

M ethyl M eth acry late B u ty l M eth a c ry la te
44 1.000 0.000
46-3 0.699 0.301
4 6 -2 0 .5 1 8 0.482
46-1 0 .2 4 3 0.757
66 0.000 1.000
Sample No. R e f ra c tiv e Index Average E r r o r P ro b ab le E r r o r
44 1.4894 ± 0.00028 ± 0.00158
46-3 1.4786 ± 0.00005 ± 0.00019
46-2 1.4739 ± 0.00007 ± 0.00023
46-1 1.4676 * 0.00007 * 0.00018
66 1 .4638 ± 0.00005 ± 0.00016
- 33 -
F ig u re 14.
A p lo t o f r e f r a c t i v e index v e rs u s mol f r a c t i o n o f th e copolymer
sam ples f o r th e m ethyl m e th a c ry la te -b u ty l m e th a c ry la te system a s determ ined
i n T able 14. The m ethyl m e th a cry late monomer i s denoted by (4) and th e
b u ty l m e th a cry late monomer i s denoted by (6)*
- 39 -
0. T h e E t h y l M e t h a c r v l a t e - B u t y l M e t h a c r y l a t e S y ste m
Table 15.
Sample Mb, Mol F r a c tio n o f Monomers i n I n i t i a l M ixture

E th y l M eth acry late B u ty l M eth acry late
55 1.000 0.000
56-3 0.6 9 8 0.3 0 2
56-2 0 .4 a 0.579
56-1 0.244 0.756
66 0.000 1.000
Sample No. R e fra c tiv e Index Average E rro r P ro b ab le E rro r
55 1.4717 ± 0.00008 ± 0.00022
56-3 1.4686 ± 0.00006 ± 0.00015
56-2 1.4661 ± 0.00005 ± 0.00014
56-1 1.4649 ± 0.00004 ± 0.00012
66 1.4638 ± 0.00005 ± 0.00016
- 40 -
F ig ure J £ *
A p lo t o f r e f r a c tiv e in d ex v e rsu s mol f r a c t i o n o f th e copolymer
samples f o r th e e th y l m e th a c ry la te -b u ty l m e th a c ry la te system a s determ ined
i n Table 15. The e th y l m e th a c ry la te monomer i s denoted by (5 ) and th e b u ty l
m e th a cry late monomer i s denoted by (6)*
- ill -
P. V a lid ity o f th e Method o f C a lib r a tio n
In o rd e r th a t any doubt a s to w hether th e copolymer c a li b r a t i o n
sam ples were tr u e copolymers o r a m ix tu re o f th e two d if f e r e n t polymers
m ight be d is p e lle d , th e fo llo w in g experim ents were perform ed.
S e p a ra te s o lu tio n s o f known c o n c e n tra tio n s o f p o ly s ty re n e , poly
m ethyl m e th a c ry la te , p o ly e th y l m e th a c ry la te and p o ly b u ty l m eth acry late
in benzene were p re p a re d . Measured volumes o f th e s e s o lu tio n s were
mixed and when hom ogeneity was c e r t a i n , polymer film s were c a s t from th e s e
s o lu tio n s . These polym er film samples were d rie d to c o n sta n t w eight and
t h e i r r e f r a c t i v e in d ic e s were measured in th e same manner a s were th e
c a l i b r a t i o n sam ples.
The d a ta f o r th e s e experim ents a re summarized in Table 16 on th e
fo llo w in g page. In a l l c a s e s , i f th e r e f r a c t i v e in d ex o f th e m ix tu res o f
polymers were p lo tte d a g a in s t th e mol f r a c t i o n o f th e sam ples, th e curves
o b ta in e d would no t be id e n t i c a l w ith th e c a li b r a t i o n c u rv e s. Hence th e
copolymer c a li b r a t io n samples must be re g a rd ed a s tr u e copolym ers.
T a b le 1 6 .
1. P o ly s ty re n e -P o l y e t h y l M e th a c ry la te M ix tu re s
Sample Mb. Mol F r a c tio n o f R e fra c tiv e P ro b ab le Mol F r a c tio n o f

P o ly sty re n e in Index E rro r P o ly sty re n e
M ixture from Curve
11-10-55- -5 0.446 1.5152 ± 0.00136 0 .4 3 2 -0 .4 6 6
11-5-55-i 0.267 1.5006 ± 0.00074 0.30 5 -0 .3 2 5
11-5-55-: L0 0,168 1.4699 ± 0.00024 0..201-0.211
P o lv sty ren e-P o Iv b u ty l M eth a c ry la te M ixtures
Sample No. Mol F r a c tio n o f R e fra c tiv e P robable Mol F r a c tio n o f

P o ly sty re n e in Index E rro r P o ly sty re n e
M ixture from Curve
11-5-66-5 0.340 1.4670 ± 0.00010 0 .0 3 3 -0 .0 4 1
11-5-66-10 0.205 1.4610 * 0.00007 0 .1 7 8 -0 .1 8 2
Polym ethyl M e th a c rv la te -P o ly e th y l M eth a c ry la te M ixture
Sample No. Mol F r a c tio n o f R e fra c tiv e P ro b ab le Mol F r a c tio n o f

Polym ethyl Meth Index E rro r Polvm ethyl Meth
a c r y la te in a c r y la te from
M ixture Curve
44-5-55-5 0.410 1.4749 ± 0.00018 0 .2 8 6 -0 .3 3 9

Polym ethyl M e th a e ry la te -P o ly b u ty l M eth acry late M ixture
Sample No. Mol F r a c tio n o f R e fra c tiv e P ro b ab le Mol F r a c tio n o f

Polym ethyl Meth Index E rro r Polym ethyl Meth
a c r y la te in a c r y la te from
M ixture Curve
44-5-66-5 0 .4 7 0 1.4700 ± 0.00015 0 .3 6 8 -0 .4 1 6
- 43 -
7. EXPERIMENTAL DATA
A» D iscussion
The r e f r a c tiv e in d e x o f th e e x p erim en tal sam ples was u sed to determ ine
t h e i r com positions. In a l l cases a sm all range o f copolym er com positions
was re a d o f f from th e c a l i b r a t i o n curve u sin g th e p ro b a b le e r r o r range o f
th e r e f r a c tiv e index o f th e ex p erim en tal sam ples. S u b s titu tio n o f th e s e
v a lu e s in th e "co p o ly m eriza tio n eq u atio n " (Page 4) gave one e q u a tio n in
two unknowns, r ^ and r 2 , f o r each e x p erim en tal d e te rm in a tio n sam ple. S in ce
th r e e samples o f v a ry in g com positions were run f o r each system a t b o th
te m p e ra tu re s, t h i s p ro ced u re gave th r e e eq u atio n s i n two unknowns, r-j_ and
r 2 , f o r each system a t b o th te m p e ra tu re s . The so lv in g o f th e th r e e p o s s i
b le p a ir s o f e q u atio n s g iv e s th r e e s e t s o f v a lu e s f o r and ^ f o r each
system a t both te m p e ra tu re s .
Once th e v a lu e s f o r th e r a t i o s o f th e r a t e c o n s ta n ts f o r each system
had been found, th e "Q" and "e" v a lu e s o f th e monomers could be c a lc u la te d
u sin g th e a r b i t r a r y v a lu e s o f Q a 1.000 and e a -0 .S 0 f o r s ty r e n e . Since
th e v a lu e s f o r sty re n e a r e a r b i t r a r y , any number o f s i g n i f ic a n t f ig u r e s
n e c e ssa ry could be assumed. The r e s u l t s o f th e s e c a lc u la tio n s a re g iv en
on th e follo w in g pag es.
In a l l c ase s v a lu e s w ith in th e sm all range o f copolymer composi
t i o n s a s in d ic a te d by th e probable e r r o r "band" w ere u sed in th e c a lc u la
tio n s . In some c a s e s , however, e i t h e r th e u pper o r low er li m i t o r some
v a lu e in between was u sed i f t h i s p a r t i c u l a r v a lu e gave b e t t e r agreem ent.
- 1|4 -
B. T h e S ty r e n e - M e t h v l A c r y l a t e S y s te m
T able 1 7 .
Sample Mol F r a c tio n R e fra c tiv e Average Probable Mol F r a c tio n o f

No. o f S tyrene In d ex E rro r E rro r S ty re n e i n Copolymer
i n M ixture
12-1S 0 .3 2 1 1.5358 ± 0.00015± 0.00056 0 .5 1 9 -0 .5 3 5 (0 .5 2 7 ave
12-2S 0.507 1.5454 ± 0 .0 0 0 3 3 ± 0.00156 0 .5 8 9 -0 .6 2 8 (0 .6 0 9 ave
12-3S 0.709 1.5590 * 0 .0 0 0 0 8 * 0.00029 0 .7 1 7 -0 .7 3 9 (0 .7 2 8 ave
U sing th e average v a lu e s f o r th e mol f r a c t i o n o f s ty re n e in th e copolymer:
Solving!! IS and. 2S IS and 3S 2S and 3S Average
0.670 0 .7 3 4 0.752 0.719 * 0 .0 3 2

*1
0.086 0.0990 0.142 0.1 0 9 ± 0.0 2 2
r2
q2 0.3 8 6 0.373 0.400 0 .3 8 6 * 0.009
e2 0 .8 9 0 .8 2 0 .7 0 0 .8 0 A 0 .0 7
D eterm inations a t 70°C.
Sample Mol F r a c tio n R e fra c tiv e Average P robable Mol F r a c tio n o f

No. o f S ty ren e Index E r ro r E rro r S ty ren e i n Copolymei
i n M ixture
12-3JR 0.259 1.5272 A 0.00011* 0.00029 0 .4 4 9 -0 .4 6 0 (0 .4 5 5 av«
1 2 -® 0.480 1.5449 A 0.00005A 0 .5 9 8 -0 .6 1 0 (0 .6 0 4 av<

o
8
o •
12-3R 0.687 1.5604 A 0 .0 0 0 1 2 ± 0.00032 0 .7 2 9 -0 .7 5 2 (0 .7 4 1 av<
U sing th e average v a lu e s f o r th e mol f r a c t i o n o f s ty re n e i n th e copolymer*
Solving:: 1R and 2R 1R and 3R 2R and 3R Average
0 .9 3 8 0.973 0.990 0 .9 6 7 * 0.019

rl
0.205 0 .2 1 2 0.23 0 .2 2 * 0 .0 1
r2
*2 0.383 0.375 0.381 0.3 8 0 A 0.003
°Z
0 .4 8 0 .4 6 0 .4 2 0 .4 5 * 0 .0 2
~ 4-5 -
C. T h e S t y r e n e - B t h v l A c r y l a t e S y s te m
T able 18.
1 . D eterm inations a t 5Q°C.
Sample Mol F r a c tio n R e fra c tiv e Average P ro b ab le Mol F r a c tio n o f

No. o f S tyrene In d ex E r ro r E rro r S ty ren e i n Copolymer
i n M ixture
13-1S 0.253 1.5140 * 0.00005 * 0.00016 0 .4 4 7 -0 .4 5 3 (0 .4 5 0 a v e .
13-2S 0.4 7 1 1.5320 * 0.00008 * 0.00025 0 . 582- 0 . 589(0.586 a v e .
13-3S 0.709 1.5511 * 0.00009 * 0.00030 0 .7 2 8 -0 .7 3 6 (0 .7 3 2 a v e .
U sing th e av erag e v a lu e s f o r th e mol f r a c t i o n o f s ty re n e i n th e copolymer:
S o lv in g : IS and 2S IS and 3S 2S and 3S Average
0.803 0.792 0.797 0 .7 9 7 * 0 .0 0 4

rl
r2 0.189 0.187 0 .1 8 0 .1 9 * 0.003
Q3 0.416 0.419 0.413 0 . 416* 0.0 0 2
e3 0.57 0 .5 8 0 .5 9 0 .5 8 ± 0 .0 1

No. o f S tyrene Index E rro r E rro r S tyrene i n Copolymer
i n M ixture
13-IRC 0.247 1.5128 ± 0.00005 ± 0.00015 0.438—0 .4 4 4 (0 .4 4 1 a v e .

13-2RC 0.435 1.5291 ± 0 .0 0 0 0 7 ± 0.00018 0 .5 6 0 -0 .5 6 6 (0 .5 6 3 a v e .
13-3R 0.743 1 .5591 * 0.00008 * 0.00023 0 .7 8 8 -0 .7 9 5 (0 .7 9 2 a v e .
U sing th e av erag e v a lu e s f o r th e mol f r a c t i o n o f s ty re n e in th e copolymer:
S o lv in g : IRC and 2RC IRC and 3R 2RC and 3R Average
rl 0.803 1.07 1.13 1 .0 0 * 0.13
r2 0.197 0.233 0.348 0.259 * 0.059
% 0.420 0.361 0.408 0.3 9 6 * 0.024
®3 0 .5 6 0 .3 9 0 .17 0 .3 7 * 0 .1 4
- 4-6 *“
C. The S ty re n e -E th v l A c ry la te System
T able IB . (C ontinued)
2 . Dat.ermi n a tio n s a t 70°C. (C ontinued)
Us-inp th e average v a lu e s f o r th e mol f r a c t io n o f sty re n e i n th e copolymer
f o r IRC and 2RC: th e low est v a lu e f o r 3R.
S o lv in g ; IRC and 2RC IRC and 3R 2RC and 3R Average
*1 0.803 1 .0 4 1.09 0 .9 4 * 0.13
0.197 0.230 0.328 0 .2 5 2 * 0.051

r2
Q3 0.420 0.333 0.406 0.386 ± 0.036
e3 0.5 6 0 .4 0 0 .2 2 0 .3 9 ± 0 .1 2
NOTE; Sample 13-3R i s p ro b ab ly in a c c u ra te sin ce th e p a i r "IRC and 2RC"

g iv e s good agreem ent w ith th e 50°C. d e te rm in a tio n s.
- 47 -
D. T h e S t.v re n e -M e th y l M e t h a c r y l a t e S y s te m
Table 19.
1 . D eterm inations a t 5Q°C.

No, o f S tyrene In d ex E rro r E r ro r S ty ren e i n Copolymer
i n M ixture
14-1S 0.257 1.5265 ± 0 .0 0 0 9 7 * 0 .0 0 5 3 4 0 .3 7 8 -0 .4 9 7 (0 .4 3 8 ave.
14-2S 0.523 1.5451 ± 0 .0 0 0 1 8 ± 0.00084 0 .6 1 2 -0 .6 3 9 (0 .6 2 6 a v e.
14-3S O.676 1.5536 ± 0.00054± 0.00249 0 .6 7 8 -0 .7 3 6 (0 .7 0 7 a v e .
Using th e average v a lu e s f o r th e mol f r a c t i o n o f s ty re n e in th e copolymer:
S olving; IS and 2S IS and 3S 2S and 3S Average
rx 0.955 0.801 0.720 0.825 ± 0.086
r2 0.245 0.221 0.074 0 .1 8 0 ± O.O67
Q4 0.398 0.435 0.355 0 .3 9 6 ± 0.027
e. 0.4 1 0 .5 2 0 .9 1 0.6ldk 0 .2 0
4
U sing th e lo w est v a lu e s f o r th e mol f r a c tio n o f s ty re n e i n th e copolymer:
Solvings IS and 2S IS and 3S 2S and 3S Average
rx 1.10 0.705 0.533 0 .7 8 ± 0 .2 1
r2 0.438 0.361 0.007 0.2 6 9 ± 0.174

D eteim inations a t 70°C.-
SamriLe Mol F ra c tio n R e fra c tiv e Average P ro b ab le Mol F r a c tio n o f

No. o f S ty ren e Index E r ro r E rro r S ty ren e i n Copolymer
i n M ixture
14-1R 0.252 1.5267 ± 0.00088 ± 0.00477 0 .3 8 6 -0 .4 9 3 (0 .4 4 0 a v e ,
14-2R 0.459 1.5445 ± 0.00035 ± 0.00187 0 .5 9 7 -0 .6 4 3 (0 .6 2 0 ave,
14-3R 0.745 1.5673 ± 0.00044 ± 0.00218 0 .8 0 2 -0 .8 5 4 (0 .8 2 8 ave,
- 4-g -
D. The Stvrene-M et h y l M eth a c ry la te System
Table 19. (Continued)
2. D eterm in atio n s a t 70°C .(C ontinued)
U sing th e average v a lu e s f o r th e raol f r a c t i o n o f s ty re n e i n th e copolym er:
S o lv in g : 1R and 2R 1R and 3R 2R and 3R Average
*1 1 .4 2 1 .5 1 .5 1 .5 ± 0 .0 3
0 .2 9 8 0 .3 0 0.33 0 .3 1 ± 0 .01
r2
0.335 0.312 0.341 0 .3 2 9 * 0.012
Q4
0.13 0 .1 5 0 .0 4 0 .1 1 ± 0 .0 4
e4
U sing th e lo w e st v a lu e s f o r th e mol f r a c t i o n o f s ty re n e in th e copolymer:
S olving: 1R and 2R IB and 3R Zt and 3R Average
rx 1.5 5 1.03 1.17 1 .25 * 0 .2 0
r2 0.430 0 .4 2 0.293 0 .4 0 ± 0 .0 7
NOTE: The above v a lu e s do n o t a g re e ■with th e v a lu e s p re v io u s ly re p o rte d

f o r t h i s system o f r ^ = 0 .5 0 and r , = 0 .5 0 ( 9 ) . These sam ples
so fte n e d o n ly s l i g h t l y a t 85°C. ana gave a r a t h e r h azy and in
d i s t i n c t l i n e in th e re fra c to m e te r f i e l d . Hence, th e s e m easure
ments may be in e r r o r and co n seq u en tly th e above v a lu e s w i l l n o t
be used in c ro s s-c h e c k in g .
- K9 -
E. T h e S t y r e n e - E t h y l M e t h a c r y l a t e S y s te m
T a b le 2 0 .
Sample Mol F r a c tio n R efra ctiv e Average P ro b ab le Mol F r a c tio n o f

No. o f S tyrene Index E rro r E rro r S ty ren e i n Copolymer
i n M ixture
15-1S 0.247 1.5104 ± 0.00024 ± 0.00090 0 .3 9 4 -0 .4 2 0 (0 .4 0 7 ave
15-2S 0.474 1.5270 ± 0.00016 ± 0.00071 0 .5 4 6 -0 .5 6 6 (0 .5 5 6 ave,
15-3S 0.750 1.5496 ± 0 .0 0 0 2 1 ± 0.00100 0 .7 3 2 -0 .7 5 2 (0 .7 4 2 ave,
U sing th e average v a lu e s f o r th e mol f r a c t i o n o f s ty re n e in th e copolymer:

Solving:: IS and 2S IS and 3S 2S and 3S Average
rl 0.670 0.706 0.714 0 .6 9 7 * 0.0 1 8
0.255 0.259 0.283 0.266 ± 0 .0 1 2

r2
q5 0.515 0.5 0 1 0.507 0.5 0 8 ± 0 .0 0 5
0.5 3 0 .5 0 0 .4 7 0 .5 0 ± 0 .0 2
Sample Mol F r a c tio n R e fra c tiv e 1 Average P ro b ab le Mol F r a c tio n o f
No. o f S ty ren e Index E r ro r E rro r S ty ren e i n Copolymer
i n M ixture
15-IR 0.247 1.5090 ± 0.00004 * 0.00009 0 .3 8 8 -0 .4 0 0 (0 .3 9 4 ave,
15-21 0 .5 2 1 1.5322 ± 0.00004 ± 0.00014 0 .5 9 4 -0 .6 0 4 (0 .5 9 9 ave,
15-3R 0.7 4 6 1.5474 ± 0.00038 ± 0.00142 0 .7 1 1 -0 .7 3 8 (0 .7 2 5 ave,

U sing th e average v a lu e s f o r th e mol f r a c tio n o f s ty re n e in th e copolymer:
Solving:: 1R and 2R 1R and 3R 2R and 3R Average
rl 0.856 0.646 0.592 0 .6 9 8 ± 0.105
0.318 0.285 0.110 0.2 3 8 ± 0.085

r2
q5 0 .4 7 0 0.547 0.452 0 .4 9 0 ± 0.038
e5 0 .3 4 0 .5 0 0.85 0 .5 6 ± 0 .1 9
NOTE: Sample 15-21 i s p ro b ab ly in a c c u ra te s in c e th e p a i r "lH and 3R" g iv e s

good agreem ent v d th th e 50°C. d e te rm in a tio n s .
- 50 =
F. T he S t y r e n e - B u t y l M e t h a c r y l a t e S y s te m
T able 21.
D eterm in atio n s a t 50°C •
Samnle Mol F r a c tio n 3R e fra c tiv e Average P ro b ab le Mol F r a c tio n of

No. o f Styrene Index E rro r E r ro r S ty ren e in Copolymer
i n M ixture
16-1SC 0.240 1.4913 ± 0.00013 ± 0.00046 0 .2 8 2 -0 .2 9 4 (0 .2 8 8 ave,
16-2SC 0.507 1.5160 ± 0.00006 ± 0.00021 0 .5 0 8 -0 .5 1 5 (0 .5 1 2 ave,
16-3S 0.749 1.5410 ± 0.00009 ± 0 .0 0 0 3 6 0 .7 1 2 -0 .7 2 0 (0 .7 1 6 ave,
Using th e average v a lu e s f o r th e mol f r a c t i o n o f sty re n e in th e copolymer:
Solving : ISC and 2SC ISC and 3S 2SC and 3S Average
rl 0.675 0.690 0.695 0 .6 8 7 ± 0.008
0.634 O.636 0.654 0 .6 4 1 ± 0.008

r2
0.709 0.700 0.706 0.705 ± 0.003
96
e6 0 .1 2 0 .1 1 0 .09 0 .1 1 ± 0 .01
D eterm inations a t 70°C •
Sample Mol F r a c tio n R e fra c tiv e Average P ro b ab le Mol F r a c tio n of

No. o f S ty ren e Index E rro r E rro r S ty ren e i n Copolymer
i n M ixture
16-IB 0.276 1.4970 ± 0.00004 ± 0.00011 0 .3 3 8 -0 .3 4 3 (0 .3 4 1 ave
16-2R 0.489 1.5156 ± 0.00006 ± 0.00016 0 .5 0 5 -0 .5 1 1 (0 .5 0 8 ave
16-3R 0.713 1.5360 ± 0.00011 ± 0.00033 0 .6 7 3 -0 .6 8 1 (0 .6 7 7 ave
Using th e average v a lu e s f o r th e mol f r a c t i o n o f sty re n e i n th e copolymer:
S o lv in g : 1R and 2ft IB and 3R 21 and 3R Average
*1 0.640 0.622 0.616 0.6 2 6 ± 0.009
r2 0.536 0.531 0.514 0.527 ± 0.009
«6 0.685 0.694 0.689 0.689 ± 0.003
% 0 .2 3 0.25 0.27 0 .2 5 ± 0 .0 1
- 51 -
G. Summary o f Q and e V alues
The "Q" and Me” v a lu e s f o r th e v a rio u s a c r y la te s and m e th a cry late s
a re summarized in Table 22 on th e fo llo w in g page. These v a lu e s were
used in c ro ss-c h e c k in g th e v a lu e s f o r th e r a t i o s o f th e r a t e c o n sta n ts
f o r th e v a rio u s a c r y la te and m e th a cry late sy stem s.
For a g iv e n monomer, th e "Q" v alu e may v a ry s l i g h t l y w ith tem pera
tu r e sin c e i t i s a measure o f th e r e a c t i v i t y o f th e monomer. The "e»
v a lu e , however, should be th e same a t a l l te m p e ra tu re s sin ce i t i s a
measure o f th e p o l a r i t y o f th e monomer. C onsequently t o t a l av erag es
o f th e "e*1 v a lu e s f o r b o th tem p eratu res have been c a lc u la te d . I t should
be emphasized t h a t a v e ry sm all e r r o r in th e d e te rm in a tio n o f th e
com position o f th e copolymer samples may g iv e r i s e to a la r g e e r r o r in
th e "e" v a lu e c a lc u la te d from i t . Hence, in c ro ss-c h e c k in g th e a c r y la te
and m e th a c ry la te system s n o t c o n ta in in g s ty re n e , i t was co n sid e re d v a lid
to use e ith e r th e 50°C.ne" v a lu e o r th e 70°C. "e" v a lu e o r th e t o t a l
average o f b o th d e te rm in a tio n s in o rd e r to give good agreem ent.
An ex cep tio n to th e above sta te m e n ts i s th e case o f th e s ty re n e -
m ethyl m e th a cry late system . Since th e r^ and r 2 v a lu e s f o r t h i s system
do no t ag ree w ith th o se p re v io u s ly re p o rte d , th e p re v io u s ly re p o rte d
v a lu e s o f Q B 0 .7 4 and e B 0 .4 have been used i n th e c ro ss-c h e c k in g .
- 52 -
Table 22.
Summary o f Q and e V alues
Monomer D eterm inations a t 50°C. D eterm in atio n s a t 70°C.
M ethyl A c ry la te Q2 = 0.386 ± 0.009 Q2 = 0.380 ± 0 .0 0 3
e 2 = 0 .8 0 ± 0.07 eg = 0 .4 5 * 0 .0 2
T o ta l Average: e^= 0 .6 3 ± 0.17
E th y l A c ry la te Q3 = 0.416 ± 0.002 Q3 = 0 .3 9 6 ± 0.024
e o = 0 .5 8 ± 0 .0 1 e3 = 0 .3 7 ± 0 .1 4
T o ta l Average: e ^ 0 .4 8 ± 0 .1 3
■KMethyl M eth acry late = 0 .3 9 6 ± 0.027 = 0.329± 0.038

e^= 0 .6 1 ± 0 .0 2 = 0 .1 1 ± 0 .0 4
E th y l M ethacrylate Q5 = 0.508 ± 0.005 Q5 = 0.490 ± 0 .0 3 8
e c = 0 .5 0 ± 0 .0 2 e 5 = 0.5 6 ± 0 .1 9
T o ta l Average: e^ 1> 0 .5 3 ± 0 .1 1
B u ty l M ethacrylate q6 = c.7 0 5 ± 0.003 = 0.689 ± 0 .0 0 3
e6 = 0 . 1 1 * 0.0 1 e6 = 0 .2 5 ± 0.01
T o ta l Average: e^_i . 0 .1 8 ± 0.07
■KThese v a lu e s were n o t u sed i n c ro ss-c h e c k in g .
NOTE: The u n d e rlin e d 11e" v a lu e s a r e p ro b ab ly th e b e s t v a lu e s .
- 53 -
H. T h e M e th y l A c r y l a t e - E t h y l A c r y l a t e S y s te m
T ab le 23.
1 . P e te rm in a tio n s a t 50°C.

No. o f M ethyl Index E r ro r E r ro r M ethyl A c ry la te i n
A c ry la te in Copolymer
M ixture
23-1SC 0.287 1.4512 ± 0 .0 0 0 1 0 ± 0.00043 0 .2 0 3 -0 .2 9 1 (0 .2 4 7 a v e .)
23-2S 0.501 1.4540 ± 0.00003 ± 0.00011 0 .4 5 6 -0 .4 8 6 (0 .4 7 1 a v e .)
23-3S 0.746 1.4571 ± 0 .0 0 0 0 7 * 0.00024 0 .7 0 1 -0 .7 5 3 (0 .7 2 7 a v e .)
U sing th e average v a lu e s f o r th e mol f r a c tio n o f m ethyl a c r y la te in th e
cotolym er:
S o lv in g ; ISC and 2S ISC and 3S 2S and 3S Average
rx 1.10* 0.968* 0.930* 0.999* * 0.067
r2 1.37* 1.30* 1.18* 1 .2 8 * ± 0.07
U sing a r b i t r a r y v a lu e s w ith in l im i t s f o r ISC (0 .2 8 9 ) and 35 (0 .734) and
th e h ig h e s t v a lu e f o r 2S:
S olving: ISC and 2S ISC and 3S 23 and 3S Average
^ 0.796 0.904 0.939 0 .8 8 0 * 0.056
r2 0.903 0.947 1 .06 0.970 * 0.060
U sing th e v a lu e s Q2 = 0.386 (50°C .) and e 2 a 0.63 ( t o t a l a v erag e ):
Q3 0.339 0.302 0.393 0 .3 4 5 * 0 .0 3 2
e^ 0 .0 6 0 .2 4 0 .5 6 0 .2 7 * 0 .1 8
Using th e v a lu e s (fe ■ 0.416 (50°C .) and e^ - 0 .5 8 ( 5Q°C. ) :
Q2 0.641 0.5 5 1 0.409 0 .5 3 4 * 0.083
e2 1.15 0.9 7 0 .65 0 .9 2 * 0 .1 8
- 5^ -
H. T h e M e th y l A c r y l a t e - E t h y l A c r y l a t e S y s te m
Table 2 3 .(C ontinued)
2 . Peterrninat io n s a t 70°C.
Sample Mol F ra c tio n R e fra c tiv e Average P robable Mol F r a c tio n o f

No. o f M ethyl Index E rro r E rro r M ethyl A c ry la te i n
M ixture
H-
H-
vn
23-1H 0.238 1.4517 0 .2 6 9 -0 .3 0 9 (0 .2 8 9 ave,
o
o
o
8
o
o
£
•
.
23-2R 0.478 1.4543 ± 0 .0 0 0 0 5 ± 0.00013 0 .4 7 6 -0 .5 1 1 (0 .4 9 4 ave,
23-3R 0.732 1.4578 ± 0 .0 0 0 0 4 * 0.00011 0 .7 6 2 -0 .7 9 1 (0 .7 7 7 ave
Using th e average v a lu e s f o r th e mol f r a c t io n o f m ethyl a c r y la te i n th e
copolymer:
S o lv in g : 1R and a t 1R and 3R 2R and 3Ft Average
rx 0 .7 0 4 1 .26* 1.53* 1 .16* ± 0 .3 1
r2 0.625 0.761* 1.34* 0.91* ± 0 .2 9
Using th e v a lu e s Qo = 0.380 (7 0 °n .) and ep = 0 .4 5 (7Q °C .):
Q3 0.360
e3 -0 .4 5 -
Using th e v a lu e s ■ 0.396 (70°C .) and e^ S 0 .5 8 (5 0 °C .):
Q2 0.374 -
e2 1*49 — — --
U sing th e lo w est v a lu e s f o r th e mol f r a c ti o n o f m ethyl a c r y la te i n th e
copolymer:
S olving: IR and 2R 1R and 3R a t and 3R Average
r± 0.676 1.17 1.40* 1.08* ± 0 .2 7
r2 0.716 0.848 1.38* 0.9 8 * ± 0 .2 6
- 55 -
H. The M ethyl A c ry la te -E th y l A c ry la te System
2. D eterm inations a t 70°C. (C ontinued)
Using th e v a lu e s g 0*396 (70°C .) and e>, a 0 ,5 8 (5CPC.)«
S olv in g : IE and 2R IE and 3R 2R and 3R Average
q2 0.905 0 .4 9 4 - 0.700 ± 0.206
e2 1.43 0.6 7 - 1 .05 ± 0 .3 8
Using th e v a lu e s Qo = 0.380 (70°C .) and e ? a 0 .63 ( t o t a l a v e ra g e );
Q3 0.329 0.307 - 0.3 1 8 ± 0.011
-0 .2 2 0 .5 4 - 0 .1 6 ± 0 .3 8
e3
•KThis d en o tes th e c a se s where r ^ r 2 exceeds 1 .0 0 , a t h e o r e t i c a l im p o s s i b ility .
NOTE: The u n d e rlin e d v a lu e s give th e b e s t agreem ent and hence a re p ro b ab ly

th e most a c c u ra te v a lu e s . The d e te rm in a tio n s a t 70°C. a re in a c c u ra te
a s in d ic a te d by t h e i r e x ce ssiv e l im i t s o f e r r o r and th e d iv e rg e n t
Hjn and ”ew v a lu e s o b ta in e d in c ro s s-c h e c k in g . However, i t i s i n t e r
e s tin g to n o te t h a t th e " b e s t v a lu e s ” l i e w ith in th e range o f
d e v ia tio n o f th e averag es o f th e r ^ and r 2 v a lu e s a t 7CPC.
- 56 -
I. T h e M e th y l A c r y l a t e - M e t h y l M e t h a c r y l a t e S y s te m
T able 24.
1 . D eterm inations a t 50°C.
A c ry la te i n Copolymer
M ixture
24- 1S 0 . 25S 1.4842 * 0.00022 * 0.00101 0 . 088- 0 , 174(0 .1 3 1 ave
24-2SC 0.496 1.4791 * 0 .0 0 0 1 2 * 0.00039 0 . 264- 0 . 296(0.280 ave,
24-3S 0.754 1.4710 ± 0.00004 * 0.00015 0 .5 4 3 -0 .5 6 5 (0 .5 5 4 ave
Using th e average v a lu e s f o r th e mol f r a c t io n o f m ethyl a c r y la te i n th e
copolymer:
S o lv in g : IS and 2SC IS and 3S 2SC and 3S Average
r^ 0 .2 4 0 .3 8 0.43* 0 .3 5 * 0.07
r2 2.50 2.27 2 . 62* 2 .4 6 * 0 .1 3
U sing th e v a lu e s Qo = 0.386 (50°C .) and eo s* 0 .8 0 ( 50°C .):
Q4 0.904 0 .7 4 4 0 .8 2 4 * 0.080
e^ 0.0 8 0.4 1 0 .2 5 * 0 .1 7
Using th e v alu es Qo m 0.3 8 6 (50°C .) and ep a 0 .63 ( t o t a l a v e ra g e ):
Q4 1.02 0.795 0 . 91* 0.11
©4 -0 .0 9 0 .2 4 0 .0 8 * 0 .1 7
Using th e average v a lu e s f o r th e mol f r a c t i o n o f m ethyl a c r y la te i n th e
opolymer f o r IS and 3S. and th e h ig h e st v a lu e f o r 2SC:
S olving: IS and 2SC IS and 3S 2SC and 3S Average
r^ 0 .4 0 4 0 .3 8 0 0.373 0.386 ± 0 .0 1 2
r2 2.28 2.27 2.22 2.2 6 ± 0 .0 2
- 57 -
I. T h e M e th y l A c r y l a t e - M e t h y l M e t h a c r y l a t e S y s te m
1 . D eterm inations a t 50°C. (C ontinued)
U sing th e v a lu e s Qo a 0.386 (50°C .) and - 0 .8 0 (5 0 °C .):
S olv in g : 13 and 2SC IS and 3S 2SC and 3S Average
Q4 0.757 0.74 4 0 .7 3 4 0.7 4 5 .± 0 .0 0 8
e^ 0 .5 1 0 .4 1 0 .3 7 0 .43 ± 0.05
Using th e v a lu e s Qo a 0.306 (50°C .) and e^ - 0 .6 3 ( t o t a l a v e ra g e ):
Q,h 0.796 0.7 9 6 0.789 0 .7 9 4 ± 0 .0 0 3
e^ 0 .3 4 0 .2 4 0.20 0 .2 6 ± 0 .05
U sing th e v a lu e s a 0 .7 4 (p re v io u s ly re p o rte d ) and e;( a 0 .4 (p re v io u s ly
r e p o r te d ) :
Q2 0 .3 7 0 .3 8 0 .3 9 0 .3 8 ± 0 .0 1
e2 0 .7 0 .8 0 .8 0 .8 ± 0 . 0 3
2 . D eterm in atio n s a t 70°C.
Sample Mol F r a c tio n R e fra c tiv e Average P robable Mol F r a c tio n o f

No. o f M ethyl Index E rro r E rro r M ethyl A c ry la te i n
A c iy la te i n Copolymer
M ixture
24-lR 0.223 1.4850 ±0.00008 ± 0 .0 0 0 2 4 0 .0 8 7 -0 .1 3 7 (0 .1 1 2 ave
24-21 0 .4 7 1 1.4802 ± 0.00011 ± 0.00033 0 .2 3 4 -0 .2 7 2 (0 .2 5 3 ave
24-3R 0.690 1.4720 ±0.00003 ± 0 .0 0 0 0 7 0 .5 0 7 -0 .5 2 2 (0 .5 1 5 ave

Using th e average v a lu e s f o r th e mol f r a c t i o n o f m ethyl a c r y la te i n th e
copolymer:
S olving: 1R and a t 1R and 3R 31 and 3R Average
rx 0 .1 6 0.554* 0.81* 0 .5 1 * ± 0.23
r2 2.95 2.34* 3.62* 2. 97* ± 0.43
- 5S -
I. The M ethyl A c ry la te-M e th y l M eth acry late System
T able 2 4 .(C ontinued)
U sing th e a v erag e v a lu e s f o r th e mol f r a c t i o n o f m ethyl a c r y la te In th e
copoivmer f o r 1R« th e h ig h e st v a lu e Tor 2R and t h e lo w est v alu e f o r 3R t
S o lv in g ; 1R and 2R 1R and 3R 31 and 3R Average
r;L 0.349 0.496 k- 0.574* 0.473#± 0.083
. r2 2.23 2.33* 2.70* 2.43* ± 0 .1 9
Using th e v a lu e s Qo - 0.3 8 0 (70°C .) and e<, = 0 .6 3 ( t o t a l a v e ra g e ):
Q, 0 .7 9 4 -
e. 0.13 -
4
U sing th e v a lu e s a 0.380 (70°C .) and e 2 = 0 .8 0 (5 0 °C .):
Q4 0.729 -
0.30 - - -
Using th e v a lu e s - 0 .7 4 (p re v io u s ly re p o rte d ) and = 0 .4 (p re v io u s ly
r e p o r te d ) :
Q2 0 .4 1 ■ “ ~ “
0 .9
*T his d enotes th e c a s e s where r ^ r ^ exceeds 1 .0 0 , a t h e o r e t i c a l im p o s s ib ility ,
NOTE: The d e te rm in a tio n s a t 79°C» a re n o t a s a c c u ra te a s th e determ ina

tio n s a t 50°C. I t i s in t e r e s t in g t o n o te , however, t h a t th e y
a g re e w ith th e ran g es o f d e v ia tio n .
- 59 -
J. T he M e th y l A c r y l a t e - E t h y l M e t h a c r y l a t e S y s te m
T able 25.

No* o f M ethyl Index E r ro r E rro r M ethyl A c ry la te i n
M ixture
25-15 0.266 1.4689 ± 0.00008 * 0.00032 0 .1 5 0 -0 .2 1 8 (0 .1 8 4 a v e .)

25-23 0.567 1.4650 ± 0 .0 0 0 0 4 * 0.00014 0 .4 4 9 -0 .4 7 2 (0 .4 6 1 a v e .)
25-3S 0.699 1.4640 * 0.00003 * 0.00008 0 .5 2 4 -0 .5 3 8 (0 .5 3 1 a v e .)

U sing th e average v a lu e s f o r th e mol f r a c tio n o f m ethyl a c r y la te i n th e
copolymer;
S olving: IS and 23 IS and 3S 2S and 3S Average
r]_ 0.71?* 0.364 0 .1 7 0 ,4 1 7 * 0.200
r2 1,66* 1.4 6 0 .58 1.23 ± 0 .4 4
Using th e v a lu e s Qo - 0.386 (50°C .) and e? - 0 .8 0 (5 0 °C .):
Q5 - 0.552 0.673 0.613 ± 0.060
e_ - -0 .0 1 -0 .7 2 -0 .3 7 4 0.36
Using th e v a lu e s 0^ m 0.50 8 (50°C .) and e^ - 0 .5 0 (5 0 °C .):
Q2 - 0.223 0.410 0 .3 1 7 * 0.094
e2 - - 0.29 - 1 .0 2 -0 .6 6 * 0 .37
Using th e h ig h e s t v a lu e s f o r th e mol f r a c t io n o f m ethyl a c r y la te i n th e
copolymer f o r 2S and 3S and an a r b i t r a r y v a lu e w ith in th e l i m i t s f o r
IS (0 .2 0 4 );
S olv in g ; IS and 25 IS and 3S 25 and 3S Average
rl 0*637 0.325 0.1 8 1 0 .3 8 4 * 0.168
r2 1.3 8 1.22 0.504 1 .03 ± 0.36
- 6o -
J. The M ethyl A c ry la te -E th y l M eth acry late System
T able 2 5 .(Continued)
Using th e v a lu e s Qo a 0.386 (50°C .) and ep = 0 .6 3 ( t o t a l a v e ra g e ):
Solvings I S and 2S IS and 3S1 2S and 3S Average
q5 0.483 0.633 0.390 0 .5 0 2 ± 0.087
0.2 7 -0 .3 2 -0 .9 2 -0 .3 2 ± 0 .4 0
e5
Using th e v a lu e s Qo a 0.386 (50°C .) and bo a 0 .8 0 (5 0 ° C .):
o.A5£ -
*5
0 J& -
c5
Using th e v a lu e s Qc = 0.508 (50°C.) and = 0 .5 0 ( 50°C. ) :
0 .4 4 1 0.669 2.19 1 .10 ± 0.73

®2
e2 0 .8 6 1.45 2.05 1.45 ± 0 .4 0
Sample Mol F r a c tio n R e f ra c tiv e Average P robable Mol F r a c tio n o f

No. o f M ethyl Index E r ro r E rro r M ethyl A c ry la te in
M ixture
25-2JR 0.259 1.4699 ± 0.00009 ± 0.00026 0 .0 8 8 -0 .1 4 5 (0 .1 1 7 ave
25-21 0.486 1.4670 * 0.00006 ± 0.00016 0 .2 9 1 -0 .3 3 0 (0 .3 1 1 ave
25-3R 0.705 1.4640 ± 0.00004 ± 0.0 0 0 1 1 0 .5 2 7 -0 .5 4 8 (0 .5 3 8 ave
U sing th e average v a lu e s f o r th e mol f r a c ti o n o f m ethyl a c r y la te i n th e
copolymer:
S olving: 1R and 2R 1R and 3R 2R and 3R Average
r 1.1* 0.665“- 0.511* 0 .8 * * 0 .2
r2 3.55* 2.90* 2.17* 2.87* ± 0 .4 7
- 6l -
J. The M ethyl A c ry la te -E th y l M eth acry late System
* T ab le 2 5 .(C ontinued)
2. D eterm inations a t 7 0 ^0 .(C ontinued)
Using th e h ig h e s t v a lu e s f o r th e mol f r a c t i o n o f m ethyl a c r y la te i n th e
copolymer;
S o lv in g ; 1R and 2 1 1R and 3R 2R and. 3H Average
rx 0.68* 0.537* 0.483 0 .5 7 * * 0 .0 8
r2 2.234- 2.11* 1 .8 5 2 . 06* ± 0 .1 4
U sing th e v a lu es Qo a 0.380 (70°C .) and eo = 0 .6 3 ( t o t a l a v e ra g e );
$5 0*635
e«j - - 0 .2 9 ~
U sing th e v a lu e s Qo = 0.38 0 (70°C .) and e n - 0 .8 0 ( 5 0 °C .h
Q5 - -
e<j — - 0 .4 6 -
U sing th e v a lu e s Q,- = 0.490 (70°C .) and e^ - 0 .5 6 (7 0 ^ 0 .);
Q2 - - 0,320
e2 Oi22
U sing th e v a lu e s Qt; » 0.490 (70°C .) and eg a 0 .5 3 ( t o t a l a v erag e );
Qg 0 .3 1 ?
e2 0 .8 7
U sing th e v a lu e s = 0.490 (7 0 °C .) and eg - 0 .5 0 (5 0 °C .):
Q2 " " 0 .3 1 4 -
©2 - — 0 .8 4 —
* T his denotes th e c a s e s where r ^ r 2 exceeds 1 .0 0 , a t h e o r e t i c a l im p o s s ib ility ,
NOTE; The u n d e rlin e d v alu es give th e b e s t agreem ent and hence a re

p ro b ab ly th e most a c c u ra te v a lu e s .
- 62 -
K. T h e E t h y l A c r y l a t e - M e t h y l M e t h a c r y l a t e S y s te m
T able 26.

No. o f E th y l Index E rro r E rro r E th y l A c ry la te in
M ixture
34-13 0.257 1.4820 ± 0 .0 0 0 0 8 ± 0.00034 0 .1 1 7 -0 .1 5 0 (0 .1 3 4 ave
34-2S 0.479 1.4750 * 0.00006 ± 0.00021 0 . 267- 0 . 284( 0.276 ave
34-3SC 0.715 1.4642 ± 0 .0 0 0 0 9 ± 0.00030 0 .5 1 7 -0 .5 4 1 (0 .5 2 9 ave
Using th e average v a lu e s f o r th e mol f r a c tio n o f e th y l a c r y la te in th e
copolymer;
S olving: IS and 2S IS and 3SC 2S and 3S Average
^ 0.232 0.451* 0 , 52?* 0 . 42± 0 .0 9
r2 2.12 2.24** 2.63* 2.33 ± 0 .2 0
Using th e average v a lu e f o r th e mol f r a c t i o n o f e th y l a c r y la te i n th e
copolymer f o r IS . th e h ig h e s t v a lu e f o r 2Sand th e low est v a lu e f o r 3SC:
r± 0.375 0.417 0.426 0.4 0 6 ± 0.021
r2 2.18 2 .2 1 2.06 2.15 ± 0 .0 6
Using th e v a lu es = 0.4 1 6 (50°C .) and e^ - 0 .5 8 (5 0 ° C .)t
Q4 0 .8 5 4 0.848 0.793 0 .8 3 2 ± 0.026
e^ 0.13 0 .3 0 0 .2 2 0 .2 2 * 0 .0 9
Using th e v a lu e s - 0 .7 4 (p re v io u s ly re p o rte d ) and e^ - 0 .4 (p re v io u s ly
r e p o r te d ) :
0 .4 0 0 .3 8 0 .4 2 0 .4 0 ± 0 .0 1
e3 0 .8 0 .7 0 .8 0 .8 ± 0.03
- 63 -
K. The E th y l A cry late-M eth y l M eth a c ry la te System
1 . D eterm inations a t 50°C»(Continued)
Using th e h ig h e s t v a lu e s f o r th e mol f r a c t i o n o f e th y l a c r y la te i n th e
copolymert
S olving: 35 and 2S IS and 3SC 2S and 3S Average
rx 0.154 0.427 0.546* 0 .3 7 6 ± 0.145
r2 1.7 1 1 .9 0 2.57* 2,06 ± 0 .3 4
U sing th e v a lu e s ■ 0.416 (50°C.) and e^ - 0 .5 5 (5 0 °C .):
q4 1.38 0.657 - 1 .0 2 ± 0 .3 6
e^ -0 .5 8 -0 .1 0 - - 0 . 3 4 ± 0 .2 4
Using th e v a lu e s - 0 .7 4 (p re v io u s ly re p o rte d ) and e^ - 0 .4 (p re v io u s ly
re p o rte d ):
Q3 0 .7 0 0 .4 8 - 0 .5 9 * 0.11
e^ 1 .6 0 .9 - 1 .3 ± 0 .4
Sample Mol F r a c tio n R e f ra c tiv e Average P ro b ab le Mol F r a c tio n o f

Ho. o f E th y l Index E r ro r E rro r E th y l A c ry la te in
M ixture
34-3R 0.254 1.4829 ± 0.00009 ± 0.00028 0 .0 9 9 -0 .1 3 2 (0 .1 1 6 a v e .)
34-21 0.470 1.4747 ± 0.00005 ± 0.00013 0 .2 7 5 -0 .2 8 8 (0 .2 8 2 a v e .)
34-3R 0.727 1.4640 ± 0.00003 ± 0.00009 0 .5 2 7 -0 .5 4 1 (0 .5 3 4 a v e .)

Using th e average v a lu e s f o r th e mol f r a c t i o n o f e th y l a c r y la te i n th e
copolymer:
S o lv in g : 3R and 3L 1R and 3R 2R and 3R Average
0.80* 0.49# 0.403 0 .5 6 ± 0 .16
r9 2.96* 2.69# 2 .1 4 2 .60 ± 0 .3 5
- 64- -
K. The E th y l A crylate-M ethyl M eth acry late System
2. D eterm inations a t 70°C .(C ontinued)
T T a tn fl th e h ig h e s t v a lu e f o r th e mol f r a c tio n o f e th y l a c r y la te i n th e
copolymer f o r 1R and th e average v a lu e s fo r. 2R and 3R:
S olv in g : 1R and 2R 1R and 3R 2H and 3R Average
r-L 0 .4 2 0.411 0.403 0 .4 1 ± 0 .01
r2 2.19 2.19 2 .1 4 2.17 ± 0 .0 2
Using th e v a lu e s ■ 0.396 (70°C .) and e^ - 0 .5 8 (5 0 °C .):
Cfy 0 ,8 0 8 0.807 0 .7 8 4 0.800 ± 0 .0 1 0
e4 0 .2 9 0.2 5 0 .1 9 0 .2 4 ± 0 .0 4
U sing th e v a lu e s (fy a 0.7 4 (p re v io u s ly re p o rte d ) and e^ - 0 .4 (p re v io u s ly
r e p o r te d ) :
0 .3 8 0 .3 8 0 .4 1 0 .3 9 ± 0 .0 1
Q3
0 .7 0 .7 0 .8 0 .7 ± 0 .0 3
e3
Using th e h ig h e s t v a lu e s f o r th e mol f r a c tio n o f e th y l a c r y la te i n th e
copolymer:1»
rl 0.487# 0.281 0 .4 1 9 0.396 ± 0.076
2.25* 2.2 1 2.11 2.19 ± 0 .0 5

r2
Using th e v a lu e s Qn = 0.396 (70°C .) and e^ = 0 .5 8 (£ 0 °C .)i
j
0.939 0 .7 7 2 0.856 ± 0.084

Q4
- -0 .1 2 0 .2 3 0 .0 6 ± 0.18
e4
Using th e v a lu e s Q». a 0 .7 4 (p re v io u s ly re p o rte d ) and e/( = 0 .4 (p re v io u s ly
re p o rte d ) 1t
q3 - 0 .4 4 0 .3 9 0 .4 2 ± 0 .0 3
e3 - 1 .1 0 .7 0 . 9 ± 0 .2
*T his denotes th e c a se s where r i r g exceeds 1 .0 0 , a t h e o r e t i c a l im p o s s ib ility .
- 65 -
L. T h e E t h y l A c r y l a t e - E t h y l M e t h a c r y l a t e S y s te m
T able 27.
1 . D eterm in atio n s a t 50°C.

No« o f E th y l Index E rro r E rro r E th y l A c ry la te i n
M ixture
35-15 0.251 1.4671 ± 0 .0 0 0 0 8 ± 0.00031 0 .1 4 4 -0 .1 7 4 (0 .1 5 9
35-2S 0.523 1.4625 ± 0.00009 ± 0.00034 0 .3 1 0 -0 .3 5 0 (0 .3 3 0
35-3S 0.736 1.4572 * 0 .0 0 0 0 8 ± 0.00029 0 .5 3 9 -0 .5 7 7 (0 .5 5 8
U sing th e average v a lu e s f o r th e mol f r a c t i o n o f e th y l a c r y la te in th e
copolymer:
S olv in g : IS and 2S IS and 3S 2S and 3S Average
0.162 0.363 0.465* 0 .3 3 ± 0 .1 1
r2 1 .5 4 1.65 2.20* 1 .8 2 ± 0 .3 0
U sing th e lo w est v a lu e f o r th e mol f r a c tio n o f e th y l a c r y la te in th e
copolymer f o r IS and th e average v a lu e s f o r 25 and 3S:
rx 0.306 0.409 0.465* 0.393 ± 0.058
r2 1 .9 0 1.95 2.28* 2 .0 4 ± 0 .1 6
Using th e v a lu e s - 0.416 (50°C .) and 63 - 0 .5 8 ( 50°C. ) :
Q5 0.884 0.769 - 0 .8 2 7 ± 0 .0 5 8
65 - 0 .1 6 0.1 0 - - 0 .0 3 ± 0 .33
U sing th e v a lu e s a 0.508 (50°C .) and eg = 0 .5 0 (5 0 °C .):
Qo 0.387 0.331 . - 0.349 ± 0.038
e3 1 .2 4 0 .9 8 - 1.11 ± 0.13
- 66 -
T able 27.(C o n tin u ed )
1 . D eterm in atio n s a t 50°C .(C ontinued)
U sing th e h ig h e s t v a lu e s f o r th e mol f r a c t i o n o f e th y l a c r y la te i n th e
copolymer;
r^ 0.181 0.538 0.714* 0 .4 7 8 ± 0.198
r2 1 -36 1 .5 4 2.55* 1 .8 2 ± 0 .5 2
Using th e v a lu e s = 0.4 1 6 (50°C .) and e i = 0 .5 8 (5 0 °C .):
Q5 1.15 0.6 0 2 0 .8 8 ± 0.28
e*j -0 .6 l 0 .1 5 -0 .2 3 ± 0 .3 8
U sing t h e v a lu e s Qk - 0 .5 0 8 (50°C .) and e„j B 0 .5 0. (5

. 0. ° C
. .)i
.
Q3 0.678 0.411 0 .5 4 5 * 0.1 3 4
e3 1.69 0.93 1.3 1 ± 0 .3 8
D eterm in atio n s a t 70°C

M ixture
3 5 -lit 0.239 1.4680 ± 0 .0 0 0 0 5 ± 0.00013 0 .1 1 6 -0 .1 3 8 (0 .1 2 7 ave,

3 5 -2 t 0.502 1.4630 ± 0 .0 0 0 0 4 ± 0.00011 0 .2 9 9 -0 .3 1 9 (0 .3 0 9 ave
35-3RC 0.694 1.4582 ± 0 .0 0 0 0 8 ± 0.00029 0 .4 9 2 -0 .5 3 2 (0 .5 1 2 ave
U sing th e average v a lu e s f o r th e mol f r a c t i o n o f e th y l a c r y la te i n th e
copolym er:
S o lv in g : lit and 2E lit and 3RC 2 t and 3RC Average
rx 0.378 0.465* 0.5 1 * 0.44*± 0.05
r2 2.10 2. 16* 3 .2 * 2.5* ± 0 .5
V.
- 67 -
Using th e average v a lu e s f o r th e mol f r a c t i o n o f e th y l a c r y la te in th e
copolymer f o r 1R and 2R and th e low est v a lu e f o r 3RC:
S o lv in g : 1R and 2R 1R and 3RC 2R and 3RC Average
rx 0 .3 7 S 0.41 6 0 .4 3 6 0.410 ± 0.021
r2 2.10 2.11 2 .1 2 2 . 1 1 * 0 .0 1
U sing th e v a lu e s a 0.396 (70°C .) and e^ « 0 .4 & ( t o t a l a v e ra g e ):
Q5 0.833 0.803 0.795 0.810 * 0.015
e5 0 .0 0 0 .1 2 0 .2 0 0 .1 1 ± 0.07
Using th e v a lu e s a 0.490 (70°C .) and e,. - 0.53 ( t o t a l a v e ra g e ):
Q3 0.301 0.28 1 0 .2 6 8 0.283 * 0.012
e3 1 .0 1 0.89 0 .8 1 0 .9 0 db 0 .0 ?
Using th e h ig h e s t v a lu e s f o r th e mol f r a c t i o n o f e th y l a c r y la te i n th e
copolymer:
rx 0.322 0.491 0 . 602* 0 ,4 7 2 * 0.100

r2 1.8 4 1.95 1.95* 1 .9 1 * 0.05
U sing th e v a lu e s a 0.396 (70°C .) and 63 a 0 .4 8 ( t o t a l a v erag e ):
Q5 0 .8 7 1 0.730 - 0.801 ± 0 .0 7 1
65 - 0 .2 4 0.27 - 0 . 0 2 ± 0.2 6
Using th e v a lu e s Qg - 0.490 (70°C .) and e c = 0.5 3 ( t o t a l averaged:
Q3 0 .4 3 1 0.281 - 0.3 5 ^ * 0.075
63 1.25 0 .7 4 - 1 .00 * 0 .2 5
*T his d enotes th e c a s e s where r ^ r 2 exceeds 1 .0 0 , a t h e o r e t i c a l

im p o s s ib ility .
- 69 -
M. The E th y l A c ry la te -B u ty l M ethacrylate System
1 . D eterm inations a t 50°C. (C ontinued)
Using th e v a lu e s Qa a 0.705 (50°C .) and - 0 .1 8 ( t o t a l av erag e ) t
S o lv in g : IS and 2S IS and 3S 25 and 3S Average
0.517 0.411 - 0 .4 6 4 ± 0 .0 5 3
e^ 0.63 0.59 - 0 .6 1 ± 0 .0 2
•KThis denotes th e c a se s where exceeds 1 .0 0 , a t h e o r e t i c a l im p o s s ib ility .
NOTE: From th e above d a ta , i t i s e v id en t t h a t sample 36-2S i s in a c c u ra te

sin c e th e p a i r IS and 3S g iv e th e b e s t agreem ent. The b e s t v a lu e s
a re u n d e rlin e d .
2. D eterm inations a t 70°C.
Mol F r a c tio n o f
M ixture
36-IR 0.258 1.4615 ± 0.00005 ± 0.00013 0 .1 0 9 -0 .1 5 2 (0 .1 3 1 a v e .)

3 6 -2R 0.489 1.4583 ± 0.00005 ± 0.00013 0 .3 H - 0 .342(0.328 a v e .)
36-3R 0.736 1.4542 ± 0 .0 0 0 0 5 ± 0.00013 0 .5 5 6 -0 .5 8 3 (0 .5 7 0 a v e .)

Using th e average v a lu e s f o r th e mol f r a c t i o n o f e th y l a c r y la te in th e
copolymer:
S o lv in g : 1R and 2R 1R and 3R 2R and 3R Average
r-L 0.69* 0.446* O.426 0 .5 9 * ± 0 .2 0
r2 2 .6 7 * 2.37* 1.81 2.28* ± 0 .3 3

Using th e h ig h e s t v a lu e f o r th e mol f r a c ti o n o f e th y l a c r y la te i n th e
copolymer f o r 1R and th e average v alu es f o r 2R and 3R:
I*! 0.49 0.443 0 .4 2 6 0 .4 5 ± 0 .0 2
r2 1.9 2 1.89 1.81 1 .8 7 ± 0 .0 4
- 70 -
M. T he E t h y l A c r y l a t e - B u t y l M e t h a c r y l a t e S y s te m
2. D eterm inations a t 70°C .(C ontinued)
U sing th e v a lu e s Qo a 0.396 (70°C .) and eg - 0 .4 8 ( t o t a l a v e ra g e ):
S o lv in g : 1R and 31 1R and 3R 2R and 3R Average
Q6 0.717 0.726 0.729 0 .7 2 4 =*=0.005
e, 0 .2 3 0.07 -0 .0 3 0 .0 9 ± 0 .0 9
W '' " '• V *

■ ■>
«6 0.699 0.696 0.693 0 .6 9 6 ± 0 .0 0 2
e6 0.33 0.17 0 .0 7 0 .1 9 ± 0 .0 9
Using th e v a lu e s Qa s 0.689 (70°C .) and eA = 0 .2 5 C70°C.):
0.382 0.403 0.433 0 .3 9 8 ± 0 .0 1 1

%
e3 0.50 0.65 0.7 5 O.63 ± 0.09

Using th e v a lu e s Qa - 0.689 (70°C .) and eA s 0 .1 8 ( t o t a l ai
% 0.3 7 6 0.393 0.4 1 8 0 .3 9 6 ± 0.015
e3 0.43 0 .5 9 0.69 0 .5 7 * 0.09

U sing th e v a lu e s Qa = 0.689 (70°C .) and e / = 0 .1 1 ( 50°C. ) :
0.369 0.382 0.403 0.385 ± 0 .0 1 2
e3 0 .3 6 0 .5 2 0 .6 2 0 .5 0 ± 0 .0 9
•WThis denotes th e c a s e s where r j r g exceeds 1 .0 0 , a t h e o r e t i c a l

impo s s i b i l i t y .
N. T h e M e th y l M e t h a c r y l a t e - E t h y l M e t h a c r y l a t e S ystem .
Table 29.

Sample Mol F ra c tio n R e fra c tiv e Average P ro b ab le Mol F r a c tio n o f
No. o f M ethyl Index E r ro r E rro r M ethyl M eth acry late
M eth acry late i n Copolymer
in M ixture
45-13 0.235 1.4740 ± 0 .0 0 0 0 1 ± 0.00004 0 .2 2 6 -0 .2 6 7 (0 .2 4 7 a v e .)
45-2S 0.4 9 4 1.4317 ± 0 .0 0 0 1 7 ± 0.00065 0 .6 1 6 -0 .7 0 1 (0 .6 5 9 a v e .)
45-3S 0.727 1.4850 ± 0 .0 0 0 1 2 ± 0.00050 0 .7 6 9 -0 .8 6 5 (0 .8 1 7 a v e .)
Using th e average v a lu e s f o r th e mol f r a c t i o n o f m ethyl m e th a c ry la te i n th e
copolymer:
5.34* 2.0?* 1 .4 6 2 .9 6 * ± 1.59

r2 2. 16# 1 ,2 3 * 0.249 1 .2 1 * ± 0 .6 4
U sing th e h ig h e st v a lu e f o r th e mol f r a c t i o n o f m ethyl m e th a cry late i n th e
copolymer f o r IS . th e low est v a lu e f o r 2S and an a r b i t r a r y v a lu e w ith in
li m i t s (0.804) f o r 3S:
il 2.69* 1.74* 1 .45 1.96* ± 0 .4 9
r2 1.23 0.986* 0.495 0 .9 1 * ± 0 .2 7

Using th e v a lu e s Q/. s 0 .7 4 (p re v io u s ly re p o rte d ) and e/. - 0.A ( n re v io u s lv
re p o r te d ) :
Q5 0 .6 5 -
e5 1 .0 -
Using th e v a lu e s Q.tj = 0.508 ( 50°C.) and _e_c s 0 .5 0 (50PC.)s
O4 0.768
e^ — — —0 .0 8 -
U sing th e v a lu e s B 0.508 (50°C .) and e5 - 0 .5 6 (7 0 °C .):
Q4 - - 0.7 4 2 -
64 — — —
0 .0 2 -
- 72 -
N. The M ethyl Met ha c r y l a t e -E th y l M eth acry late System

No. o f M ethyl Index E rro r E r ro r M ethyl M eth a c ry la te
i n M ixture
45-3R 0.285 1.4752 ± 0.00003 ± 0.00010 0 .3 1 6 -0 .3 5 2 (0 .3 3 4 awe,
45-2R 0.505 1.4302 ± 0.00014 ± 0 .0 0 0 4 5 0 .5 5 5 -0 .6 2 0 (0 .5 8 8 ave
45-3R 0.729 1.4843 ± 0 .0 0 0 3 2 ± 0 .0 0 1 2 0 0 .7 1 6 -0 .8 6 0 (0 .7 8 8 ave

Using th e average v a lu e s f o r th e mol f r a c tio n o f m ethyl m e th a cry late In th e
copolymer:
S o lv in g : 1R and 2R Ut and 3R 2R and 3R Average
1.69* 1.5* 1.37 1 .5 * ± 0 .1
r2 0.931* 0.86* 0.696 0 .8 3 * * 0.09

U sing th e v a lu e s g .0 .7 4 (p re v io u s ly re p o rte d ) and e/, - 0 .4 (p re v io u s ly
r e p o r te d ) :
Q5 - - ' 0 .5 8
e_ - 0 .6
5
U sing th e v a lu e s (fe - 0.490 (70°C .) and - 0 .5 6 (7 0 °C .):
% 0.623
% 0 .3 4
U sing th e h ig h e st v a lu e f o r th e mol f r a c t io n o f m ethyl m e th a cry late fo r
1R. and a r b i t r a r y v a lu e s w ith in th e l i m i t s f o r 31(0.610) and 3Et(0.804):
t 1 1 . 88* 1 . 61* 1.52 1 . 67* ± 0.14
r2 0.884* 0.807* O.645 0.779*4 0.089

U3ing th e v a lu e s Q;, n 0 .7 4 (p re v io u s ly re p o rte d ) and ej, a 0 .4 ( p re v io u s ly
re p o rte d ):
Q5 0 .5 1
e5 — — 0 .5 —
- 73 -
N. T h e M e th y l M e t h a c r y l a t e - E t h y l M e t h a c r y l a t e S y s te m
2. D eterm inations a t 70°C. (C ontinued)
Using th e v a lu e s Qc = 0.490 (70°C .) and et; - 0 .5 6 (7 0 °C .):
Solving? 1R and 2R 1R and 3R 2E and 3R Average
Q4 0.702
e4 - - 0 .4 2 - -
Using th e v a lu e s Qg - 0.490 (70°C .) and e^ - 0.53 ( t o t a l average)?
Q4 0.705
e4 0 .3 9
•HThis d en o tes th e c a se s where r ] r 2 exceeds 1 .0 0 , a t h e o r e t i c a l

im p o s s ib ility .
NOTE: In both o f th e se d e te n n in a tio n s , i t i s e v id e n t t h a t samples

45-1S and 45-1R a re in a c c u ra te sin c e th e p a ir s "2S and 3S” and
"2R and 3R" give th e b e s t agreem ent.
- 7* -
0. T h e M e th y l H e t h a c r y l a t e - B u t y l M e t h a c r y l a t e S y s te m
Table 30.

Kb. o f M ethyl In d ex E rro r E rro r M ethyl M eth acry late
M eth a c ry la te i n Copolymer
i n M ixture
46-1S 0.243 1.4667 * 0.00012 * 0.00039 0 .1 6 3 -0 .2 2 7 (0 .1 9 5 a v e .)
46- 2S 0.515 1.4722 ± 0.00009 * 0.00033 0 .4 3 0 -0 .4 7 4 (0 .4 5 2 a v e .)
46-3S 0.736 1.4800 * 0.00006 * 0.00020 0 .7 3 1 -0 .7 5 9 (0 .7 4 5 a v e .)
U sing th e average v a lu e s f o r th e mol f r a c ti o n o f m ethyl m e th a c ry la te in th e
copolymer:
S olving: IS and 2S IS and 3S 2S and 3S Average
r-L 0.S27* 1.27* 1 . 61* 1.27* * 0 .2 6
r2 1.36* 1.54* 2.42* 1.77* ± 0 .4 3

U sing th e h ig h e s t v a lu e s f o r th e mol f r a c t i o n o f m ethyl m e th a cry late i n th e
copolymer f o r IS and 2S and th e lo w est v alu e f 6 r 3S:
v1 0.730 1 . 01* 1 . 17* 0 . 97* * 0.16

r2 1.03 1.13* 1.50* 1.25* ± 0 .2 2
U sing th e v a lu e s = 0 .7 4 (p re v io u s ly re p o rte d ) and ej, - 0 .4 (p re v io u s ly
r e p o r te d ) :
06 0 .5 9 -
®6 “° ‘1 “
U sing th e v a lu e s Qa = 0.705 (50°C .) and e a - 0 .1 1 (5QQC.):
•04 0.726 -
e^ 0 .6 4 - - -
U sing th e v a lu e s ■ 0.705 ( 50°C.) and e^ = 0 .1 8 ( t o t a l a v e ra g e ):
04 0.716 -
e, 0 .7 1 -
- 75 -
0. The M ethyl M eth a c ry la te -B u ty l M eth a c ry la te System
2. D eterm in atio n s a t 70°C.
Sample Mol F r a c tio n R e f ra c tiv e Average P ro b ab le Mol F r a c tio n o f

No. o f M ethyl Index E r ro r E rro r M ethyl M eth acry late
i n M ixture
4 6 -IR 0.258 1.4680 ± 0 .0 0 0 0 4 ± 0.00015 0 .2 4 4 -0 .2 8 0 (0 .2 6 2 a v e .)
46-2R 0.503 1.4730 ± 0.00004 * o .00017 0 .469- 0 .4 9 8(0.484 a v e . ;
46-3R 0.726 1.4801 ± 0 .0 0 0 0 3 ± 0.00010 0.737-Q.761 (0.749 a v e .)
Using th e average v a lu e s f o r th e mol f r a c t i o n o f m ethyl m e th a c ry la te in th e
copolymer;
S o lv in g ; IR and 2R IR and 3R 2R and 3R Average
*1 0 .936 1.19* 1.34* 1 . 16* ± 0 .1 4
r2 0.951 1.04* 1.40* 1.13* ± 0 .1 8
Using th e v a lu e s Q, - 0 .7 4 (p re v io u s ly re p o rte d ) and e/ - 0 .4 (p re v io u s ly
r e p o r te d ) ;
«6 0 .7 1 -
06 0 .1 -
U sing th e v a lu e s Qa = 0.6S9 (70°C .) and eA - 0 .2 5 rvnOg.'W
«4 0.789 — —
% 0 .5 9 -
U sing th e v a lu e s QA = 0.689 (70°C .) and eA s 0 .1 8 ( t o t a l a v e ra g e ):

.a.
«4 0.771
0 .5 2 -
e4
U sing th e v a lu e s QA • 0.689 (70°C .) and e6 ■ 0 .1 1 (5 0 o c .);
04 0.753 -
e4 0.4 5 ~
- 76 -
0. The Methyl H ethacrylate-B utyl M ethacrylate System
Table 30»(Continued)
2 . D eterm inations a t 70°C .(C ontinued)
U sing th e a v erag e v alu e f o r th e mol f r a c t io n o f m ethyl m e th a c ry la te in th e
copolymer f o r IR . th e h ig h e st v a lu e f o r Z i and th e low est v a lu e f o r 3R:
S o lv in g : IE and 2R IR and 3R 2R and 3R Average
T± 0 .9 0 2 1.08* 1 . 16* i 1.05#* 0.10
r2 0.941 1.00* 1.21* 1.05** 0.11
U sing th e v a lu e s (fy » 0 .7 4 (p re v io u s ly re p o rte d ) and e;|= 0 .4 (p rev io u sly -
re p o rte d ) :
Q6 0 .7 0 -
e^ 0 .0 - -
Using th e v a lu e s = 0.689 (70°C .) and e^ - 0 .2 5 (7 0 °C .)t
Q4 0.812 -
e^ 0 .6 6 - - -
U sing th e v a lu e s - 0.687 (70°C .) and e^ ■ 0 .1 8 ( t o t a l a v e ra g e ):
Q4 0.789
e4 0.5 9
Using th e v a lu e s Qa a 0.689 (70°C .) and e^ = 0 .1 1 (5 0 °C .):
% 0.766 -
0 .5 2 -
*T his d enotes th e c a se s where r-j_r2 exceeds 1 .0 0 , a t h e o r e t i c a l im p o s s ib ility
NOTE: From th e above i t i s ev id en t th a t sam ples 46-3S and 46-3R a re

in a c c u ra te s in c e th e p a ir s "IS and 2S" and "IR and 2R" g iv e th e
b e s t agreem ent.
~ 77 -
P. The E thyl M ethacr.vlate-Butyl M ethacrylate System
T able 31.
Sample Hoi F r a c tio n R e fra c tiv e Average P ro b ab le Hoi F r a c tio n o f

No. o f E th y l Index E rro r E rro r E th y l M eth a c ry la te
in M ixture
56-2SX 0.479 1.4666 * 0 .0 0 0 1 1 * 0.00038 0 .414- 0 . 540(0.477 a v e .)
56-2SC 0.506 1.4661 ± 0 .0 0 0 0 5 * 0 .0 0 0 1 6 0 .3 7 4 -0 .4 5 8 (0 .4 1 6 a v e .)
5 6-30 0.745 1.4691 * 0 .0 0 0 1 2 * 0 .0 0 0 5 0 0 .6 8 2 -0 .8 1 4 (0 .7 4 8 a v e .)
Using th e av erag e v a lu e s f o r th e mol f r a c tio n o f e th y l m e th a c ry la te in th e
copolymer f o r 2SC and 3S and th e low est v a lu e f o r 2SX:
S olving: 2SX and 2SC 2SX and 3S 2SC and 3S Average
r-L -0 .1 1 4 (a ) 1.39* 1.63* 0.99** 0.40
r2 0.25 2.03* 2 .9 6* 1 .75** 1 .0 0
U sing th e low est v a lu e s f o r th e mol f r a c t i o n o f e th y l m e th a cry late f o r 2SX
and 3S and an a r b i t r a r y v alu e w ith in li m i t s f o r 2SC (0 .4 0 3 ):
S o lv in g : 2SX and 2SC 2SX and 35 2SC and 3S Average( o f 2SX and 3S and
2SC and 3S)
rx -0 .3 1 9 * 0.697 0.441 0 .5 6 9 * 0.128

r2 -0.0065* 1 .2 2 1.82 1 .5 2 * 0.30
Using th e v a lu e s Qr- - 0.508 (5 0 ^0 .) and e,. - 0 .5 0 ( 5 0 °C .):
S olving: 2SX and 2SC 2SX and 3S 2SC and 3S Average
Q6 - 0.597 0 .9 1 1 0 .7 5 4 * 0.157
e6 - 0 .1 0 0 .03 0 .0 7 * 0 .0 4
-70(
- 7° -
P. The E th y l M ethacr.ylate-But.yl M ethacrylate System
Table 31«(Continued)
1 . D eterm inations a t 50°C .(C ontinued)
U sing th e v a lu e Qa = 0.705 (50°C .) and e^ - 0 .1 8 ( t o t a l a v e ra g e );
Solving? 2SX and 2SC 23X and 3S 2SC and 3S Average
Q5 - 0.621 0 .4 2 2 0 .5 2 2 * 0.100
e5 - 0 .5 8 0 .6 5 0 .6 2 ± 0 .0 4
(a ) T h is r e s u l t i s o b v io u sly in a c c u ra te .
2. D eterm inations a t 70°C.

No. o f E th y l Index E rro r E rro r E th y l M eth acry late
M ethacrylate i n Copolymer
i n M ixture
5 6 -m 0.265 1.4652 * 0.00006 ± 0.00016 0 .2 4 8 -0 .3 3 3 (0 .2 9 1 a v e .)
56-2R 0.489 1.4670 * 0 .0 0 0 0 2 ± 0.00005 0 .5 0 4 -0 .5 4 9 (0 .5 2 7 a v e .)
56-3R 0.702 1.4688 * 0.00006 * 0.00020 0 .6 8 2 -0 .7 5 2 (0 .7 1 7 a v e .)
U sing th e average v a lu e s f o r th e mol f r a c t i o n o f e th y l raettiacrv late i n th e
copolymer?
Solving? IE and 21 IE and 3R 2R and 3R Average
^ 1.22* 1.04 0.970 1 .0 8 * 0 .1 0
r2 0.908* 0.845 0.697 0.817 * 0 .0 8 0
Using th e lo w est v a lu e s f o r th e mol f r a c t i o n o f e th y l m e th a c rv la te i n th e
copolymer?
rx 1.47* 0.908 0.7 4 1 1.04*± 0 .2 9
r2 1.31* 1.09 0 .6 5 1 1 .02*4 0 .3 7
- 79 -
P. The E th y l M ethacrylate-B ut y l M ethacrylate System
Table 3 1 . (C ontinued)
2. D eteim in atio n s a t 70°C. (C ontinued)
Using th e v a lu e s a 0.490 (70°C .) and eg » 0 .5 6 (7 0 °C .):
S o lv in g : IR and 2R IR and 3R . 2R and 3R Average
Q6 - 0.425 O .46S 0 .4 4 7 * 0 .2 2
e6 - 0 .4 6 -0 .2 9 0 .0 9 * 0 .30
U sing th e v a lu e s Qa » 0.689 (70°C .) and e/, = 0 .25 (7 0 °C .):
Q5 - 0.649 1 .3 2 0 .9 9 * 0 .3 4
e5 - 0.35 1 .1 0 0 .7 3 * 0.38
#T his denotes th e c a s e s where exceeds 1 .0 0 , a t h e o r e t i c a l im p o s s ib ility
NOTE: From th e above i t i s e v id en t t h a t sam ples 56-1R and 56-2R a re

in a c c u ra te . Also samples 56-2SX and 56-2SC a re in a c c u ra te .
— £>0 —
Q. Summary o f and r ^ V alues
T able 3 2 .
System Average V alues Probable Best Values

'1 . S tyrene-M ethyl A c ry la te
50°C. r1 = 0.719 ± 0 .0 3 2 ib = 0.75

r2 = 0.109 ± 0 .0 2 2 rt = 0.14
70°C. 11= 0.967 ± 0.019 rj = 0 .9 4
r2 = 0 .2 2 ± 0 .0 1 r2 = 0.21
2. S ty re n e -E th y l A c ry la te
50°C. rx = 0.797 ± 0 .0 0 4 rL = 0.79

r2 = 0.19 ± 0.003 r2 = 0.19
70 C. r1= 1.00 ± 0 . 1 3 ri = 0.80
r2 = 0.259 ± 0 .0 5 9 r2 = 0.20
3 . S tyrene-M ethyl M eth a c ry la te
50OC. r 1=: 0.825 ± 0 .0 8 6 These r e s u l t s a re

r2= 0.180 ± 0 .0 6 7 in a c c u ra te and hence
70°C. r ,= 1 .5 ± 0 . 0 3 a re n o t u sed .
rj= 0 .3 1 * 0 .0 1
4 . S ty re n e -E th y l M eth a c ry la te
50°C. 11= 0.697 ± 0.018 ri = 0 .6 7

r2 = 0.266 ± 0.012 r2 = 0 .2 6
70°C. r1= 0.698 ± 0.105 ri = 0.65
r2 = 0.238 ± 0.085 r2 = 0.29
5 . S ty re n e -B u ty l M e th a c ry la te
50°C. r1= 0.687 ± 0.008 ri = 0.68

r2= 0.641 ± 0.008 = O.63
70°C. r^ = 0.626 ± 0.009 r^ = O.64
r2= 0.527 ± 0.009 1*2 = 0 .5 4
6 . M ethyl A c ry la te -E th y l A c ry la te
500C. rx = 0.880 ± 0.056 il = 0 .9 4

r2 = 0.970 ± 0.060 r2 = 1.06
70°C. r-i = 1.08* ± 0 .2 7 r, = 0 .9 4
r2= 0.98* ± 0.26 r2 = 1.06
7 . M ethyl A crylate-M et h y l M eth acry late
50°C. r!= 0.380 ± 0 .0 1 2 i l = 0 .3 8

r2 = 2.26 ± 0 .0 2 r2 = 2.27
70OC. ri _ 0.4 7 3 * * 0.083 i l = 0 .3 5
r2 = 2.43* * 0 .1 9 1*2 = 2.23
81 -
Q. Summary of r^ and Values (Continued)

System. Average V alues Probable Best Values
S. M ethyl A c ry la te -E th y l M ethacry late
50°C. r, = 0.3 3 4 ± 0.168 r l = 0 .6 4

r2= 1.03 * 0 .3 6 r 2 = 1.38
70°C. 11= 0.57* * 0 .0 8 *1 = 0 .4 8
r2= 2.06* ± 0 .1 4 r 2 = 1.85
9 . E th y l A crylate-M ethyl M ethacry late
50°C. rs = 0.406 ± 0.021 r-, = 0 .4 2

r2 = 2.15 ± 0 .0 6 T2 = 2.21
r. = 0.41 ± 0 .0 1 r-, = 0 .4 2
1*2 = 2.17 ± 0 .0 2 r 2 = 2.19
10. E th y l A c ry la te -E th y l M ethacry late
50°0. r1 = 0.478 ± 0 .1 9 8 r^ = 0 .4 8 (a v e rag e )

r2= 1.82 ± 0 .5 2 r 2 = 1.82
70°C. rn = 0.472 ± 0.100 r-, = 0 .4 7 ( average)
r2= 1 .9 1 ± 0.05 4 = 1.9 1
11. E th y l A crylate-B u.tyl M eth acry late
50°C. rj_= 0.506 ± 0.047 = O.46

r2 = 1.67 ± 0 .1 8 1*2 = 1.85
70°C. r^ = 0.45 ± 0 .0 2 1*1 = 0 .4 4
r2 = 1.87 * 0 .0 4
r2 = ^
12. M ethyl M e th a c ry la te-E th y l M eth acry late
50°C. ft* 1.96* ± 0 .4 9 xs = 1.47

r2 = 0.91*± 0 .2 7 r„ - 0 .6 4
70°C. r7= 1.67* * 0 .1 4 4 = 1.52
r2 = 0.779* * 0.089 4 = 0.65
13. M ethyl M ethacrylat e-B ut y l M eth acry late
50°C. 1^ = 0.97* ± 0 .1 6 15, = 0 .96

r 2 = 1.25* * 0 .2 2 r2 = 1.03
(a v e rag e s low ered w ith in
l i m i t s to agree)
70°C. rx = 1 . 16* ± 0 .1 4 i l = 0.93
r 2 = 1.13* * 0 .1 8 r2 = 0.95
- 22 -
Q. Summary o f r^ and rp Values (Continued)
System Average V alues Probable Best Values
14. E th y l Met ha c r y l a t e-B ut y l M ethacrylate
50°C. is = 0.569 * 0.128

r 2 = 1 .52 ± 0 .3 0 5 =
70°C. r]_= 1.04-5* 0.29 r = 0 .75
(lo w er l im it o f average)
r 2 = 1.025* 0 .3 7 r? = 1 .3 9
(upper l i m i t o f average)
*-This denotes th e cases where r i r 2 exceeds 1 .0 0 . a t h e o r e t i c a l im p o s s ib ility .
- 83 -
VI. CONCLUSION
In c o n c lu sio n , from th e r ^ and and "Q" and "e" v a lu e s , i t i s
e v id e n t t h a t th e p resen ce o f a s u b s titu e n t i n th e a c r y la te s t r u c tu r e
h a s a v e ry d e f i n i t e e f f e c t on th e b eh av io r o f th e substance i n copoly
m e riz a tio n .
The e f f e c t o f th e n a tu re o f th e s u b s tit u e n t, however, i s q u ite
s m a ll. From th e s e m easurem ents, i t seems e v id en t t h a t t h i s e f f e c t i s
m easurable a lth o u g h in some c a se s th e d iffe re n c e may be w ith in th e
l i m i t s o f e r r o r o f th e m easurem ents.
M ethyl a c r y la te and e th y l a c r y la te seem to be o f th e same g e n e ra l
o rd e r o f r e a c t i v i t y a lth o u g h e th y l a c r y la te i s s l i g h t l y more r e a c ti v e .
The "e* v a lu e s o f th e two monomers a r e q u ite s im ila r alth o u g h t h a t o f
m ethyl a c r y la te i s s l i g h t l y h ig h e r in d ic a tin g a double bond o f g r e a te r
p o la rity .
Of th e m e th a c ry la te s , m ethyl m e th a c ry la te i s th e most r e a c tiv e ,
follow ed by b u ty l m e th a c ry la te and e th y l m e th a c ry la te in t h a t o rd e r.
The "e" v a lu e s , in o rd e r in d ic a tin g d e crea sin g p o la r ity o f th e double
bond, a re th o s e o f e th y l m e th a c ry la te , m ethyl m e th a cry late and b u ty l
m e th a c ry la te . No e x p la n a tio n o f th e above b e h av io r i s advanced.
- 84 -
V II. BIBLIOGRAPHY
1. A bere, J . , G o ld fin g e r, G ., Mark, H ., and N aidus, H ., Arm. N. Y. Acad. S c i . ,
Mb 267 (1943)
2. A lfr e y , T ., and G o ld fin g e r, G ., J . Chem. P h y s ., 12 , 205 (1944)
3. Mayo, F . , and Lew is, F . M ., J . Am. Chem. S o c ., 66 , 1594 (1944)
4» W all, F . T ., J . Am. Chem. S o c ., 66 , 2050 (1944)
5. A lfr e y , T ., and P r ic e , C. C ., J . PoLy. S c i . , 2 , 101 (1947)
6». P r ic e , C. C ., J . P o ly . S c i . , % , 772 (1943)
7. A lfr e y , T ., G o ld fin g e r, G ., and Mark, H ., J o u r. A ppl. P h y s ., 2J±. , 700 (1943)
8. D a n ie ls , F . , Mathews, J . H ., and W illiam s, J . W., e t c . , "E xperim ental
P h y s ic a l C hem istry" McGraw-Hill Boole Company, I n c . , New York, 4 th Ed. (1949)
9. Mayo, F . and Lew is, F . M ., J . Am. Chem. S o c ., 66 , 1594 (1944)
Lew is, F . M.,Mayo, F . , and H ulse, W. F . , J . Am. Chem. S o o ., 6£, 1701 (1945)

The Kinetics of Copolymerization of Various Acrylate Systems

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The Kinetics of Copolymerization of Various Acrylate Systems

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VARIOUS ACRYLATE SYSTEMS

John W illiam V anderhoff

A d is s e r ta tio n subm itted to th e F a c u lty o f th e Graduate

School o f A rts and Sciences o f th e U n iv e rsity

requirem ents f o r th e degree o f

The a u th o r w ishes to express h is g ra titu d e to

Dr. George G o ldfinger whose i n t e r e s t , encouragement and

a s s is ta n c e made t h i s in v e s tig a tio n p o s s ib le .

The a u th o r a lso w ishes to express h is a p p re c ia ­

tio n to th e Rohm & Haas Company who su p p lied th e monomers

II. In tro d u c tio n

B. Statem ent of th e Problem— —----------------------------------- — - 4

III. E xperim ental Procedure

B. C a lib ra tio n o f Method------------ :---------------------------------------- 7

C. E xperim ental D eterm inatio n s-— ------ 9

IV. C a lib ra tio n Data

A. TheStyrene-M ethyl A c ry la te System —------------------ 11

B. TheS ty ren e-E th y l A cry late System------------------------- 23

C. The Styrene-M ethyl M ethacrylate System ------------- 15

D. The S ty ren e-E th y l M ethacry late System -------------------- — 17

E. The S tyrene-B utyl M ethacrylate System------------------ - 19

F. The M ethyl A c ry la te -E th y l A cry late System-------------- 21

G. The Methyl A crylate-M ethyl M ethacrylate System------ 23

H. The M ethyl A c ry la te -E th y l M ethacrylate System------- 25

I. The M ethyl A c ry la te-B u ty l M ethacrylate System------- 27

J. The E th y l A crylate-M ethyl M ethacrylate System— —-----29

K. The E th y l A c ry la te -E th y l M ethacrylate System - 31

L. The E th y l A c ry la te-B u ty l M ethacrylate System-— --- 33

M. The Methyl M eth acry late-E th y l M ethacrylate System- 35

N. TheMethyl M ethacrylate-B u ty l M ethacrylate System——— 37

0. The E th y l M ethacrylate-B u ty l M ethacrylate System— — - 39

P. V a lid ity of th e Method o f C a lib ra tio n —— -------------------- 41

V. E xperim ental Data

A. D iscussion ----------------------------- —-------------------------------- 43

B. The Styrene-M ethyl A cry late System- --------- 44

C. The S ty ren e-E th y l A c ry la te System------------- ----- ,— . 45

D. The Styrene-M ethyl M ethacrylate System----------------------— 47

E. The S ty ren e-E th y l M ethacrylate System ----------------- 49

F. The S tyrene-B utyl M ethacry late System---— — —— — — 50

G. Summary o f Q and e V alues— --------------- — -------------------- 51

H. The Methyl A c ry la te -E th y l A cry late System-------------------- 53

I. The Methyl A crylate-M ethyl M ethacrylate System --- 56

J. The Methyl A c ry la te -E th y l M ethacrylate System --------------------59

K. The E th y l A crylate-M ethyl M ethacrylate System——-------------- 62

L. The E th y l A c ry la te -E th y l M ethacrylate System-------------- — 65

M. The E th y l A c ry la te -B u ty l M ethacrylate System--------------- 68

N. The Methyl M eth acry late-E th y l M ethacrylate System 71

0. The Methyl M eth acry late-B u ty l M etriacrylate System—— 74

P. The E th y l M eth acry late-B u ty l M ethacrylate System----------------77

Q. Summary o f r-j_ and r 2 V alues—--------------------------------------- 80

V I. Conclusion— ———----------— —--------------------------------— — 83

V II. B ibliography— — -------------------- — --------------- 84

This in v e s tig a tio n *ra.s undertaken to add th e p re v io u s ly u n rep o rted

v a lu e s f o r th e r a t i o s of th e r a te c o n sta n ts f o r v a rio u s two-component

a c r y la te and m e th a cry late copolym erization systems t o th e c o n sid e ra b le

amount o f d a ta a lre a d y re p o rte d f o r o th e r systems and to determ ine i f

S ix monomers were chosen f o r t h i s stu d y : s ty re n e , m ethyl a c r y la te ,

e th y l a c r y la te , m ethyl m e th a c ry la te , e th y l m e th a cry late , and b u ty l

m e th a c ry la te . A ll but one o f th e f i f t e e n p o s sib le system s were m easurable

From t h i s in v e s tig a tio n i t was determ ined t h a t th e presence o f a

s u b s titu e n t lias a v e ry d e f in ite e f f e c t on th e r a ti o s o f th e r a te c o n sta n ts

and t h a t th e n a tu re o f th e s u b s titu e n t has a sm all but m easurable e f f e c t

t r a t i o n s o f th e monomers in th e i n i t i a l polymer form , m^ and mg, and th e

The a u th o r a lso w ishes to express h is a p p re c ia

+ Mx 11 > M-j

M]* + m2 12 , Mg

e th y l a c r y la te , m ethyl m e th a c ry la te , e th y l m e th a c ry la te , and b u ty l m ethacry

sample to polym erize t o a conversion o f about 5$ , th e n stopping th e re a c

occu rs. Above th e "ap p aren t second-order t r a n s i t i o n p o in t" , th e re fra c

p a r tic u la r polymer sample. Therefore i t was n e ce ssa ry to ta k e th e r e fra c