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Makromol. Chem., Macromol. Symp.

7, 67-74 (1987)
FORMATION AND PROPERTIES OF THERMOSETTING AND HIGH Tg
POLYMERIC MATERIALS

John K. G i l l h a m
Polymer M a t e r i a l s Program, Department o f Chemical Engineering,
P r i n c e t o n U n i v e r s i t y , Princeton, New Jersey 08544, USA

A b s t r a c t - I n t e r r e l a t i o n s h i p s between r e a c t i o n c o n d i t i o n s
and m a t e r i a l p r o p e r t i e s o f t h e r m o s e t t i n g and h i g h Tg
polymers a r e discussed from t h e p o i n t o f view o f a
g e n e r a l i z e d time-temperature-transformation (TTT) diagram.

INTRODUCTION
T h i s a r t i c l e p e r t a i n s p r i n c i p a l l y t o t h e f o r m a t i o n and p r o p e r t i e s o f h i g h
Tg polymeric glasses which are made by t h e t r a n s f o r m a t i o n o f l i q u i d t o
The area i s o f p a r t i c u l a r imporamorphous s o l i d by chemical r e a c t i o n .
tance i n t h e making o f composites, coatings, and adhesives by thermos e t t i n g "cure" r e a c t i o n s i n which m u l t i f u n c t i o n a l molecules o f low
molecular weight a r e converted i n t o network macromolecules.
An attempt
has been made t o produce a g e n e r a l i z e d model f o r t h e f o r m a t i o n and propert i e s o f thermosetting systems which a l s o i n c o r p o r a t e s l i n e a r systems:
an
example o f t h e former i s t h e c u r e o f a neat epoxy r e s i n ; an example o f t h e
l a t t e r i s t h e p o l y m e r i z a t i o n o f neat s t y r e n e monomer below t h e g l a s s t r a n s i t i o n o f polystyrene.
T h i s a r t i c l e w i l l t h e r e f o r e emphasize t h e r mosetting systems w i t h some r e f e r e n c e t o l i n e a r systems.
The s i m p l e s t
model f o r chemical s e t t i n g assumes a s i n g l e r e a c t i o n mechanism and no
phase separation.

THE

TIME-TEMPERATURE-TRANSFORMATION

(TTT) ISOTHERMAL CURE DIAGRAM

A time-temperature-transformation (TTT) isothermal c u r e diagram ( F i g . 1 )


may be used t o p r o v i d e an i n t e l l e c t u a l framework f o r understanding and comp a r i n g t h e cure and p h y s i c a l p r o p e r t i e s o f thermosetting systems ( 1 , Z ) .
The main f e a t u r e s o f such a diagram can be obtained by measuring t h e times
t o events t h a t occur d u r i n g isothermal cure a t d i f f e r e n t temperatures,
These events i n c l u d e t h e onset o f phase separation, g e l a t i o n ,
TCure.
v i t r i f i c a t i o n , f u l l cure, and d e v i t r i f i c a t i o n .
Phase s e p a r a t i o n may occur,
f o r example, by p r e c i p i t a t i o n o f rubber from s o l u t i o n i n rubber-modified
formulations, o r by t h e f o r m a t i o n o f monomer-insoluble o l i g o m e r i c species,
by t h e f o r m a t i o n o f g e l p a r t i c l e s , and by c r y s t a l l i z a t i o n i n c r y s t a l l i z a b l e
systems.
G e l a t i o n corresponds t o t h e i n c i p i e n t f o r m a t i o n o f an i n f i n i t e
molecular network, which g i v e s r i s e t o l o n g range e l a s t i c behavior i n t h e
macroscopic f l u i d .
I t occurs a t a d e f i n i t e conversion f o r a g i v e n system
according t o F l o r y ' s theory o f g e l a t i o n ( 3 ) . A f t e r g e l a t i o n t h e m a t e r i a l
c o n s i s t s o f normally m i s c i b l e s o l ( f i n i t e molecular weight) and g e l
( i n f i n i t e molecular w e i g h t ) f r a c t i o n s , t h e r a t i o o f t h e former t o t h e
l a t t e r decreasing w i t h conversion. V i t r i f i c a t i o n occurs when t h e glasst r a n s i t i o n temperature, Tg, r i s e s t o t h e isothermal temperature o f cure.
The m a t e r i a l i s l i q u i d o r rubbery when Tcure > Tg; i t i s g l a s s y when Tcure

< Tg. D e v i t r i f i c a t i o n occurs when t h e g l a s s - t r a n s i t i o n temperature


decreases through the isothermal temperature, as i n degradation.
The
diagram d i s p l a y s t h e d i s t i n c t s t a t e s encountered on cure due t o chemical

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reactions. These states include liquid, sol/gel rubber, gel rubber
(elastomer), ungelled (sol) glass, gelled glass, and char. The gelled
glass region in the TTT cure diagram is divided into two parts by the fullcure line; in the absence of degradation (Fig. 1 , devitrification and
char), the top and lower parts can be designated fully cured gel glass and
undercured sol/gel glass regions, respectively. The technological terms,
A - , B- and C-stage resins correspond to sol glass, sol/gel glass, and fully
cured gel glass, respectively. The illustration also displays the critical
temperatures Tgm, elTg, and Tgo, which are the glass-transition temperature of the fuyly cured system, the temperature at which gelation and
vitrification occur simultaneously, and the glass-transition temperature of
the reactants, respectively.

LOG TIME

Fig.

1.

Time-temperature-transformation (TTT) isothermal cure diagram for


a thermosetting system, showing three critical temperatures, ie,
Tgm, gelTg, Tgo, and the distinct states o f matter, ie, liquid,
sol/gel rubber, gel rubber (elastomer), gelled glass, ungelled (or
sol) glass, and char. The full-cure line, ie, Tg = Tgm, divides
the gelled glass region into two parts: sol/gel glass and fully
cured gel glass. Phase separation occurs prior to gelation.
Successive isoviscous contours shown in the liquid region differ
by a factor of ten. The vitrification process below gelTg has
been constructed to be an isoviscous one. The transition region
approximates the half width of the glass transition.

Much of the behavior of thermosetting materials can be understood in terms


of the TTT cure diagram through the influence of gelation, vitrification,
and devitrification upon properties. Gelation retards macroscopic flow, and
growth of a dispersed phase (eg, as in rubber-modified systems).
Vitrification retards chemical conversion. Devitrification, due to thermal
degradation, marks the lifetime for the material to support a substantial
load.

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The isothermal TTT cure diagram i s more l i m i t e d f o r t h e c u r i n g o f l i n e a r
rubber systems than f o r t h e r m o s e t t i n g systems because i n p r a c t i c e o n l y t h e
Gelation i n the vulcanization
r e g i o n above Tgm i s r e l e v a n t f o r t h e former.
o f rubbers occurs a t low conversions i n comparison w i t h t y p i c a l thermos e t t i n g systems.
The u n g e l l e d g l a s s y s t a t e i s t h e b a s i s o f commercial molding m a t e r i a l s
since, upon h e a t i n g , t h e u n g e l l e d ( s o l ) m a t e r i a l f l o w s b e f o r e g e l l i n g
through f u r t h e r r e a c t i o n .
Formulations can be processed as s o l i d s (eg,
> ambient temperature; they can be processed
molding compositions) when T
as l i q u i d s (eg, as c a s t i n g f j u i d s ) when Tgo < ambient temperature.
The g l a s s - t r a n s i t i o n temperature o f t h e m a t e r i a l a t t h e composition
corresponding t o g e l a t i o n i s gelTg, s i n c e g e l a t i o n occurs as t h e m a t e r i a l
v i t r i f i e s when t h e temperature o f cure i s gelTg ( 4 ) . The g e l a t i o n curve
( F i g . 1 ) t h e r e f o r e corresponds t o Tg = gelTg.
Temperature gelTg i s c r i t i c a l i n d e t e r m i n i n g t h e upper temperature f o r s t o r i n g r e a c t i v e m a t e r i a l s
However, c u r e below g e l T g
t o a v o i d g e l a t i o n (which r e l a t e s t o "pot l i f e " ) .
e v e n t u a l l y leads t o g e l a t i o n .
The morphology developed i n two-phase systems, f o r example, those i n which
r u b b e r - r i c h domains n u c l e a t e and grow as a dispersed phase, depends on
t h e temperature o f cure.
The r e a c t i o n temperature determines t h e comp e t i t i o n between thermodynamic and k i n e t i c ( i e , t r a n s p o r t ) f a c t o r s which
a f f e c t s t h e amount, t h e composition, and t h e d i s t r i b u t i o n o f dimensions o f
t h e dispersed phase. As an example, r e a c t i o n a t i n t e r m e d i a t e temperatures
can r e s u l t i n a maximum i n t h e amount o f p r e c i p i t a t e d phase which may g i v e
r i s e t o a minimum i n t h e t i m e t o t h e onset o f phase s e p a r a t i o n (as shown
i n F i g . 1 ) . For optimum mechanical p r o p e r t i e s , a two-phase system i s
cured f i r s t a t one temperature t o p r o v i d e a p a r t i c u l a r morphology, and
subsequently a t a h i g h e r temperature t o complete t h e r e a c t i o n s o f t h e
m a t r i x ( 5 , 6 ) . The Tga, o f t h e m a t r i x w i l l be determined by t h e e x t e n t o f
phase separation.
I n composite systems, shrinkage stresses due t o volume c o n t r a c t i o n o f t h e
r e s i n on i s o t h e r m a l cure b e g i n t o develop w i t h adhesion o f t h e c u r i n g
r e s i n t o a r i g i d inclusion.
T h i s occurs a f t e r g e l a t i o n above gelTg and
b e f o r e v i t r i f i c a t i o n below g e l T
The t e n s i l e s t r e s s e s i n t h e r e s i n and
t h e corresponding compressive s?resses on an i n c l u s i o n a f f e c t composite
behavior,
One consequence i s f i b e r - b u c k l i n g i n r e s i n / f i b e r composites.
A
r e l a t e d consequence o f the shrinkage due t o cure and t h e d i f f e r e n t coeff i c i e n t s o f expansion and c o n t r a c t i o n o f t h e c o n s t i t u e n t s i n b r i t t l e
r e s i n / f i b e r composites i s t h e f o r m a t i o n o f s p i r a l and h e l i c a l cracks i n
Their l a r g e surface
t h e r e s i n around i s o l a t e d f i l a m e n t s and yarns ( 7 , 8 ) .
areas per u n i t volume o f m a t r i x may c o n t r i b u t e t o t h e toughening o f
f i b e r / r e s i n composites.

Prolonged i s o t h e r m a l c u r e a t temperature Tcure

below Tgm would l e a d t o Tg

= TCure i f t h e r e a c t i o n s were quenched by t h e process o f v i t r i f i c a t i o n .


I n p r a c t i c e , Tg i s h i g h e r than TCure because i t can i n c r e a s e d u r i n g t h e
h e a t i n g scan employed f o r measurement. Although v i t r i f i c a t i o n has been
Tg, as u s u a l l y measured, does n o t
d e f i n e d t o occur when Tg = Tcure,
correspond t o t h e g l a s s y s t a t e , b u t r a t h e r t o a s t a t e approximately h a l f way between t h e rubbery and glassy s t a t e s ; t h e r e f o r e r e a c t i o n s a t Tcure
continue beyond t h e assigned t i m e t o v i t r i f i c a t i o n . which a l s o r e s u l t s i n
T > Tcure.
Furthermore, t h e e x t e n t s t o which r e a c t i o n s proceed i n t h e
gyassy s t a t e depend on t h e i n f l u e n c e o f t h e glassy s t a t e on t h e r e a c t i o n
mechanism. However, even t h e i n t r a m o l e c u l a r r e a c t i o n s i n v o l v e d i n t h e
i m i d i z a t i o n o f polyamic a c i d s t o polyimides a r e r e s t r i c t e d by t h e v i t r i f i c a t i o n process, l e a d i n g again t o Tg being c o n t r o l l e d by t h e temperature

and t h e time o f cure.


I n p r a c t i c e , f o r epoxies and polyimides, Tg i s
g r e a t e r than Tcure
by about 3O-5O0C a f t e r "normal" isothermal cure below
(9,10,11,12).
T h i s corresponds approximately t o the h a l f - w i d t h o f the
;%ss
t r a n s i t i o n temperature r e g i o n s i n c e Tg (as measured) increases
through the i s o t h e r m a l temperature TCure t o about TCure + 30 t o 5OoC a f t e r
which t h e r e a c t i o n r a t e i s c o n t r o l l e d by t h e low p h y s i c a l r e l a x a t i o n r a t e s
o f t h e g l a s s y s t a t e . The h a l f - w i d t h o f t h e g l a s s t r a n s i t i o n r e g i o n which
i s indicated i n Figure 1 varies since the width o f the glass t r a n s i t i o n
depends on t h e v a l u e o f Tg.
C o r r e l a t i o n s between macroscopic behavior and molecular s t r u c t u r e o f the
r e a c t a n t s a r e most c l e a r l y d e f i n e d i n f u l l y cured m a t e r i a l s .
F u l l cure i s
and more s l o w l y by c u r i n g
a t t a i n e d most r e a d i l y by r e a c t i o n above T
The f u l l
below Tgm t o t h e f u l l - c u r e l i n e o f t h e TTqm&re diagram (10).
cure l i n e corresponds t o Tg = Tgm.
I n p r a c t i c e f u l l c u r e i s i n general n o t a unique s t a t e because t h e s t a t e
I n commonly used systems
depends upon t h e time-temperature r e a c t i o n path.
t h i s i s a consequence o f competing chemical r e a c t i o n s w i t h d i f f e r e n t a c t i v a t i o n energies.
Furthermore, m a t e r i a l p r o p e r t i e s a l s o depend on t h e
r e a c t i o n p a t h f o r p h y s i c a l reasons, such as t h e d e n s i t y o f t h e p o l y m e r i z i n g system depending on t h e temperature o f r e a c t i o n .
S i m i l a r l y , the
time-temperature p a t h o f c o o l i n g a f t e r cure a f f e c t s , f o r example, d e n s i t y
and behavior a t room temperature.
A t h i g h temperatures, non-curing chemical r e a c t i o n s r e s u l t i n degradation.
Thermal degradation can r e s u l t i n d e v i t r i f i c a t i o n as t h e g l a s s - t r a n s i t i o n
temperature decreases through t h e isothermal temperature due t o a reduct i o n i n c r o s s - l i n k i n g o r formation o f p l a s t i c i z i n g material.
Degradation
can a l s o r e s u l t i n v i t r i f i c a t i o n , eg, char f o r m a t i o n ( F i g . 1 ) . as t h e
g l a s s - t r a n s i t i o n temperature increases through t h e isothermal temperature
because o f an increase i n c r o s s - l i n k i n g o r v o l a t i l i z a t i o n o f low molecular
weight p l a s t i c i z i n g m a t e r i a l s (12).
I n h i g h T systems, c u r e and thermal
degradation r e a c t i o n s compete.
There i s a nee! t o o b t a i n h i g h temperature
polymers from low temperature processing.

The l i m i t i n g v i s c o s i t y i n t h e f l u i d s t a t e i s c o n t r o l l e d by g e l a t i o n above
gelTg, and by v i t r i f i c a t i o n below e l T g .
A t g e l a t i o n , t h e weight-average
molecular weight and zero shear-raqe v i s c o s i t y become i n f i n i t e , although
t h e number-average molecular weight i s very low. V i s c o s i t y i n t h e v i c i n i t y o f v i t r i f i c a t i o n below g e l T g , i ~ described by t h e
Williams-Landel-Ferry (WLF) equation ( 1 3 ) .
The t i m e t o reach a s p e c i f i e d v i s c o s i t y ( F i g . 1) i s o f t e n used as a pract i c a l method f o r measuring g e l a t i o n times. Although t h i s i s o v i s c o s i t y
approach i s i n c o n s i s t e n t w i t h the isoconversion t h e o r y o f g e l a t i o n , above
temperature gelTg, t h e apparent a c t i v a t i o n energies obtained from t h e temp e r a t u r e dependence o f the t i m e t o reach a s p e c i f i e d v i s c o s i t y approach
t h e t r u e a c t i v a t i o n energy f o r t h e chemical r e a c t i o n s l e a d i n g t o g e l a t i o n
w i t h increase o f t h e s p e c i f i e d v i s c o s i t y ( 1 ) .
The t i m e t o g e l a t i o n can be computed from t h e r e a c t i o n k i n e t i c s and the
conversion a t g e l a t i o n , which i s constant according t o F l o r y ' s t h e o r y o f
gelation.
The t i m e t o v i t r i f i c a t i o n can be computed from t h e r e a c t i o n
k i n e t i c s and t h e conversion a t v i t r i f i c a t i o n (14.15.16). which increases
w i t h Tcure.
Since v i t r i f i c a t i o n occurs when t h e g l a s s - t r a n s i t i o n temp e r a t u r e reaches t h e temperature o f cure, computation o f t h e time t o
v i t r i f y r e q u i r e s knowledge o f t h e r e l a t i o n s h i p between Tg and conversion.
F i g u r e 2 shows t h a t T increases w i t h conversion a t an i n c r e a s i n g r a t e .
I n t h e absence o f d i f q u s i o n c o n t r o l , t h e general k i n e t i c equation
describing the r e a c t i o n is:

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dX/dt = A - e x p [ - E A / (RTq f ( X )
where X i s t h e e x t e n t o f r e a c t i o n , EA t h e a c t i v a t i o n energy, and t h e o t h e r
c h a r a c t e r s have t h e i r usual s i g n i f i c a n c e .
The times t o g e l a t i o n and t o
v i t r i f i c a t i o n can be computed versus temperature u s i n g t h i s equation when
X e l ( f o r g e l a t i o n ) , a r e l a t i o n s h i p between X and T g . ( f o r v i t r i f i c a t i o n )
( 2 i g . 2 ) , and t h e r e a c t i o n k i n e t i c s a r e known. The i n f l u e n c e o f d i f f u s i o n
c o n t r o l on t h e r e a c t i o n r a t e can be deduced i n p r i n c i p l e from t h e d i f ferences between t h e e x p e r i m e n t a l l y measured and t h e computed g e l a t i o n and
v i t r i f i c a t i o n curves.

Xgel
I

I
I
I

F i g . 2.

CONVERSION ( X )

Tg vs conversion a t v i t r i f i c a t i o n f o r r e a c t a n t s d i f f e r i n g i n
f u n c t i o n a l i t y (101 > 011). The conversions a t g e l a t i o n a r e also
included.
The diagram can be used to demonstrate t h e e f f e c t of
i n c r e a s i n g f u n c t i o n a l i t y of t h e r e a c t a n t s on g e l a t i o n , v i t r i f i c a t i o n , and t h e temperatures gelTg. Tgo, and Tgm.

The S-shaped v i t r i f i c a t i o n curve obtained e x p e r i m e n t a l l y i n t h e absence o f


thermal degradation has been matched by computation f o r one epoxy system
from temperature Tgo t o temperature Tgm ( 1 5 ) .
The v i t r i f i c a t i o n curve i s g e n e r a l l y S-shaped ( 1 6 ) . A t temperatures immed i a t e l y above Tgo, t h e t i m e t o v i t r i f i c a t i o n passes through a maximum
because o f t h e opposing i n f l u e n c e s o f t h e temperature dependences o f t h e
v i s c o s i t y and t h e r e a c t i o n r a t e constant.
Immediately below Tgm, t h e time
t o v i t r i f i c a t i o n passes through a minimum ( 1 7 ) because o f t h e opposing
i n f l u e n c e s o f t h e temperature dependence o f t h e r e a c t i o n r a t e constant and
t h e decreasing c o n c e n t r a t i o n o f r e a c t i v e s i t e s a t v i t r i f i c a t i o n as Tgm i s

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approached.
Knowledge o f t h e minimum time and t h e corresponding temp e r a t u r e i s u s e f u l i n molding technology.
Cure of f i n i t e specimens a t temperatures below t h a t f o r the minimum t i m e
f o r v i t r i f i c a t i o n ( F i g . 1 ) w i l l lead t o t h e h o t t e r i n s i d e v i t r i f y i n g
b e f o r e t h e o u t s i d e when t h e r e a c t i o n i s exothermic. Conversely, cure a t
higher temperatures would l e a d i n p r i n c i p l e t o t h e o u t s i d e v i t r i f y i n g
before the inside:
i n t h i s case i n t e r n a l stresses develop as t h e i n s i d e
c o n t r a c t s r e l a t i v e t o t h e v i t r i f i e d o u t s i d e due t o t h e volume c o n t r a c t i o n
o f p o l y m e r i z a t i o n . S i m i l a r l y , c o o l i n g cured m a t e r i a l from above Tgm w i l l
lead t o t h e o u t s i d e v i t r i f y i n g b e f o r e t h e i n s i d e ; i n t e r n a l s t r e s s e s i n
t h i s case w i l l be minimized by c o o l i n g v e r y s l o w l y ( i . e . , annealing).
These stresses, which a r e due t o non-isothermal c o n d i t i o n s i n neat
systems, a r e supplemented i n composites by the d i f f e r e n t i a l shrinkage
stresses which were r e f e r r e d t o e a r l i e r i n t h e a r t i c l e .
The conversion a t v i t r i f i c a t i o n can be computed i n p r i n c i p l e by r e l a t i n g
t h e g l a s s - t r a n s i t i o n temperature t o c o n t r i b u t i o n s from t h e molecular
weight and t h e c r o s s - l i n k i n g d e n s i t y , b o t h o f which vary w i t h conversion
(16).
For p o l y m e r i z a t i o n p r i o r t o g e l a t i o n (and f o r l i n e a r
p o l y m e r i z a t i o n ) , t h e computation i s s i m p l i f i e d by t h e absence o f cross1i n k i n g .
The f r a c t i o n a l e x t e n t o f r e a c t i o n a t v i t r i f i c a t i o n and t h e t i m e t o
v i t r i f y , l i k e g e l a t i o n , decrease w i t h i n c r e a s i n g f u n c t i o n a l i t y o f t h e
The e f f e c t o f i n c r e a s i n g f u n c t i o n a l i t y on g e l a t i o n ,
reactants ( 1 2 ) .
can be understood
v i t r i f i c a t i o n , and t h e temperatures gelTg, Tgo, and T
by c o n s i d e r i n g t h e X-vs-T
and the X el
relationships?such
as those i n
For example, t f e f i g u r e S ~ O W Show temperature e l T g f o r t h e
F i g u r e 2.
m a t e r i a l o f lower f u n c t i o n a l i t y can be higher than t h a t
h i g h e r functionality.

03

I n c r e a s i n g r e a c t i o n t i m e a t any temperature leads t o i n c r e a s i n g converThe modulus and d e n s i t y a t t h e


s i o n , Tg, and c r o s s - l i n k i n g d e n s i t y .
c u r i n g temperature a l s o increase. However, upon c o o l i n g i n t e r m i t t e n t l y
from t h e c u r i n g temperature t o a temperature w e l l below Tg, eg, room temp e r a t u r e f o r h i g h Tg m a t e r i a l s , t h e modulus and d e n s i t y can decrease,
whereas e q u i l i b r i u m a b s o r p t i o n o f water can increase w i t h i n c r e a s i n g
e x t e n t o f cure. A common b a s i s f o r these i n t e r r e l a t e d phenomena i s t h e
i n c r e a s i n g f r e e volume a t room temperature w i t h i n c r e a s i n g e x t e n t o f cure
(18).

The concept o f t h e TTT cure diagram can be extended t o non-isothermal


c o n d i t i o n s f o r forming and annealing polymeric m a t e r i a l s . For example, a
continuous h e a t i n g time-temperature-transformation (CHT) diagram r e s u l t s
from h e a t i n g a r e a c t i v e system from (say) 25 t o 300OC a t a s e r i e s o f d i f f e r e n t r a t e s o f i n c r e a s i n g temperature.
The v i t r i f i c a t i o n curve w i l l be
j o i n e d t o a d e v i t r i f i c a t i o n curve t o form an envelope ( 1 9 ) . T h i s d e v i t r i f i c a t i o n i s a consequence o f t h e r i s i n g g l a s s t r a n s i t i o n temperature event u a l l y n o t i n c r e a s i n g a t t h e same r a t e as t h e r a t e o f r i s e o f temperature.
Such a diagram i s u s e f u l i n molding technology f o r d e f i n i n g timetemperature cure paths i n which v i t r i f i c a t i o n does n o t occur, f o r example,
so as t o o b t a i n f u l l cure. Conversely v i t r i f i c a t i o n can be an e s s e n t i a l
p a r t o f a cure c y c l e so as t o c o n t r o l r e a c t i o n r a t e s which c o u l d r u n o u t
o f c o n t r o l because of t h e exothermic n a t u r e o f a r e a c t i o n .
The polymeriz a t i o n o f 250 g a l l o n s o f epoxy t o encapsulate a magnetic c o i l i n Princeton
U n i v e r s i t y ' s experimental Tokomak nuclear f u s i o n r e a c t i o n i s accomplished
by h e a t i n g a t a v e r y low r a t e o f temperature increase; t h e r e a c t i o n r a t e
i s c o n t r o l l e d i n t h e process by t h e Tg i n c r e a s i n g i n concert w i t h t h e
temperature u n t i l Tgm, i . e . , f u l l cure, i s a t t a i n e d .

73
LINEAR POLYMERIZATION AND THE TTT DIAGRAM
T h i s s e c t i o n attempts, i n a general manner, t o i n c o r p o r a t e l i n e a r p o l y m e r i z a t i o n o f neat systems i n t o t h e concept o f t h e TTT diagram.
O i f u n c t i o n a l l i q u i d monomers can be transformed i n t o g l a s s y l i n e a r p o l y meric m a t e r i a l s by r e a c t i o n below t h e maximum g l a s s t r a n s i t i o n temperature
o f t h e polymer, TP.,
The time t o v i t r i f i c a t i o n curve f o r t h e isothermal
f r e e - r a d i c a l p o l y m e r i z a t i o n o f neat s t y r e n e versus t h e isothermal temp e r a t u r e o f r e a c t i o n , Trx, has been computed i n t h e absence o f d i f f u s i o n
control (20).
The c a l c u l a t i o n i n v o l v e d using t h e w e l l e s t a b l i s h e d chemic a l k i n e t i c s from zero conversion t o t h e conversion corresponding t o T -

Trx.
Since t h e neat m i x t u r e a t any t i m e c o n s i s t s o f mostly monomer an8
polymer ( n e g l e c t i n g i n i t i a t o r and a c t i v e c h a i n r a d i c a l s ) , t h e p r o p o r t i o n
o f polymer t o monomer (i.e.,
t h e conversion) was c a l c u l a t e d from t h e g l a s s
t r a n s i t i o n temperatures o f t h e monomer (-100C) and polymer (+lOOC) and
Tg
TCqre.
The computed v i t r i f i c a t i o n curves f o r t h e f r e e - r a d i c a l p o l y m e r i z a t i o n o f s t y r e n e and f o r a l i n e a r - f o r m i n g step-growth p o l y m e r i z a t i o n
were S-shaped.

Phase s e p a r a t i o n can occur i n neat l i n e a r p o l y m e r i z a t i o n as a consequence


o f i n s o l u b i l i t y o f oligomer o r polymer. T h i s has been a p a r t i c u l a r l y
important c o n s i d e r a t i o n i n t h e s y n t h e s i s by step-growth p o l y m e r i z a t i o n o f
h i g h Tg l i n e a r polymers, which o f n e c e s s i t y have r e l a t i v e l y i n f l e x i b l e
chain structures.
P r e c i p i t a t i o n o f t e n e f f e c t i v e l y removes t h e growing
species from t h e r e a c t i o n medium, thereby l i m i t i n g t h e molecular weight.
I n t h e same type o f p o l y m e r i z a t i o n the r e a c t i o n temperature must be such
t h a t v i t r i f i c a t i o n a l s o does n o t occur ( i . e .
Phase s e p a r a t i o n
can be analogous t o v i t r i f i c a t i o n i n limitini:tl:c:%!weight
and Tg - .
(Use o f e x o t i c s o l v e n t s overcomes t h e problems o f i n s o l u b i l i t y and v i t r i f i c a t i o n i n the s y n t h e s i s o f h i g h Tg r i g i d molecules:
however, these
s o l v e n t s must be subsequently removed, o f t e n by ingeneous methods.)
Although chemical g e l a t i o n does n o t occur i n l i n e a r p o l y m e r i z a t i o n , l o n g
range e l a s t i c i t y can develop i n t h e p o l y m e r i z i n g f l u i d as t h e consequence
o f entanglements between polymer molecules.
These w i l l occur a t lower
conversions f o r c h a i n r e a c t i o n s where h i g h molecular weight polymer forms
throughout the r e a c t i o n , than f o r step-growth p o l y m e r i z a t i o n s where h i g h
molecular weight polymer develops o n l y l a t e i n p o l y m e r i z a t i o n .
The s i t u a t i o n i s more complex f o r t h e conversion o f l i q u i d monomers i n t o
Polymerization o f neat monomer above Tgm
polymers which can c r y s t a l l i z e .
can lead t o s o l i d i f i c a t i o n because o f c r y s t a l l i z a t i o n .
(The maximum
m e l t i n g temperature,, , T
i s g r e a t e r than t h e maximum g l a s s t r a n s i t i o n
temperature, TgOp.) P o l y m e r i z a t i o n below Tgco,can l e a d t o s o l i d i f i c a t i o n as
the r e s u l t of v i t r i f i c a t i o n o r c r y s t a l l i z a t i o n .
The m e l t i n g temperature
range, as w e l l as t h e g l a s s t r a n s i t i o n temperature should be d i r e c t l y
i t i s w e l l known t h a t T
, of a
r e l a t e d t o the temperature o f r e a c t i o n :
l i n e a r polymer i s d i r e c t l y r e l a t e d t o t h e isothermal temperature o f
crystallization.
Acknowledqements - F i n a n c i a l support has been p r o v i d e d by
t h e O f f i c e o f Naval Research.

REFERENCES
1.

Gillham i n J. V. Dawkins, ed., Developments


Polymer
C h a r a c t e r i s a t i o o , Vol. 3, Applied Science Publishers, Ltd.,
London, 1982, Chapt. 5, pp. 159-227.

J. K .

74
2.
3.
4.
5.

6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.

J. K. Gillham, Encvclopedia of Polymer Science and Enqineerinq,


Second Edition, 3 , 519 (1986).
P. J. Flory, Principles gf Polymer Chemistry, Cornell University
Press, Ithaca, N.Y., 1953.
P. G. Babayevsky and J. K. Gillham, J. Appl. Polym. Sci. 17, 2067
(1973).
L. C. Chan, J. K. Gillham, A. J. Kinloch, and S. J. Shaw, Adv. Chem.
Ser. 208, 235 (1984).
Ibid., 261 (1984).
J. K. Gillham, P. N. Reitz and M. J. Doyle, Polym. Enq. Sci. 8, 227
(1968).
M. 6. Roller, Polym. Ens. Sci. 10, 692 (1979).
J. 6. Enns and J. K . Gillham, Adv. Chem. Ser. 203, 27 (1983).
X. Peng and J. K. Gillham, J. Appl. Polym. Sci. 30, 4685 (1985).
G. Palmese and J. K . Gillham, Proc. Am. Chem. SOC. Div. Polvm. Mat:
Sci.
55, 390 (1986).
L . E h a n , H. N. NaB, and J . K . Gillham, Polym. Prepr. Am. Chem.
Coat. Plast. Chem. 48, 566 (1983); J- Appl. Polym.
SOC. Div.
-Sci.
_ 29, 3307 (1984).
J. D. Ferry, Yiscoelastic Properties of Polymers, 3rd ed., John Wiley
& Sons, Inc., New York, 1980.
H. E. Adabbo and R . J. J. Williams, J. Appl. Polvm. Sci. 27, 1327
(1982).
J. 6. Enns and J. K. Gillham, J. Appl. Polvm. Sci. 28, 2567 (1983).
M. T. Aronhime and J. K. Gillham, J. Coat. Technol. 56(718), 35
(1984).
J. K. Gillham, J. A. Benci and A. Noshay, J. Appl. Polym. Sci. 18,
951 (1974).
M. T. Aronhime, X. Peng, J. K. Gillham and R . D. Small, J- Appl.
Polym. Sci., 2 , 3589 (1986).
A. F. Lewis, M. J. Doyle and J. K. Gillham, Polym. Enq. Sci. 10, 683
(1979).
M. T. Aronhime and J. K. Gillham, J. Appl. Polvm. Sci. 29, 2017
( 1984).

w,

m.