Polymer Synthesis

1 . Introduction
2 . Polycondensation
3 . Radical Polymerization
4 . Ionic Polymerization
4a. Anionic Polymerization
4b. Cationic Polymerization
5 . Ring Opening etat!esis Polymerization
". #. e!l
Ob$ecti%es o& t!e 'ecture Course
Introduction to Polymer C!emistry
Introduction and discussion o& se%eral met!odologies &or t!e synt!esis o&
macromolecules (it! a &ocus on linear polymers .
)ome *se&ul +e,tboo-s
... Co(ie/ Polymers0 C!emistry and P!ysics o& modern materials/ "lasgo(/
1lac-ie Academic/ 1221 .
#.". 3lias/ An introduction into Polymers )cience/ 4C#/ 5ein!eim/ 1226 .
. P. )te%ens/ Polymer C!emistry/ An introduction/ O*P/ 1222 .
1 . Synthesis of Polymers
+!ere are a number di&&erent met!ods o& preparing polymers &rom suitable
monomers/ t!ese are step-growth polymerisation/ addition polymerisation
and insertion polymerisation .

Condensation or Step-growth Polymerization
)tep gro(t! polymerisation is usually used &or monomers (it! &unctional
groups suc! as 7O#/ 7COO# etc. It is usually a succession o& non7catalysed/
c!emical condensation reactions associated (it! t!e elimination o& lo(7
molar7mass side7products/ eg./ (ater .
Addition Polymerization :
*sually addition polymerizations in%ol%e t!e polymerisation o& ole&inic
monomers. Polymerisation occurs %ia a c!ain reaction. +!e monomers are
con%erted into polymers by opening o& t!e double bond (it! a &ree radical or
ionic initiator. +!e product/ t!en/ unli-e t!at obtained &rom step7gro(t!
polymerisation/ !as t!e same c!emical composition as t!e starting monomer .
Insertion Polymerization :
*sually addition polymerizations in%ol%e t!e polymerisation o& ole&inic
monomers. Polymerisation occurs %ia an insertion o& a monomer at t!e end
o& t!e gro(ing c!ain/ mediatied by a catalyst. +!e catalyst stays at t!e end o&
t!e gro(ing c!ain. Polymers synt!esised by insertion polymerisation are
typically c!aracterised by a %ery !ig! stereoregularity. An e,ample &or suc! a
polymerisaiton tec!ni8ues is t!e 9ie ler7:atta ;1 merisation. Anot!er e,am Ie
on (!ic! (e (ill
contentrate in t!is course is t!e <etat!esis< polymerisation .
Natural Polymers: generally !a%e more comple, structures t!an synt!etic
polymers and are not discussed &urt!er !ere .
= )ee Polypeptides and Proteins and :ucleic Acids courses .>
Elastomers can be eit!er man made or natural/ and are t!ere&ore s!o(n as
a common subgroup. +!is term is used to describe elastically de&ormable/
solid polymers .
asi! "efinitions
A polymer is a large molecule constructed &rom many smaller structural units
called monomers. co%alently bonded toget!er in any concei%able pattern .
A repeat unit must possess t(o or more bonding sites in order to &orm
a polymer .
5!en only one species or building bloc- is used to &orm a polymer/ t!e
product is called a homopolymer .
I& t!e polymer c!ains are composed o& t(o types o& monomer unit/ t!e
material is -no(n as a !opolymer# &or t!ree monomer units it is called
a terpolymer$ etc .
% . Poly!ondensation
ono&unctional molecules lead to
1i&unctional molecules are re8uired to synt!esise linear c!ains
3,amples0 Polyesters
Polyamides
Poly!ar&onates
Poly!ondensation
t!e number a%erage degree o& polymerization
+!e number o& molecules present is determined by counting t!e number o&
end groups
"efinition: 'he num&er a(erage degree of polymerisation )*
n
)
+otal number o& molecules
Originally present >monomers
"efinition: p is t!e &raction o& t!e &unctional groups
t!at !a%e reacted .
Or0 P is t!e probability t!e one suc! group ta-en at
random !as reacted .

i. e. t!e concentration o& one o& t!e &unctional groups/c/
present a&ter a &raction p !as been reacted/ is related to t!e initial
concentration o& suc! groups
+!e number o& molecules >:/ :o= can simply be con%erted to concentrations
>c/ co= so t!at 0
+!e :umber A%erage olecular 5eig!t/ )+
n
, is simply 0

o
re&ers to t!e molecular mass o& t!e monomers
+!e :umber A%erage ?egree o& Polymerisation as a @unction o& Con%ersion
Rami&ications 0
#ig! molecular (eig!t is only ac!ie%ed at %ery !ig! degrees o& con%ersion .
At 2;A con%ersion >p B ;.2;= number a%erage degree o& polymerization is
only 1; C
38ui%alent to number a%erage molecular (eig!t o& D1;;; gEmole .
At 25A con%ersion >p B ;.25= number a%erage degree o& polymerization is
only 2; C
38ui%alent to number a%erage molecular (eig!t o& D 2;;; gEmole .
:eed to !a%e con%ersions o& 22.5A to obtain molecular (eig!ts in t!e range
o& 2;/;;; gEmole
An industrial nig!tmare C
Pol(amides
= i > Preparation by direct amidation o& diacids .
n #OOC7C#
2
C#
2
C#
2
C#
2
7COO# F n #
2
:7>C#
2
=
G
7:#
2

Adipic acid #e,amet!ylenediamine
= 1 / G 7 !e,ane7dicarbo,ylic acid = > 1/G7diamino!e,ane >
#eat - 7 2n #2;
= #:7>C#
2
=
G
7:#7OC7C#
2
C#
2
C#
2
C#
2
7CO >
n

:ylon HGG initially prepared at ?u Pont0 t!e polymer repeat unit contains si,
carbon atoms &rom t!e diamine monomer and si, carbon atoms &rom t!e
diacid monomer .
= ii > Pol%condensation o& diacid c!lorides (it! diamines
n CIOC7C#
2
C#
2
C#
2
C#
2
7COCI
F 2n 3t
3
:
Adipoyl c!loride C#CI
3
F IIIIIIIIIIIIIIIIIIJI
7 2n #CI
n #
2
:7>C#
2
=
G
7:#
2

C#
2
C#
2
C#
2
7CO=n >#:7>C#
2
=
G
K :# OC K C#
2
= alternati%e >
= iii > Preparation by amidation o& dicarbo,%lic esters .
= i% > Preparation &rom monomer salts
Reason &or t!is met!od0 Precisely e8ui%alent amounts o& t!e monomers are
re8uired.+!is is o&ten di&&icult on an industrial scale .
)o a solution to t!is problem &or <nylons< is to con%ert t!e acid and amine
>(!ic! is a base= to salts/ (!ic! (ill precipitate out o& solution in t!e &orm o& a
10 1 comple,. +!is is t!e desired stoic!iometry .

Polyesters
Polyesters are synt!esised by t!e typical esteri&ication reactions/ (!ic! can
be generalised as &ollo(s/ (!ere : is a nucleop!ile 0
Preparation &rom an!ydrides0 Poly>et!ylene maleate=
Preparation &rom esters0 Poly>et!ylene terep!t!alate=/ ?acron/ ylar
Preparation &rom acid c!lorides0 Poly >1/47butylene isop!t!alate=
Poly!ar&onates
Poly!ar&onates are polyesters deri%ed &rom t!e reactions bet(een carbonic
acid >or its deri%ati%es= (it! di!ydro,y compounds >diols= .
= i > Preparation by t!e )c!otten71aumann reaction
= ii > Preparation by transesteri&ication
'e,an is a commercially a%ailable polycarbonate. It !as a !ig! impact
strengt! and %ery good t!ermal and mec!anical stability belo( 25;
o
C and is
almost una&&ected by (ater and many inorganic and organic sol%ents .
. . /adi!al Polymerization
*sually/ many lo( molecular (eig!t al-enes undergo rapid polymerization
reactions (!en treated (it! small amounts o& a radical initiator .
@or e,ample/ t!e polymerization o& et!ylene is carried out at !ig! pressure
>1;;; to 3;;; atm= and !ig! temperature >1;; to 25;LC= (it! a radical
catalyst/ eg/ benzoyl pero,ide .
Step 1: Initiation
Step %: Propagation
Step .: 'ermination
+!ermodynamic considerations &or t!e &ree radical polymerization
Chain growth
Acti%ation energy &or c!ain gro(t! muc! lo(er t!an &or initiation .
"ro(t! %elocity less temperature dependent t!an initiation
Resonance e&&ect0 R more electronegati%e t!an #
)ubstituents are incorporated in 1/3 position >!ead7to7tail lin-age= 0
Initiators /adi!al Polymerization for
= i > +!ermal ?ecomposition
*sually applied to organic pero,ides or azo compounds/ eg benzoyl
pero,ide .
= ii > P!otolysis
*sually applies to metal iodides/ metal al-yls/ and azo compounds/ eg/ a/aM7
azobisisobutyronitrile AI1: is decomposed by radiation o& A. B 3G; nm
= iii > Redo, Reactions
Radicals are produced in a redo, reaction in solution/ eg/ t!e reaction
bet(een t!e &errous ion and !ydrogen pero,ide in solution produces !ydro,yl
radicals .
Al-yl !ydropero,ides can also be used in place o& !ydrogen pero,ide/ in
addition a similar reaction is obtained (!en Cerium >I4= sulp!ate o,idises an
alco!ol/ eg /
= i% > Persulp!ates
Ce3F F #F F RC>O#=#
Persulp!ates are o&ten used in emulsion polymerizations .
?ecomposition occurs in t!e a8ueous p!ase/ and t!e resulting radical
di&&uses into t!e !ydrop!obic droplets containing t!e monomer .
= % > lonising Radiation
a/ N/ y and ,7rays can be used to initiate t!e polymerization reaction. 3$ection
o& an electron is &ollo(ed by dissociation and electron capture to produce a
radical .
In!ibitors and Retarders
Retarders0 C!ain trans&er reagents can lo(er t!e a%erage lengt! o& t!e
polmer c!ain. )ome c!ain trans&er reagents produce radicals (it! lo(
acti%ities. I& t!e re7initiation process is slo(/ t!e polymerization rate
decreases because t!ere is a build up o& radicals leading to increased
termination by coupling. 5!en t!is occurs t!e reagent responsible is called
a retarder. @or e,ample/ nitrobenzene acts in t!is (ay in t!e polymerisation
o& styrene .
In!ibitors0 In e,treme cases an added reagent can suppress polymerization
completely by reacting (it! t!e initial radical species and con%erting t!em all
e&&iciently into unreacti%e materials. +!is process is called in!ibition. +!e
di&&erence bet(een retardation and in!ibition/ !o(e%er/ is one o& degree .
+!e stabilized radical dip!enyl picryl !ydrayl >?PP#= is an e,cellent in!ibitor/
and is e,tensi%ely used as a radical sca%enger because its stoic!iometry o&
reaction is 10 1 .
C!ain 1ranc!ing ?uring Radical Polymerization
= i > )!ort C!ain 1ranc!ing0 c!ain branc!ing o&ten occurs in radical
polymerization processes. )!ort c!ain branc!ing arises (!en t!e radical end
o& a gro(ing c!ain bends bac- on t!e polymer c!ain created and abstracts a
!ydrogen &rom it. In e&&ect t!is trans&ers t!e acti%e site o& polymerization to
t!e internal region o& t!e gro(ing polymer/ lea%ing a s!ort/ non7reacting c!ain
>a branc!ed c!ain= at t!e end o& t!e polymer bac-bone/ no( in a di&&erent
direction. +!us uncontrolled c!ain branc!ing leads to !ig!er %iscosity and a
less !omogeneous polymer .
C!ain 1ranc!ing ?uring Radical Polymerization

= ii > 'ong C!ain 1ranc!ing0 In long c!ain branc!ing abstraction o& !ydrogen is
not intramolecular but intermolecular/ ie/ abstraction ta-es place by t!e
reaction o& t!e end o& one polymer c!ain (it! t!e middle o& anot!er c!ain .
C!ain branc!ing is common in radical polymerization0 s!ort c!ain branc!ing
is about 5; times more li-ely to occur t!an long c!ain branc!ing. C!ain
branc!ing occurs in all -inds o& polymers ot!er t!an polyet!ylene/ eg/
polystyrene/ polypropylene/ etc .
Chain ran!hing in Polyethylene
0ow "ensity Polyethylene 0"PE
As seen earlier/ t!e radical polymerization o& et!ylene leads to c!ain
branc!ing and as a conse8uence to t!e &ormation o& a lo( density polymer.
'o( density polyet!ylene is partially crystalline >5;7G;A= and melts around
115 ?C. '?P3 (as t!e &irst plastic (it! an annual production e,ceeding 1
billion Ib >in 1252=/ by 1262 t!is !ad reac!ed 6.2 billion IbEyear .
1igh "ensity Polyethylene 1"PE
#ig! density polyet!ylene tends to !a%e a large proportion o& linear c!ains
>ie/ contains less t!an one side c!ain per 2;; carbon atoms in t!e main
c!ain=. #?P3 is !ig!ly crystalline >2;A= (it! a melting point abo%e 126
o
C.
#?P3 can be produced in se%eral (ays/ including radical polymerization o&
et!ylene at e,tremely !ig! pressures/ coordination polymerization o& et!ylene
>eg/ (it! a catalyst suc! as +iCI4 dispersed in a colloidal suspension (it! a
sol%ent suc! as !eptane= and polymerization on supported metal7o,ide
catalysts. In 1256 5 billion IbEyear !ad been reac!ed in production .
0inear 0ow "ensity Polyethylene 00"PE
'inear lo( density polyet!ylene is a copolymer o& et!ylene (it! an a7 ole&in
suc! as butene/ !e,ene or octene. +!e addition o& an a7ole&in is designed to
simulate t!e s!ort c!ain branc!ing and density o& con%entional branc!ed
polyet!ylene (it!out t!e occurence o& long c!ain branc!ing. +!is produces
polymers (it! good melt7&lo( and p!ysical properties. ''?P3 !as been one
o& t!e &astest gro(ing ne( plastics in recent years >1 billion Ib produced in
12O2. +!e ma$or use o& t!is plastic is in (aste bags .
Atom 'ransfer /adi!al Polymerisation
Compared to t!e &ree radical polymeriation t!e concentration o& &ree radical at
a gi%en time is small/ t!us less side reactions are obser%ed .
Sta&le 2ree /adi!al Polymerisation
+!is is a %ery mild polymerisaiton tec!ni8ue/ (!ic! ma-es use o& +3PO as
a protecti%e group &or t!e gro(ing c!ain .
3 . Ioni! Polymerization
Ionic polymerization is more comple, t!an &ree7radical polymerization0
(!ereas &ree radical polymerization is non7speci&ic/ t!e type o& ionic
polymerization procedure and catalysts depend on t!e nature o& t!e
substituent >R= on t!e %inyl >et!enyl= monomer .
Cationic initiation is t!ere&ore usually limited to t!e polymerization o&
monomers (!ere t!e R group is electron7donating/ (!ic! !elps stabilise t!e
delocation o& t!e positi%e c!arge t!roug! t!e p orbitals o& t!e double bond .
Anionic initiation/ re8uires t!e R group to be electron (it!dra(ing in order to
promote t!e &ormation o& a stable carbanion >ie/ 7 and 7I e&&ects !elp
stabilise t!e negati%e c!arge= .
is a onomer *nit. As t!ese ions are associated (it! a counter7ion or
gegen7ion t!e sol%ent !as important e&&ects on t!e polymerization procedure .
Ioni! Polymerization
4 ii 5 Chain Propagation
C!ain propagation depends on 0
4 a 5 Ion Separation
+!e separation bet(een t!e ionic part o& t!e propagating polymer c!ain and
t!e corresponding counter ion >"egen7ion= determines t!e stereoc!emistry o&
reaction o& a polymerising monomer .
4 & 5 Nature of the Sol(ent
Polar and !ig!ly sol%ating media are re8uired in order to dissol%e t!e ionic
catalysts and propagating polymer c!ains. #o(e%er/ many common polar
sol%ents cannot be used because t!ey (ould react (it!/ or ot!er(ise
neutralise/ t!e ionic initiator/ eg/ sol%ents incorporating !ydro,yl and
sometimes carbonyl groups >alco!ols and -etones= . )ol%ents o& lo(
dielectric constant s!ould be used since t!is results in a closer association o&
t!e counter7ion and t!e c!ain end as an ion pair. #o(e%er/ e%en in lo(
polarity sol%ents suc! as tetra!ydro&uran >+#@= or dic!loromet!ane >?C=
ion pair separation %aries greatly .
4 ! 5 Nature of the !ounter-ion
+!e nature o& t!e counter7ion can e&&ect t!e stereoc!emistry o& t!e polymer
product as (ell as in&luencing t!e rate o& polymerization .
3a Anioni! Polymerization
In%ol%es t!e polymerization o& monomers t!at !a%e strong electron7
(it!dra(ing groups/ eg/ acrylonitrile/ %inyl c!loride/ met!yl met!acrylate/
styrene etc. +!e reactions can be initiated by met!ods >b= and >c= as s!o(n
in t!e s!eet on ionic polymerization/ eg/ &or mec!anism >b=
+!e gegen7ion may be inorganic or organic and typical initiators include
P:#
2
/ n71u'i/ and "rignard reagents suc! as al-yl magnesium bromides. I&
t!e monomer !as only a (ea- electron7(it!dra(ing group t!en a strong base
initiator is re8uired/ eg/ butyllit!iumQ &or strong electron7(it!dra(ing groups
only a (ea- base initiator is re8uired/ eg/ a "rignard reagent. Initiation
mec!anism >c= re8uires t!e direct trans&er o& an electron &rom t!e donor to
t!e monomer in order to &orm a radical anion. +!is can be ac!ie%ed by using
an al-ali metal eg /.
Anionic polymerizations are similar to cationic reactions Q
= i > +!ey are generally rapid at lo( temperatures/ eg/ t!e abo%e reaction is
ac!ie%ed in li8uid ammonia at 12OP .
= ii > +!ey are slo(er and less sensiti%e to c!anges in temperature t!an
cationic polymerization .
= iii > Reaction rates are dependent on t!e dielectric constant o& t!e sol%ent/ t!e
resonance stability o& t!e reacti%e anion/ t!e electronegati%ity o& t!e initiator
and t!e solubility o& t!e gegen7ion .
= i% > +!ere is no &ormal termination step/ but t!e reaction is %ery sensiti%e to
small traces o& impurities/ eg (ater/ O
2
/ CO
2
etc. +!is latter group o&
compounds can be used as termination reagents .
Anioni! Polymerization of Styrene
Assuming steady state conditions/ t!e concentration o& propagating species
is 0
and t!e lengt! o& t!e polymer c!ains depends on t!e number o& initiations
+!us
+!e acti%ation energy &or trans&er is larger t!an &or propagation/ and so t!e
c!ain lengt! decreases (it! increasing temperature .
0i(ing Polymerizations
In ionic polymerization reactions/ eg./ t!e polymerisation o& styrene (it!
potassium amide as s!o(n pre%iously/ t!ere is no automatic termination step.
+!ere&ore/ i& t!e impurities t!at are responsible &or termination are
suppressed or some!o( e,cluded &rom t!e polymerisation reaction/ t!en t!e
reacti%e carbanion end o& t!e gro(ing polymer (ill remain reacti%e ><li%e<=
e%en (!en all o& t!e monomer initially present in t!e reaction %essle !ad
been consumed in t!e reaction .
Conse8uently/ i& more o& t!e same or a di&&erent monomer is added to t!e
reaction/ t!e polymerization process could continue and t!e polymer c!ains
(ould continue to propagate. +!is is an e&&icient (ay o& controlling polymer
molecular (eig!t and synt!esising bloc- copolymers .
+!ese acti%e polycarbanions (ere &irst called <li%ing polymers< by )z(arc.
One o& t!e &irst li%ing polymer systems &ound (as t!e polymerization o&
styrene initiated (it! sodium nap!t!alene .
4 i 5 Initiation
+!e initiation process is ac!ie%ed by adding sodium to a solution o&
nap!t!alene in an inert sol%ent/ suc! as tetra!ydro&uran >+#@=. +!e sodium
&orms an addition compound/ and by trans&erring an electron/ produces a
green nap!t!alene anion radical .
0i(ing Polymerizations
4 ii 5 Propagation
Addition o& styrene results in electron trans&er &rom t!e nap!t!yl radical to t!e
monomer to &orm a red styryl radical anion/ eg /.
It is possible t!at t!e dianion &orms and addition t!en occurs at bot! ends o&
t!e gro(ing polymer c!ain/ eg /.
+!us/ t!e absence o& a termination and a trans&er reaction means t!at t!e
c!ains (ill remain acti%e almost inde&initely. +!e utility o& t!e approac! can be
demonstrated by adding more styrene in order to produce !ig!er molecular7
(eig!t polystyrene or by adding a di&&erent reacti%e monomer to &orm a bloc-
copolymer .
Anioni! /ing 6pening Polymerizations
Ring opening polymerizations o& o,iranes/ t!iiranes and t!ietanes can be
initiated by anionic and cationic processes/ but lactams and lactones are
easier opened by anionic met!ods. eg/ preparation o& polyet!ylene o,ide
'actones can be used to prepare polyesters/ but as seen earlier/ ring size is
important/ eg/ t!e 57membered ring y7butyrolactone (ill not polymerize
(!ereas t!e si, membered ring O7%alerolactone (ill .
'actams (ill also undergo ring opening and polymerization to produce
polyamides/ eg/ nylon7G can be prepared &rom t!e (ater catalysed reaction o&
caprolactam .

+ypically t!is reaction is better controlled by using a t(o component catalyst
system. +!e lactam is reacted (it! a base to produce an acti%ated monomer/
(!ic! t!en reacts (it! a promoter suc! as acyl lactam/ t!is in turn initiates
t!e ring opening gro(t! o& t!e linear polymer. Ob%iously/ t!e preparation o&
nylons t!is (ay is o& commercial importance .
3&. Cationi! Polymerization
4 i 5 Initiation
4 ii 5 Propagation
C!ain gro(t! ta-es place t!roug! t!e repeated addition o& a monomer in a
!ead7to7tail manner to t!e ion (it! retention o& t!e ionic c!aracter t!roug!out
Cationi! Polymerization
4 iii 5 'ermination
+ermination o& cationic polymerization reactions are less (ell7de&ined t!an in
&ree7radical processes. +(o possibilities e,ist as &ollo(s 0
= a > *nimolecular rearrangement o& t!e ion pair
#ydrogen abstraction occurs &rom t!e gro(ing c!ain to regenerate t!e
catalyst7eo7catalyst comple,. Co%alent combination o& t!e acti%e centre (it!
a catalyst7eo7catalyst comple, &ragment may occur gi%ing t(o inacti%e
species. +!e -inetic c!ain is terminated and t!e initiator comple, is reduced a
more e&&ecti%e route to reaction termination .
= b > 1imolecular trans&er reaction (it! t!e monomer
Re&ormation o& t!e monomer7initiator comple,/ ensuring t!at t!e -inetic c!ain
is not terminated by t!e reaction .
Cationi! Polymerization
Initiation
@or initiation o& t!e type0 F F I< >
F
l0 i is typically a strong 'e(is Acid.
3lectrop!ilic initiators are dra(n &rom t!ree groups 0
= i > Classical protonic acids or acid sur&aces 7 #CI/ #
2
);
4
/ #CI;
4
= ii > 'e(is acids or @riedel7Cra&ts catalysts 7 1@
3
M AICI
3
/ +iCI
4
/
= iii > Carbenium ion salts
'e(is Acids are t!e most important initiators/ !o(e%er/ t!ey are not
particularly acti%e and t!ere&ore re8uire a co7catalyst to act as a proton donor/
eg /
Initiation t!en becomes a t(o step mec!anism/ as &ollo(s 0
+!e use o& a co7catalyst is di&&icult to demonstrate in practice/ !o(e%er/
consider t!e polymerization o& isobutylene. +!e reaction does not proceed
under an!ydrous conditions using 1@
3
as t!e catalyst/ but (it! trace amounts
o& (ater present reaction proceeds rapidly/ eg /
+!e comple, reacts (it! t!e monomer to produce a carbenium ion c!ain
carrier (!ic! e,ists as an ion pair (it! R1@3;#S .
Sta&le Car&onations
any uncertainties (it! t!e catalyst cocatalysts described pre%iously
= @riedel Cra&ts catalysts > can be remo%ed by using stable/ (ell7de&ined
initiators 0
eg/ trip!enyl met!yl and tropylium salts o& general &ormula

Initiation t!en occurs by one o& t!e &ollo(ing met!ods 0
= i > ?irect Addition

= ii > #%dride 3,traction

= iii > 3lectron +rans&er

Cationi! polymerization
3,ample o& a cationic polymerisation/ using boron tri&loride >1@
3
= as initiator .
Cationi! /ing 6pening Polymerization
Cyclic momomers suc! as lactones/ lactams/ cyclic amines and cyclic et!ers
can undergo ring opening and subse8uent polymerization (it! cationic
initiators. Ring opening depends on ring size/ and conse8uently ring strain/
eg/ tetra!ydropyran and 1 A7dio,ane do not ring open because t!ey !a%e
stable si, membered ring structures/ but et!ylene o,ide/ trimet!ylene o,ide/
and tetra!ydro&uran >(!ic! !a%e smaller ring sizes= and !e,amet!ylene
o,ide >(!ic! !as a larger ring size t!an si,= all can be induced to polymerize/
eg/ one mec!anism in%ol%es t!e primary interaction o& t!e catalyst system
(it! t!e monomer to &orm t!e o,onium ion (!ic! acts as t!e initiating
species .
Propagation t!en occurs in a predominantly ):2 type o& substitution reaction .
Alternati%ely ring clea%age can be ac!ie%ed (it! t!e catalyst to &orm an ionic
species/ t!is attac-s anot!er monomer producing ring opening and
regeneration o& t!e acti%e site .
+!e reaction can produce commercially use&ul polymers/ but because o& t!e
lo( ceiling temperatures and t!e tendency o& t!e polymer to unzip/ end7
capping may be re8uired/ eg/ poly&ormalde!yde >an engineering plastic= can
be prepared &rom 1/3/57trio,ane using boron tri&luoride et!erate as t!e
initiator/ and stabilising (it! acetylation o& t!e terminal group .
6ther Polymeriza&le /ing Systems
Ring Opening etat!esis Polymerisation 5/6+P4
+!e reaction in%ol%es a cyclic ole&in and a metal7al-ylidene as a catalyst. +!e
polymer is &ormed %ia a cyclobutane. +!e double bonds are rearranged
>gree-0 meta B c!angeQ tit!emi B place=. A <ne(< ole&in t!at is generated
remains attac!ed to t!e catalyst as part o& a gro(ing polymer c!ain .
Propagation
+!e dri%ing &orce &or t!e ROP reaction is t!e relie& o& ring strain. +!ere&ore/
t!e second step s!o(n abo%e is essentially irre%ersible. )trained cyclic
ole&ins suc! as t!ose s!o(n belo( !a%e su&&icient ring strain to ma-e t!is
process possible. onomers based on norbornene deri%ati%es are especially
popular/ as t!ey can be readily synt!esized &rom ?iels7Alder reactions (it!
cyclopentadiene. Only t!e unsubstituted bonds are ring7opened >it is %ery
di&&icult to metat!esize or /6+P tri7and tetrasubstituted ole&ins= .
Catalysts
A (ide %ariety o& catalyst !as been e,plored. I& t!e catalyst is too acti%e it can
start to metat!esize unstrained ole&inic bonds in t!e polymer c!ain/ leading to
c!ain scission
Chain S!ission
'ermination >(it! alde!yde/ controlled=
+!e ROP tec!ni8ue is a li%ing polymerisation and polymers (it! %ery !ig!
molecular (eig!ts can be ac!ie%ed. @or a controlled termination o& t!e
reaction alde!ydes can be used .
+!e product is an <end7capped< polymer and t!e catalyst is deacti%ated as a
<metal o,o< group .
+odel 7uestions .
In t!e &ollo(ing t!ere are some 8uestions/ (!ic! mig!t be o& use in
e%aluating your -no(ledge o& t!e sub$ect matter o& t!e course. It s!ould ta-e
you only a &e( minutes to complete ans(er t!e 8uestions. +!e correct
ans(ers are included .
5!ic! is t!e correct statementT +!e intermediate A/ s!o(n belo( is 0
a. a reaction intermediate in t!e &ree radical polymerization
b. a reaction intermediate in t!e atom trans&er radical polymerization
c. a reaction intermediate in t!e stable radical polymerization
d. a byproduct in t!e initiation step in t!e anionic polymerization
e. none o& t!e abo%e .
5!ic! is t!e correct statementT Polymet!acrylates can be synt!esized
= a > only by using a radical polymerisation met!od
= b > only by using an anionic polymerisation met!od
= c > by a polyesteri&ication tec!ni8ue
= d > by a cationic polymerisation
= e > 1y eit!er a radical polymerization or an anionic polymerization .
5!ic! is t!e correct statementT An anionic polymerization o& styrene
= a > is best carried in a protic sol%ent
= b > can be carried out (it! )b@
5
used as initiator
= c > re8uires t!at t!e initiator is acti%ated by traces o& (ater
= d > can proceed as a reaction in +#@ at 2;LC
= e > can proceed as a reaction in +#@ belo( ; LC .
5!ic! is t!e correct statementT A etat!esis polymerization
= a > is initiated by butyl7lit!ium in aprotic media
= b > proceeds %ia a &our membered cyclic transition state .
= c > is a polymerisation (it! 1@ 3 as a co7catalyst
= d > yields polyesters in !ig! yields
= e > is a mild reaction in t!e gasp!ase .
Anwers :
5!ic! is t!e correct statementT +!e intermediate A/ s!o(n belo( is 0
) a ( a reaction intermediate in the free radical polymerization A free radical
polymerization involves free radicals in the growing chain. There is none in
structure A, this is the wrong answer .
) b ( a reaction intermediate in the atom transfer radical polymerization This is
the right answer
) c ( a reaction intermediate in the stable radical polymerization A stable free
radical polymerization involves the formation of a protected growing chain, by
the reaction of the growing chain with and stable organic radical eg TEM!.
This is not the case. This is the wrong answer .
) d ( a byproduct in the initiation step in the anionic polymerization There are no
"byproducts" in the initiation step in the anionic polymerization, unless you
would count the counter#ion as a byproduct .$owever generous you are with
thisassingment" A " does not %t, so this is the wrong answer .
) e ( none of the above .
This is the wrong answer .
&hich is the correct statement' o(ymethacry(ates can be synthesized
= a > only by using a radical po(ymerisation method Methacrylates can be
polymerized using radical polymerization techni)ues, however other methods
are possible too, so this is the wrong answer .
= b > only by using an anionic po(ymerisation method This is the wrong answer
as polymethacryalets can be polymerized using radical polymerisaiton
techni)ues .
= c > by a po(yesteri%cation techni)ue This is the wrong answer .
= d > by a cationic po(ymerisation This is the wrong answer as cationic
polymerisation re)uires the presence of electron donating groups ne*t to the
cation .
= e > by eit!er a radical polymerisation or an anionic polymerisation .
+!is is t!e rig!t ans(er .
5!ic! is t!e correct statementT An anionic polymerisation o& styrene
a. is best carried in a protic sol%ent +!is is ob%iously (rong as a protic
sol%ent (ould react immediately (it! t!e anion and terminate t!e reaction .
b. can be carried out (it! )b@ 5 used as initiator )b@s is used as a co7
initiator in t!e cationic polymerization. +!is is t!e (rong ans(er .
c. re8uires t!at t!e initiator is acti%ated by traces o& (ater 5ater (ould react
immediately (it! t!e anions and 8uenc! t!e reaction. +!is is t!e (rong
ans(er .
d. can proceed as a reaction in +#@ at 2;LC +!e boiling point o& +#@ is G6LC.
+!is is t!e (rong ans(er .
e. can proceed as a reaction in +#@ belo( ; LC .
+!is is t!e rig!t ans(er. Anionic polymerizations are o&ten carried out in +#@
at temperatures mostly (ell belo( 73;LC .
5!ic! is t!e correct statementT A etat!esis polymerization
= a > is initiated by butyl7lit!ium in aprotic media +!is is t!e (rong ans(er.
1utyl7lit!ium initiates anionic polymerizations .
= b > proceeds %ia a &our membered cyclic transition state .
+!is is t!e rig!t ans(er .
= c > is a polymerisation (it! 1@ 3 as a co7catalyst 1@3 is used as a co7
catalyst in t!e cationic polymerizations. )o/ t!is is t!e (rong ans(er .
= d > yields polyesters in !ig! yields +!is is t!e (rong ans(er. +!e
met!at!esis polymerization is not a condensation reaction .
= & > is a mild reaction in t!e gas p!ase .
+!is is t!e (rong ans(er. Organic polymers are not prepared in t!e gas
p!ase .