Mechani sms of Thermal Oxi dati on of Pol y(bi sphenol A carbonate)

Sabrina Carroccio and Concetto Puglisi

I stituto per la Chimica ela Tecnologia dei Materiali Polimerici, Consiglio NazionaledelleRicerche.
VialeA. Doria, 6 - 95125 Catania, I taly
Giorgio Montaudo*
Dipartimento di ScienzeChimiche, Universita` di Catania. VialeA. Doria, 6 - 95125 Catania, I taly
Received November 29, 2001; Revised Manuscript Received February 7, 2002
ABSTRACT: I n the attempt to fi nd evi dence on the structure of the speci es produced i n the thermal
oxi dati ve degradati on of bi sphenol A-pol ycarbonate (PC), two pol ycarbonate sampl es, one capped
(i ncompl etel y) wi th phenyl groups at both ends (PC1) and the other one capped (i ncompl etel y) wi th tert-
butyl phenyl groups at both ends (PC2), were used. The two PC sampl es were heated at 300 and 350 C
under atmospheri c ai r for up to 180 mi n, produci ng a THF-i nsol ubl e gel at the l onger heati ng ti mes. The
oxi dati ve process was fol l owed as a functi on of the exposure ti me by SEC,
1
H NMR, MALDI -TOF, and
SEC/MALDI -TOF techni ques. The SEC curves showed extensi ve degradati on, up to the formati on of very
l ow mol ar mass ol i gomers. Hi ghl y val uabl e structural i nformati on on the thermal l y oxi di zed PC speci es
was obtai ned by usi ng MALDI -TOF mass spectrometry. The MALDI -TOF spectra of the thermal l y oxi di zed
PC1 and PC2 sampl es showed the presence of pol ymer chai ns contai ni ng acetophenone, phenyl -substi tuted
acetone, phenol s, benzyl al cohol , and bi phenyl termi nal groups. Formati on of acetophenone and phenol
end groups was confi rmed by
1
H NMR anal ysi s. The mechani sms accounti ng for the formati on of thermal
oxi dati on products of PC i nvol ve the operati on of several si mul taneous reacti ons: (i ) hydrol ysi s of carbonate
groups of PC to form free bi sphenol A end groups; (i i ) oxi dati on of the i sopropenyl groups of PC; (i i i ) oxi -
dati ve coupl i ng of phenol s end groups to form bi phenyl groups. The presence of bi phenyl uni ts among
the thermal oxi dati on products confi rmed the occurrence of cross-l i nki ng processes, whi ch i s responsi bl e
for the formati on of the i nsol ubl e gel fracti on. The MALDI -TOF anal ysi s of the oxi dati on products of
PC2 sampl e, capped wi th tert-butyl phenyl groups at both ends, unvei l ed a speci fi c anti oxi dant acti on of
these termi nal groups, whi ch are abl e to sl ow the rate of thermal oxi dati on of PC2 compared to PC1
sampl e.
Introduction
The thermal and oxi dati ve degradati on reacti ons
occurri ng on pol y(bi sphenol A carbonate) (PC) have
recei ved conti nued attenti on,
1-14
si nce PC i s an i mpor-
tant engi neeri ng thermopl asti c materi al whi ch i s sub-
jected to i njecti on mol di ng operati ons at temperature
above 300 C.
At thi s temperature, thermal and oxi dati ve degrada-
ti on reacti ons are l i kel y to occur, and therefore, the
understandi ng of the overal l process i s of cruci al i m-
portance.
Speci es formed i n the thermal oxi dati on processes of
many pol ymeri c materi al s are often very reacti ve, do
not accumul ate, and are present onl y i n mi nor amounts
among the reacti on products.
Because of thi s, conventi onal anal yti cal techni ques
may be i nadequate i n establ i shi ng the structure of
the oxi dati on products, and despi te the si zabl e l i terature
exi sti ng on the thermooxi dati ve degradati on of PC,
11-14
i nformati on on the speci es produced i n the oxi dati on i s
sti l l scarce and the structural assi gnments tentati ve.
Modern mass spectrometry offers the opportuni ty to
expl ore the fi nest structural detai l s i n pol ymers.
15-17
Matri x-assi sted l aser desorpti on i oni zati on-ti me-of-
fl i ght (MALDI -TOF) mass spectrometry provi des mass-
resol ved spectra, whi ch al l ow the detecti on of qui te l arge
mol ecul es even i n compl ex mi xtures. The MALDI -TOF
spectra ori gi nati ng from i ons of i ntact pol ymer chai ns
show enough resol uti on to al l ow the structural i denti -
fi cati on of ol i gomers up to 30 000 Da and above i n some
cases.
15-21
The study of pol ymer degradati on phenomena by
MALDI -TOF
9,22-28
i nvol ves the col l ecti on of several
MALDI -TOF spectra at di fferent ti mes and/or temper-
ature to observe the structural changes i nduced by heat
and l i ght under an i nert and/or oxi di zi ng atmosphere.
The parti al l y degraded pol ymer sampl e can be di rectl y
anal yzed, and the recorded MALDI -TOF spectrum
ari ses from a mi xture of nondegraded and degraded
chai ns.
Thi s opens new vi stas i n studyi ng pol ymer degrada-
ti on and deserves careful expl orati on, due to the rel -
evance of these phenomena i n everydays practi ce.
We have recentl y reported on the thermal degradati on
of PC
9
and on the products of thermal oxi dati on of Nyl on
6,
28
usi ng MALDI -TOF as the mai n anal yti cal tech-
ni que.
On these occasi ons, we have remarked on the surpri s-
i ngl y hi gh amount of structural i nformati on that can
be extracted from the anal ysi s of MALDI -TOF spectra
of thermal or thermal l y oxi di zed pol ymers.
We have now performed the thermal oxi dati on of PC
by heati ng at 300 and 350 C i n atmospheri c ai r. Two
pol ycarbonate sampl es, one capped (i ncompl etel y) wi th
phenyl groups at both ends (PC1) and the other one
capped (i ncompl etel y) wi th tert-butyl phenyl groups at
both ends (PC2), were used. A THF-i nsol ubl e gel ,
correspondi ng to cross-l i nked pol ymer chai ns, was
produced at l onger heati ng ti mes.
The oxi dati ve process was fol l owed as a functi on of
the exposure ti me by SEC,
1
H NMR, MALDI -TOF, and
SEC/MALDI -TOF techni ques. The SEC curves showed
4297 Macromolecules 2002, 35, 4297-4305
10.1021/ma012077t CCC: $22.00 2002 Ameri can Chemi cal Soci ety
Publ i shed on Web 04/19/2002
extensi ve degradati on, up to the formati on of very l ow
mol ar mass ol i gomers. The MALDI -TOF spectra of the
thermal l y oxi di zed PC1 and PC2 sampl es showed the
presence of pol ymer chai ns contai ni ng acetophenone,
phenyl -substi tuted acetone, phenol s, benzyl al cohol and
bi phenyl termi nal groups. Formati on of acetophenone
and phenol end groups was confi rmed by
1
H NMR
anal ysi s.
Experimental Section
Materials. Basi c materi al s were commerci al products ap-
propri atel y puri fi ed before use. The PC1 sampl e was obtai ned
by Si gma-Al dri ch Chemi cal Co. and PC2 sampl e was from TEI
JI N (Japan). 2-(4-Hydroxypheni l azo)benzoi c aci d (HABA) was
purchased from Al dri ch Chemi cal Co. and used as suppl i ed.
Thermal Oxidative Degradation of PC. The thermal
oxi dati on was carri ed out on mol ten PC sampl es i n the
presence of atmospheri c ai r at 300 and 350 C. Fi rst, 100 mg
of sampl e was pl aced i n a gl ass vessel and heated for 30, 45,
60, 90, 120, and 180 mi n i n a el ectri c furnace, wi thout sti rri ng.
The oxi di zed PC sampl es were treated wi th THF and fi l tered.
The THF sol ubl e porti ons were dri ed and stored for the
successi ve anal yses, the sol i d resi due were dri ed under vacuum
and wei ghed. Resi due val ues are reported i n Tabl e 1.
SEC Analysis and Molar Mass Determination. The
anal yses were performed on a Waters 600 A apparatus,
equi pped wi th fi ve Ul trastyragel col umns (7.8 300 mm) (i n
the order 10
5
, 10
3
, 500, 10
4
, and 100 pore si ze) connected i n
seri es, and a Waters R401 di fferenti al refractometer. Then 90
L of a CHCl 3 PC sol uti on (0.5%) was i njected and el uted wi th
CHCl 3 at fl ow rate of 1 mL/mi n. The mol ar masses of PC
sampl es were determi ned by the SEC/MALDI method.
18-21
Undegraded PC sampl e was fracti onated to col l ect several
equal vol ume fracti ons of about 0.165 mL each (correspondi ng
to 12 drops). The mol ar mass of each col l ected fracti on was
determi ned by MALDI -TOF. The absol ute cal i brati on curves
obtai ned by pl otti ng the l og M
w of some SEC sel ected fracti on
as a functi on of the correspondi ng el uti on vol ume al l owed the
cal cul ati on of mol ar masses of undegraded and thermal l y
oxi di zed PC sampl es by the Pol ymer Lab Cal i ber software. The
cal cul ated data were reported i n Tabl e 1.
MALDI-TOF Analysis. MALDI -TOF mass spectra were
obtai ned usi ng a Voyager-DE STR i nstrument, equi pped wi th
a ni trogen l aser emi tti ng a 337 nm wi th a 3 ns pul se wi dth
and worki ng i n posi ti ve i on mode. The accel erati ng vol tage
was 20-25 kV, and the gri d vol tage and del ay ti me (del ayed
extracti on, ti me l ag) were opti mi zed for each sampl e to obtai n
the hi gher mol ar mass val ues. The l aser i rradi ance was
mai ntai ned sl i ghtl y above threshol d. The MALDI -TOF spec-
tra i n Fi gures 4 and 7 were recorded i n l i near mode. Al though
refl ecti on MALDI -TOF spectra showed a hi gher resol uti on,
they were not shown here because the i ntensi ty of the l ess
abundant thermal oxi dati on products were cl ose to the back-
ground noi se l evel . The resol uti on of the MALDI spectra was
about 1000 (M/M) and the accuracy of mass determi nati on
was about 0.02% for masses i n the range 1000-5000.
The sampl es for the MALDI anal yses were prepared by
mi xi ng adequate vol umes of the matri x sol uti on (HABA, 0.1
M i n THF) and pol ymer sol uti on (2 mg/mL i n THF) to obtai n
a 1:1 or 1:3 rati o (sampl e/matri x)v/v. 1 L of a 0.1 M sol uti on
of sodi um tri fl uoroacetate (NaTFA) i n THF was added to ai d
Table 1. Thermal Oxidation Residue, THF Insoluble
Residue, and Molar Mass Distribution Data of
PC1 and PC2 Polycarbonate Samples Thermal
Oxidized at 300 and 350 C
oxi dati on
resi due
a
i nsol ubl e
resi due
b
PC1 PC2
temp
(C)
heati ng
ti me
(mi n) PC1 PC2 PC1 PC2 Mw
c
Mn
c
Mw
c
Mn
c
0 100 100 0 0 21000 16000 20000 13000
300 30 100 100 0 0 18800 13900 19200 11500
60 100 100 0 0 18300 12100 18000 11000
90 100 100 0.8 0 19000 11500 17000 10500
120 100 100 3 0 17600 9800 16500 10500
150 100 100 6.8 9.40 16800 9000 16000 9700
180 100 100 13 13.90 15600 8400 15500 9300
350 15 100 100 0 0 15900 12000 10500 6500
45 98.7 98 10 11.30 14400 7300 9300 5600
60 97.7 98 14.7 13.65 9300 4450 8530 5000
75 97 97 23.5 17.23 7880 4010 8000 4650
90 96 97 24.5 16.00 6200 3730 7600 4000
120 96 96 25 16.54 5500 2700 7000 3600
150 95.5 95.5 25.6 19.77 5200 2350 5400 3000
180 94.5 95 28.6 18.02 4900 2200 4900 2574
a
Percent of resi due wi th respect to the i ni ti al wei ght of sampl es.
b
Percent of THF-i nsol ubl e fracti ons obtai ned from the thermal
oxi di zed resi due.
c
Obtai ned by SEC/MALDI -TOF method (see
Experi mental Secti on).
Figure 1. Percent of i nsol ubl e gel formed i n the thermal
oxi dati ve degradati on of (a) PC1 and (b) PC2 sampl es at 300
and 350 C as a functi on of the heati ng ti me.
Figure 2. GPC traces of PC2 sampl e thermal l y oxi di zed at
350 C for 0, 45, and 150 mi n.
4298 Carrocci o et al . Macromolecules, Vol. 35, No. 11, 2002
cati oni zati on. Then 1 L of each sampl e/matri x mi xture was
spotted on the MALDI sampl e hol der and sl owl y dri ed to al l ow
matri x crystal l i zati on.
The rel ati ve amount of speci es reported i n Fi gures 5 and 6
was obtai ned as the rati o I A/I T, where I A i s the sum of the peaks
i ntensi ty of each speci es i n the mass range 2000-5000 and I T
corresponds to the sum of the i ntensi ty of al l peaks appeari ng
i n the same mass range.
NMR Spectroscopy.
1
H NMR anal yses were carri ed out
at room temperature by a
UNI TY
I NOVA Vari an i nstrument
operati ng at 500 MHz usi ng deuterated chl oroform as sol vent
and tetramethyl si l ane as i nternal standard.
Results and Discussion
Two pol ycarbonate sampl es beari ng two di fferent
types of chai n ends, PC1 sampl e capped wi th phenyl
groups and PC2 sampl e wi th tert-butyl -phenyl groups,
were subjected to thermal oxi dati on by heati ng at 300
and 350 C i n atmospheri c ai r up to 180 mi n.
At l onger exposure ti mes (Tabl e 1) the thermooxi di zed
sampl es showed gel formati on and were subjected to
extracti on wi th THF, to have a sol ubl e porti on sui tabl e
for SEC, NMR, and MALDI -TOF anal yses.
I n Fi gure 1, parts a and b are reported the percent
amount of THF-i nsol ubl e gel formed at 300 and 350 C,
respecti vel y, as a functi on of the heati ng ti me. The
amount of gel formed at 300 C, after 180 mi n heati ng,
i s about 10%for both PC sampl es, but the gel formati on
onset i s shi fted at a hi gher heati ng ti me (150 mi n) i n
the PC2 sampl e wi th respect to the PC1 sampl e (90
mi n). Thi s fact, together wi th the l ower gel amount
(20%) formed i n PC2 at 350 C, as compared to PC1
(30%), i s taken as an i ndi cati on that the cross-l i nki ng
process i s sl i ghtl y sl ower i n PC2.
I n Fi gure 2 are shown the GPC traces of some ther-
mal l y oxi di zed PC2 sampl es. The degradati on process
i s al ready evi dent after 45 mi n exposure, and at 150
mi n, one observes promi nent si ngl e peaks most l i kel y
due to di hydroxyl -termi nated PC ol i gomers (see bel ow).
The mol ar masses of the bl ank PC sampl es and those
of the THF sol ubl e fracti ons of thermal l y oxi di zed PC1
Figure 3. I nverse of degree of pol ymeri zati on (1/DP) as a
functi on of ti me of PC1 and PC2 sampl es thermooxi di zed at
300 C.
Figure 4. MALDI -TOF mass spectra, i n the range 2800-
3400 Da, of PC1 sampl es: (a) undegradated; themooxi di zed
at 300 C for (b) 90 and (c) 180 mi n.
Figure 5. Rel ati ve amount vs heati ng ti me of speci es B, C,
and D speci es as obtai ned from the MALDI spectra of ther-
mooxi di zed PC1 sampl e at 300 C.
Macromolecules, Vol. 35, No. 11, 2002 Thermal Oxi dati on of Pol y(bi sphenol A carbonate) 4299
and PC2 sampl es were determi ned by the SEC/MALDI
method.
18-21
Data shown i n Tabl e 1 i ndi cate that the degradati on
process i s fai rl y extensi ve, produci ng a steady reducti on
of the mol ar mass wi th the reacti on ti me.
The i nverse pol ymeri zati on degree (1/DP), shows a
fai r l i neari ty agai nst heati ng ti me for both PC sampl es
thermal l y oxi di zed at 300 C (Fi gure 3), i ndi cati ng that
the process proceeds by a random chai n sci ssi on of the
pol ymer mol ecul es.
29,30
The MALDI spectra of the pri sti ne PC1 and PC2
sampl es have been al ready reported,
20
and therefore
onl y expanded porti ons i n the mass range 2000-4000
Da are presented here.
The MALDI spectrum of the PC1 sampl e, reported
i n Fi gure 4a, shows peaks bel ongi ng to four di fferent
mass seri es. The most i ntense peak seri es, at m/z
2779 + n254.2, i s due to sodi ated i ons of PC1 chai ns
termi nated wi th phenyl groups at both ends (speci es B,
Tabl e 2).
A second seri es of peaks appeari ng wi th l ow i ntensi ty
at m/z 2793 + n254.2, can be assi gned to the sodi ated
i ons of PC1 chai ns termi nated wi th bi sphenol A groups
(BPA-OH) at both ends (speci es D, Tabl e 2). A thi rd
seri es of peaks at m/z 2819 + n254.2 are due to sodi ated
i ons of PC cycl i c chai ns (speci es A, Tabl e 2). The l ast
seri es of peaks at m/z 2913 + n254.2, corresponds to
sodi ated i ons of PC chai ns termi nated wi th phenyl
group at one end and a BPA-OH groups at the other
end (speci es C, Tabl e 2).
The MALDI mass spectra of PC1 heated at 300 C i n
ai r for 90 and 180 mi n (Fi gure 4b-c) show an i ncreased
number of peaks wi th respect to the bl ank sampl e,
i ndi cati ng that the thermal oxi dati on reacti ons are
produci ng several termi nal groups.
The most i ntense peaks i n the MALDI spectrum
recorded after 90 mi n of heati ng (Fi gure 4b) are due to
D speci es (Tabl e 1), beari ng BPA-OH groups at both
ends. The i ntensi ty of the cycl i c ol i gomers (speci es A)
i s strongl y reduced whereas they di sappear after 180
mi n of heati ng at 300 C (Fi gure 4c). The phenyl -
termi nated ol i gomers (B speci es) appear wi th reduced
i ntensi ty i n both spectra i n Fi gure 4b,c.
The assi gnment of speci es A (Fi gure 4c) to cycl i c PC
chai ns has been confi rmed by the SEC/MALDI method.
I n fact, the MALDI spectra of the l ower mass SEC
fracti ons of 90 mi n thermal l y oxi di zed PC sampl e show
a doubl e di stri buti on of peaks wi th the rati o of M
cycl e
/
M
l i near
) 1.2, typi cal for the si mul taneous presence of
cycl i c and l i near ol i gomers.
20,21
The l arge amount of PC1 chai ns contai ni ng BPA-
OH as end groups (speci es D), i s an i ndi cati on that an
extensi ve hydrol ysi s reacti on of the carbonate functi onal
groups, i s occurri ng, ei ther due to the atmospheri c ai r
moi sture or to the water produced duri ng the PC
autoxi dati on whi ch may al so pl ay a si gni fi cant rol e.
The ki neti cs of the process i s shown i n Fi gure 5, i n
whi ch the rel ati ve amount of the B, C and D speci es i s
reported as a functi on of the heati ng ti me. I t can be
noted the strong decrease of the i ntensi ty of speci es
B, together wi th the correspondi ng i ncrement of spe-
ci es D.
I nstead, the amount of PC1 chai ns termi nated wi th
phenyl groups at one end and BPA-OH at the other
end (C speci es) remai ns al most constant, presumabl y
Figure 6. Rel ati ve amount vs heati ng ti me of speci es L, N,
and Q speci es as obtai ned from the MALDI spectra of ther-
mooxi di zed PC1 sampl e at 300 C.
Figure 7. MALDI -TOF mass spectra, i n the range 3500-
4000 Da, of PC2 sampl es: (a) undegradated; thermooxi di zed
at 300 C for (b) 90 and (c) 180 mi n.
4300 Carrocci o et al . Macromolecules, Vol. 35, No. 11, 2002
because these ol i gomers al so ari se from the hydrol ysi s
degradati on reacti on of hi gher mol ar mass PC1 chai ns
capped wi th phenyl groups at both ends (B speci es).
The structural assi gnment (Tabl e 2) of the peaks
l abel ed as E, I , Q i n the MALDI spectra i n Fi gure 4b-c,
corresponds to thermal oxi dati on products wi th phenyl -
substi tuted acetone end groups, whereas peaks O, V, N
(Tabl e 2) are assi gned to oxi di zed PC1 chai ns contai ni ng
phenol groups. Al l these speci es mi ght ari se through the
hydroperoxi de decomposi ti on (Scheme 1, route a), as
shal l be di scussed bel ow.
Peaks L and S, assi gned to oxi di zed PC1 chai ns
beari ng acetophenone chai n ends (Tabl e 2), are thought
to be formed accordi ng to hydroperoxi de decomposi ti on
(Scheme 1, route b), whi ch al so produces benzyl al cohol
end groups (peak G, Tabl e 2).
Peaks N, T and V (Tabl e 2) are thought to correspond
to speci es contai ni ng bi phenyl uni ts, most l i kel y formed
by the oxi dati ve coupl i ng of two phenyl ri ngs of si mpl e
phenol s and/or bi sphenol A uni ts (Scheme 3).
11,13
Thi s reacti on creates bi phenyl bri dges between the
l i near PC chai ns, promoti ng the generati on of char-l i ke
Table 2. Structural Assignments of Sodiated Ions Appearing in the MALDI-TOF Spectra of Thermooxidized PC1 and
PC2 Samples
Macromolecules, Vol. 35, No. 11, 2002 Thermal Oxi dati on of Pol y(bi sphenol A carbonate) 4301
structures and the gel formati on i n the thermooxi dati ve
reacti on.
I n Fi gure 6 i s reported the i ntensi ty of sel ected
MALDI peaks rel ated to representati ve compounds
formed i n the thermal oxi dati on process. The amount
of oxi di zed speci es E and M i ncreases steadi l y i n the
fi rst part of the process and then tends to l evel for l onger
heati ng ti mes, whereas the amount of Q speci es steadi l y
decreases at l onger heati ng ti me.
The l evel i ng and/or decrease of oxi di zed speci es wi th
ti me i s onl y apparent, bei ng rel ated to the i nterveni ng
cross-l i nki ng phenomena i n the oxi dati on process. I n
fact, the cross-l i nked fracti on (whi ch contai ns a major
porti on of the oxi di zed products), becomes i nsol ubl e and
cannot be detected by MALDI , si nce onl y the sol ubl e
materi al can be anal yzed by MALDI .
I n Fi gure 7a i s reported the MALDI -TOF mass
spectrum of the bl ank PC2 sampl e i n the mass range
3500-4000Da, where cycl i c ol i gomers (A) are the most
i ntense peaks fol l owed by the tert-butyl phenyl end-
capped chai ns (B) and by the PC2 chai ns (C) contai ni ng
one BPA-OH group at one end and a tert-butyl phenyl
group at the other end. (Tabl e 2). Speci es D, contai ni ng
BPA-OH groups, at both ends (Tabl e 2) i s obtai ned i n
a very l ow amount i n thi s PC sampl e.
The MALDI mass spectra of PC2 sampl e heated at
300 C i n ai r for 90 and 180 mi n (Fi gure 7b,c) show an
i ncreased number of peaks, most l i kel y due to thermal
oxi dati on.
After 90 mi n of heati ng, the most i ntense peaks i n
the MALDI spectrum (Fi gure 7b) are due to C and B
speci es together wi th the D speci es, whereas the i nten-
si ty of the cycl i c speci es (A) i s strongl y reduced, i ndi cat-
i ng the presence of an extensi ve hydrol ysi s reacti on.
After 180 mi n of heati ng, the i ntensi ty of B speci es
strongl y decreases, peaks C and D become the most
i ntense and the cycl i c ol i gomers (A speci es) total l y
di sappear.
The ki neti cs of the degradati on process i ndi cates that
the i ntensi ty of A, B, C, and D speci es i s very si mi l ar
to that observed for PC1 sampl e and wi l l not be reported
for brevi ty; however, i t shoul d be poi nted out that the
hydrol ysi s process of the PC2 sampl e i s si gni fi cantl y
sl ower than that for the PC1 sampl e.
I n fact, the i ntensi ty of B and C peaks correspondi ng
to PC chai ns wi th free BPA-OH end groups (Fi gure
7b,c), i s al ways hi gher than B and C peaks of PC1
sampl e (Fi gure 4b,c).
The structural assi gnments of the peaks appeari ng
i n the MALDI spectra i n Fi gure 7b,c are l i sted i n Tabl e
2.
Peaks l abel ed by F, H, L, M, S, and Z, appeari ng wi th
noti ceabl e i ntensi ty, have been assi gned to PC chai ns
beari ng acetophenone chai n ends, produced accordi ng
to Scheme 1 (route b).
The same oxi dati on pathway accounts for the pres-
ence of the G peaks correspondi ng to benzyl al cohol
termi nated PC chai ns.
Peaks E and I are due to speci es beari ng phenyl -
substi tuted acetone termi nal groups, and peaks N and
O are due to chai ns wi th phenol end groups, al l
generated accordi ng to Scheme 1 (route a).
Peaks M and Z i n Fi gure 7b,c were assi gned (Tabl e
2) to speci es contai ni ng bi phenyl bri dges, formed by
oxi dati ve coupl i ng of two aromati c ri ngs.
The ki neti cs of formati on of the oxi dati on products of
PC2 sampl e i s very si mi l ar to that observed for PC1 and
wi l l not be reported here for brevi ty.
The presence of a hi gher amount of PC chai ns
termi nated wi th acetophenone end groups i n the PC2
sampl e, as compared to PC1, mi ght be ascri bed to the
di fferent structure of the thermi nal groups. I n fact, the
tert-butyl moi ety of PC2 chai ns may al so undergo
oxi dati on processes vi a the formati on of a hydroperox-
i de, whi ch can decompose
12
(Scheme 2) produci ng the
same type of compounds formed i n the thermal oxi -
dati on of i sopropenyl groups (Scheme 1, route b). Thi s
hypothesi s i s al so supported by the presence of the
i ntense peaks R (Fi gure 7b,c) correspondi ng to a com-
pound wi th methyl ol groups (Tabl e 2) most l i kel y
formed i n the i ni ti al stage of oxi dati on of tert-butyl chai n
ends.
12
Furthermore, the presence of the tert-butyl cappi ng
groups i n PC2 sampl e mi ght be al so abl e to generate
resonance-stabilized radicals acting as antioxidant agents
(Scheme 2). Thi s mi ght expl ai n the di fferent rate of gel
formati on and mol ar mass decreases of PC2 sampl e wi th
respect to PC1 sampl e (Fi gures 1 and 2).
The thermal oxi dati on process of sampl e PC2 was al so
i nvesti gated by 500 MHz
1
NMR anal ysi s.
I n parts a-c of Fi gure 8 are reported the
1
H NMR
spectra of the PC2 sampl e thermooxi di zed at 300 for
Scheme 1. Thermal Oxidative Degradation Process of
Poly(bisphenol A carbonate)
4302 Carrocci o et al . Macromolecules, Vol. 35, No. 11, 2002
180 mi n (Fi gure 8b) and at 350 C for 120 mi n (Fi gure
8c), respecti vel y. Because of the l ow amount of chai n
ends, the NMR spectra have been expanded and onl y
the spectral regi ons i n whi ch appear end groups si gnal s
are shown here.
The si ngl et peak at 2.6 ppm (methyl protons) and the
two mul ti pl ets centered at 8.02 and 8.25 ppm (aromati c
protons) correspond to the acetophenone termi nal groups
(Fi gure 3b,c).
The two mul ti pl ets centered at 6.65 and 7.05 ppm are
due to aromati c protons of BPA-OH thermi nal groups
(Fi gure 8b,c).
The si ngl et peaks appeari ng i n the i nterval between
4.89 and 4.95 ppm (Fi gures 8b,c), can be assi gned to
the OH protons of the BPA-OH termi nal groups. The
l atter assi gnment was confi rmed by the
1
H NMR
spectrum of a sampl e consti tuted of l ow mol ar mass PC
ol i gomers termi nated wi th BPA-OH at both ends
(Fi gure 8d).
The NMR spectra therefore ni cel y confi rm the forma-
ti on of acetophenone and phenoxy end groups, whi ch
were among the several oxi dati on products detected by
the MALDI anal ysi s reported above.
Thermal Oxidation Mechanisms. Thermal oxi da-
ti on pathways of PC were fi rst proposed by Factor
et al .
11,13
These workers anal yzed the base hydrol y-
si s products deri ved from a PC sampl e that was oven-
aged at 140 C, and found p-hydroxybenzoi c aci d
and p-hydroxybenzophenone among the hydrol ysi s prod-
ucts.
I n pri nci pl e, base hydrol ysi s mi ght catal yze rear-
rangement reacti ons of the pri sti ne oxi dati on products,
and the temperature used i s rather l ow i n order to
si mul ate the oxi dati on and degradati on processes oc-
curri ng i n the processi ng condi ti ons of PC. I n fact,
degradati on processes operati ng on PC are a functi on
of the temperature.
8,9
The present oxi dati on studi es were carri ed out at 300
and 350 C i n order to si mul ate cl osel y the PC process-
i ng condi ti ons.
Pure oxi dati on i s not the onl y reacti on occurri ng when
the PC sampl es are processed above 300 C.
Hydrol yses of PC chai ns i nduced by the contact wi th
atmospheri c ai r and al so the Schmi tt-Kol be i somer-
i zati on of the carbonate group are al so occurri ng.
2-14
The mechani sms accounti ng for the thermal oxi dati on
products of PC up to 350 C i nvol ve at l east the
fol l owi ng: (i ) oxi dati on and decomposi ti on of the i so-
propenyl groups of BPA (Scheme 1); (i i ) cross-l i nki ng
reacti ons through the oxi dati ve coupl i ng of BPA uni ts
to form bi phenyl groups (Scheme 3).
The MALDI data presented above support a pri mary
oxi dati on mechani sm l eadi ng to the i ni ti al formati on of
methyl ene radi cal s whi ch undergo rearrangement to a
more stabl e benzyl i c radi cal .
The subsequent reacti on wi th oxygen produces a
hydroperoxi de i ntermedi ate, whi ch may decompose by
two paral l el pathways (Scheme 1, routes a and b).
Al l the four ki nds of end groups predi cted by thi s
reacti on scheme have been detected by MALDI (Tabl e
Scheme 2
Scheme 3
Macromolecules, Vol. 35, No. 11, 2002 Thermal Oxi dati on of Pol y(bi sphenol A carbonate) 4303
2), so that the overal l process depi cted i n Scheme 1 i s
i n general agreement wi th the ori gi nal proposal of
Factor et al .
11,13
Al so, the presence i n the PC2 sampl e of a hi gher
amount of PC chai ns termi nated wi th acetophenone end
groups, as compared to PC1, can be expl ai ned by
Scheme 1.
I n fact, the tert-butyl moi ety of PC2 chai ns may al so
undergo oxi dati on processes vi a a methyl l oss and the
formati on of a hydroperoxi de, whi ch can decompose
12
(Scheme 2) produci ng the same type of compounds as
formed i n the thermal oxi dati on of i sopropenyl groups
(Scheme 1, route b).
The tert-butyl cappi ng groups i n PC2 mi ght be abl e
to gener ate r esonance-stabi l i zed i sopr opyl r adi cal s
(Scheme 2), whi ch can act as anti oxi dant agents, hel pi ng
rati onal i zi ng al so the di fferent rate of gel formati on and
mol ar mass decrease of PC2 wi th respect to the PC1
sampl e (Fi gures 1 and 2).
The presence of compounds contai ni ng bi phenyl uni ts
among the oxi dati on products of PC, was al so reported
by Factor et al .,
11,13
and we have detected i n the MALDI
spectra fi ve PC ol i gomers possessi ng structures whi ch
woul d i ndi cate the presence of bi phenyl uni ts al ong the
chai n (Tabl e 2).
Qui te recentl y, however, Tsuge et al .
14
anal yzed by
reacti ve pyrol ysi s GC/MS at 400 C some thermal l y
oxi di zed PC sampl es and detected some reacti ve py-
rol ysi s products contai ni ng doubl ed bi sphenol A uni ts
that they assi gned to the coupl i ng of two methyl radi -
cal s formed from the oxi dati on of the i spropyl i dene
bri dges.
Figure8.
1
H NMR spectra of PC2 sampl es: (a) undegraded; (b) thermooxi di zed at 300 C for 180 mi n; (c) thermooxi di zed at 350
C for 120 mi n; (d) l ow mol ar mass PC sampl e termi nated wi th BPA-OH groups at both ends.
4304 Carrocci o et al . Macromolecules, Vol. 35, No. 11, 2002
The structures proposed by Tsuge et al . (1)
14
are
i someri c wi th the those contai ni ng bi phenyl uni ts (2).
From a detai l ed anal ysi s (omi tted for brevi ty) of the
el ectron i mpact spectra reported i n the paper of Tsuge
et al .,
14
we fi nd no basi s to support thei r proposal and
prefer to retai n the bi phenyl assi gnment for the struc-
tures detected by the MALDI spectra.
Conclusion
The data col l ected i n our study show that the thermal
oxi dati ve degradati on processes produce a sensi bl e
reducti on of the mol ar mass of the PC sampl es, wi th
formati on of phenyl -substi tuted acetone, acetophenone,
benzyl al cohol , bi phenyl , and phenol s as PC chai n ends.
I t shoul d be remarked that, for the fi rst ti me, the
MALDI mass spectra al l owed the determi nati on of the
speci es predi cted from the thermal oxi dati on mechani sm
i n Scheme 1, whereas i n previ ous studi es
11,13,14
some of
these compounds had escaped detecti on.
The detecti on of PC ol i gomers contai ni ng bi phenyl
uni ts i s an i ndi cati on of the oxi dati ve pathways con-
tri buti ng to the gel formati on.
The accurate MALDI anal ysi s of the oxi dati on prod-
ucts of PC2 sampl e, capped wi th tert-butyl phenyl
groups at both ends, unvei l ed the anti oxi dant acti on of
these termi nal groups, whi ch are abl e to sl ow the rate
of thermal oxi dati on of PC2 (Scheme 2).
The resul ts presented here show that hi ghl y val uabl e
structural i nformati on on the thermal oxi dati on prod-
ucts of PC can be obtai ned by matri x-assi sted l aser
desorpti on i oni zati on (MALDI ) mass spectrometry.
Acknowledgment. Parti al fi nanci al support from
the I tal i an Mi ni stry for Uni versi ty and for Sci enti fi c and
Technol ogi cal Research and from the Nati onal Counci l
of Research (CNR, Rome) i s grateful l y acknowl edged.
Many thanks are due to Mr. Roberto Rapi sardi for hi s
conti nuous and ski l l ful techni cal assi stance wi th MAL-
DI -TOF MS.
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