Trans-Etherification of Aromatic Polyetherketone and Trans-Etherification between Aromatic ...

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Polymer Journal, Vol. 24, No.2, pp 173-186 (1992)
Trans-Etherification of Aromatic Polyetherketone and
Trans-Etherification between Aromatic Polyetherketone
and Aromatic Polyethersulfone
Isaburo FuKAWA,* Tsuneaki TANABE, and Hiroshi HACHIYA
Mizushima Technical Research Laboratory, Asahi Chemical Industry Co., Ltd.,
Shionasu-Kojima, Kurashiki 711, Japan
(Received June 21, 1991)
ABSTRACT: Poly( oxy-1 ,4-phenylene-carbonyl-1 ,4-phenylene-oxy-1 ,4-phenylene-carbonyl-
1,4-phenylene-carbonyl-1,4-phenylene) (PEKEKK) was heated in the presence of potassium
carbonate at 340oC to yield another aromatic polyetherketone, which contained not only the
original EKEKK repeating unit but also the EK and EKK repeating units. This indicates that
trans-etherification reaction occurs between molecules of PEKEKK. Poly( oxy-1 ,4-phenylene
carbonyl-1 ,4-phenylene) (PEK) reacted with poly( oxy-1 ,4-phenylene-sulfonyl-1 ,4-phenylene) (PES)
in the presence of potassium carbonate at 300oC to yield a trans-etherification product, i.e., a block
copolymer of P(EK)I(ES). A further reaction decreased the crystallinity of the block copolymer
to yield a random copolymer.
KEY WORDS Trans-Etherification I Aromatic Polyetherketone I Aromatic
Polyethersulfone I Potassium Carbonate I NMR Spectra I Block Copolymer I
Random Copolymer I
Several polyetherketones1- 4 have been method. PEK was also produced by self-con
prepared by nucleophilic polycondensation densation of 4-phenoxybenzoyl chloride in the
(NP)5 - 7 or electrophilic polycondensation presence of Friedel-Crafts catalyst by the EP
(EP). 8- 11 Poly( oxy-1 ,4-phenylene-oxy-1 ,4- method.
pheny1ene-carbonyl-1 ,4-pheny1ene) (PEEK) is We recently found that the heating of 4,4'
produced by the condensation of 4,4' -difluo (dibenzoyl)diphenyl ether (KEK) (I) and
robenzophenone with hydroquinone in the 4,4' -bis(4 -methylbenzoyl)diphenyl ether (II) at
presence of potassium carbonate by the NP 300°C in the presence of potassium carbonate
method. gave 4-( 4-methylbenzoyl)-4' -(benzoyl)diphenyl
PEK was produced by the condensation of ether (III). III is trans-etherification product of
4,4' -difluorobenzophenone and dipotassium I and II as shown below.
salt of 4,4' -dihydroxybenzophenone by the NP
@-co--@-o- -@-co-@
(I)
cH, --@-co--@-o- -@-co-@
CH --@-CO--@-0--@-CO--@-CH, (II)
3
(III)
On the other hand, heating KEEK (IV) with of potassium carbonate at 300oC gave no
methyl substituted KEEK (V) in the presence trans-etherification product.
173
I. fUKAWA, T. TANABE. and H. HACHIYA
@-co-@-o-@-o-@-co-@
+
(IV)
cH, -@-co -@-o -@-o -@-co -@-cH,
-B
(V)
This fact indicated that the consecutive ether in vacuo before use. PES was purchased from
linkage such as KEEK was stable against the ICI Co., Ltd.
trans-etherification reaction.
We assumed that the trans-etherification Monomer Synthesis
reaction occurred between molecules of aro 1) 1,4-Bis(4-fiuorobenzoyl)benzene was pre
matic polyetherketones. However, it was not pared by the reaction of terephthaloyl chloride
easy to confirm this trans-etherification reac with excess fiuorobenzene in the presence of
tion on the typical polyetherketones such as aluminum chloride. 2) 4,4' -diphenoxybenzo
PEEK and PEK. The trans-etherification phenone was prepared by the reaction of
reaction would not take place on PEEK, 4,4'-difiuorobenzophenone with phenol in the
considering the behavior ofKEEK as described presence of potassium carbonate in benzo
above. The trans-etherification reaction of phenone solvent at 260oC.
PEK cannot be detected by NMR even if the
trans-etherification occurs, because the chemi Polycondensation
cal structure of PEK is not changed by the PEKEKK (NP). A mixture of 36.4g (0.17
trans-etherification reaction. mol) of 4,4'-dihydroxybenzophenone, 56.9 g
To clarify the reaction of (0.18 mol) of 1, 4-bis(4-fiuorobenzoyl)benzene,
aromatic polyetherketone, PEKEKK was pre 25.0 g (0.18 mol) of potassium carbonate, and
pared and reacted with potassium carbonate. 300 g of benzophenone was placed in a 1 liter
Then the chemical structure of the reaction autoclave with a stirrer. After replacing the
product was analyzed by NMR spectra. atmosphere with nitrogen, the temperature was
Furthermore, utilizing the trans-etherifica raised to 300°C in 35 min and kept at 300oc
tion reaction, the block copolymers of for 30 min. Generated water was continuously
P(EK)/(ES) were produced from PEK and removed from the autoclave with nitrogen gas
PES. flow. Then the autoclave was closed and the
temperature was raised to 340°C. The tempera
ture was kept at 340°C for 4 hours.
EXPERIMENTAL
After that, 8 g (0.036 mol) of 4,4' -difiuo
Materials robenzophenone was added to the reaction
4,4' -dihydroxybenzophenone, 4,4' -difiuoro mixture and was made to react with the
benzophenone, diphenyl sulfone, benzophe polymer for 20 min. Solidified product was
none, terephthaloyl chloride, aluminum chlo crushed in water and washed with acetone and
ride, dimethylformamide, benzoyl chloride, water several times.
and methylene chloride were purchased from Reduced viscosity (RV) of the obtained
Tokyo Kasei Co., Ltd. and purified by distil polymer was 0.81 dl g-1.
lation or recrystallization before use. PEKEKK (EP). 10.2g (50mmol) of tere
Potassium carbonate powder was purchased phtaloyl chloride, 18.4g (51 mmol) of 4,4'
from Takasugi Seiyaku Co., Ltd. and was dried diphenoxybenzophenone, 75.3 g (565 mmol) of
174 Polym. 1., Vol. 24, No.2, 1992
Synthesis of PES/PEK Blockcopolymer by Trans-Etherification
aluminum chloride, 0.05 g (0.4 mmol) of RVof0.8ldlg-1.
benzoyl chloride, 16.5 g of dimethylformamide,
and 200 ml of methylene chloride were mixed Analysis
at - 30oC and allowed to react at ooc for RV was measured at a concentration of
15 min and then at 20°C for 1.5 hours. The 0.1 g dl-1 at 25oc by using an Ubbelhode
reaction mixture was pulverized in methanol viscometer. Concentrated sulfuric acid (98%)
and washed well with methanol, 7 wt% hydro was used as a solvent for crystalline polymers
chloric acid, hot water and hot acetone. RV of and NMP was used for amorphous polymers.
the obtained polymer was 0.98 dl g-1. 1H and 13C NMR spectra were measured on
2 wt% solution of deuteriosulfuric acid
Trans-Etherification (D 2 SO 4) by a JEO L FX- 400 spectrometer.
P EKEKK. A mixture of 20 g of PEKEKK Hexamethyldisiloxane (0.0 ppm) and dioxane
and 3 g of potassium carbonate was heated in (67.4ppm) were used the internal standards for
100 g of diphenyl sulfone solvent at 340°C for 1H and 13C NMR, respectively.
6 hours. The obtained reaction mixture was
treated as the same manner as the preparation
RESULTS AND DISCUSSION
of PEKEKK (NP) described above.
PEK/PES. A mixture of 5g of PEK (RV Trans-Etherification of PEKEKK
0.7dlg-1), 5g ofPES·(RV 0.4dlg-1) and 5g Synthesis of P EKEKK. PEKEKK (EP) was
of potassium carbonate was heated at 300°C prepared by electrophilic polycondensation of
in the presence of20 g ofbenzophenone solvent 4,4' -diphenoxybenzophenone with terephtha
for 3 hours. Then the reaction product was loyl chloride in the presence of aluminum
crushed to powder in water and the powder chloride catalyst. The 13C NMR spectrum of
was washed with acetone and NMP. Thus PEKEKK (EP) was shown in Figure 1.
obtained polymer was a block copolymer with
@-o-@-co -@-o-@ +ClOC -@-coc1 ......
-t@-o -@-co -@-o -@-co -@-cot-
+HCl
PEKEKK (NP) was produced by the carbonate. The 13C-NMR spectrum of PE
nucleophilic polycondensation of 4,4' -dihy KEKK (NP) is shown in Figure 2 and was
droxybenzophenone with 1,4-bis(4-fluoroben identical to that of PEKEKK (EP).
zoyl) benzene in the presence of potassium
Ho-@-co-@-oH+F-@-co-@-co-@-F+K,co,
+-o-@-co-@-o-@-co-@-co-@++2KF+H,O+CO,
Trans-Etherification of PEKEKK. PEKEKK shown in Figures 3-5. The spectrum was more
(NP or EP) was heated in the presence of complex than that of the original PEKEKK
potassium carbonate at 340oC for 6 hours. 13C (NP or EP). Extra peaks appeared in the
NMR spectrum of the reaction product was spectrum of the product and were coincident
Polym. J., Vol. 24, No.2, !992 175
I. fUKAWA, T. TANABE, and H. HACHIYA
,......=
·od t.r.> 0) 0
,......tv:>
",..<...1. ',...... c--.i 0 0
t..v..:.>.. C,..'.-..J. C,..'.-..J.
t-
C'-l t.r.>
,=0...0... =cv:i 0U)J C,.'.-J. ...0)
....... c,.v..:.:.>. cv:i
C....'-..J.
PP
, • 1• ' t c • 1 t 1 1 1• • 1 1 • • 1 1 t 1 • 1 c 1 • 1 1 1 1 1 t t 1 1 1 1 1 1 1 I' • 1 1 1 • 1 1 1 I' 1 1 1 ' ' 1 • t 11 1 '' n nr
clo i?llfi lflll I 'lG I £i0 150 14TJ 1:3ll I ell I I 0 I tfi
'-----·-------·-·-
Figure I. 13C NMR spectra of PEKEKK. Electrophilic polycondensation.
UJ 0) 0
C'..J UJ c--.i
",,......<...... I'.oM..O.... .t.v..:.>.. ,C0.. .'-..J. 0C '-J
=
c-.l
C0 ..J = t-
=
,M.... .. ........
M
,C...'-..J.
rrr
n tTTTrrtl r-nt rnr'ltn·n-rrrrprnr nrr11T1TTTTTt"f' 111 rt11f11T1 nTn-rp rrrrt n-rrnrrrrrTTfTnTrrrnl rn1 rnl'll rnt rtl r
210 cOG I'JO lBO 1'10 160 ISO 14D 1:30 120 110 I ICi
Figure 2. 13C NMR spectra of PEKEKK. Nucleophilic polycondensation.
with the peaks of PEKK or PEK. quartenary carbons were distinguished by a
13C NMR spectra of PEK, PEKEKK and comparison of proton coupled spectra and
PEK K were assigned and are summarized in decoupled spectra.
Table I. The peaks of tertially carbons and The extra peaks were 203.1 ppm (PEKK
176 Polym. J., Vol. 24, No.2, 1992
Synthesis of PES/PEK Blockcopolymer by Trans-Etherification
(1)
,-mrttlljilliltlilj'''''''''i'''''''''l'''''''''l'''''''''l'''''''''l'''''''''l'''''''''l'''''''"
em; I !:1!1 19(! I t I n
( 2)
==
C'-1
pp
21iG L'li'l I IIJf.: I I 0
(3)
Figure 3. Comparison of 13C NMR spectra (190-210ppm): (I) PEKEKK; (2) PEKEKK after the
heating with K C0 at 340"C; (3) PEKK.
2 3
Polym. J., Vol. 24, No.2, 1992 177
I. FUKAWA, T. TANABE, and H. HACHIYA
(1)
rr
nnrrnqnt tTl """1'' rt nrrryt rnn n 'ln nn nrp 11 rn n '11 n ttt"tl"f1tT1"1Ttnt·1 nnt nrryrrrmrnp-ntiTnT'fTTT'Tl'Tn
IGO IGG IG'1 IGi? !GO I Y
(2)
C"':>
=00 U";)
....... = ccv.o;)
= .......
=
......
tTTTtll'"lTtlltlt,rytTITTrftTll 1111 11"T'1TTTTflTT11n1 t I I t1'T') Tl Tl tl tTTlnTt ti"T'TT'flTI tl tTT'l tl ftTTT1TJTtl"TITrT'T'f"Nn
I 'lG I I I I m I GG I GY I I GO I Sll I I 'l
(3)
rr
11tT1TrTT"Jf"fftnfT1T""""ITI rTfTI trtTII--rTfl rl fl tnrr I 1"1 I I rttlrt"I"TII n-,.nTtl trn-p-t fl tt rTrfl fTTI ftTT'[fll fl HT,fftTtln
I I I 'li? I I m I GG I G'l I I GO I 50 I I 'l
Figure 4. Comparison of 13C NMR spectra (155-176ppm): (I) PEKEKK; (2) PEKEKK after the
heating with K C0 at 340°C; (3) PEKK.
2 3
178 Polym. J., Vol. 24, No.2, 1992
Synthesis of PES/PEK Blockcopolymer by Trans-Etherification
(1)
t-
u-:i =
.C..'.-...l
M
.C..'.-...l
PIS IYO lJ'j IJli 1<?5
(2) = =
..--<
,.....; =
C'-.l
N,... ..; = .<.."..:.) .N.-- < "·-'·'
'""'
..--< 00
M =
..--<
= 00 =
M..... .. LI":> ...,;.
C'J N
t- = ..--<
=
.'".."...'
1'10 r3n ll?S J20 ! 0
(3) 00
t-- t- =
= N N.... ...
'""' .<.."..:.)
..--< =
N
= LI":>
M N... ...
..--<
Figure 5. Comparison of 13C NMR spectra (II0-145ppm): (I) PEKEKK; (2) PEKEKK after the
heating with K C0 at 340"C; (3) PEKK.
2 3
Polym. 1., Vol. 24, No.2, 1992 179
I. FUKAWA, T. TANABE, and H. HACHIYA
Table I. Assignment of 13C NMR spectra of PEK, PEKK, and PEKEKK'
Structure Tertially carbon Quarternary carbon
Adjacent Next-adjacent PEK PEKK PEKEKK PEK PEKK PEKEKK
132.7 132.5 136.2 135.9
( 7) (12) ( 6) (II)
---- -·------
I 140.7 141.1 125.0 125.7
( 3) ( 8) ( 4) ( 9)
•co-@-o•
138.4 138.5 124.9 123.9
( 3) ( 3) ( 4) ( 4)
I 120.8 120.9 166.6 168.2
( 2) ( 7) ( I) ( 6)
120.1 120.0 164.7 163.4
( 2) ( 2) ( 1) ( 1)
I 200.8 202.0
•o-@-,o-@-o• ( 5) ( 5)
-CO-
203.1 202.0
( 5) (10)
' PEK
5 10
I 2 34 1234 6789 1112
PEKK-
12 34 6 7
b The sign of • represents para-phenylene unit.
203.1 ppm), 201.5 (PEK, 200.8), 166.6 (PEKK, EK were formed by the trans-etherification
166.6), 165.0 (PEK, 164.7), 140.7 (PEKK, reaction between the molecules of PEKEKK
140.7), and 125.0 (PEKK, 125.0). These results as shown below.
indicate that both repeativng uni ts of EKK and
l
1--+ (E K E K K) EKE K (E K K E K)
(E KE K K) E K K (E K E K K)
....
(E K K E K) E K K E K (E K K E K) (E K K E K) E K K E K K (E K E K K)
------------·-------
Trans-Etherification during Polycondensa shows that the trans-etherification also occurs
tion. When the nucleophilic polycondensation during polycondensation.
reaction of 4,4' -dihydroxybenzophenone with
1, 4-bis( 4-fluorobenzoyl)benzene was carried Trans-Etherification between PEK and PES
out at higher temperature in the presence of Block copolymer of PEK and PES. It was
higher amount of potassium carbonate, these reported that the stepwise polycondensation of
extra peaks were also observed in the NMR PEEK and PES gave a P(EEK)/(ES) block
spectrum of the obtained PEKEKK. This copolymer.12
180 Polym. J., Vol. 24, No.2, 1992
Synthesis of PESiPEK Blockcopolymer by Trans-Etherification
F --@-o--@-o --<Q)tnco-@-F
Nao --@-o -<QJmso, -@-oN
+
a
tt-@-co--@-o--@-oM@-so,-@-07m+
We tried to prepare the P(EK)/(ES) block unit of PEK or PES block was about 20.
copolymer using the trans-etherification reac The Tm of the product was 342 and 384CC
tion between PEK and PES. annd its Tg was 222oc. Its RV was 0.8dlg-1
and its X-ray diffraction pattern (Figure 7) was
PEK +PES P(EK)/(ES)
similar to that of PEK.
(EK-Jm-EK--fES)q Reaction of P EK with PES in Diphenyl
Sulfone Solvent. The reaction of PEK with PES
in the presence of potassium carbonate was
carried out in diphenyl sulfone solvent instead
( ES-)p--EK -fEK)n
of benzophenone solvent (Table II).
PEK was reacted with PES in the presence of A mixtures of PES and PEK with several
potassium carbonate in benzophenone solvent weight ratios (PES/PEK= 1/9-9/1) reacted
or in diphenyl sulfone solvent. The reaction with potassium carbonate at 260°C for 3 hours
product was wholly insoluble in NMP solvent. or 300°C for I, 3 or 5 hours in order to clearify
This shows that the unreacted PES did not the effect of the reaction conditions on the
remain in the reaction product because PES is properties of the product. The product was
soluble in NMP, though PEK is insoluble in characterized by DSC ( Tc, T m' and Tg) and
NMP. The formation of the block copolymer X-ray diffraction. A higher melting point and
was confirmed by the 1 H-NM R spectra of the larger heat of fusion (!1H) indicated the
products. presence of a more perfect PEK block or higher
Reaction of PEK with PES in benzophenone molecular weight PEK block in the product.
solvent. For example, 5 g of PEK (RV Higher Tg indicated the presence of a more
0.7dlg-1) and 5g of PES (RV 0.4dlg-1) perfect PES block or the higher molecular
was heated at 300oc for 3 hours in the presence weight PES block in the product. As the Tg of
of 5 g of potassium carbonate in benzophenone PES was higher than that of PEK, the Tg of
solvent to yield 9.9 g of the product, which any copolymer of PES/PEK were lower than
was insoluble in NMP. The product showed that of PES.
new peaks at 6.83, 6.91, 7.54, and 7.66ppm Higher reaction temperature gave a block
in addition to the peaks of PEK (7.03, copolymer with lower melting point and lower
7.78 ppm) and PES (6.73, 7.43 ppm) as shown crystallinity (No. 01 vs. No. 08, No. 02 vs. No.
in Figure 6. The new peaks coincided with 09, and No. 03 vs. No. 10 in Table II). The
those of the alternate copolymer (PEKES) longer reaction time at 300°C decreased the
and were assigned to the structure of melting point and crystallinity of the block
-@-o-@-co-@-o-@-so,-'" copolymer (No. 04, 08, and 12 of PES/
The in
PEK = 3/7 in Table IT, and No. 05, 09, and
tensity ratio of new peaks, PEK block peaks 13 of PES/PEK = 5/5 in Table II). The Tg of
and PES block peaks in the NMR spectrum, block copolymer decreased with increase of
indicated that the average number of repeating reaction time.
Polym. J .. Vol. 24. No.2. 1992 181
I. fUKAWA, T. TANABE, and H. HACHIYA
(1)
Pi" I
- ,.......--.,-----r--T--r--r-t·'"'""T--,.- ...,..-,----,.-
6.0 G
( 2)
J
'\J' -
pl.j \...,....
..- ""--.-v. .........
o.n 6 5
(3)
o.o s s
Figure 6. Comparison of 1H NMR spectra: (1) 1H NMR spectrum of PES: (2) 1H NMR spectrum of
P (EK)/(ES) block copolymer: (3) 1 H NMR spectrum of PEK.
182 Polym. J., Vol. 24, No.2, 1992