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a
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK
b
College of Material Science and Chemical Engineering, Zhejiang University, Hangzhou 310027, PR China
Received 16 August 2002; received in revised form 29 October 2002; accepted 29 October 2002
Abstract
Ring-opening polymerization of D ,L -lactide (LA) was catalyzed by the well-defined bis(trimethyl triazacyclohexane)
praseodymium triflate ½ðMe3 TACÞ2 PrðOTfÞ3 (Cat) for the first time. The effect of the [LA]/[Cat] molar ratio, solvents,
temperature, and reaction time were investigated in detail. The results show that the praseodymium catalyst is very
efficient in the melt polymerization, giving D ,L -PLA with molecular weights of 104 in good conversion. The importance
of the triazacyclohexane was shown by comparison to the poor catalytic activity of PrðOTfÞ3 .
Ó 2002 Elsevier Science B.V. All rights reserved.
Keywords: Ring-opening polymerization; Polylactide; Praseodymium; Lanthanide triflates; Lewis acid catalyst
1566-7367/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved.
PII: S 1 5 6 6 - 7 3 6 7 ( 0 2 ) 0 0 2 4 4 - 3
34 R.D. K€
ohn et al. / Catalysis Communications 4 (2003) 33–37
for examples, triflic acid [4] and its esters, can LnðOTfÞ3 Lewis acid catalysts. Here we report the
initiate a cationic polymerization. Secondly, alkali preliminary results of ring-opening polymerization
metal alkoxides, phenoxides and carboxylates [3] of D ,L -LA by this catalyst (see Fig. 2).
are active to initiate an anionic polymerization of
lactide. The last but not the least, so called ‘‘co-
ordination–insertion’’ catalysts, based on organo- 2. Results and discussion
metallic complexes such as ½ðn-BuOÞ3 Al2 and
SnðOctÞ2 [5]. The lactide plays temporarily the role ½ðMe3 TACÞ2 PrðOTfÞ3 was found to be able to
of a ligand coordinated to the metal atom by the catalyze the polymerization of D ,L -lactide in vari-
carbonyl O atom activating the lactide for inser- ous solvents without the requirement of any addi-
tion according to Fig. 1. Some lanthanide catalysts tional reagent. The optimal yield (95% at
belonging to this category, for instance LnðOiPrÞ3 [LA]:[Cat] ¼ 1000) and molecular weight of the
[6], LnðacacÞ3 [7], LnðnaphÞ3 ; LnðOctÞ3 and others polymer (18,000) was obtained in melt polymeri-
[8], were found to be efficient in the polymerization zation at 170 °C (18 h). Under the same conditions,
of lactide. Lewis acid catalysts without OR- or PrðOTfÞ3 was a poor catalyst giving low molecular
similar nucleophilic groups, e.g. SnðOTfÞ2 and weight D ,L -PLA (5700) in medium yields (74%).
ScðOTfÞ3 [9], can be used when an alcohol is added Thus, the additional ligands have significantly im-
as the initiating group. proved the catalyst. GPC showed a much lower Mn
During the last 10 years, N-substituted 1,3,5- (6200) and a PDI of 2.72 indicating fast inter- and
triazacyclohexane ( R3 TAC ), which can act as a six- intramolecular transesterification [12] leading to an
electron donor ligand, is causing more and more average of 21 polymer chains per metal. This was
interest in coordination chemistry and catalysis. also confirmed by NMR analysis of the polymer.
This ligand is easily accessible and highly variable The 13 C NMR region for the methane carbon at-
due to its simple preparation from primary amines oms showed two major signals at 69.1 and 68.9
and formaldehyde. The acute N-metal-N angle ppm (ratio 1:3) expected for poly-rac-D ,L -lactide
of around 60° makes triazacyclohexanes sterically [13] but also signals at 69.4, 69.3 and 69.0 that can
little demanding facially coordinating ligands. The only derive from transesterification. The major
ring strain upon j3 -coordination facilitates a observable end group is the alcohol HOCMeHC
potential hemi-lability towards j1 -coordination. ð@OÞA with signals at 4.4 (CMeH) ð1 HÞ and 20.5
Thus triazacyclohexanes should be interesting an- (CH3 ), 66.6 (HOC), and 174.7 ppm (C@O) ð13 CÞ
cillary ligands for catalysis. Its chromium(III) [14] at intensities suggesting an NMR-determined
complexes activated by MAO are highly active ho- Mn of only 3200. No additional signals of similar
mogeneous ethylene polymerization catalysts that intensity for the other end group could be detected.
resemble the Phillips catalyst in many important However, much smaller signals at 2.8 ð1 HÞ and 37.1
properties [10]. The first lanthanide complex with and 72.4 ppm ð13 CÞ may correspond to protonated
triazacyclohexane, ½ðMe3 TACÞ2 PrðOTfÞ3 , was Me3 TAC of approximately the amount added with
synthesized recently [11] as modification to existing the catalyst. Thus, we suspect that hydroxide from
deprotonation of trace amounts of water in the
lactide with Me3 TAC can act as the initiator
Fig. 1. Mechanism of the lactide insertion into metal alkoxides. Fig. 2. Molecular structure of ðj3 -Me3 TACÞ2 PrðOTfÞ3 .
R.D. K€
ohn et al. / Catalysis Communications 4 (2003) 33–37 35
Table 1
Effect of various solvents on the polymerization of D ,L -lactide
a
Solvent THF Dichloromethanea Ethyl acetatea Toluenea No solventb
Yield (%) 88 82 79 84 95
Mg ð104 Þ 1.03 0.83 1.26 1.18 1.80
a
[LA]/[Cat] ¼ 1000, reflux or 80 °C, 24 h.
b
[LA]/[Cat] ¼ 1000, 170 °C, 18 h, vacuum.
36 R.D. K€
ohn et al. / Catalysis Communications 4 (2003) 33–37
tains at 120° (PDI ¼ 1.85), 180° (2.72) and 200 °C of the apparent first-order rate constant kapp
(3.46) showed average number of polymer chains against the catalyst concentration is shown in Fig.
per metal is 14, 21 and 45, respectively. 6. A fractional order of 1/2 in the catalyst con-
centration is found. This is not uncommon for ring
2.3. The effect of the molar ratio [LA]/[Cat] on the opening polymerization of lactones ([16] and ref-
polymerization erences therein) and can be explained by a fast
equilibrium between an active mononuclear com-
Fig. 5 shows both the polymer yield and mo- plex with an inactive dinuclear complex as the
lecular weight as a function of the molar ratio resting state of the catalyst. The solution behavior
[LA]/[Cat] when polymerization was carried out at of the precatalyst ½ðMe3 TACÞ2 PrðOTfÞ3 has al-
170 °C for 18 h. The molecular weight increased ready shown a tendency to dimerize with loss of
gradually but not linearly with the [LA]/[Cat] ratio one of the two Me3 TAC [11]. Formation of alk-
as a result of transesterification. A logarithmic plot oxide groups as good bridging ligands during the
catalysis should favor this dimerization.
3. Conclusions
4. Experimental
sensitive compounds were carried out under an National Natural Science Foundation of China
atmosphere of nitrogen or argon using standard (20074028).
Schlenk line or glove box techniques.
Polymerization. The polymerization was per-
formed in a 20 ml ampoule that was thoroughly References
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