Polymer Degradation and Stability 93 (2008) 19091916

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Polymer Degradation and Stability

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Effect of type of peroxide on cross-linking of poly(L-lactide)

Masumi Takamura a, b, *, Tomoyuki Nakamura a, Tatsuhiro Takahashi b, Kiyohito Koyama b
a b

Functional Chemicals and Polymers Research Laboratory, NOF Corporation, 82, Nishimon, Taketoyo-cho, Chita-gun, Aichi 470-2345, Japan Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510, Japan

a r t i c l e i n f o
Article history: Received 8 May 2008 Received in revised form 29 June 2008 Accepted 3 July 2008 Available online 11 July 2008 Keywords: Poly(L-lactide) Cross-link Peroxide Hydrogen abstraction ability

a b s t r a c t
Poly(L-lactide) (PLLA) was cross-linked with various types of peroxides under constant mole ratios of peroxide-derived radicals to PLLA during reactive extrusion. Peroxides were classied into three groups according to their decomposition rates (Group I: fast, Group II: moderate and Group III: slow) and comparisons were performed within each group. Cross-linking behavior was readily understood in terms of free radical efciency and hydrogen abstraction ability of radicals. In the case of Groups II and III, the weight-average molecular weight (Mw) of cross-linked PLLA increased with overall hydrogen abstraction ability, because slow decomposition caused uniform cross-linking in molten PLLA. In Group I, Mw and gel fraction were higher than other groups despite Group Is lower hydrogen abstraction ability, leading to the conclusion that peroxide decomposition localized in solid PLLA caused partial cross-linking because of rapid decomposition. Furthermore, the efciency of peroxide-induced cross-linking was investigated using the CharlesbyPinner equation. 2008 Elsevier Ltd. All rights reserved.

1. Introduction Poly(L-lactide) (PLLA) is a remarkable material of considerable contemporary interest not only as a biodegradable polymer but also as a bio-based polymer (one not derived from petroleum resources). Although PLLA has high mechanical strength and high modulus, one of the limitations for using PLLA is its low melt strength, resulting in processing instabilities. In order to overcome this disadvantage, it is common to introduce branching structures in PLLA by various methods, including chemical cross-linking [14], radiation-induced cross-linking [1,57] and peroxide-induced cross-linking [14,814]. Because of its simplicity, peroxideinduced cross-linking has been widely applied through the addition of small amounts of peroxide during extrusion. Peroxides are classied into seven different types, providing a broad range of reactivity according to their chemical structures: diacyl peroxides, peroxyesters, diperoxyketals, dialkyl peroxides, hydroperoxides, ketoneperoxides and peroxydicarbonates. Sodergard et al. [9] investigated peroxide-induced cross-linking of PLLA using several types of peroxides in an extruder. They proposed that dialkyl peroxides having no carbonyl groups, such as dicumyl peroxide and di-t-butyl peroxide, degraded PLLA while hydroperoxides and peroxides with carbonyl groups stabilized the polymer. However, their experiments were carried out using a constant 0.5% weight ratio of peroxides (of various molecular weights) to PLLA,

resulting in different mole ratios of peroxide-derived radicals to polymer. In addition, they compared the various cross-linking processes of PLLA without taking the different peroxide decomposition rates into consideration; that is, PLLA changed from solid to liquid during extrusion, and rapidly decomposed peroxides could have induced cross-linking in solid PLLA. On the basis of the foregoing considerations, the rst aim of this paper was to investigate the detailed relationship between the type of peroxide and the resulting cross-linking of PLLA, while keeping the mole percent of peroxide-derived radicals constant, and taking into account the decomposition rate of the various peroxides. Peroxide-induced cross-linking of polymers is believed to follow three key steps: (i) the generation of primary radicals derived from thermal decomposition of peroxides, (ii) hydrogen abstraction from polymer chains by primary radicals to generate polymer radicals, and (iii) the bimolecular recombination of polymer radicals to form carboncarbon cross-links. (i) Primary radical generation ROOR / 2ROprimary radicals (ii) Hydrogen abstraction RO D Ppolymer / Ppolymer radical D ROH (iii) Bimolecular recombination of polymer radicals

* Corresponding author. Functional Chemicals and Polymers Research Laboratory, NOF Corporation, 82, Nishimon, Taketoyo-cho, Chita-gun, Aichi 470-2345, Japan. E-mail address: masumi_takamura@nof.co.jp (M. Takamura). 0141-3910/$ see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymdegradstab.2008.07.001

2P / PPcross linking

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Since peroxides play an important part in both step (i) and step (ii), many researchers have been studying the effect of peroxide type on the cross-linking of polymers such as polyethylene [15] and polypropylene [16,17]. Lazar et al. [17], for example, proposed that the reactivity of the primary radicals and their diffusion rates inuenced the efciency of cross-linking in polypropylene. Recently Watanabe et al. [18] proposed a new method for determining the hydrogen abstraction ability of peroxides using the amethylstyrene dimer (MSD) trapping technique. This technique is based on addition-fragmentation reactions between free radicals and MSD. When peroxides are decomposed in a mixture of hydrogen donor substrates and MSD, some peroxide-derived radicals are directly trapped by MSD, while others abstract hydrogen from substrates to give trapping products. Thus, the yield of trapping products generated by hydrogen abstraction from a substrate reects the hydrogen abstraction ability of a given peroxide. This technique is useful to estimate overall hydrogen abstraction ability of various peroxide-generating free radicals; however, there are few papers that describe the connection between overall hydrogen abstraction ability and the cross-linking of polymers. With this in mind, the second aim of this paper was to establish a quantitative relationship between the hydrogen abstraction ability of peroxides (measured using the MSD trapping technique) and the cross-linking of PLLA.

ratio of residual peroxide to initial peroxide was 0.0001. The relationship between lifetime and the ratio of residual peroxide to initial peroxide was calculated by the following equation, using the thermal decomposition parameters of the peroxides:

lifetime s lnthe ratio of residual peroxide to initial peroxide=kd

where kd (s1) is the rst-order rate constant [19] of each peroxide. The overall hydrogen abstraction ability of each peroxide was measured using the MSD trapping technique [19]. The molar concentrations of MSD, cyclohexane (hydrogen donor substrate) and peroxide were xed at 1.0 M, 6.9 M and 0.05 M, respectively. 2.2. Cross-linking All cross-linking reactions were carried out using a single-screw extruder (Laboplastmil: Toyoseiki Co. LTD, Tokyo, Japan; D 20 mm, L/D 25) with a xed temperature prole for the extruder (Zone 1/Zone 2/Zone 3/Die 180  C/185  C/190  C/ 190  C). The cross-linking procedure was as follows. First, 500 g of PLLA (7.95 mmol calculated from Mn of PLLA) were blended with peroxide in zip-lock plastic bags before extrusion. For peroxides that were solids at room temperature (LPO, BPO and DCP), 0.5 g of acetone was sprinkled over the blended sample of PLLA and peroxide followed by drying in a vacuum oven for 8 h at room temperature. The amounts of added peroxides are listed in Table 1, from which it can be seen that the number of moles of peroxidederived radicals was xed at 7.95 mmol. That is, the molar ratio of peroxide-derived radicals to PLLA was basically one-to-one except in the experiments where the inuence of the amount of added peroxide was studied. Next, the blended sample was poured into a feeder attached at the front barrel, and the screw speed was set at 150 rpm. Extrusion time was measured as the time from sample insertion into the feeder until each cross-linked PLLA strand was extruded. About 400 g of each extruded sample were obtained and dried in a vacuum oven for 24 h at 40  C. The residual peroxide in each extruded sample was measured by iodometry in chloroform solution [20] (for all peroxides except DCP) or by gas chromatography [21] (for DCP). Samples containing residual peroxide (namely those extruded with TBTH, BTBV and DCP) were extruded again and dried as before. After ensuring that none of the samples had any residual peroxide, they were dried in a vacuum oven for 2 h at 90  C to remove water and were stored in a desiccator. Furthermore, to provide reference samples for PLLA in Group I, Group II and Group III, neat PLLA without peroxide was extruded once (none1), twice (none2) and three times (none3), respectively. Peroxides having a relatively high hydrogen abstraction ability (BPO, TBEC, TBPB and DCP) were selected for studying the inuence of the amount of added peroxide on cross-linking. Except for BPO,

2. Experimental 2.1. Materials The commercial-grade PLLA (LACEA H100; D-conguration 1.5%; residual lactide 0.14%) used in this study was provided by Mitsui Chemicals, Tokyo, Japan. The number-average (Mn) and weightaverage (Mw) molecular weights of untreated PLLA were 63,000 g/ mol and 132,000 g/mol, respectively, as measured by size exclusion chromatography (SEC). Peroxides: dilauroyl peroxide (LPO, melting point 54  C), dibenzoyl peroxide (BPO, melting point 106  C; immediate decomposition), t-butyl peroxy-2-ethylhexanoate (TBEH), OO-(tbutyl) O-(2-ethylhexyl) peroxycarbonate (TBEC), t-butyl peroxy3,5,5-trimethylhexanoate (TBTH), t-butyl peroxy benzoate (TBPB), n-butyl 4,4-di-(t-butyl peroxy) valerate (BTBV) and dicumyl peroxide (DCP, melting point 39  C) were obtained from NOF Corporation, Tokyo, Japan and were used as received. The peroxides were classied into three groups according to their decomposition rates at 190  C (Group I, fast; Group II, moderate; Group III, slow) and their physical and thermal properties are listed in Table 1. The lifetime was one of the measures used to quantify peroxide decomposition rate and was dened here as the time when the

Table 1 Peroxides used in this study and their respective amounts Group I Type Diacyl peroxides Peroxyesters Peroxyesters Chemical name (abbreviation, purity) Dilauroyl peroxide (LPO, 98%) Dibenzoyl peroxide (BPO, 75%a) t-Butyl peroxy-2-ethylhexanoate (TBEH, 97%) OO-(t-Butyl) O-(2-ethylhexyl) peroxycarbonate (TBEC, 97%) t-Butyl peroxy-3,5,5-trimethylhexanoate (TBTH, 97%) t-Butyl peroxy benzoate (TBPB, 97%) n-Butyl 4,4-di-(t-butyl peroxy) valerate (BTBV, 95%) Dicumyl peroxide (DCP, 98%) Mw (g/mol) 399 242 216 246 230 194 334 270 Lifetime (s)b 2 5 11 68 110 108 190 190 Peroxide amounts (g/kg PLLA)c 3.24 2.57 1.77 2.06 1.89 1.57 1.38 2.19

II

III
a

Diperoxyketals Dialkyl peroxides

Moisture content 25%. Lifetime at 190  C calculated using decomposition parameters (DE and A) from Ref. [19]. Lifetime (s) ln(ratio of residual peroxide to initial peroxide)/Aexp(DE/RT), where the ratio of residual peroxide to initial peroxide 0.0001, R 8.31 J mol1 K1(gas constant) and T 463 K. c Radical content was xed at one peroxide molecule per PLLA molecule.
b

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cross-linked PLLA was not obtained in the extruder when the mole ratio of radicals to PLLA exceeded 3:1 because of increased melt viscosity. 2.3. Characterization Molar mass measurements were obtained by SEC relative to polystyrene standards with chloroform as the eluent. The system was based on an LC10A (Shimadzu Co. LTD, Kyoto, Japan) and 2 GMHHRH(20)HT columns (TOSOH Co. LTD, Tokyo, Japan). The sample concentration was 0.5 wt% in chloroform and solutions were ltered with a 0.5-mm lter before injection. The gel fraction was the weight percent of gel after ltration of 0.2 wt% cross-linked PLLA in chloroform. To obtain further information on gel formation, the sizes of swollen gel particles of cross-linked PLLA dispersed in chloroform were measured by laser light scattering analysis using an LA-920 (Horiba Co. LTD, Kyoto, Japan) over a diameter range from 0.02 to 2000 mm. Swollen gel size was dened as the median diameter because the size distributions were very similar. Melt ow index (MFI) was measured according to ISO 1133 using a melt ow indexer TYPE C-5059D (Toyoseiki Co. LTD, Tokyo, Japan) operating at 190  C with a 2.16-kg load. 3. Results and discussion 3.1. Effect of type of peroxides on cross-linking of PLLA 3.1.1. Group I: peroxides with high decomposition rate Table 2 shows the effect of peroxide type on Mw and gel fraction of cross-linked PLLA. In order to clarify the relationship between the chemical structures of peroxide-derived radicals and their hydrogen abstraction ability, the structures of the radicals and the hydrogen abstraction ability of each peroxide [18,19] are also listed in Table 2. The thermal decomposition mechanisms [19] of these peroxides are shown separately in Scheme 1. It should be noted at the outset that all cross-linked PLLAs had an Mw higher than that of none1, implying that cross-linking reactions predominated over degradation processes. For diacyl peroxides, the Mw of BPO-induced cross-linked PLLA was 1.1 times higher than for LPO, with a 12-fold greater gel fraction. Since the hydrogen abstraction ability of BPO was ve times higher than that of LPO, BPO-generated radicals induced local cross-links in PLLA during extrusion. This was because different reactions (diffusion or decomposition or hydrogen abstraction) of peroxide or peroxide-induced radicals occurred under MSD trapping conditions and under reactive extrusion; that is, in the former case, peroxide, MSD and hydrogen donor substrates were dissolved uniformly and the radicals reacted with MSD or hydrogen donor substrates in accordance with theoretical predictions. However, in the latter case, localized peroxide decomposition in solid PLLA

caused the partial cross-linking of PLLA because of the short peroxide lifetime relative to the extrusion time. The reason why LPO-induced cross-linking was substantially less than for BPO was due to the lower free radical efciency (f) of LPO and the lower hydrogen abstraction ability of its derived radicals. In the explanation shown in Scheme 1, LPO and BPO gave rise to lauroyloxy (ILa) and benzoyloxy radicals (IBa), respectively. In the MSD trapping technique [22], ILa was converted to undecyl radicals (ILb) by releasing CO2, while 30% of IBa were converted to phenyl radicals (IBb) at 140  C. Furthermore, a marked cage effect resulted in recombination of ILb radicals caused a lower f ((1), while IBa and IBb had a higher f (z1) because of a less pronounced cage effect [22]. In comparison, TBEH-induced cross-linked PLLA showed intermediate cross-linking between that of LPO and BPO. The primary radicals produced by TBTH were alkanoyloxy radicals (2-ethylhexanoyloxy radicals: (IEa) having similar decomposition behavior to LPO and t-butoxy radicals, (IEb) with a higher hydrogen abstraction ability than ILa). This situation resulted in a lower crosslinking efciency compared to BPO, but higher than that for LPO (Scheme 4). 3.1.2. Group II: peroxides with moderate decomposition rate Table 3 shows the effect of the type of peroxide on cross-linking. Also, the thermal decomposition mechanisms [19] of these peroxides are shown in Scheme 2. First, all cross-linked PLLAs had a higher Mw than did none2, so this group was more effective than Group I. Generally speaking, the Mw and gel fraction of cross-linked PLLA tended to increase with increasing hydrogen abstraction ability of the peroxide. This was because similar reactions of peroxides or peroxide-derived radicals occurred in the MSD trapping method and during extrusion; that is, peroxide decomposition dispersed in molten PLLA caused uniform cross-linking of PLLA because the peroxide lifetime was approximately equal to the extrusion time. Peroxides having lower overall hydrogen abstraction ability caused less cross-linking due to their lower f and the lower hydrogen abstraction ability of their derived radicals. This is explained in Scheme 2, in which TBEC, TBTH and TBPB give rise to 2-ethylhexylcarbonate (IIEa) and t-butoxy radicals (IIEb); 3,3,5-trimethylhexanoyloxy (IITa) and t-butoxy radicals (IITb); and benzoyloxy (IIBa) and t-butoxy radicals (IIBb), respectively. IITa changed to 2,2,4-trimethylpentyl radicals (IITd) by releasing CO2. Furthermore, a more pronounced cage effect [22] resulted in the recombination of IITd radicals and a lower f ((1) gave rise to t-butoxy 2,2,4-trimethylpentane. TBPB induced greater cross-linking in PLLA than did TBEC, even though their respective primary radicals (IIBa and IIEa) were not affected by the cage effect or by decarboxylation [22,23]. This was because the higher hydrogen abstraction ability of IIBa caused more extensive cross-linking than did IIEa.

Table 2 Effect of Group I peroxides on cross-linking of PLLA Type Abbreviation Structure of peroxide-derived radicalsa (order of predominance) ILb > ILa IBa > IBb IEd > IEb > IEc > IEa Hydrogen abstraction ability (%)b 3 15 26 Lifetimec/ extrusion timed (s/s) 2/70 5/62 11/62 /55 Molar mass (104) Mn(g/mol) 5.4 5.6 5.7 5.7 6.3 Mw(g/mol) 12.9 14.4 13.8 12.5 13.2 Gel fraction (wt%) 0.2 2.4 0.7

Diacyl peroxide Peroxy-ester None1 Neat PLLA

a b

LPO BPO TBEH

Structure of radicals given in Scheme 1. Yield of hydrogen abstraction from cyclohexane using a-methylstyrene dimer technique, measured at 100  C. c Lifetime at 190  C calculated using decomposition parameters (DE and A) from Ref. [19]. Lifetime (s) ln(ratio of residual peroxide to initial peroxide)/Aexp(DE/RT), where the ratio of residual peroxide to initial peroxide 0.0001, R 8.31 J mol1 K1(gas constant) and T 463 K. d Time between the introduction of the PLLA/peroxide blend into the feeder and extrusion of the cross-linked PLLA strand.

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Scheme 1. Thermal decomposition mechanisms of Group I peroxides.

3.1.3. Group III: peroxides with low decomposition rate Table 4 shows the effect of the type of peroxide on cross-linking. Also, the thermal decomposition mechanisms [19] of these peroxides are shown in Scheme 3. First, all the cross-linked PLLAs had a higher Mw than did none3, so this group was also more effective than Group I. Generally speaking, both the Mw and gel fraction of cross-linked PLLA tended to increase with overall hydrogen abstraction ability of peroxide, as

in the case of Group II. PLLA cross-linked by DCP gave a higher Mw than did BTBV. DCP produced cumyloxy radicals (IIIDa) as primary radicals, of which 60% formed methyl radicals (IIIDb) and acetophenone by b-scission [18]. The decomposition behavior of BTBV is complicated; it has been reported that there are two decomposition steps [19]. Overall, since predominantly alkyl radicals (IIIBb) having lower hydrogen abstraction ability were generated, the crosslinking efciency of BTBV was lower than that of DCP.

Table 3 Effect of Group II peroxides on cross-linking of PLLA Type Abbreviation Structure of peroxidederived radicalsa (order of predominance) IIEa > IIEb > IIEc IITd > IITb > IITc > IITa IIBa > IIBb > IIBd > IIBc Hydrogen abstraction ability (%)b 49 36 55 Lifetimec/ extrusion timed (s/s) 68/109 110/99 108/109 /110 Molar mass (104) Mn (g/mol) 5.7 5.5 5.5 5.3 6.3 Mw (g/mol) 15.3 13.2 16.5 11.4 13.2 Gel fraction (wt%) 1.1 0.1 0.7

Peroxyesters None2 Neat PLLA

a b c

TBEC TBTH TBPB

Structure of radicals given in Scheme 2. Yield of hydrogen abstraction from cyclohexane using a-methylstyrene dimer technique measured at 140  C. Lifetime at 190  C calculated using decomposition parameters (DE and A) from Ref. [19]. Lifetime (s) ln(ratio of residual peroxide to initial peroxide)/Aexp(DE/RT), where the ratio of residual peroxide to initial peroxide 0.0001, R 8.31 J mol1 K1(gas constant) and T 463 K. d Time between the introduction of the PLLA/peroxide blend into the feeder and extrusion of the cross-linked PLLA strand.

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Scheme 2. Thermal decomposition mechanisms of Group II peroxides.

3.2. Relationship between hydrogen abstraction ability of peroxides and cross-linking of PLLA Fig. 1 shows the relationship between the hydrogen abstraction ability of peroxide and the Mw or gel fraction of cross-linked PLLA. The peroxides were separated into two classes (Class 1, Group I; Class 2, Groups II and III) according to the temperature of measurement of hydrogen abstraction ability. The rst major conclusion drawn from Fig. 1 was that there was an obvious
Table 4 Effect of Group III peroxides on cross-linking of PLLA Type Abbreviation Structure of peroxidederived radicalsa (order of predominance) IIIBa, IIBb > IIBd, IIBc IIIDa > IIIDb

relationship between the overall hydrogen abstraction ability of peroxide and the Mw or gel fraction of cross-linked PLLA in each class, except for BPO. The hydrogen abstraction ability of BPO exerted a greater inuence on gel fraction than on Mw, as mentioned before. The second important conclusion was that both the Mw and gel fraction of cross-linked PLLA were higher for Class 1 (Group I) than for Class 2 (Groups II and III) despite the lower overall hydrogen abstraction ability of the former class. This was due to the inuence

Hydrogen abstraction ability (%)b 44 60

Lifetimec/ extrusion timed (s/s) 190/198 190/209 /165

Molar mass (104) Mn (g/mol) 5.6 5.5 5.2 6.3 Mw (g/mol) 13.8 16.6 10.9 13.2

Gel fraction (wt%) 0.4 1.5

Diperoxy-ketal Dialkylperoxide None3 Neat PLLA

a b

BTBV DCP

Structure of radicals given in Scheme 3. Yield of hydrogen abstraction from cyclohexane using a-methylstyrene dimer technique measured at 140  C. c Lifetime at 190  C calculated using decomposition parameters (DE and A) from Ref. [19]. Lifetime (s) ln(ratio of residual peroxide to initial peroxide)/Aexp(DE/RT), where the ratio of residual peroxide to initial peroxide 0.0001, R 8.31 J mol1 K1(gas constant) and T 463 K. d Time between the introduction of the PLLA/peroxide blend into the feeder and extrusion of the cross-linked PLLA strand.

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Scheme 3. Thermal decomposition mechanisms of Group III peroxides.

of partial cross-linking of PLLA caused by the decomposition of a large fraction of the peroxide (radical concentration (1 per PLLA molecule), which could not diffuse in molten PLLA. BPO especially, because it decomposed immediately upon melting, produced the highest concentration of radicals with high hydrogen abstraction ability, resulting in the highest gel fraction measured.

The nal important conclusion was that TBEH gave a higher Mw and gel fraction of cross-linked PLLA than did TBTH, despite their similar chemical structure and the lower hydrogen abstraction ability of the former. Denisov et al. [24] summarized the cage effect of peroxides in molten (liquid) and solid polymer. In this paper, the diffusion constants of molecules in solid polymer

Scheme 4. Order of hydrogen abstraction ability, CO2-releasing ability and b-scission ability of various radicals.

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Fig. 1. Effect of overall hydrogen abstraction ability of peroxide (closed symbols: measured at 100  C, open symbols: measured at 140  C) on Mw and gel fraction of cross-linked PLLA.

(D: 1071010 cm2 s1) were smaller by a factor of 101106 than in molten (liquid) polymer (D: 105106 cm2 s1), resulting in a higher cage effect. It was therefore unexpected that TBEH-induced greater cross-linking in solid PLLA than did TBTH in molten PLLA; this could only be attributed to the fact that TBEH-induced crosslinking was affected more by its higher radical content derived from local dispersion in solid PLLA than the lower f resulting from its high cage effect. 3.3. Inuence of amount of added peroxide on cross-linking of PLLA In order to clarify the marked differences between the crosslinking attained with Class 1 versus Class 2, the inuence of the amount of added peroxide was investigated. Fig. 2 shows the relationship between the Mw of cross-linked PLLA and the corresponding gel fraction. Two independent relationships of direct proportionality between Mw and gel fraction were found for each class. The sizes of swollen gel particles of PLLA cross-linked using different mole ratios of BPO to PLLA (BPO, BPO-2 and BPO-5) were 51 mm, 337 mm and 509 mm, respectively, while the particle sizes of cross-linked PLLA except for BPO could not be measured because of low gel content. Taken together, these experimental results indicated that a higher concentration (radical concentration (1 per PLLA molecule) of PLLA macroradicals derived from hydrogen abstraction by BPO-induced radicals led in part to greater cross-linking in the network structure of the polymer. On the other hand, since Class 2 peroxides decomposed after being dispersed uniformly in molten PLLA, the resulting crosslinked polymer included a negligible amount of gel. In addition, the Mw of cross-linked PLLA increased with increasing radical number or hydrogen abstraction ability. Fig. 3 shows the relationship between the Mw and MFI of crosslinked PLLA. Two independent inverse proportional relationships between Mw and MFI could be seen for each class. This indicated a different cross-linked PLLA structure in each class because the MFI of Class 1 cross-linked PLLA was higher than for Class 2, despite having a similar Mw. In general, the efciency of cross-linking is investigated using the CharlesbyPinner equation [25]. This equation, originally derived for radiation cross-linked polymers, has been modied for peroxide cross-linking [26]:

Fig. 2. Relationship between Mw of cross-linked PLLA and gel fraction, including dependence on amount of added peroxide (arabic numeral after the hyphen indicates radical mole content relative to PLLA).

S S0:5 E1 2Mn I1 p=q

(1)

where S is the sol fraction; p and q are the fractions of repeat units of polymer undergoing scission and cross-linking, respectively; Mn is the number-average molecular weight of the polymer before cross-linking; [I] is the concentration of decomposed peroxide in mol/g; and E is the cross-linking efciency. (2Mn[I])1 is the mole

Fig. 3. Relationship between Mw of cross-linked PLLA and MFI, including dependence on amount of added peroxide (arabic numeral after the hyphen indicates radical mole content relative to PLLA).

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at constant radical content, grouping peroxides with similar lifetimes. The cross-linking behavior for each of three groups of peroxides (Groups I, II and III), classied according to lifetime, was readily explained by appealing to the free radical efciency f of the peroxide and the hydrogen abstraction ability of peroxide-derived radicals. For Class 1 peroxides (Group I), both Mw and gel fraction were higher than for the other two groups despite the lower hydrogen abstraction ability of the former. This implied that peroxide decomposition localized in solid PLLA caused the partial crosslinking of PLLA because of the smaller ratio of peroxide lifetime to extrusion time. For Class 2 peroxides (Groups II and III), a direct proportionality was observed between the hydrogen abstraction ability of the peroxide and the Mw of cross-linked PLLA, because slow OP decomposition caused uniform cross-linking in molten PLLA. Taking into account the amount of added peroxide, two independent relationships were observed between Mw and gel fraction or MFI in each class. This indicated a different cross-linked PLLA structure in each class. Applying the CharlesbyPinner equation for cross-linking efciency to these systems showed that cross-linking induced by BPO was different from that of other peroxides.
Fig. 4. CharlesbyPinner plots for the cross-linking of PLLA as a function of the amount of added peroxide.

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ratio of radicals to polymer chains in this paper. A plot of S S0.5 against (2Mn[I])1 is shown in Fig. 4. The intercept of the S S0.5 axis gives the ratio of the chain scission to cross-linking probability, p/q, which was 1.5 for BPO/PLLA and 0.25 for TBEC/PLLA, TBPB/PLLA and DCP/PLLA. This value of p/q for DCP/PLLA was about the same as that previously obtained at 192  C (p/q 0.30) [1], despite the reaction occurring in an extruder in our case. As can be seen from Fig. 4, p/q for BPO/PLLA was lower than those for TBEC/PLLA, TBPB/PLLA and DCP/PLLA, indicating that chain scission occurred during BPO/PLLA cross-linking. However, considering the results of Fig. 2, it was thought that this was caused by the partial network structure mentioned above. Chodak and Lasar [17] have reported CharlesbyPinner plots of several types of peroxide for the cross-linking of polypropylene (PP), in which p/q for BPO/PP was 0.9 and that for TBPB/PP was 0.15. This was different from our value of p/q 1.5 for BPO/PLLA, but in good agreement with p/q 0.25 measured for TBPB/PLLA. The ratio p/q for BPO/PLLA was lower than for BPO/PP chiey because the induced decomposition of BPO led to a higher melt viscosity, despite the lower degradation of PLLA compared with PP. 4. Conclusions The details of the relationship between peroxide type and cross-linking of PLLA during reactive extrusion were investigated