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Polymer Degradation and Stability 93 (2008) 347e352


Synthesis of polymeric antioxidants based on ring-opening metathesis

polymerization (ROMP) and their antioxidant ability for preventing
polypropylene (PP) from thermal oxidation degradation
Boyong Xue, Kenichi Ogata, Akinori Toyota*
Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei-shi, Tokyo 184-8588, Japan
Received 28 September 2007; received in revised form 1 December 2007; accepted 5 December 2007
Available online 15 December 2007


Norbornene derivatives 1e5 bearing hindered phenol groups were synthesized and undergone ring-opening metathesis polymerization
(ROMP) with Grubbs 1st generation catalyst to prepare the corresponding polymeric antioxidants. After hydrogenation with p-toluenesulfonyl-
hydrazide (TSH), polymeric antioxidants with saturated polymer chain were prepared. The resulting polymeric antioxidants were characterized
by gel permeation chromatography (GPC), 1H NMR and differential scanning calorimetry (DSC). As to polymerization activity, monomer 1 had
the highest ROMP activity, while monomer 5 could not undergo homopolymerization due to the steric hindrance. The antioxidant ability of these
polymeric antioxidants which was determined by oxidation induction temperature (OIT) in polypropylene (PP) system is to protect PP against
thermal oxidation. Results showed that the OIT of PP increased obviously when PP was stabilized by the adding of polymeric antioxidants.
2007 Elsevier Ltd. All rights reserved.

Keywords: Antioxidant; Ring-opening metathesis polymerization; Stabilization; Oxidation induction temperature

1. Introduction popular industrial approaches to enhance physical persistence

of stabilizers are oligomerization and alkylation. For example,
Generally, all polyolefin products require stabilizer against Chimasorb 944 was introduced in the market as oligomeric
uncontrolled oxidation which causes undesirable changes in light stabilizer at the beginning of the 1980s for some special
the polymer, including chain scission, crosslinking, discolor- demanding applications such as fiber, rigorous environments
ation, as well as decline in mechanical and physical properties. and so on. Many researchers have engaged in this field and re-
The addition of antioxidants which contain hindered phenol ported some polymeric antioxidants via some fascinating
group is a convenient and effective way to prevent polyolefin methods in recent years. Malshe et al. [6] prepared an oligo-
from degradation. However, low molecular weight antioxi- meric antioxidant by condensation reaction of monoalkylated
dants easily give off bad smell and depart from the polymers phenol and formaldehyde in the presence of acid catalyst. Wi-
by the physical loss such as migration, evaporation, and ex- len et al. [7] bound hindered phenol group in the polyolefin
traction. Consequently, antioxidant efficiency loss and poten- chain through copolymerization of ethylene and vinyl mono-
tial environmental issue arise [1e5]. To achieve long term mer bearing hindered phenol group. Another useful method
stabilizing efficiency and avoid potential toxicity, polymeric was chemical modification. Robert et al. [8] introduced a gen-
antioxidants have gained much interest to overcome the phys- eration of polysiloxane based antioxidants with high extraction
ical loss and to enhance compatibility and durability. The most resistance and outstanding stabilization efficiency. Arefjev
et al. [9] described a polymeric form of antioxidant prepared
via chemical graft of dextran and hindered phenol. Literatures
* Corresponding author. Tel./fax: 81 (0)42 388 7162. reported a method to graft hindered phenol group to polyolefin
E-mail address: a-toyota@cc.tuat.ac.jp (A. Toyota). by melt processing with free radical initiators [10e12].

0141-3910/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
348 B. Xue et al. / Polymer Degradation and Stability 93 (2008) 347e352

The present work shows a novel polymeric antioxidant reflux for 2 h. On cooling, the product was separated out
synthesized by ring-opening metathesis polymerization of hin- and recrystallized from toluene. Yield: 7.2 g, 65.5%. Mp:
dered phenol functionalized norbornene derivatives. After 166  C. 1H NMR (CDCl3, 300 MHz, d): 6.31 (s, 2H, e
hydrogenation with p-toluenesulfonylhydrazide (TSH), poly- CH]CHe), 3.55 (s, 2H, eCHe), 3.49 (s, 2H, eCHCOOe),
meric antioxidants with saturated polymer chain were 1.53e1.77 (q, 2H, 3J 3 Hz, eCH2e).
prepared too. The antioxidant ability to prevent PP from deg-
radation was evaluated primarily by oxidation induction tem- 2.3.2. Synthesis of 3-(3,5-di-tert-tubyl-4-
perature (OIT) measurement. hydroxyphenyl)-propanol
To a suspending mixture of LiAlH4 (0.84 g; 0.022 mol) and
2. Experimental 20 mL diethyl ether, a solution of b-(3,5-di-tert-butyl-4-
hydroxyphenyl)methyl propionate (5.84 g; 0.02 mol) in
2.1. Materials 30 mL diethyl ether was added dropwise with stirring under
nitrogen atmosphere at 0e5  C for a period of 30 min. The re-
Lithium aluminum hydride (LiAlH4), p-toluenesulfonylhy- action mixture was heated to reflux for 30 min and then cooled
drazide (TSH), p-toluenesulfonic acid monohydrate, to room temperature. Fifty milliliters of water and 50 mL of
polypropylene (typical Mn 5000; typical Mw 12,000; mp 160e 10% sulfuric acid were added in sequence. The organic phase
165  C) and Grubbs 1st generation catalyst were available was washed twice with water (50 mL), separated, and then
from Aldrich. 2-[3-(3,5-Di-tert-tubyl-4-hydroxyphenyl)- dried over anhydrous magnesium sulfate. Removal of diethyl
propionyloxy]methyl-5-norbornene (1), 2,2-bis[3-(3,5-di-tert- ether under reduced pressure left yellow viscous oil. Crystalli-
tubyl-4-hydroxyphenyl)-propionyloxy]methyl-5-norbornene (2), zation from n-hexane gave the product. Yield: 4.53 g, 85.5%.
2-endo-3-endo-bis[3-(3,5-di-tert-tubyl-4-hydroxyphenyl)-pro- Mp: 66  C. 1H NMR (CDCl3, 300 MHz, d): 6.98 (s, 2H,
pionyloxy]methyl-5-norbornene (3) and b-(3,5-di-tert-butyl-4- AreH), 5.03 (s, 1H, AreOH), 3.65e3.74 (m, 2H, a-CH2),
hydroxyphenyl)methyl propionate were prepared according 2.54e2.66 (m, 2H, g-CH2), 1.81e1.94 (m, 2H, b-CH2), 1.42
to literature procedures [13,14]. TLC aluminum sheets (Silica (s, 18H, t-Bu).
gel 60 F254, MERCK), Silica Gel 60N (spherical, neutral,
KANTO CHEMICAL) and 5-norbornene-2-carboxylic acid 2.3.3. Synthesis of exo, endo-5-norbornene-2-carboxylic
(KANTO CHEMICAL) were used as-received. Dichlorome- acid 3-(3,5-di-tert-tubyl-4-hydroxyphenyl)-propyl ester (4)
thane and xylene (KOKUSAN CHEMICAL) were dehydrated 3-(3,5-Di-tert-tubyl-4-hydroxyphenyl)-propanol (2.64 g;
by standard methods before use. All other reagents and solvents 0.01 mol), 5-norbornene-2-carboxylic acid (2 mL) and p-tol-
were purchased from TOKYO CHEMICAL and were used uenesulfonic acid (0.11 g; 0.58 mmol) were mixed with tolu-
without further purification. ene (100 mL). The reaction mixture was heated to reflux
under nitrogen atmosphere for 5 h. During the reflux, the water
2.2. Measurements was separated from the reaction system continuously by azeo-
trope. After washing twice with 50 mL of water, the organic
H NMR spectra were recorded on a JEOL JNM-AL300 phase was separated, dried over anhydrous magnesium sulfate
spectrometer. Melting point and the glass-transition tempera- and filtered. Removal of toluene under reduced pressure left
ture (Tg) were determined by a SHIMADZU DSC-60 differen- brown viscous oil which was subjected to column chromatog-
tial scanning calorimeter (DSC). A heating rate of 10  C/min raphy on silica gel with 1:5 (v/v) ethyl acetate/hexane as elu-
and nitrogen atmosphere were consistently employed. The ent (Rf 0.60 and 0.65, mixture of exo- and endo-) to give the
oxidation induction temperature (OIT) was determined with product as a colorless oil. Yield: 2.50 g, 65.0%. 1H NMR
a PerkineElmer Diamond DSC with a gas switch equipment (CDCl3, 300 MHz, d): 6.95 (s, 2H, AreH), 5.92e6.19 (m,
between nitrogen and oxygen. The number-average molecular 2H, eCH]CHe), 5.03 (s, 1H, eOH), 4.02e4.13 (m, 2H,
weights (Mn) and polydispersity index (PDI) of the polymers eCH2OCOe), 2.22e3.20 (m, 5H, eArCH2e, eCHe in
were determined with a JASCO gel permeation chromatogra- 1,2,4 position of norbornene ring), 1.21e1.95 (m, 24H, t-Bu,
phy (GPC) equipped with a Shodex K-805L chromatograph b-CH2, eCH2e in 3,7 position of norbornene ring).
column and a JASCO RI-2031 detector, using chloroform as
an eluent at a flow rate of 1.0 mL/min, calibrated by polysty- 2.3.4. Synthesis of 5-norbornene-2-endo-3-endo-
rene standards at 40  C. dicarboxylic acid, bis[3-(3,5-di-tert-tubyl-
4-hydroxyphenyl)-propyl] ester (5)
2.3. Monomer synthesis 3-(3,5-Di-tert-tubyl-4-hydroxyphenyl)-propanol (7.95 g;
0.03 mol), 5-norbornene-2-endo-3-endo-dicarboxylic anhy-
2.3.1. Synthesis of 5-norbornene-2-endo-3- dride (2.46 g; 0.015 mol) and p-toluenesulfonic acid (0.33 g;
endo-dicarboxylic anhydride 1.74 mmol) were mixed with toluene (100 mL). The reaction
To maleic anhydride (15.9 g; 0.16 mol) in 50 mL of tolu- mixture was heated to reflux under nitrogen atmosphere for
ene, cyclopentadiene (14 g; 0.21 mol) was added dropwise 5 h. After a series of steps, also used in the synthesis process
with stirring under nitrogen atmosphere at 0e5  C for a period of monomer 4, the remaining brown viscous oil was subjected
of 15 min. Then, the reaction mixture was heated slowly to to column chromatography on silica gel with 1:5 (v/v) ethyl
B. Xue et al. / Polymer Degradation and Stability 93 (2008) 347e352 349

acetate/hexane as eluent (Rf 0.38) to give the product as 2.6. Evaluation of oxidation induction temperature (OIT)
a colorless oil. Yield: 6.37 g, 63.0%. 1H NMR (CDCl3,
300 MHz, d): 6.95 (s, 4H, AreH), 6.26 (s, 2H, eCH]CHe), All of the samples were prepared according to the follow-
5.03 (s, 2H, eOH), 3.97e4.13 (m, 4H, eCH2OCOe), ing process. In a typical experiment, a 100 mL flask was
3.29e3.30 (t, 2H, eCHCOOe), 3.14e3.16 (t, 2H, eCHe), charged with 2.0 g of polypropylene, 0.4 mL of P1/CHCl3 sol-
2.43e2.57 (m, 4H, eArCH2e), 1.20e1.93 (m, 42H, t-Bu, vent (5 mg/mL) and 30 mL o-dichlorobenzene under nitrogen
b-CH2, eCH2e in 7 position of norbornene ring). atmosphere. The mixture was stirred at 135  C for 1 h to dis-
solve PP completely, then was cooled and poured into metha-
nol (100 mL). The white PP powder stabilized by 0.1% of
2.4. General polymerization procedure polymeric antioxidant P1 was collected and dried under
vacuum at 80  C for 6 h.
In a typical experiment (Scheme 1), a 25 mL flask was A sample of 2.5 mg was placed in an aluminum pan. After
charged with monomer 1 (200 mg; 0.52 mmol) under nitrogen placing the uncovered sample pan together with an empty
atmosphere. CH2Cl2 of 1.66 mL and 1.44 mL of Grubbs 1st reference pan in a calibrated DSC oven, an oxygen atmosphere
generation catalyst dichloromethane solution (8 mmol/L) was employed. Then, the sample and the reference were
were added into the flask by syringe in sequence. The mixture heated continuously at 15  C/min under pure oxygen gas
was stirred at room temperature for 3 h. Ethyl vinyl ether flow (20 mL/min). OIT was determined by the onset of the de-
(0.3 mL) was added to the mixture to quench the reaction composition process that is characterized by an exothermic
and stirred for additional 10 min. The resulting polymer was peak shown by the DSC in the heat flow [15].
precipitated in excess of methanol and purified by reprecipita-
tion from chloroform and methanol. The reprecipitated poly-
mer was collected and then dried under vacuum for 6 h at 3. Results and discussion
30  C to yield 200 mg of P1 as a white solid (100.0% yield).
3.1. Monomer synthesis and characterization

2.5. General hydrogenation procedure Monomers 1e3 were synthesized by acylation reaction,
while monomers 4 and 5 were synthesized by esterification
In a typical experiment (Scheme 1), a 50 mL flask was of 3-(3,5-di-tert-tubyl-4-hydroxyphenyl)-propanol with nor-
charged with 126 mg of polymer P1 (Run 3), 0.30 g of p-tol- bornene carboxyl acid and dicarboxylic anhydride, respec-
uenesulfonylhydrazide (TSH/double bonds mole ratio 5), tively. The olefinic proton signals of monomer 4 appeared in
15 mL of xylene and a trace of 2,6-di-tert-butyl-4-methylphe- the range of 5.92e6.19 ppm as three batch of peaks. However,
nol (BHT) under nitrogen atmosphere. The reaction mixture all of them in monomer 5 were shifted to the same displace-
was heated at 135  C for 3 h. The onset of the reaction was de- ment (d 6.08) due to the symmetrical structure of 5. The
noted by vigorous evolution of gas. After the reaction was fin- substituent of monomers 4 and 5 contained the same func-
ished, the mixture was allowed to cool and poured into excess tional groups as that of monomers 1e3. However, the group
of methanol. The hydrogenated polymer was further purified connecting the hindered phenol unit to the norbornene ring,
by dissolving it in chloroform and reprecipitating it with meth- named anchor group in some literatures [16], was different.
anol. The resulting hydrogenated polymer was collected and The anchor group in monomers 4 and 5 was carboxylic ester,
then dried under vacuum for 6 h at 30  C to yield 110 mg of but that in monomers 1e3 was methoxyl. Although the differ-
HP1 as a white solid (87.3% yield). According to the same ences between the anchor groups of monomers were incon-
procedure, P2 (Run 6), P3 (Run 10) and P4 (Run 16) were spicuous, they had a great influence on the polymerization
hydrogenated to prepare HP2e4, respectively. activity, which is depicted in the following discussion (Fig. 1).

t-Bu Ru
O Cl Ph
O n

p-toluenesulfonylhydrazide n
Xylene O

Scheme 1. Typical scheme for the synthesis of polymeric antioxidants.

350 B. Xue et al. / Polymer Degradation and Stability 93 (2008) 347e352

PCy3 O
t-Bu of monomer 5 was infeasible, even for prolonged reaction time
Cl (CH2)2 OH (13 h). It can be found that Mn increased with the increase of
Ru t-Bu [M]/[C] under the same reaction time on the whole. However,
Cl Ph it is necessary to be mentioned that the amount of living species
1 initiated will decrease when the catalyst ratio is increased. Con-
O t-Bu O t-Bu sequently, increasing molecular weight caused by decreasing
(CH2)2 OH (CH2)2 OH catalyst ratio was at the expense of conversion rate. When
O t-Bu O t-Bu monomer 4 was polymerized at [M]/[C] 1000 for 3 h (Run
O t-Bu O t-Bu
13), the number of monomer units linked to polymer chain
(CH2)2 OH (CH2)2 OH
O t-Bu O
was so low that the yield and the Mn were less than those of
Run 12 to a certain extent. The yield and Mn of polymer P4 in-
2 3
creased by extending the reaction time from 3 to 13 h as shown
t-Bu OH
in Runs 14 and 15 in Table 1. P1e3 had a higher Tg than P4,
which could be attributed to the relative rigidity of the polymer
C t-Bu
O O side chain in P1e3 (the alkyl in side chain of P4 was longer
OH O than that of the rest). According to the results shown in Table 1,
t-Bu O
it also can be seen that yield of P1 was higher evidently than
4 5 that of other three under the same [M]/[C] ratio. In other words,
t-Bu OH
catalyzed by RuCl2(PCy3)2(]CHPh), monomer 1 has higher
Fig. 1. Monomers 1e5 and catalyst used for the synthesis of polymeric activity for ROMP than other monomers evidently although
antioxidants. they have a similar structure. Analogically, monomer 3 has
higher activity for ROMP than monomer 2, and monomer 4
3.2. Polymerization and characterization has the lowest activity for ROMP among them except monomer
5 that lose the activity for ROMP completely. Judging from the
All monomers 1e5 were subjected to ROMP by using typ- aforementioned result, it is considered that the ROMP activity
ical ruthenium catalyst RuCl2(PCy3)2(]CHPh) at molar ratio of the monomers depends on the substituent and stereostruc-
of monomer to catalyst ([M]/[C]) varied from 30 to 2000. ture. It has been established that the rate-determining step is
The yield of polymer, number-average molecular weight the formation of the metallacyclobutane ring along the propa-
(Mn), polydispersity index (PDI) and glass-transition tempera- gation of polymer chain in metathesis with Grubbs 1st genera-
ture (Tg) are summarized in Table 1. Monomers 1e4 could be tion catalyst [17]. The PCy3 dissociation is also a crucial step to
polymerized in all range of [M]/[C]. Unfortunately, the ROMP provide available coordination site for binding approaching
monomer and formatting metallacyclobutane. Unfavorable ste-
ric interactions existed during the coordination of Ru with the
Table 1
ROMP of norbornene monomers 1e5
double bond of an approaching monomer (Fig. 2a) and the for-
mation of a metallacyclobutane (Fig. 2b), as well as an intramo-
Run Monomer [M]/[C]a Yield (%) Mn/104 PDI Tg ( C)
lecular complex between the ruthenium center and the adjacent
1 1 30 100.0 2.35 1.60 67.2
2 1 45 100.0 2.55 1.54 67.5
3 1 205 97.4 14.4 1.97 70.7
4b 1 1000 99.8 e e 73.2 Cl
5 2 45 80.1 2.69 1.07 72.3 Ru
6 2 205 78.7 8.49 1.14 75.4
7 2 1000 27.4 16.7 1.13 75.4 O Cl
8 3 45 82.2 3.02 1.30 80.1
9 3 205 80.4 8.58 2.39 80.3 O
10 3 1000 53.8 32.1 1.37 80.4
11 4 45 58.8 2.12 1.47 62.1 O Ph
12 4 205 41.5 3.49 1.58 62.8
13 4 1000 7.9 3.44 1.47 62.8 a
14c 4 205 53.1 4.64 1.11 61.2
15c 4 1000 46.4 21.3 1.20 61.8 Ph
16c 4 2000 28.5 26.8 1.49 62.7
17c 5 45 Trace e e e O
18c 5 205 Trace e e e O
O O PCy3 Ru
Polymerization conditions: monomer 200 mg; methylene chloride solvent; O
total volume of solvent was 3.1 mL; polymerization was carried out at room O O Cl Cl
temperature for 3 h; the reaction was terminated by addition of 0.3 mL of ethyl
vinyl ether. b c
[Monomer]/[catalyst]. = hindered phenol
The resulting polymer was insoluble.
Polymerized for 13 h. Fig. 2. Steric interaction and intramolecular complex.
B. Xue et al. / Polymer Degradation and Stability 93 (2008) 347e352 351

carbonyl formed during the propagation of polymer chain Table 2

(Fig. 2c) should account for the activity loss of monomer 5 pri- OIT of PP sample stabilized by polymeric antioxidants
marily. It was suggested that a high shielding of the double Sample (PPepolymeric antioxidant) OIT ( C)
bond could be a postulated reason for unsuitability of endo- PPeblank 173.4
2,3-diester norbornene derivatives employed as ROMP mono- PPeP1 178.7
mers [18]. Comparing polymerization results of monomer 1 PPeP2 178.9
PPeP3 179.6
(3) with those of monomer 4 (5), the ROMP activity could be PPeP4 180.4
improved significantly when a eCH2Oe fragment inserted be- PPeHP1 182.5
tween carbonyl and norbornene ring. This result indicates that PPeHP2 182.9
prolonging the distance between carbonyl and norbornene ole- PPeHP3 182.7
finic bond of the monomer is a useful way to eliminate or abate PPeHP4 183.1
negative effects on ROMP activity. In addition, polymerization
of monomers 2 and 3 give polymer double density of functional
3.4. Antioxidant ability
group at the sacrifice of ROMP activity. Two anchor groups of
monomer 2 were located in the same position of norbornene
A simple method to check the ability of the stabilizer
ring. During the polymerization, both of two anchors should
system is to determine the oxidation induction temperature
approach to the Ru metal center, and then should facilitate
(OIT) of the material. OIT measurement was set up in recent
the formation of intramolecular complex. As a consequence,
years and was suggested by several authors to be a convenient
monomer 3 had a higher ROMP activity than monomer 2.
method to quickly screen the relative efficiency of the stabi-
lized polymers under conditions designed to accelerate aging.
3.3. Hydrogenation and characterization It was suggested that OIT measurement was always reproduc-
ible and should be preferred in all cases [15,21]. The stabiliza-
After hydrogenation, polymeric antioxidants HP1e4 with tion effect of these polymeric antioxidants to prevent PP from
saturated polymer chain were prepared. An excess amount thermal oxidation is summarized in Table 2. It can be seen that
of TSH (5 eq. of double bonds) was used as precursor to OIT of PP increased more than 5  C after stabilization by 0.1%
generate diimide (NH]NH) in situ. Simultaneously, the gen- (wt%) of polymeric antioxidants. All of the polymeric antiox-
erated diimide reduced unsaturated polymers and gave off idants showed their antioxidant ability to protect PP from ther-
nitrogen gas. Herein, an important and very useful feature of mal oxidation. Because the added amount of every polymeric
diimide hydrogenation was its selectivity. Only nonpolar dou- antioxidant was almost equal in mole, the extent of OIT in-
ble bonds were active but polar double bonds and aromatic crease was nearly equal to each other and no obvious differ-
ring systems were inert [19]. There was no olefinic resonance ence between them was observed. However, it should be
(d 5.10e5.35) visible after hydrogenation, as was instanced mentioned that the antioxidant efficiency of polymeric antiox-
by the 1H NMR spectrum of polymers P1 and HP1 (Fig. 3). idants HP1e4 was a little higher than unsaturated ones P1e4
However, the phenyl proton resonance (d 6.95), phenol comparatively. It was reasonable to associate this result with
proton resonance (d 5.03) and methylene proton resonance the thermal stability of polymeric stabilizers themselves. It
adjacent to ester group (d 3.70e4.10) still remained, which is well known that saturating the polymer chain results in in-
indicated that the hindered phenol functional group and ester creasing of thermal stability of polymer itself. Therefore, hy-
group did not change at all. Tg of HP1e4 was 66.5  C, drogenated polymeric antioxidants had low decomposition
68.8  C, 77.8  C and 54.7  C, respectively. The decrease in property and then performed long persistent antioxidant effi-
Tg caused by hydrogenation should be attributed to the rotation ciency. Unfortunately, other important merits of polymeric an-
around the hydrogenated carbonecarbon single bond which tioxidants, such as good compatibility with base resin, low or
made polymer chain mobility easier [20]. no physical loss and good durability, could not be character-
ized clearly by OIT accelerated aging method. With regard
to long persistence efficiency of these polymeric antioxidants,
it has to be studied rather critically.

4. Conclusions

Polymers P1e4 were prepared via ROMP and were used as

polymeric antioxidants to prevent polypropylene from thermal
oxidation degradation. It is noticeable that consideration of the
monomers structure was important during rational design and
synthesis of functionalized norbornene monomers for ROMP.
Prolonging the distance between anchor group of monomer
and norbornene olefinic bond to avoid negative steric interac-
Fig. 3. 1H NMR spectra of polymers P1 and HP1 (solvent: CDCl3). tion and intramolecular complex was an efficient way to get
352 B. Xue et al. / Polymer Degradation and Stability 93 (2008) 347e352

high ROMP activity. After hydrogenation, polymeric antioxi- [9] Arefjev DV, Domnina NS, Komarova EA, Bilibin AY. Sterically hindered
dants HP1e4 with saturated polymer chain were obtained. phenoledextran conjugates: synthesis and radical scavenging activity.
Eur Polym J 1999;35(2):279e84.
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The authors would like to thank Sasakawa Scientific Re- Polym Degrad Stab 2004;84(3):499e503.
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monomers via ROMP. Polymer 2007;48(15):5005e15.
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