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Polymer Degradation and Stability 93 (2008) 347e352

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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

Abstract

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

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

0141-3910/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.12.001
348 B. Xue et al. / Polymer Degradation and Stability 93 (2008) 347e352
The present work shows a novel polymeric antioxidant
synthesized by ring-opening metathesis polymerization of hin-
dered phenol functionalized norbornene derivatives. After
hydrogenation with p-toluenesulfonylhydrazide (TSH), poly-
meric antioxidants with saturated polymer chain were
prepared too. The antioxidant ability to prevent PP from deg-
radation was evaluated primarily by oxidation induction tem-
perature (OIT) measurement.
2. Experimental
2.1. Materials
Lithium aluminum hydride (LiAlH4), p-toluenesulfonylhy-
drazide (TSH), p-toluenesulfonic acid monohydrate,
polypropylene (typical Mn 5000; typical Mw 12,000; mp 160e
165  C) and Grubbs 1st generation catalyst were available
from Aldrich. 2-[3-(3,5-Di-tert-tubyl-4-hydroxyphenyl)-
propionyloxy]methyl-5-norbornene (1), 2,2-bis[3-(3,5-di-tert-
tubyl-4-hydroxyphenyl)-propionyloxy]methyl-5-norbornene (2),
2-endo-3-endo-bis[3-(3,5-di-tert-tubyl-4-hydroxyphenyl)-pro-
pionyloxy]methyl-5-norbornene (3) and b-(3,5-di-tert-butyl-4-
hydroxyphenyl)methyl propionate were prepared according
to literature procedures [13,14]. TLC aluminum sheets (Silica
gel 60 F254, MERCK), Silica Gel 60N (spherical, neutral,
KANTO CHEMICAL) and 5-norbornene-2-carboxylic acid
(KANTO CHEMICAL) were used as-received. Dichlorome-
thane and xylene (KOKUSAN CHEMICAL) were dehydrated
by standard methods before use. All other reagents and solvents
were purchased from TOKYO CHEMICAL and were used
without further purification.
2.2. Measurements
1
H NMR spectra were recorded on a JEOL JNM-AL300
spectrometer. Melting point and the glass-transition tempera-
ture (Tg) were determined by a SHIMADZU DSC-60 differen-
tial scanning calorimeter (DSC). A heating rate of 10  C/min
and nitrogen atmosphere were consistently employed. The
oxidation induction temperature (OIT) was determined with
a PerkineElmer Diamond DSC with a gas switch equipment
between nitrogen and oxygen. The number-average molecular
weights (Mn) and polydispersity index (PDI) of the polymers
were determined with a JASCO gel permeation chromatogra-
phy (GPC) equipped with a Shodex K-805L chromatograph
column and a JASCO RI-2031 detector, using chloroform as
an eluent at a flow rate of 1.0 mL/min, calibrated by polysty-
rene standards at 40  C.
2.3. Monomer synthesis
2.3.1. Synthesis of 5-norbornene-2-endo-3-
endo-dicarboxylic anhydride
To maleic anhydride (15.9 g; 0.16 mol) in 50 mL of tolu-
ene, cyclopentadiene (14 g; 0.21 mol) was added dropwise
with stirring under nitrogen atmosphere at 0e5  C for a period
of 15 min. Then, the reaction mixture was heated slowly to
reflux for 2 h. On cooling, the product was separated out
and recrystallized from toluene. Yield: 7.2 g, 65.5%. Mp:
166  C. 1H NMR (CDCl3, 300 MHz, d): 6.31 (s, 2H, e
CH]CHe), 3.55 (s, 2H, eCHe), 3.49 (s, 2H, eCHCOOe),
1.53e1.77 (q, 2H, 3J 3 Hz, eCH2e).
2.3.2. Synthesis of 3-(3,5-di-tert-tubyl-4-
hydroxyphenyl)-propanol
To a suspending mixture of LiAlH4 (0.84 g; 0.022 mol) and
20 mL diethyl ether, a solution of b-(3,5-di-tert-butyl-4-
hydroxyphenyl)methyl propionate (5.84 g; 0.02 mol) in
30 mL diethyl ether was added dropwise with stirring under
nitrogen atmosphere at 0e5  C for a period of 30 min. The re-
action mixture was heated to reflux for 30 min and then cooled
to room temperature. Fifty milliliters of water and 50 mL of
10% sulfuric acid were added in sequence. The organic phase
was washed twice with water (50 mL), separated, and then
dried over anhydrous magnesium sulfate. Removal of diethyl
ether under reduced pressure left yellow viscous oil. Crystalli-
zation from n-hexane gave the product. Yield: 4.53 g, 85.5%.
Mp: 66  C. 1H NMR (CDCl3, 300 MHz, d): 6.98 (s, 2H,
AreH), 5.03 (s, 1H, AreOH), 3.65e3.74 (m, 2H, a-CH2),
2.54e2.66 (m, 2H, g-CH2), 1.81e1.94 (m, 2H, b-CH2), 1.42
(s, 18H, t-Bu).
2.3.3. Synthesis of exo, endo-5-norbornene-2-carboxylic
acid 3-(3,5-di-tert-tubyl-4-hydroxyphenyl)-propyl ester (4)
3-(3,5-Di-tert-tubyl-4-hydroxyphenyl)-propanol (2.64 g;
0.01 mol), 5-norbornene-2-carboxylic acid (2 mL) and p-tol-
uenesulfonic acid (0.11 g; 0.58 mmol) were mixed with tolu-
ene (100 mL). The reaction mixture was heated to reflux
under nitrogen atmosphere for 5 h. During the reflux, the water
was separated from the reaction system continuously by azeo-
trope. After washing twice with 50 mL of water, the organic
phase was separated, dried over anhydrous magnesium sulfate
and filtered. Removal of toluene under reduced pressure left
brown viscous oil which was subjected to column chromatog-
raphy on silica gel with 1:5 (v/v) ethyl acetate/hexane as elu-
ent (Rf 0.60 and 0.65, mixture of exo- and endo-) to give the
product as a colorless oil. Yield: 2.50 g, 65.0%. 1H NMR
(CDCl3, 300 MHz, d): 6.95 (s, 2H, AreH), 5.92e6.19 (m,
2H, eCH]CHe), 5.03 (s, 1H, eOH), 4.02e4.13 (m, 2H,
eCH2OCOe), 2.22e3.20 (m, 5H, eArCH2e, eCHe in
1,2,4 position of norbornene ring), 1.21e1.95 (m, 24H, t-Bu,
b-CH2, eCH2e in 3,7 position of norbornene ring).
2.3.4. Synthesis of 5-norbornene-2-endo-3-endo-
dicarboxylic acid, bis[3-(3,5-di-tert-tubyl-
4-hydroxyphenyl)-propyl] ester (5)
3-(3,5-Di-tert-tubyl-4-hydroxyphenyl)-propanol (7.95 g;
0.03 mol), 5-norbornene-2-endo-3-endo-dicarboxylic anhy-
dride (2.46 g; 0.015 mol) and p-toluenesulfonic acid (0.33 g;
1.74 mmol) were mixed with toluene (100 mL). The reaction
mixture was heated to reflux under nitrogen atmosphere for
5 h. After a series of steps, also used in the synthesis process
of monomer 4, the remaining brown viscous oil was subjected
to column chromatography on silica gel with 1:5 (v/v) ethyl
 B. Xue et al. / Polymer Degradation and Stability 93 (2008) 347e352
acetate/hexane as eluent (Rf 0.38) to give the product as
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),
5.03 (s, 2H, eOH), 3.97e4.13 (m, 4H, eCH2OCOe),
3.29e3.30 (t, 2H, eCHCOOe), 3.14e3.16 (t, 2H, eCHe),
2.43e2.57 (m, 4H, eArCH2e), 1.20e1.93 (m, 42H, t-Bu,
b-CH2, eCH2e in 7 position of norbornene ring).
2.4. General polymerization procedure
In a typical experiment (Scheme 1), a 25 mL flask was
charged with monomer 1 (200 mg; 0.52 mmol) under nitrogen
atmosphere. CH2Cl2 of 1.66 mL and 1.44 mL of Grubbs 1st
generation catalyst dichloromethane solution (8 mmol/L)
were added into the flask by syringe in sequence. The mixture
was stirred at room temperature for 3 h. Ethyl vinyl ether
(0.3 mL) was added to the mixture to quench the reaction
and stirred for additional 10 min. The resulting polymer was
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
30  C to yield 200 mg of P1 as a white solid (100.0% yield).
2.5. General hydrogenation procedure
In a typical experiment (Scheme 1), a 50 mL flask was
charged with 126 mg of polymer P1 (Run 3), 0.30 g of p-tol-
uenesulfonylhydrazide (TSH/double bonds mole ratio 5),
15 mL of xylene and a trace of 2,6-di-tert-butyl-4-methylphe-
nol (BHT) under nitrogen atmosphere. The reaction mixture
was heated at 135  C for 3 h. The onset of the reaction was de-
noted by vigorous evolution of gas. After the reaction was fin-
ished, the mixture was allowed to cool and poured into excess
of methanol. The hydrogenated polymer was further purified
by dissolving it in chloroform and reprecipitating it with meth-
anol. The resulting hydrogenated polymer was collected and
then dried under vacuum for 6 h at 30  C to yield 110 mg of
HP1 as a white solid (87.3% yield). According to the same
procedure, P2 (Run 6), P3 (Run 10) and P4 (Run 16) were
hydrogenated to prepare HP2e4, respectively.
Cl
t-Bu
O Cl
CH2 CH2 OH
O n
t-Bu
p-toluenesulfonylhydrazide
Xylene
Scheme 1. Typical scheme for the synthesis of polymeric antioxidants.
349
2.6. Evaluation of oxidation induction temperature (OIT)
All of the samples were prepared according to the follow-
ing process. In a typical experiment, a 100 mL flask was
charged with 2.0 g of polypropylene, 0.4 mL of P1/CHCl3 sol-
vent (5 mg/mL) and 30 mL o-dichlorobenzene under nitrogen
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
polymeric antioxidant P1 was collected and dried under
vacuum at 80  C for 6 h.
A sample of 2.5 mg was placed in an aluminum pan. After
placing the uncovered sample pan together with an empty
reference pan in a calibrated DSC oven, an oxygen atmosphere
was employed. Then, the sample and the reference were
heated continuously at 15  C/min under pure oxygen gas
flow (20 mL/min). OIT was determined by the onset of the de-
composition process that is characterized by an exothermic
peak shown by the DSC in the heat flow [15].
3. Results and discussion
3.1. Monomer synthesis and characterization
Monomers 1e3 were synthesized by acylation reaction,
while monomers 4 and 5 were synthesized by esterification
of 3-(3,5-di-tert-tubyl-4-hydroxyphenyl)-propanol with nor-
bornene carboxyl acid and dicarboxylic anhydride, respec-
tively. The olefinic proton signals of monomer 4 appeared in
the range of 5.92e6.19 ppm as three batch of peaks. However,
all of them in monomer 5 were shifted to the same displace-
ment (d 6.08) due to the symmetrical structure of 5. The
substituent of monomers 4 and 5 contained the same func-
tional groups as that of monomers 1e3. However, the group
connecting the hindered phenol unit to the norbornene ring,
named anchor group in some literatures [16], was different.
The anchor group in monomers 4 and 5 was carboxylic ester,
but that in monomers 1e3 was methoxyl. Although the differ-
ences between the anchor groups of monomers were incon-
spicuous, they had a great influence on the polymerization
activity, which is depicted in the following discussion (Fig. 1).
PCy3
Ru
Ph
PCy3
O
t-Bu
O
CH2 CH2 OH
t-Bu
n
O
t-Bu
O
CH2 CH2 OH
t-Bu
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
O
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
PCy3
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
t-Bu
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
O
in Runs 14 and 15 in Table 1. P1e3 had a higher Tg than P4,
t-Bu
O
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
t-Bu
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
PCy3
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
O O
8 3 45 82.2 3.02 1.30 80.1
O O
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
O
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 O PCy3 Ru
Polymerization conditions: monomer 200 mg; methylene chloride solvent; O
Ru
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
a
[Monomer]/[catalyst]. = hindered phenol
b
The resulting polymer was insoluble.
c
Polymerized for 13 h. Fig. 2. Steric interaction and intramolecular complex.
 B. Xue et al. / Polymer Degradation and Stability 93 (2008) 347e352
carbonyl formed during the propagation of polymer chain
(Fig. 2c) should account for the activity loss of monomer 5 pri-
marily. It was suggested that a high shielding of the double
bond could be a postulated reason for unsuitability of endo-
2,3-diester norbornene derivatives employed as ROMP mono-
mers [18]. Comparing polymerization results of monomer 1
(3) with those of monomer 4 (5), the ROMP activity could be
improved significantly when a eCH2Oe fragment inserted be-
tween carbonyl and norbornene ring. This result indicates that
prolonging the distance between carbonyl and norbornene ole-
finic bond of the monomer is a useful way to eliminate or abate
negative effects on ROMP activity. In addition, polymerization
of monomers 2 and 3 give polymer double density of functional
group at the sacrifice of ROMP activity. Two anchor groups of
monomer 2 were located in the same position of norbornene
ring. During the polymerization, both of two anchors should
approach to the Ru metal center, and then should facilitate
the formation of intramolecular complex. As a consequence,
monomer 3 had a higher ROMP activity than monomer 2.
3.3. Hydrogenation and characterization
After hydrogenation, polymeric antioxidants HP1e4 with
saturated polymer chain were prepared. An excess amount
of TSH (5 eq. of double bonds) was used as precursor to
generate diimide (NH]NH) in situ. Simultaneously, the gen-
erated diimide reduced unsaturated polymers and gave off
nitrogen gas. Herein, an important and very useful feature of
diimide hydrogenation was its selectivity. Only nonpolar dou-
ble bonds were active but polar double bonds and aromatic
ring systems were inert [19]. There was no olefinic resonance
(d 5.10e5.35) visible after hydrogenation, as was instanced
by the 1H NMR spectrum of polymers P1 and HP1 (Fig. 3).
However, the phenyl proton resonance (d 6.95), phenol
proton resonance (d 5.03) and methylene proton resonance
adjacent to ester group (d 3.70e4.10) still remained, which
indicated that the hindered phenol functional group and ester
group did not change at all. Tg of HP1e4 was 66.5  C,
68.8  C, 77.8  C and 54.7  C, respectively. The decrease in
Tg caused by hydrogenation should be attributed to the rotation
around the hydrogenated carbonecarbon single bond which
made polymer chain mobility easier [20].
Fig. 3. 1H NMR spectra of polymers P1 and HP1 (solvent: CDCl3).
351
Table 2
OIT of PP sample stabilized by polymeric antioxidants
Sample (PPepolymeric antioxidant) OIT ( C)
PPeblank 173.4
PPeP1 178.7
PPeP2 178.9
PPeP3 179.6
PPeP4 180.4
PPeHP1 182.5
PPeHP2 182.9
PPeHP3 182.7
PPeHP4 183.1
3.4. Antioxidant ability
A simple method to check the ability of the stabilizer
system is to determine the oxidation induction temperature
(OIT) of the material. OIT measurement was set up in recent
years and was suggested by several authors to be a convenient
method to quickly screen the relative efficiency of the stabi-
lized polymers under conditions designed to accelerate aging.
It was suggested that OIT measurement was always reproduc-
ible and should be preferred in all cases [15,21]. The stabiliza-
tion effect of these polymeric antioxidants to prevent PP from
thermal oxidation is summarized in Table 2. It can be seen that
OIT of PP increased more than 5  C after stabilization by 0.1%
(wt%) of polymeric antioxidants. All of the polymeric antiox-
idants showed their antioxidant ability to protect PP from ther-
mal oxidation. Because the added amount of every polymeric
antioxidant was almost equal in mole, the extent of OIT in-
crease was nearly equal to each other and no obvious differ-
ence between them was observed. However, it should be
mentioned that the antioxidant efficiency of polymeric antiox-
idants HP1e4 was a little higher than unsaturated ones P1e4
comparatively. It was reasonable to associate this result with
the thermal stability of polymeric stabilizers themselves. It
is well known that saturating the polymer chain results in in-
creasing of thermal stability of polymer itself. Therefore, hy-
drogenated polymeric antioxidants had low decomposition
property and then performed long persistent antioxidant effi-
ciency. Unfortunately, other important merits of polymeric an-
tioxidants, such as good compatibility with base resin, low or
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-
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-
dants HP1e4 with saturated polymer chain were obtained.
All of the polymeric antioxidants showed high antioxidant
ability that was characterized by the increase of oxidation in-
duction temperature (OIT) of polypropylene.
Acknowledgements
The authors would like to thank Sasakawa Scientific Re-
search Grant from The Japan Science Society for their finan-
cial support.
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