Anionic Grafting Polymerization of Propylene Sulfide

onto Human Hair in Water

HISATOYO MORINAGA,1 BUNGO OCHIAI,1 HIDEHARU MORI,1 TAKESHI ENDO1,2
1
Department of Polymer Science and Engineering, Faculty of Engineering, Yamagata University, 4-3-16 Jonan,
Yonezawa, Yamagata 992-8510 Japan
2
Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Izuka, Fukuoka 820-8555, Japan

Received 3 November 2005; accepted 27 March 2006

DOI: 10.1002/pola.21478
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Natural human hair was modified by the graft polymerization of propyl-
ene sulfide in an aqueous medium. The amount of the polymer grafted onto the
reduced hair was 0.15–0.19 g on 1.0 g of hair. The grafted polymer was isolated by
the hydrolysis of the hair in the polymer-grafted hair under basic conditions and was
confirmed to be poly(propylene sulfide) by 1H NMR, 13C NMR, and Fourier transform
infrared spectra. The number-average molecular weights of the isolated polymers
from the grafted products were 10,000–12,000. V C 2006 Wiley Periodicals, Inc. J Polym Sci

Part A: Polym Chem 44: 3778–3786, 2006

Keywords: anionic polymerization; graft polymerization; human hair; ring-opening
polymerization; polysulfides

INTRODUCTION portant in numerous commercially important

Various synthetic polymers have been used as
cosmetic tools for hair care. The coating of poly-
mers [e.g., polyacrylates, poly(vinyl pyrrolidone),
and amino acid modified cationic polymers] on
the surface of hair improves the characteristics of
hair, such as the moisture content, antistatic
effect, and tensile strength.1–4 However, the life-
time of the coating is a few days because the poly-
mers adhere weakly to hair by noncovalent inter-
actions, including hydrogen bonds, hydrophobic
interactions, and van der Waals forces. A promis-
ing approach for a longer lifetime is the formation
of covalent bonds between polymers and hair.
The manipulation and control of surface-
grafted polymers have become progressively im-
Correspondence to: T. Endo (E-mail: tendo@me-henkel.
fuk.kindai.ac.jp)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 3778–3786 (2006)
V
C 2006 Wiley Periodicals, Inc.
3778
technologies, such as biotechnology and advanced
microelectronics. In particular, much attention
has been paid to surface-initiated polymerization
from a variety of substrates, the so-called graft-
ing-from approach, and to the design of surface
macromolecular architectures, such as polymer
brushes.5 Because of such industrial and scientific
interest, we have focused on the modification of
natural human hair by the ring-opening polymeri-
zation of cyclic monomers initiated from func-
tional groups inherently existing in hair. In this
study, the cystine residues that existed in hair
were used as thiol/thiolate precursors, which
could be employed as initiators for the surface-ini-
tiated polymerization of propylene sulfide. Thio-
late anions are well-known initiators for the
polymerization of thiiranes.6,7 Nicol et al.6 devel-
oped a living polymerization system of propylene
sulfide with 1,8-diazabicyclo[5.4.0]-undec-7-ene
(DBU) as a base, using a thiol/thiolate initiating
system. Recently, Hubbell et al.7 reported that the

ring-opening polymerization of propylene sulfide
initiated by thiolate anion proceeded anionically
in an oil-in-water emulsion in a living process.
They demonstrated that the living emulsion poly-
merization of propylene sulfide could be attained
in water with DBU as a base and 1,3-propanedi-
thiol as an initiator in the presence of a surfactant
(Pluronic F-127). On the basis of these results, we
selected propylene sulfide as a cyclic monomer for
polymerization by human hair in water. Because
human hair contains a considerable amount of
moisture, surface-initiated polymerization in an
aqueous medium may extend the scope of this fac-
ile and straightforward strategy for generating
polymer-coated hair.
EXPERIMENTAL
Materials
Propylene sulfide was purchased from Tokyo
Kasei Kogyo (Tokyo, Japan) and used as re-
ceived. DBU was purchased from Tokyo Kasei
Kogyo and was distilled under reduced pressure
before use. Pluronic F-127 was purchased from
Sigma Chemical (Missouri). The reducing agent
(Venezel; thioglycolic acid salts) for permanent
treatment was purchased from Daria (Nagoya,
Japan). Natural human hair was provided by
L’Oréal (Paris, France). Before the polymeriza-
tion, the hair was washed with chloroform to
remove impurities and then dried in vacuo at
room temperature. This procedure was repeated
until the weight of the hair became constant. In
another case, the hair was reduced by the reduc-
ing agent at room temperature for 15 min and
was washed with distilled water. The reduced
hair containing water was wiped with paper and
used for the polymerization.
Graft Polymerization of Propylene Sulfide on Hair
All polymerizations were conducted in a glass
tube under air. The hair (0.10 g, 50.0 mm long)
was added to a glass tube containing distilled
water (1.00 mL). Three different procedures were
employed.
Polymerization with a Surfactant and DBU
A surfactant, Pluronic F-127 (0.010 g), and DBU
(1.5 mg, 0.010 mmol) were added to a glass tube
containing the hair. The reaction mixture was
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
POLYMERIZATION OF PROPYLENE SULFIDE 3779
stirred at room temperature for 1 h to allow
DBU to penetrate into the hair. After propylene
sulfide (37.1 mg, 0.50 mmol) was added to the
reaction mixture, the mixture was stirred at
room temperature for 1 h to allow propylene sul-
fide to penetrate into the hair. Then, the polym-
erization was conducted at 60 8C for 24 h. After
the reaction, the washing treatment using chlo-
roform and the drying treatment of the product
were repeated until the weight of the polymer-
grafted hair became constant. The weight frac-
tion of the grafted polymer was determined by
the gravimetric increase from the original hair.
All the data are given as average values of at
least triplicate experiments.
Polymerization with a Surfactant
After propylene sulfide (37.1 mg, 0.50 mmol)
was added to a glass tube containing the hair
(0.10 g, 50.0 mm long) and the surfactant (Plur-
onic F-127; 0.010 g), the mixture was stirred at
room temperature for 1 h to allow propylene sul-
fide to penetrate into the hair. Then, the polym-
erization was conducted at 60 8C for 24 h. The
washing procedures were conducted in the same
way described previously.
Polymerization with DBU
The reaction mixture containing the hair (0.10 g,
50.0 mm long) and DBU (1.5 mg, 0.010 mmol) was
stirred at room temperature for 1 h. After propyl-
ene sulfide (37.1 mg, 0.50 mmol) was added to the
reaction mixture, the mixture was stirred at room
temperature for 1 h. Then, the polymerization
was conducted, followed by the aforementioned
washing treatment.
Isolation of the Grafted Polymer from the Product
The isolation of the grafted polymers was car-
ried out as follows. The polymer-grafted hair
(0.10 g) was added to a glass tube containing an
aqueous NaOH solution (1.00 N, 1.00 mL), and
the mixture was stirred at 100 8C for 1 h. The
pH of the solution was adjusted to neutrality
(pH 7.0) by the addition of an aqueous HCl solu-
tion (1.00 N). Then, the polymer was extracted
with chloroform from the neutralized solution.
The polymer isolated from the grafted product
was purified by precipitation into hexane.
For comparison, a control polymer was syn-
thesized by the bulk polymerization of propylene
3780 MORINAGA ET AL.

rate of 1.0 mL/min, and the molecular weights

Figure 1. Grafted amounts of poly(propylene sulfide)
(see Table 1 for detailed polymerization conditions for
runs 1–4).
sulfide with DBU as a catalyst at 60 8C for 24 h
[number-average molecular weight (Mn) ¼ 11,800,
weight-average molecular weight/number-aver-
age molecular weight (Mw/Mn) ¼ 2.03].
Measurements
1
H and 13C NMR spectra were recorded on a
JEOL JNM-EX270 spectrometer (270 MHz) with
tetramethylsilane as an internal standard in
CDCl3. The molecular weights (Mn and Mw) and
molecular weight distribution (Mw/Mn) were de-
termined with a gel permeation chromatography
(GPC) apparatus equipped with a refractive-index
detector (TriSEC model 302, Viscotek), GPC/size
exclusion chromatography (SEC) pump unit (AT-
2002, Asahi Techneion), and polystyrene gel tandem
columns (TSKgel G2500HXL, G3000HXL, G4000HXL,
and GMHXL, Tosoh) with chloroform as an elu-
ent at 40 8C. The system was operated at a flow
were calibrated with polystyrene standards.
Specific optical rotations were measured with a
Jasco DIP-1000 digital polarimeter equipped
with a sodium lamp as a light source at 25 8C.
Thermal analyses were performed on a TG/DTA
6200 (Seiko Instruments) and DSC 6200 (Seiko
Instruments). The glass-transition temperature
(Tg) was measured by differential scanning calo-
rimetry (DSC). The sulfur content of the product
was determined with a PerkinElmer model
2400II CHNS/O elemental analyzer. Scanning
electron microscopy (SEM) images were obtained
with a SEMEDX III type N scanning electron
microscope at an acceleration voltage of 3.0 kV.
Fourier transform infrared (FTIR) spectra of
the grafted products were recorded by a Horiba
FT-210 FTIR spectrometer with the KBr pellet
technique.
RESULTS AND DISCUSSION
Graft Polymerization of Propylene Sulfide on Hair
The graft polymerization of propylene sulfide
onto human hair was conducted under various
conditions. In all cases, the polymerization was
carried out in water at 60 8C for 24 h. Figure 1
and Table 1 show the results of the graft polymer-
ization. Because the monomer was immiscible
with water, a heterogeneous, white dispersion
was observed during the reaction without the sur-
factant. On the other hand, polymerization in the
presence of the surfactant led to a homogeneous
dispersion, with no evidence of any microscopic
precipitation. However, the effect of the surfac-
tant on the weight fraction of the grafted polymer
was negligible. The reduction treatment of the
hair by a commercial reducing agent (thioglycolic

Table 1. Polymerization of Propylene Sulfide from the Hair Surfacea

DBU Surfactant Pretreatment Yield Conversion

Run (mM) (mM) for Hair (g of Polymer/g of Hair)b (%)c

1 10 1.2 Reduction 0.19 6 0.04 51 6 10

2 10 0 Reduction 0.18 6 0.01 49 6 3.0
3 0 1.2 Reduction 0.15 6 0.04 41 6 11
4 10 1.2 No reduction 0.01 6 0.01 3.0 6 3.0

Polymerization conditions: 0.50 mmol of propylene sulfide, 0.10 g of hair, 60 8C, and 24 h.
a

All results are averages of triplicate experiments.

b
Chloroform-insoluble part.
c
Calculated from the weight fraction of the grafted polymers.

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 POLYMERIZATION OF PROPYLENE SULFIDE 3781

Figure 2. SEM images of the hair (A) before and (B) after the graft polymerization
(run 1 in Table 1).

acid salt) had a significant influence on the
amounts of the grafted polymers. In the case of
the polymerization with the treated hair, the
weight fractions of the surface-attached polymers
obtained after the washing treatment were 0.15–
0.19 g of poly(propylene sulfide)/g of hair (runs 1–
3). A calculation from the weight fraction of the
grafted polymers showed that approximately 40–
51% of the monomer polymerized from the sur-
face of the hair treated with the reducing agent.
On the other hand, the amount of the grafted
polymer was only 0.01 g for 1.00 g of the hair
without the reduction (run 4). The addition of
DBU weakly affected the weight fraction. Figure
2 shows SEM images of the hair before and after
the polymerization of propylene sulfide (run 1 in

Figure 3. FTIR spectra of (A) blank hair, (B) a simple blend (50:50 wt %) of poly
(propylene sulfide) and blank hair, and (C) polymer-grafted hair (run 2 at Table 1).
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
3782 MORINAGA ET AL.
Scheme 1
Table 1). The surface of the hair grafted by 15 wt
% poly(propylene sulfide) showed a small amount
of damage, though to a lesser degree. The surface
of the polymer-grafted hair was as scalelike as
the original hair. However, the diameter of the
polymer grafted hair was 1.3–1.4 times greater
than that of the hair before the polymerization.
These results suggest that the formation of the
grafted polymers occurs mainly inside the hair
surface.
The successful preparation of polymer-grafted
hair was confirmed by FTIR measurements and
elemental analyses. Figure 3 shows FTIR spectra
of hair before and after the graft polymerization
and of a mixture of hair and poly(propylene sul-
fide). The spectrum of the polymer-grafted hair
shows absorption bands at 3000–2800, 1730–
1600, and 800–600 cm
1 assignable to C

H,
C¼¼O (amide bonds inherently existing in the
hair), and C

S, respectively. These characteristic
peaks are also found in the spectrum of the simple
blend of poly(propylene sulfide) and blank hair
[50:50 wt %; Fig. 3(B)]. Hence, the spectrum of the
product obtained by the polymerization appears
as the superposition of the spectra of the two com-
ponents, the hair and poly(propylene sulfide), sug-
gesting that the polymers were conjugated with
the hair. To obtain quantitative information on
the composition of the covalently attached poly-
mers, the atomic composition of a sample (run 3
in Table 1) was evaluated by elemental analysis.
The atomic composition of the sample was as fol-
lows: C, 46.0%; H, 7.2%; N, 11.4%; S, 14.8%. These
values are apparently different from those of the
blank hair (C, 44.0%; H, 6.7%; N, 14.4%; S, 4.1%).
Scheme 2
In particular, a significant increase in the sulfur
content of the polymer-grafted hair (14.8%) from
that of the blank hair (4.1%) was attributable to
polymerization. The weight of the poly(propylene
sulfide) calculated from this composition (20 wt %)
was close to the weight fraction of the grafted
polymer determined by the gravimetric increase
from the original hair. These results indicate the
formation of the composite of hair and poly(pro-
pylene sulfide).
To prove that polymers simply absorbed to
the hair surface could be readily removed by the
washing treatment with chloroform, a control
experiment was conducted with a simple mix-
ture of the reduced hair and poly(propylene sul-
fide). The mixture was stirred in water at 60 8C
for 24 h, and then the remaining hair was
washed with chloroform. As expected, a negligi-
ble amount of the polymer could be attached to
the hair surface (<1.0 wt %).
The better grafting amounts of poly(propyl-
ene sulfide) obtained from the reduced hair are
postulated to have arisen from the formation
of thiol groups by the reducing treatment
(Scheme 1). The basicity of the reducing agent,
which converts thiol to nucleophilic thiolate,
may help to increase the amount of the grafted
poly(propylene sulfide). This assumption is sup-
ported by the fact that the addition of DBU had
no significant influence on the weight fractions
of the grafted polymers, probably because of the
sufficient shift from thiol into thiolate treated
simply by the reducing agent. Another possible
reason for the difference in the amounts of the
grafted polymers between treated and non-
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 POLYMERIZATION OF PROPYLENE SULFIDE 3783

Figure 4. 1H NMR spectra of (A) poly(propylene sulfide) obtained from bulk poly-
merization without hair and (B) the isolated poly(propylene sulfide) (run 2 in Table 2).

treated hairs is the swelling of the hair by the
reduction treatment, so that the space between
cuticles is expanded, allowing better penetration
of propylene sulfide into the hair. The surface of
human hair is normally covered by layers of
hydrophobic cuticles (length ¼ 80–100 lm, thick-
ness ¼ 0.5–1.0 lm, space between cuticles <1 lm),
whereas the inside of the cuticles is hydrophilic.
Hence, the swelling of hair takes place gra-
dually in water, especially under alkaline con-
ditions. For these reasons, the reduction treat-
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
ment plays an important role in the swelling
phenomenon.
Isolation of Grafted Poly(propylene sulfide)
from Hair
To understand the growth characteristics of sur-
face-initiated polymerization as well as the mo-
lecular parameters of the grafted polymers, we
attempted to isolate these chains from the
grafted products. The treatment of polymer-
3784 MORINAGA ET AL.

Figure 5. 13C NMR spectra of (A) poly(propylene sulfide) obtained by bulk polymer-
ization without hair and (B) the isolated poly(propylene sulfide) (run 2 in Table 2).

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Figure 6. FTIR spectra of (A) poly(propylene sul-
fide) obtained by bulk polymerization without hair
and (B) the isolated poly(propylene sulfide) (run 2 at
Table 2).
grafted hair in an aqueous NaOH solution at
100 8C for 1 h gave a detached polymer. Under
the basic conditions, human hair was decom-
posed by the chain scission of the amide link-
ages, whereas poly(propylene sulfide) was intact
without destruction, as shown in Scheme 2.
The isolated poly(propylene sulfide)s were
characterized by SEC, FTIR, NMR, and DSC.
The Mn’s of the isolated polymers ranged from
10,000 to 12,000 (Mw/Mn ¼ 1.6–3.6), as can be
seen in Table 2. Human hair is known to be
approximately 80–90% proteins, whose gross
cystine residue content is 14.9%.8 In general,
about 20% of the cystine residues can be re-
duced to give cystein residues by commercial
reductants used for permanent hair treatment.
Therefore, 0.21 mmol of thiol groups is supposed
to be involved in 1.00 g of the hair after the
reducing treatment. From this value, it can be
calculated that the molar ratios of the consumed
monomers per thiol group on the surface are
approximately 10–12 (runs 1–3, Table 1), if the
polymerizations are initiated homogeneously
from all the thiol groups existing on the hair
surface with negligible unfavorable side reac-
tions. The molecular weights of the grafted
poly(propylene sulfide)s calculated from the
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POLYMERIZATION OF PROPYLENE SULFIDE 3785
degree of polymerization are 700–900 g/mol,
which are much lower than the Mn’s estimated
from SEC. On the basis of the SEC results and
the theoretical calculations, it can be derived
that approximately 7% of the thiol groups act as
initiating groups for the graft polymerization. In
other words, at least 7% of the thiol groups exist
on the surface of hair, where the monomer is
readily accessible. Because of the possibility of
polymerizations initiated by other nucleophilic
groups, such as amino groups, in the lysine resi-
due, the actual initiating efficiency may be lower
than this value.
The 1H and 13C NMR spectra of an isolated
graft polymer are depicted in Figures 4 and 5,
respectively. Poly(propylene sulfide) prepared by
a conventional bulk polymerization with DBU
(Mn ¼ 11,800, Mw/Mn ¼ 2.03) was used for com-
parison. The 1H NMR spectrum of the isolated
graft polymer shows the signals assignable to
poly(propylene sulfide) at 1.2–1.5, 2.5–2.8, and
2.8–3.1 ppm. The characteristics peaks at 21.0–
21.7, 38.7–39.3, and 41.5–42.2 ppm, attributed
to poly(propylene sulfide), can be clearly observed
in the 13C NMR spectrum (Fig. 5). Moreover, the
absorption bands at 3000–2800 and 800–600 cm
1,
which are assigned to the absorption of C

H
and C

S, can be clearly observed in the FTIR
spectrum of the isolated graft polymer (Fig. 6).
These results indicate the formation of poly(pro-
pylene sulfide) by the surface-initiated ring-
opening polymerization.
The microstructure of the isolated polymer was
compared with that of the control sample. As
shown in Figure 5(A), the 13C NMR spectrum of
the poly(propylene sulfide) obtained by a conven-
tional bulk polymerization without hair shows
two split signals assignable to the methine carbon
at 41.8 and 41.9 ppm, which may be attributable
to the meso and racemo dyads, respectively, on
Table 2. Molecular Weights of Poly(propylene
sulfide) Isolated from the Polymerization Productsa
Run M nb Mw/Mnb
1 10,000 6 2,800 2.3 6 0.40
2 12,000 6 890 3.6 6 0.14
3 11,000 6 1,200 1.6 6 0.26
4 —c —c
a
See Table 1 for detailed polymerization conditions for
runs 1–4.
b
Determined by GPC (with chloroform and a polystyrene
standard) of the isolated poly(propylene sulfide).
c
Not determined.
3786 MORINAGA ET AL.
the basis of the report by Ivin et al.9 In the 13C
NMR spectrum of the isolated poly(propylene sul-
fide), the signal at 41.9 ppm is significantly lower
than that in the spectrum of poly(propylene sul-
fide) obtained with bulk polymerization [Fig. 5(B)].
This indicates that the isolated poly(propylene
sulfide) contained a higher amount of meso dyad
than that obtained by the bulk polymerization,
and this is also supported by the signals around
39 ppm. This affected the Tg value of isolated
poly(propylene sulfide). The Tg (
36.5 8C) of
isolated graft poly(propylene sulfide) (run 2 at Ta-
ble 2) was approximately 7 8C higher than that
(Tg0 ¼
43.6 8C) of poly(propylene sulfide) ob-
tained from bulk polymerization without hair,
whose Mn was 11,800 g/mol, because of the regu-
lated tacticity.10 A possible reason for the im-
proved tacticity is the electrostatic effects of the
functional groups on the surface of hair (e.g.,
amino groups, carboxyl groups, hydroxyl groups,
and thiol groups) on the propagating end, al-
though the mechanism to increase the meso dyad
is unclear.
In this work, racemic propylene sulfide was
employed for the surface-initiated polymeriza-
tion. It is possible that the chiral environment in
hair may affect the polymerizability of either
enantiomer, as is the case for the stereoselective
polymerization of propylene sulfide from chiral
initiators.11 In this case, the specific optical rota-
tion of the isolated poly(propylene sulfide) was
very low ([a]D ¼
0.44 8) and identical to that of
poly(propylene sulfide) obtained from bulk poly-
merization without hair ([a]D0 ¼
0.55 8), indi-
cating the formation of optically inactive poly-
mers.
CONCLUSIONS
The graft polymerization of propylene sulfide
onto hair successfully proceeded to afford hair
modified with poly(propylene sulfide) in an aque-
ous medium. The reduction treatment of hair
significantly increased the amount of grafted poly
(propylene sulfide). The molecular weight of grafted
poly(propylene sulfide) was higher than that
assumed from the thiol groups existing in hair,
indicating that only a small number of the thiol
groups in the hair may initiate the graft polymer-
ization of propylene sulfide. The technique used
in this study may be applied to the coating of hair
by covalently attached polymers with emulsion
cosmetic tools. For further study, we are now
evaluating the characteristics of hair modified by
this graft polymerization.
The authors gratefully acknowledge the financial sup-
port for this work provided by L’Oréal.
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