Synthesis and properties of long-chain aromatic telechelic monodispersed diols radical-initiated, addition of 2-mercaptoethanol onto α, ω nonconjugated dienes

Article abstract of DOI:10.1080/10426507.2011.625512

The synthesis of aromatic telechelic mono dispersed diols produced from the radical-initiated addition reaction of a twofold excess of 2-mercaptoethanol onto original α, ω nonconjugated dienes reaction is presented. These novel α, ω nonconjugated dienes were prepared by addition reaction of m-isopropyl α, α' dimethyl benzylisocyanate with mono dispersed telechelic diols obtained by fractionation of oligo(ethylene terephthalate)s. In these cases, the long chain α, ω diols were produced selectively and quantitatively. The products are soluble in most organic solvents in contrast to classical oligo (ethylene terephthlate)s and posses a lower glass transition and melting temperatures. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Figures S1-S3.

Full text of DOI:10.1080/10426507.2011.625512

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Synthesis and Properties of Long-Chain
Aromatic Telechelic Monodispersed
Diols Radical-Initiated, Addition
of 2-Mercaptoethanol onto α, ω
Nonconjugated Dienes
Bernard Boutevin a , Bruno Ameduri a , Abderrahmane Elidrissi b
Rachid Touzani b c
&
a Laboratory of Macromolecular Chemistry, UMR (CNRS) 5076 , Ecole
Nationale Supérieure de Chimie de Montpellier , Montpellier Cedex
1 , France
b LCAE-URAC18, Department of Chemistry, Science Faculty ,
Mohamed Ier University , Oujda , Morocco
c Faculté Pluridisciplinaire de Nador , Université Mohammed Ier ,
Nador , Morocco
Published online: 31 Jan 2012.
To cite this article: Bernard Boutevin , Bruno Ameduri , Abderrahmane Elidrissi & Rachid Touzani
(2012) Synthesis and Properties of Long-Chain Aromatic Telechelic Monodispersed Diols Radical-
Initiated, Addition of 2-Mercaptoethanol onto α, ω Nonconjugated Dienes, Phosphorus, Sulfur, and
Silicon and the Related Elements, 187:4, 482-494, DOI: 10.1080/10426507.2011.625512
To link to this article: http://dx.doi.org/10.1080/10426507.2011.625512
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Phosphorus, Sulfur, and Silicon, 187:482–494, 2012
Copyright ꢀC Universite´ Mohamed Premier
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.625512
SYNTHESIS AND PROPERTIES OF LONG-CHAIN
AROMATIC TELECHELIC MONODISPERSED DIOLS
RADICAL-INITIATED, ADDITION OF
2-MERCAPTOETHANOL ONTO α, ω NONCONJUGATED
DIENES
Bernard Boutevin,1 Bruno Ameduri,1 Abderrahmane Elidrissi,2
and Rachid Touzani2,3
1Laboratory of Macromolecular Chemistry, UMR (CNRS) 5076, Ecole Nationale
Supe´rieure de Chimie de Montpellier, Montpellier Cedex 1, France
2LCAE-URAC18, Department of Chemistry, Science Faculty, Mohamed Ier
University, Oujda, Morocco
3Faculte´ Pluridisciplinaire de Nador, Universite´ Mohammed Ier, Nador, Morocco
GRAPHICAL ABSTRACT
Abstract The synthesis of aromatic telechelic mono dispersed diols produced from the radical-
initiated addition reaction of a twofold excess of 2-mercaptoethanol onto original α,ω noncon-
jugated dienes reaction is presented. These novel α,ω nonconjugated dienes were prepared by
addition reaction of m-isopropyl α,αꢀdimethyl benzylisocyanate with mono dispersed telechelic
diols obtained by fractionation of oligo(ethylene terephthalate)s. In these cases, the long chain
α,ω diols were produced selectively and quantitatively. The products are soluble in most or-
ganic solvents in contrast to classical oligo (ethylene terephthlate)s and posses a lower glass
transition and melting temperatures.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental
resource: Figures S1-S3.
Keywords α, ω nonconjugated dienes; 2-mercaptoethanol; telechelic monodispersed diols;
polyurethanes; thermal properties; solubility
Received 24 July 2011; accepted 17 September 2011.
Address correspondence to Abderrahmane Elidrissi, LCAE-URAC18, Department of Chemistry, Science
Faculty, Mohamed Ier University 60000, Oujda, Morocco. E-mail: ab.elidrissi@yahoo.fr
482

LONG CHAIN AROMATIC TELECHELIC MONODISPERSED DIOLS
483
INTRODUCTION
Telechelic polymers are generally moderate molecular weight polymers that bear
functional groups at both chain ends. They are characterized by the nature and the number
of those functional groups. The first, and still most important, interest of telechelics comes
from the fact that functional end groups can be involved in coupling reactions, leading
to block copolymers, polymers networks, segmented polymer networks, and soft polymer
networks.1–5 On the industrial scale, several materials are produced. Among them, the
oldest and most important ones are the polyurethane’s synthesized from coupling telechelic
hydroxy polymers with α,ω- diisocyanates.
The polyurethanes are produced with an extremely wide range of physical and chem-
ical properties.6–10 Telechelics have been also used for the synthesis of linear segmented
copolymers leading to many new materials with various properties obtained by appropriate
combinations of soft and hard segments. These telechelics are the basis of the develop-
ment of the thermoplastics elastomers.11,12 New developments in this field are obtained
by exploration of combination of telechelics with exceptional properties such as low glass
transition temperature, high melting temperatures increased thermal stabilities, liquid crys-
talline properties, and dynamic mechanical thermal characteristics.13–15
Telechelic or α,ω-difunctional precursors are required to obtain high molecu-
lar weight materials with satisfactory properties. Synthesis and use of fluorinated or
hydroxy polybutadienes telechelics were described, their properties were also investi-
gated.16,17 Telechelic diols are important precursors for polycondensates, such as polyesters,
polyurethanes, polycarbonates, and silicones, and can also be used to introduce pho-
tocrosslinkable functions into polymeric systems. In addition they can full in a wide range
of recent applications.18–24 Long hydrocarbon chain ethers and ketones with bis-terminated
hydroxy or carboxyl groups have been synthesized and evaluated for their potential to
favorably alter lipid disorders including metabolic syndrome.25
Interestingly, recent investigations have shown that both mechanical properties of the
resulting polyurethanes26,27 and their thermostability28–31 were improved when a monodis-
persed diol was used compared to a polydispersed one.32 Long-chain heteroatom containing
telechelic diols were synthesized with well-defined end group reactivity, and are well suited
for the preparation of high molecular weight block copolymers.33–35 It was also noted that
the radical telomerization23,27–30 was more adequate than the redox one 36–38 or any other
conventional techniques38,39 to produce such compounds selectively and in high yields.
In the case of the radical monoaddition of undecenic derivatives with α,ω-dithiols,
improving their solubility, polar groups could be introduced either from the monomer27–30
or the dithiols.29 Previous structures mainly involved aliphatic derivatives.
However, only a few research articles have mentioned the synthesis of aromatic
telechelic monodispersed diols.39–45 Hence, it was interesting to prepare such compounds
from the same above pattern that involves aromatic α,ω-dienes prepared by addition of
oligo (ethylene terephthalate) to commercially available m-isopropyl α,αꢀ-dimethylbenzyl
isocyanate.32,46
Moreover, the literature mentions that polydispersed ethylene terephthalate polymers
are available and usually they are prepared according to different methods (polytranses-
terification,47–49 polyesterification,50–54 and polycondensation55–62). These methods require
two steps, and sometimes it is difficult to control their kinetics.48,49 Thus, it was of interest
to prepare similar compounds bearing different functions on their backbone with a new
method.

484
B. BOUTEVIN ET AL.
RESULTS AND DISCUSSION
The syntheses of long chain aromatic telechelic monodispersed diols were performed
by radical addition of 2-mercaptoethanol with telechelic dienes [(B, 1), (B, 2), (B, 3)]
according to Scheme 1, in which the synthesis of ethylene terephthalate oligomers is first
described.
O
C
O
C
O
C
O
C
H3C
O
HO (CH2)2 OH
H
O
(CH2)2
O
O
(CH2)2 OH
O
CH3
+
x
(A,x)
CH3
C
CH3
CH3
C
NCO
(A,x)
C
NHC
O
CNH
O
CH3
CH3
CH3
THF
(A,x)
H2C
C
+
H2C
C
C
CH2
DBTDL
CH3
( B,x )
CH3
H3C
initiator
2 HO (CH2)2 SH
( B,x )
+
HO (CH2)2
S
( B,x )
S
(CH2)2 OH
solvent
( C,x )
Scheme 1
Synthesis of Oligo (Ethylene Terephthalete)s
It is known that the preparation of oligo (ethylene terephthalate) can be achieved by
polytransesterification,34–36 by polyesterification,37–42 and by polycondensation.30,31 In this
present case, we have chosen to prepare ethylene terephthalate oligomers by transesterifi-
cation of dimethyl terephthalate and ethylene glycol as per Scheme 2.
O
C
O
C
O
C
O
C
H3C
O
HO (CH2)2 OH
H
O
(CH2)2
O
O
(CH2)2 OH
O
CH3
+
x
(A,x)
;
x = 1, 2, 3
Scheme 2
The different low molecular weight oligomers can be separated by fractionated pre-
cipitation and the first two products were obtained owing to their solubility into boiling
water and THF, respectively. Both of them were easily identified by size exclusion chro-
matography and were characterized by IR and NMR. The IR spectra show expected broad
bands at 3400–3600 cm−1 assigned to the hydroxy groups and sharp frequency at 1700
cm−1 for the carbonyl of ester function. The 1H NMR spectra exhibit a singlet at 8.15 ppm
characteristic of the aromatic ring whereas both methylene groups in the α and β positions
that represent the hydroxy end groups gave triplets at 3.75 and 4.35 ppm, respectively; the

LONG CHAIN AROMATIC TELECHELIC MONODISPERSED DIOLS
485
singlet centered at 4.70 ppm corresponds to both methylene groups located between the
terephthalic groups.
The signals centered at about 134 and 165 ppm in 13C NMR spectrum of (A, 1)
are characteristic of both different aromatic carbon atoms and to the carbonyl groups,
respectively. Those at 59 and 67 ppm correspond to the methylene groups while that
adjacent to the ester function is low field shifted. The signal at 63 ppm in the 13C NMR
spectrum of the dimer is assigned to methylene group located between the aromatic rings.
The insolubility of the diol (A, 2) inhibits the preparation of (A, 3), and its conden-
sation between terephthaloyl chloride was unsuccessful. Thus, from the above results, it is
noted that the increase of the length of alkylenic chain of terephthalate oligomers improves
their solubility. Ester functions also contribute to such an improvement although their effect
seems slightly less important.
Synthesis of Aromatic Telechelic Nonconjugated Monodispersed
Dienes (B, x)
The synthesis of aromatic telechelic nonconjugated monodispersed dienes was per-
formed by the addition reaction of oligo (ethylene terephthalate) to the monoisocyanate
(m-isopropyl- α,αꢀ- dimethylbenzyl) isocyanate according to Scheme 3.
CH3
C
NCO
O
C
O
C
CH3
H
O
(CH2)2
O
O
(CH2)2 OH
+
H2C
C
x
CH3
(A,x)
THF DBTDL
O
O
C
CH3
C
CH3
NHC
O
O
(CH2)2
O
C
O
(CH2)2
O
CNH
O
C
x
CH3
CH3
H2C
C
C
CH2
( B,x )
CH3
H3C
Scheme 3
The reaction was catalyzed by the dibutyl tin dilaurate (DBTDL) and was monitored
by FTIR. It was stopped when the frequency band of the NCO function at 2270 cm−1
disappeared. The IR spectra of the dienes (B, x) exhibit the presence of a band at 1720 cm−1
assigned to the vibration of the urethane group (–OCONH–) free from hydrogen bonding,
and the absence of any broad band in the 3400–3600 cm−1 range characteristic of hydroxy
group. The dienes were characterized by means of 1H and 13C NMR. The 1H NMR spectra
of these compounds show
• the absence of signals assigned to the hydroxy protons of telechelic diols;
• the presence of two singlets centered at δ = 5.00–5.35 ppm of ethylenic aromatic bonding;
and
• a new signal appears at 5.60 ppm attributed to the proton of ( NHCOO ) aliphatic
urethane group.
The 13C NMR spectra show a characteristic signal centered at 165 ppm of the carbonyl
urethane group. The ester carbonyl leads to a signal at 165.3 ppm. The most important was

486
B. BOUTEVIN ET AL.
Figure 1 1H NMR spectrum of (B, 2).
the obtention of telechelic nonconjugated monodispersed dienes with yields higher than
90% using simply an addition reaction. IR, 1H, and 13C NMR characteristics are detailed
1
in the experimental part. Figure 1 shows the H NMR spectrum of Bis[2-(m-isopropyl
α,αꢀ-dimethylbenzylcarbamoyl) ethoxy terephthaloyloxy] ethyl (B, 2)
Synthesis of Long Chain Monodispersed Diols
The radical initiated addition of thiol to dienes was previously described,17–19 and it
was shown that radical initiation in the presence of peroxides was the most adequate to
produce the expected diols in quantitative yields.17,18
The synthesis of aromatic monodispersed diols was performed under similar condi-
tions from the radical bis-monoaddition of 2-mercaptoethanol onto a long chained noncon-
jugated telechelic monodispersed dienes as per Scheme 4.
Scheme 4

LONG CHAIN AROMATIC TELECHELIC MONODISPERSED DIOLS
487
First, a model reaction was carried out with a telechelic diene produced from
low molecular weight oligo (ethylene terephthalate), (case where x = 1). Such a reac-
tion involved the initial molar ratios (R0 and C0) [thioalcohol]0/[telechelic diene]0 and
[initiator]0/[telechelic diene]0 of 2 and 0.02, respectively. Tertbutyl peroxypivalate was
◦
chosen as the initiator.18 The reactions were carried out at 70 C for 4 h and monitored
by size exclusion chromatography. After the reaction, the diol was precipitated twice and
then recrystallized from methanol. The resulting diol was characterized by IR and NMR
spectroscopy.
The IR spectrum of (C, x) showed the absence of the band corresponding to an
olefenic group at 1640 cm−1, but the presence of a broad band at about 3500 cm−1 assigned
1
to the vibration of the hydroxy groups. The H NMR spectrum exhibits the absence of
signals corresponding to ethylenic protons and of mercapto function at 5.00–5.35 and 1.95
ppm, respectively. The presence of a broad singlet centered at 1.60 ppm corresponded to
the methylenic chain and of triplets at 2.75 ppm and 3.50 ppm was assigned to methylene
groups adjacent to sulfur atoms and to the hydroxy end groups, respectively. The other
signals are similar to those of the corresponding telechelic dienes. It was noted that the RS◦
radical produced in the initiation step has reacted with the less hindered side of the double
band as observed previously17,18,42,43 or in work performed by Nuyken44,45 or Klemm.46,47
The 13C NMR spectrum exhibits the expected singlets corresponding to the different
carbon atoms of diol (C, 1). As indicated in the experimental part, it does not show any
ethylenic atoms at 115 and 139 ppm assigned to ethylenic carbon of telechelic dienes. They
are in good agreement with different peaks predicted by others authors.48,49 Such a diol was
obtained quantitatively and selectively (i.e., α- monoaddition).
The synthesis of other diols (C, x), x = 2, 3, was performed in similar conditions
as described above in the presence of initiator. Each SEC curve of the produced diol
shows a unique sharp peak. The expected diols were obtained selectively and in yields
1
higher than 90%. Figure 2 shows the H NMR spectrum of Bis{2-[m-(2-hydroxyethy
lthiaisopropyl)α,αꢀ-dimethylbenzyl-carbamoyl]ethoxyterephthaloyloxy} ethyl (C, 2).
Physical Properties of Diols (C, x)
The solubility and the thermal characteristics (melting and glass transition tempera-
tures) of the different long-chained aromatic diols were studied.
Solubility: It was observed that oligo (ethylene terephthalate) being polydispersed or
fractionated (i.e., monodispersed) is partially soluble in common organic solvents, except
in THF. However, when these substances are functionalized with mercapto groups, the ester
function confers to the corresponding compounds an improved solubility.
Furthermore, all diols produced by radical bis monoaddition of 2-mercaptoethanol
onto telechelic dienes exhibit a very good solubility in most organic solvents at room
temperature. The best nonsolvent to favor their precipitation and their purification was
fluorinated solvents, e.g., CF3CH2CF2CH3 and ClCF2CFCl2. This good solubility arises
from the presence of a polar function such as an ester group, which favored hydrogen
bonding.
Melting and Glass Transition Temperature
Table 1 lists the glass transition (Tg) and melting temperatures (Tm) of oligo (ethylene
terephthalate)s and those of the corresponding diols, determined by means of calorimetry.

488
B. BOUTEVIN ET AL.
Figure 2 1H NMR spectrum of (C, 2).
It is observed that oligo (ethylene terephthalate)s do not exhibit any glass transition tem-
perature but their melting temperatures are high. It is observed too that for the same degree
of polymerization, the Tm decrease when the length of methylenic chain increase. Tm of
oligo(tetramethylene terephthalate) < Tm of oligo (ethylene terephthalate).42
However, each corresponding diol produced from the radical bis monoaddition of 2-
mercaptoethanol onto α, ω-telechelic diene exhibits a semicrystalline behavior evidenced by
a sharp endotherm. It seems that such substances also exhibit amorphous zones as evidenced
by the presence of a jump in heat capacity assigned to a glass transition temperature.
More interesting, the Tm of such diols is much lower than those of the starting diols
(about 70 ◦C–100 ◦C). It is considered that the polar ester groups stiffen the molecules, but
the long methylenic chain increases their softness as if is evidenced by a low Tg. This is in
agreement with previous investigations.20,42
Moreover, from Table 1, it is noted for the same terephthalate series that the values
of both Tg and Tm temperatures increase when the degree of polymerization of diols (C,
x) increases too. The aromatic groups in these compounds became higher. Furthermore,
it was observed that for the same degree of polymerization18 the diols produced from
monodispersed oligo(tetramethylene terephthalate)s exhibit lower Tg and Tm values than

LONG CHAIN AROMATIC TELECHELIC MONODISPERSED DIOLS
489
Table 1 Molecular weights (Ma, Mb, Mc), melting (Tm), and glass transition (Tg) temperatures of telechelic diols
(A, x) and (C, x). Ma: molecular weights theoretically expected; Mb: calculated from OH titration; Mc: determined
from 1H NMR
(A, x) and (C, x)
Ma
Mb
Mc
Tm/◦C
Tg/◦C
O
O
C
H
O
(CH2)2
O
C
(CH2)2
O
OH
x
(A,x)
(A, 1)
(A, 2)
(A, 3)
(A, ∞)
254
446
639
—
nd
250
440
640
—
109
169
199
67–12563
none
none
none
250–31063
nd
nd
—
CH3
NHCO
OC
COO(CH2)2
O
O(CH2)2O
C
x
2
CH3
HO(CH2)2SCH2 CH
CH3
(C,x)
(C, 1)
(C, 2)
(C, 3)
812
1004
1196
790
980
1150
800
990
1170
71
113
123
−9
11
15
those of oligo (ethylene terephthalate)s starting materials. This behavior arises from the
tetramethylene groups, which bring softness into these molecules.
EXPERIMENTAL PART
Materials
The starting materials were purchased from Aldrich and did not require further purifi-
cation prior to use; the m-isopropyl α, αꢀ-dimethyl benzylisocyanate (m-TMI) was delivered
from Cyanamid Company. The reactions were monitored by size exclusion chromatogra-
phy (SEC) using a Waters Associates apparatus equipped with a Knauer HPLC (Model 64)
pump; tetrahydrofuran (THF) was used as the eluent (flow rate 1.5mL/min at 30 ◦C). The
separation was carried out with a set of four Polymers Lab columns, the pore diameters of
which were 10.000, 1000, 500, and 100 Å. The detection was performed with a Knauer
differential refractomer, and Fourier transform infrared (FTIR) spectra were conducted
with a Nicolet 510 (P) spectrometer. The accuracy of the bonds was given with an error of
2.0 cm−1 and the letters VS, S, M, or W indicate Very Strong, Strong, Medium, or Weak
intensity, respectively. The different pure telomers were characterized by 1H and 13C NMR
1
spectroscopy at room temperature. H and 13C NMR spectra were recorded on Bruker
AC 250, AC 200, or CW 360, by using deuterated chloroform (CDCl3) as the internal
reference and solvent, respectively. The letters: s, d, t, q, and m designate singlet, doublet,
triplet, quadruplet, and multiplet, respectively. DSC scans for compounds C1, C2, and C3
are located in the Supplemental Materials (Figures S 1–S 3).
Differential scanning calorimetry (DSC) measurements were conducted with a
PerkinElmer DSC 4 apparatus equipped with a TADS microcomputer; the apparatus was

490
B. BOUTEVIN ET AL.
calibrated with indium that has a melting temperature of 156.6 ◦C and an enthalpy of fusion
of 28.5 J/g. A first scan◦was conducted at a heating rate of 40 ◦C/min up to 100 ◦C, it was
then quenched to −70 C, and left for 5 min at that temperature before a second scan at
◦
heating rate of 10 C/min, this gave the glass transition temperature (Tg) values reported
in this paper, taken at half height of the jump in the heat capacity at the glass transition,
and those of melting temperature (Tm) corresponds to the value of the maximum of the
endothermic peak. The hydroxy end groups were titrated with an acetic anhydride/pyridine
mixture. The residual acetic acid was titrated with sodium hydroxide.
Synthesis of Telechelic Monodispersed Diols: Ethylene Terephthtalate
Oligomers
In a two-necked round-bottom flask equipped with a condenser and a distillation
device, dimethyl terephthalate and an excess of ethylene glycol in a 1:12 molar ratio were
introduced.
Zinc acetate (100 mL of ethylene glycol; 0.4 mmol) was added as a catalyst and
chloroacetic acid (250 mL of ethylene glycol; 1 mmol) was added to prevent the catalyst
from being inhibited. Methanol was recovered by distillation. The mixture was cooled and
dropwise added into deionized water, and the precipitate was heated up to 70 ◦C for 24 h
under vacuum. The mixture was heated up to 100 ◦C and quickly filtered to separate diol
DP3, soluble in boiling water. Then, this filtrate was cooled down to 10 ◦C and the crystals
were dried under pressure at 80 ◦C.
Bis (2-hydroxyethyl) Terephthalate (A, 1). Tm = 109 ◦C, no Tg was observed
by DSC. IR (KBr, cm−1): 3600–3200 (S, broad); 2950 (S); 2890 (M); 1950 (W); 1700 (VS);
1500 (W); 1450 (M); 1400 (S); 1270 (VS); 1140 (S); 1070 (S); 1020 (S); 900 (S); 870
(M); 840 (M); 730 (S); 500 (M). 1H NMR (DMSO d6) δ: 3.75 (m, 4H); 4.50 (t, 4H); 5.00
(t, 2H); 8.15 (s, 4H). 13C NMR (DMSO d6) δ: 59.2; 67.1; 129.5; 133.8; 165.3; C12H14O6
(254.24). Calculated: C (56.69), H (5.55); Found: C (57.08), H (5.28). Diol DP5 is soluble
in boiling THF; hence, it can be separated from the higher molecular weight diols. White
powder was obtained.
◦
Bis (2-hydroxyethoxy Terephthaloyloxy) Ethyl (A, 2). Tm = 169 C, no Tg
was observed by DSC. IR (KBr, cm−1): 3600–3200 (S, broad); 2950 (S); 2890 (M); 1960
(W); 1700 (VS); 1500 (W); 1450 (W); 1410 (M); 1340 (M); 1270 (VS); 1130 (S); 1070 (S);
1
1020 (M); 900 (M); 870 (M); 830(W); 730 (VS); 500 (M). H NMR (DMSO d6) δ: 3.75
(t, 4H); 4.35 (t, 4H); 4.70 (s, 4H); 5.00 (t, 2H); 8.15 (s, 8H). 13C NMR (DMSO d6) δ: 56.2;
59.1; 63.3; 129.6; 129.7; 133.4; 134.0; 165.1; 165.2; C22H22O10 (446.41). Calculated: C
(59.19), H (4.97); Found: C (59.93), H (4.71).
Synthesis of Higher Boiling-Point Oligo (Ethylene Terephthalate) (A, 3).
In a three-necked round-bottom flask equipped with a condenser, a dropping funnel and
saturated with a nitrogen flow were introduced terephthaloyl chloride and diol (A, 1) in an
initial mole ratio 1:6. THF was used as the solvent. Pyridine was added to such a mixture in
a 2:1 mole ratio with a reference to diol (A, 1). The medium was refluxed for 4 h and then
the warmed white solid produced was filtered off twice and washed. It was recrystallized
from DMSO.
Bis [2-(2-hydroxyethoxy Terephthaloyloxy) Ethyl] Terephthalate (A, 3).
Tm = 199 ◦C, no Tg was observed by means of DSC. IR (KBr, cm−1): ν = 3600–3200 (S,
broad); 2940 (S); 2880 (M); 1960 (W); 1700 (VS); 1520 (W); 1460 (W); 1420 (M); 1340
(M); 1280 (VS); 1130 (S); 1070 (S); 1030 (M); 900 (M); 880 (M); 850 (W); 730 (VS); 490

LONG CHAIN AROMATIC TELECHELIC MONODISPERSED DIOLS
491
(M). 1H NMR (DMSO d6) δ: 3.75 (m, 4H); 4.35 (m, 4H); 4.70 (m, 8H); 4.90 broad signal
shifted with dilution (m, OH, 2H); 8.15 (s, aromatic protons, 12H). 13C NMR (DMSO d6) δ:
56.2; 59.1; 63.3; 129.6; 129.7; 133.4; 134.0; 165.1; 165.2; C32H30O14 (638.58). Calculated:
C (60.19), H (4.74); Found: C (61.28), H (4.56).
Synthesis of Aromatic Telechelic Monodispersed Dienes
Synthesis from Oligo (Ethylene Terephthalate)s. All the experiments were
performed under nitrogen using standard Schlenk techniques. THF was distilled by the
usual methods64 and stored under nitrogen. Typical procedure of the addition was as
follows: in a Schlenk flask containing m-isopropyl α,αꢀ- dimethylbenzylisocyanate was
added, respectively, to a solution of monodispersed oligo (ethyleneterephthalate)s (A, 1),
(A, 2), and (A, 3) in THF in a molar ratio 2:1 ([OH]/[NCO] = 1).
The DBTDL was added to the solution as a catalyst. The mixture was flushed with
N2 several times and was heated at 80 ◦C for 5 h under stirring. The reaction was stopped
when the frequency absorption band in IR spectroscopy of NCO at 2270 cm−1 disappeared.
The mixture was poured into methanol, which led to separation of the product. It was
collected by filtration, washed with methanol, and dried under vacuum to give a series of
monodispersed aromatic telechelic dienes (B, 1), (B, 2), and (B, 3). In each case, the yields
were quantitative.
Bis [2-(m-isopropyl α,αꢁ-dimethylbenzylcarbamoyl) Ethyl] Terephthalate
(B, 1). Tm = not determined. IR (KBr, cm−1): ν = 3360 (VS); 2920 (S); 2880 (M); 1720
(VS); 1660 (W); 1600 (M); 1580 (M); 1510 (S); 1450 (M); 1410 (M); 1390 (W); 800 (M);
735 (S); 700 (M). 1H NMR (CDCl3) δ: 1.60 (s, 12H); 2.10 (s, 6H); 4.30 (s, 4H); 4.45 (s,
4H); 5.60 (s, 2H); 7.25–7.45 (d, 8H); 8.10 (s, 4H); 5.05–5.35 (s, 4H, ethylenic protons).
13C NMR (CDCl3) δ: 59.2; 67.1; 129.6; 133.8; 165.3; C38H44O8N2 (656.74). Calculated:
C (69.43), H (6.69), N (4.26); Found: C (70.50), H (7.10), N (4.50).
Bis[2-(m-isopropyl α,αꢁ-dimethylbenzyl Carbamoyl) Ethoxy Tereph-
thaloyloxy] Ethyl (B, 2). Tm = not determined. IR (KBr, cm−1): ν = 3360 (VS); 2920
(S); 2880 (M); 1720 (VS); 1670 (W); 1610 (M); 1580 (M); 1500 (S); 1450 (M); 1410 (M);
1
1380 (W); 800 (M); 730 (S); 700 (M). H NMR (CDCl3) δ: 1.60 (s, 12H); 2.10 (s, 6H);
4.30 (s, 8H); 4.45 (s, 8H); 5.00–5.35 (s, 4H, ethylenic protons); 5.60 (s, 2H); 7.25–7.45
(d, 8H); 8.10 (s, 8H). 13C NMR (CDCl3) δ: 59.1; 63.2; 67.1; 129.6; 129.7; 133.4; 134.0;
165.1; 165.2; C48H52O12 N2 (848.48). Calculated: C (67.92), H (6.13), N (3.30); Found: C
(68.10), H (6.60), N (3.50).
Bis{2-[2-(m-isopropyl α,αꢁ-dimethylbenzyl Carbamoyl) Ethoxytereph-
thaloyloxy] Ethyl} Terephthalate (B, 3). Tm = not determined. IR (KBr, cm−1): ν =
3360 (VS); 2920 (S); 2880 (M); 1710 (VS); 1675 (W); 1610 (M); 1580 (M); 1500 (S);
1450 (M); 1410 (M); 1380 (W); 800 (M); 730 (S); 705 (M). 1H NMR (CDCl3) δ: 1.60 (s,
12H); 2.10 (s, 6H); 4.30 (s, 4H); 4.45 (s, 4H); 5.00–5.35 (s, 4H; ethylenic protons); 5.60 (s,
2H); 7.25–7.45 (d, 8H); 8.10 (s, 8H). 13C NMR (CDCl3) δ: 59.2; 67.1; 129.5; 133.8; 165.3;
C58H60O16 N2 (1040.58). Calculated: C (66.92), H (5.76), N (2.69); Found: C (67.20), H
(5.95), N(2.96).
Synthesis of Long Chain Aromatic Telechelic Monodispersed Diols
These diols were all prepared in the same way according to the following experimental
procedure: in a three-necked round-bottom flask equipped with a condenser and nitrogen

492
B. BOUTEVIN ET AL.
flow, a mixture composed of 2-mercaptoethanol and (B, 1), (B, 2), (B, 3) in a 2:1 molar
ratio was introduced and dissolved in acetonitrile as the solvent. This medium was heated
up to 75 ◦C under stirring; then, AIBN was added into the flask in the [(initiator)/(telechelic
diene)] molar ratio of 0.02. The solution was kept stirring at 75 ◦C under nitrogen for 4 h.
The experiment was monitored using SEC and it was observed that, after 3 h, 90% of 2-
mercaptoethanol was consumed. After the reaction was completed, the diol was precipitated
and recrystallized from methanol. For all these syntheses, the yields of three diols were
quantitative.
Bis{2-[m-(2-hydroxyethylthiaisopropyl)α,αꢁ-dimethylbenzylcarbamoyl]
ethyl}terephthalate (C, 1). Tm = 71 ◦C, Tg = −9 ◦C. IR (KBr, cm−1): ν = 3600–3000
(S, broad); 1720 (VS); 1520 (m); 1450 (W); 1280 (S); 1260 (S); 1240 (S); 1120 (M); 1100
(S); 1020 (M); 880 (W); 740 (S); 710 (M). 1H NMR (CDCl3) δ: 1.30 (d, 6H); 1.60 (s, 12
H); 2.40 (m, 4H); 2.75 (m, 4H); 2.85 (m, 2H); 3.50 (t, 4H); 3.90 (t, 2H); 4.30 (s, 4H); 4.45
(s, 4H); 4.70 (s, H); 5.40 (s, 2H); 7.05–7.20 (d, 8H); 8.10 (s, 4H). 13C NMR (CDCl3) δ:
20.7; 22.5; 28.8; 29.2; 35.0; 40.3; 55.0; 60.2; 60.8; 61.8; 62.9; 63.6; 66.8; 122.3; 123.5;
125.0; 128.2; 129.5; 133.4; 133.6; 133.9; 145.2; 147.0; 154.2; 165.3; 165.6; C42H56O8
N2 S2 (812.74). Calculated: C (62.01), H (6.89), N(3.44); Found: C (62.45), H (7.15), N
(3.50).
Bis{2-[m-(2-hydroxyethylthiaisopropyl)α,αꢁ-dimethylbenzylcarbamoyl]
ethoxyterephthaloyl-oxy} Ethyl (C, 2). Tm = 113 ◦C, Tg = 11 ◦C. IR (KBr, cm−1):
ν = 3600–3000 (S, broad); 1720 (VS); 1520 (M); 1450 (W); 1280 (S); 1260 (S); 1240 (S);
1120 (M); 1100 (S); 1020 (M); 880 (W); 740 (S); 710 (M). 1H NMR (CDCl3) δ: 1.30 (d,
6H); 1.60 (s, 12H); 2.40 (m, 4H); 2.75 (m, 4H); 2.85 (m, 2H); 3.50 (t, 4H); 3.90 (t, 2H);
4.30 (s, 8H); 4.45 (s, 4H); 4.70 (s, H); 5.40 (s, 2H); 7.05–7.20 (d, 8H); 8.10 (s, 8H). 13C
NMR (CDCl3) δ: 20.7; 22.5; 28.8; 29.2; 35.0; 40.3; 55.0; 60.2; 60.8; 61.8; 62.9; 63.6;66.8;
122.3; 123.5; 125.1; 128.2; 129.6; 133.4; 133.6; 133.9; 145.2; 147.0; 154.2; 165.3; 165.6;
C52H64O13 N2 S2 (1004.05). Calculated: C (62.12), H (6.37), N (2.78); Found : C (62.50),
H (6.60), N (2.95).
Bis(2-{2-[m-(2-hydroxyethylthiaisopropyl) α,αꢁ-dimethylbenzylcarbamoyl]
Ethoxy Terephthaloyl-oxy} Ethyl) Terephthalate (C, 3). Tm = 123 ◦C, Tg = 15 ◦C.
IR (KBr, cm−1): ν = 3600–3000 (S, broad); 1720 (VS); 1520 (M); 1450 (W); 1280 (S);
1260 (S); 1240 (S); 1120 (M); 1100 (S); 1020 (M); 880 (W); 740 (S); 710 (M). 1H NMR
(CDCl3) δ: 1.30 (d, 6H); 1.60 (s, 12H); 2.40 (m, 4H); 2.75 (m, 4H); 2.85 (m, 2H); 3.50
(t, 4H); 3.90 (t, 2H); 4.30 (s, 12 H); 4.45 (s, 4H); 4.70 (s, H); 5.40 (s, 2H); 7.05–7.20 (d,
8H); 8.10 (s, 12H). 13C NMR (CDCl3) δ: 20.7; 22.5; 28.8; 29.2; 35.0; 40.3; 55.0; 60.2;
60.8; 61.8; 62.9; 63.6; 66.8; 122.3; 123.5; 125.0; 128.2; 129.5; 133.4; 133.6; 133.9; 145.2;
147.0; 154.2; 165.3; 165.6; C62H72O18 N2 S2 (1196.58). Calculated: C (62.17), H (6.01);
N (2.34); Found: C (63.20), H (6.70), N (2.65).
CONCLUSION
The synthesis of telechelic aromatic monodispersed diols with molecular weights
between 800 and 1200 g/mol can be simply achieved by the bis monoaddition of telechelic
aromatic monodispersed dienes with 2-mercaptoethanol, initiated with azo¨ıques and per-
oxides. Such reactions are quick, easy to perform and to scale up, and lead to the diols in
quantitative yields.
These diols are soluble in most organic solvents. They exhibit a semicrystalline be-
havior with lower melting temperature than those of oligo(ethylene terephthalate). The

LONG CHAIN AROMATIC TELECHELIC MONODISPERSED DIOLS
493
telechelic aromatic monodispersed dienes were produced by addition reaction of m-
isopropyl α, αꢀ dimethyl benzylisocyanate to oligo (ethylene terephthalate). The latter
compounds were obtained by esterification of dimethyl terephthalate with ethylene glycol,
followed by fractionation. Such aromatic telechelic long-chain diols are interesting pre-
cursors of well-defined architectured polymers such as the polyesters polycarbonates or
polyurethanes.
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