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Synthesis of hydroxyl-terminated polybutadiene possessing high content of

1,4-units VIA anionic polymerization

Article  in  Chinese Journal of Polymer Science · September 2010

DOI: 10.1007/s10118-010-9121-y

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Chinese Journal of Polymer Science Vol. 28, No. 5, (2010), 715720 Chinese Journal of Polymer Science
© Chinese Chemical Society
Institute of Chemistry, CAS
Springer-Verlag Berlin Heidelberg 2010

SYNTHESIS OF HYDROXYL-TERMINATED POLYBUTADIENE POSSESSING

HIGH CONTENT OF 1,4-UNITS VIA ANIONIC POLYMERIZATION*

Ji-ming Chena, b, Zai-jun Lua**, Guang-qin Panb, Yong-xin Qib, Jian-jun Yib and Hai-jian Baib
a
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
b
Institute of Lanzhou Petrochemical Company, Petrochina, Lanzhou 730060, China

Abstract The hydroxyl-terminated polybutadiene (HTPB) possessing high content of 1,4-units was synthesized by anionic
polymerization of butadiene, using alkyllithium containing silicon-protected hydroxyl group as initiator and cyclohexane as
solvent. The polymers were characterized by GPC, IR and 1H-NMR. The mechanical properties of cured films were also
evaluated. The results show that the content of 1,4-units for HTPBs made by anionic polymerization reaches up to 90%. The
molecular weight distribution is very narrow (≤ 1.05). The functionality of hydroxyl groups approaches 2. Compared with
free radical HTPB, the elongation at break of anionic HTPB films increased by 70%, while the tensile strength remained
nearly unchanged. This new HTPB can be very useful in solid propellant.

Keyword: Hydroxyl-terminated polybutadiene; Anionic polymerization; 1,4-Unit; Mechanical properties.

INTRODUCTION
Hydroxyl-terminated polybutadiene (HTPB) is a telechelic liquid rubber containing hydroxyl groups. It was
widely used as the binder for solid propellant of missiles and rockets[1] due to its good mechanical properties
after curing[2]. Recently, the synthesis of high performance HTPB is highly desired because the shooting range
of missiles has been progressively enhanced. It is well-known that the performance of HTPBs is greatly affected
by their chain microstructures. For example, with increasing the content of 1,4-units, the glass transition
temperature (Tg) of polybutadienes decreases, exhibiting a rubbery state[3]. By contraries, polybutadienes exhibit
a plastic state with decreasing the content of 1,4-units. In order to obtain high performance HTPB, the high
content of 1,4-units is considered as one of the important molecular parameters.
HTPB made by traditional radical polymerization (abbreviated as radical HTPB) has a maximum 1,4-unit
content of 79%[4, 5] and a broad molecular weight distribution. In addition, its ill-defined hydroxyl distribution
easily causes the nonuniform cross-linking network and worse mechanical properties. Although the living
radical polymerization was extensively developed recently[68], the content of 1,4-units was still not improved.
On the contrary, HTPB made by anionic polymerization (abbreviated as anionic HTPB) can give high 1,4-unit
content of 90%, narrow molecular weight distribution and well-defined hydroxyl distribution in principle. These
characteristics are very useful in improving the performance of HTPB. Therefore, the synthesis of anionic HTPB
has attracted much attention.
Typical anionic HTPB is prepared using naphthalene lithium as difunctional initiator in THF solvent. Its
microstructure is mainly 1,2 configuration due to the use of polar solvent[9, 10]. To obtain the high content of

*
This work was financially supported by the Lanzhou Petrochemical Company.
**
Corresponding author: Zai-jun Lu (鲁在君), E-mail: [email protected]
Received August 17, 2009; Revised October 2, 2009; Accepted October 16, 2009
doi: 10.1007/s10118-010-9121-y
716 J.M. Chen et al.

1,4-units, difunctional intiators soluble in non-polar solvents, such as 1,3-bis(1-lithio-methylhexyl)benzene, has

been developed[3, 11, 12]. However, the association of diinitiators and the addition of polar additives affected the
polymerization process and polymer microstructure[13]. It seems that the best method is to choose the
monofunctional initiator containing a protected hydroxyl group. Schuls[14] synthesized anionic HTPB using
hydroxyl-carrying mixed acetals as protected monofunctional initiator, but the solubility of formed initiator is
not good in hydrocarbon solvent.
More recently, our group[15] reported the synthesis of hydroxyl-terminated polyisoprene (HTPI) with 90%
of 1,4-unit content by anionic polymerization, using a novel protective monofunctional initiator with good
solubility in hydrocarbon solvent. To our knowledge, this is the highest content of 1,4-units among the reported
HTPIs. In this article, our aim is to extend this method to synthesize the anionic HTPB, whose properties can
meet the urgent requirements in advanced solid propellant.

EXPERIMENTAL
Materials
Tert-butyldimethylsilyloxy propyllithium (CH3)3CSi(CH3)2O(CH2)3Li (BPL) was synthesized according to the
reported method[16]. Butadiene (Qilu petrochemical company) was purified by distillation over CaH2.
Cyclohexane (Sinopharm Shanghai Chemical Reagent Co. Ltd.) was dried and distilled over CaH2 twice.
Ethylene oxide (Sinopharm Shanghai Chemical Reagent Co. Ltd.) was distilled over KOH. Radical HTPB
(Lanzhou Petrochemical Company) has hydroxyl value 0.5238 mmol/g, Mn = 8100 (GPC), 4400 (VPO), and
Mw/Mn = 1.55. Toluenediisocyanate (TDI) (Aldrich, 2,4- 80% and 2,6- 20%) was used as received.
Synthesis of Anionic Polymerized HTPB
To a 5 liter reactor charged with argon, 2500 mL cyclohexane, 500 mL butadiene and 96.4 mL BPL
(0.80 mol/L) were added. The reaction was carried out at 50°C for 2.5 h. Subsequently, 23.0 mL ethylene oxide
was added and reaction was continued for 1 h. 17.5 mL degassed methanol was injected to terminate the
reaction. After acidic hydrolysis with HCl, the viscous polymer was isolated with ethanol and dried under
vacuum. 1H-NMR (CDCl3, ): 5.0 (1,2-unit ＝CH2), 5.40 (1,2-unit ―CH＝), 1.3 (1,2-unit ―CH2―), 5.38
(1,4-unit ―CH＝), 2.03, 2.12 (1,4-unit ―CH2―), 3.6 (CH2OH), 0.90 ((CH3)3C―Si), 0.04 ((CH3)2Si―). IR
(KBr, cm1): 33003500 (―OH), 725 (cis-1,4), 966 (trans-1,4), 911 (vinyl 1,2).
Preparation of Cured Films
To a 500 mL reactor, 200 g (0.05 mol) HTPB and 9.25 g (0.053 mol) TDI were added and stirred for 1 h.
Subsequently, the mixture was poured into a mould. After reaction at room temperature for 72 h, a film with
2 mm thickness was obtained.
Measurements
1
H-NMR spectra were recorded on a Bruker AV400 spectrometer with CDCl3 as solvent and without addition of
the internal reference. IR spectra were recorded on a Nicolet 560 with KBr pellets. GPC measurements were
carried out in THF (1 mL/min) at 35°C with a Waters 515 pump equipped with three styragel columns and a
refractive index detector. Monodisperse PS samples were used as standards for calibration. Mechanical property
measurements were performed on an RG-300 electronic universal testing machine (Shenzhen Reger instrument
co.) with a crosshead speed of 100 mm/min at 25°C. The sample standard distance was 40 mm. Hydroxyl group
value was determined by acetylation reagent titration method according to GJB 1327A-2003.

RESULTS AND DISCUSSION

Synthesis and Characterization of Anionic HTPB
It is well-known that the microstructure of polybutadiene prepared anionically is determined mainly by polarity
of the solvent. When nonpolar solvents are used, high 1,4-units content is obtained. The BPL was used as
initiator because it can be fully soluble in nonpolar solvents such as hexane, cyclohexane and benzene. This
Anionic Polymerization of Hydroxyl-terminated Polybutadiene Possessing High Content of 1,4-Units 717

makes it possible to perform anionic polymerization of butadiene in nonpolar solvents and obtain high content
of 1,4-units. Meanwhile, BPL is also a kind of monofunctional initiator. It can avoid the “pseudo-gel”
phenomena which often occurred in difunctional initiator systems. Scheme 1 illustrates the synthetic route of
anionic HTPB. In the presence of cyclohexane solvent, butadienes were initiated by BPL and polymerized to
produce living polybutadiene (PB). Living PB was subsequently capped with ethylene oxide and terminated
with methanol to form PB-OH. In order to improve the hydroxyl group yield, the ethylene oxide was purified by
butyllithium. After removal of silicon protecting group by acid, anionic HTPB was obtained.

Scheme 1 Synthetic route of anionic HTPB

Figure 1 shows the GPC curves of anionic HTPB and radical HTPB. The curve of anionic HTPB shows a
single sharp peak, indicating a narrow molecular weight distribution (Mw/Mn = 1.03, Mn = 8400), while the peak
of radical HTPB is broad, indicating the polydisperse distribution (Mw/Mn = 1.55). This is because the living
anionic polymerization proceeded without chain transfer and chain termination reactions in comparison with
radical polymerization. This led to the narrow molecular weight distribution and good control on the molecular
weight.

Fig. 1 GPC curves of anionic HTPB (a) and free radical HTPB (b)

Figure 2 shows 1H-NMR spectra of anionic HTPB at different reaction stages. For PB, two peaks at
 = 0.90 and 0.04 due to protons of tert-butyl ((CH3)3C―Si) and methyl ((CH3)2 ―Si) groups were clear
observed. After end-capping with ethylene oxide, a new peak at  = 3.6 appeared (see Fig. 2 PB-OH and
HTPB), indicating the formation of -hydroxyl groups. After acidic hydrolysis, the peaks at  = 0.90 and 0.04
disappeared (see Fig. 2 HTPB), which suggested that the protective groups were removed completely and
-hydroxyl groups were exposed.
718 J.M. Chen et al.

Fig. 2 1H-NMR spectra of PB, PB-OH, and HTPB

Figure 3 shows the FT-IR spectrum of anionic HTPB. The peaks at 33003500 cm1 confirmed the
existence of hydroxyl groups. The characteristic peaks due to microstructures of polybutadiene chains were also
observed at 725 cm1 (cis-1,4), 966 cm1 (trans-1,4) and 911 cm1 (vinyl 1,2), respectively.

Fig. 3 FT-IR spectrum of anionic HTPB

Table 1. Microstructure characterization of anionic HTPB and radical HTPB

a Hydroxyl valuec Ccis1,4 (%) Ctrans-1,4 (%) C1,2 (%)
Samples Mnb
(mmol/g) IRd 1
H-NMRe IR 1
H-NMR IR 1
H-NMR
HTPBA 4200 0.4810 35.15 35.09 54.83 54.52 10.02 10.39
HTPBR 4400 0.5238 20.96 20.56 57.60 57.45 21.44 21.99
a
HTPBA: synthesized by anionic polymerization using BPL in cyclohexane at 50°C for 2 h., HTPBR:
synthesized by radical polymerization using H2O2 in ethanol at 117°C for 3 h; b Measured by VPO; c Determined
by acetylation reagent titration method; d Ccis1,4 = 17667A725/(17667A725 + 3674A911 + 4741A966), Ctrans1,4 =
4741A967/(17667A725 + 3674A911 + 4741A966), C1,2 = 3674A911/(17667A725 + 3674A911 + 4741A966), where A725,
A911 and A966 are areas of characteristic absorption peaks, respectively; e 2C1,2/[C1,2 + 2(1C1,2)] = I4.815.01/I5.38,
Ctrans-1,4/(1C1,2Ctrans-1,4) = I2.03/I2.12, where I is the integral area of corresponding absorption peak.
Anionic Polymerization of Hydroxyl-terminated Polybutadiene Possessing High Content of 1,4-Units 719

The microstructure content of HTPBs can be calculated from IR and 1H-NMR spectra, and the results were
summarized in Table 1. The data calculated from IR spectra was in good agreement with those from 1H-NMR
spectra. The 1,4-unit content of anionic HTPB reached ca. 90%, which was ca. 12% higher than that of radical
HTPB.
The hydroxyl value and average functionality of HTPBs are listed in Table 2. The functionality of anionic
HTPB (fn) approached to 2. This was in good agreement with the theoretical value assuming each HTPB had
two hydroxyl groups at both chain ends. The functionality of radical HTPB was bigger than 2. The reason is
radical HTPB is a mixture containing a variety of polybutadienes of varying number and site of hydroxyl
groups.

Table 2. Hydroxyl value and average functionality of anionic HTPBs and radical HTPB
Mn Hydroxyl valued
Samples a b Mw/Mnc fne
Theor. Meas. (mmol/g)
HTPBA1 3000 3100 1.05 0.6211 1.92
HTPBA2 4000 4200 1.03 0.4810 1.93
HTPBA3 5000 5100 1.04 0.3804 1.94
HTPBR 　 4400 1.55 0.5238 2.30
a
Mn theor. = weight of monomer/mole number of initiator; b Measured by VPO; c determined by GPC;
d
Determined by acetylation reagent titration method; e Number average functionality, fn = Mn  hydroxyl
value/1000[17]

Influence of Solvent Composition on Microstructure of Anionic HTPB

Table 3 shows the influence of mixed solvent composition on microstructure of anionic HTPB. The total
contents of 1,4-units decreased from 89.98% to 7.20% with increasing the volume ratio of THF to cyclohexane.
Therefore, we can control the microstructure content by the polarity of mixed solvents.

Table 3. The influence of solvent composition on microstructure of anionic HTPB

Samplesa THF/Cyclohexaneb Cis-1,4c (%) Trans-1,4 (%) Vinyl-1,2 (%)
HTPBA4 0/100 35.15 54.83 10.02
HTPBA5 25/75 22.97 3.66 73.37
HTPBA6 50/50 7.26 6.57 86.17
HTPBA7 75/25 4.34 7.89 87.77
HTPBA8 100/0 0 7.20 92.80
a
HTPBA: synthesized by anionic polymerization using BPL in corresponding mixed solvent composition at 50C
for 2 h; The butadiene volume was 500 mL, the BPL volume was 96.4 mL, the mixed solvent composition volume
was 2500 mL,the ethylene oxide volume was 23.0 mL and the degassed methanol volume was 17.5 mL; b Volume
ratio; c Calculated from FT-IR

Fig. 4 Stress-extension curves of cured films based on (a) anionic HTPB and (b) radical HTPB
 720 J.M. Chen et al.

Mechanical Properties of HTPB Films

Figure 4 shows the stress-strain curves of cured films based on anionic and radical HTPBs. The tensile strengths
of these two kinds of cured films were 0.56 MPa and 0.57 MPa, respectively. However, the elongation at break
of the anionic HTPB film was 687.5%, increasing by 70% compared with that of the radical HTPB film. The
reason may be that the narrow molecular weight distribution of anionic HTPB led to the formation of uniform
cross-linking network, which facilitated the transport and dispersion of the stress. However, radical HTPB had
the broad molecular weight distribution and ill well-defined hydroxyl groups. The cross-linking network was
nonuniform after curing. This easily caused stress concentration and low elongation at break.

CONCLUSIONS
In conclusion, HTPB with high 1,4-unit content of 90% has been successfully synthesized via anionic
polymerization using alkyllithium with silicon-protected hydroxyl group as initiator and cyclohexane as solvent.
The polymer exhibited narrow molecular weight distribution (Mw/Mn ≤ 1.05) and controllable molecular weight
and microstructure. Its functionality approached 2. Compared with radical HTPB, the cured film based on
anionic HTPB retained the tensile strength, but increased the elongation at break by 70%. This is very useful to
develop the high performance binder for solid propellant.

ACKNOWLEDGEMENTS We greatly thank Ms. Jing Yu, Mr. Yaoheng Zhang, and Mr. Ying Huang for good suggestion
and measurements.

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