Polymer Bulletin 33, 557-561 (1994) Polymer Bulletin

9 Springer-Verlag 1994

Characterization of hydroxyl-terminated polybutadiene

I, N M R analysis of hydroxylated end groups
w, D. Vilar 1, S, M, C. Menezes 2, and L. Akcelrud 1"*
1 Instituto de Quimica, Universidade Federal do Rio de Janeiro, Brazil
2 Petrobr&s Research Center (CENPES), Rio de Janeiro, Brazil

ABSTRACT
C o m m e r c i a l samples of hydroxyl terminated p o l y b u t a d i e n e s (HTPB) were
a n a l y s e d by IH and 13C NMR spectroscopy, in regard to h y d r o x y l a t e d end groups.
The r e s u l t s w e r e d i s c u s s e d and compared with those reported so far.

INTRODUCTION

There are two industrial processes for the synthesis of HTPB using
h y d r o g e n p e r o x i d e as initiator. The first is American and is e m p l o y e d by A t o c h e m
and the c o m m e r c i a l products are R45M and R45HT. This process uses isopropanol
as solvent i. The second process is Brazilian, and it was d e v e l o p e d by Petrobras
and is e m p l o y e d by Petroflex. The latter HTPB is c o m m e r c i a l i z e d under the
t r a d e n a m e s of L i q u i f l e x P and Liquiflex H. This process uses ethanol as solvent 2.
The c h a r a c t e r i z a t i o n of HTPB has been e x t e n s i v e l y e x p l o r e d in the
literature. The structural features of these telechelic p r o d u c t s s p e c i a l l y
f u n c t i o n a l i t y and types of hydroxyls dictate the rate of curing r e a c t i o n s and
the ultimate properties of the materials produced from them, mostly
polyurethanes. Molecular weight, funcionality and the relations between
molecular weight distribution and functionality distribution have been
i n v e s t i g a t e d by means of conventional techniques, such as end groups analysis,
vapor pressure osmometry, gel permeation chromatography, thin layer
chromatography. Structure and the nature of hydroxyl end groups were studied by
IH and [3C NMR spectroscopy. Undoubtedly the major contribution to NMR
c h a r a c t e r i z a t i o n of HTPB is due to Pham, who p u b l i s h e d a series of papers on the
suject ~9.
This paper presents the results obtained with R45M, R45HT, L i q u i f l e x H and
L i q u i f l e x P by IH and ~3C NMR studies, focusing on the nature of the terminal
hydroxyl groups. This subject has aroused some argument in the l i t e r a t u r e l~n and
is c o n s i d e r e d further in our discussion.

EXPERIMENTAL

HTPB - Commercial samples are A t o c h e m products R45M & R45HT, and P e t r o f l e x

p r o d u c t s L i q u i f l e x P & Liquiflex H. NMR - VRX-300 V a r i a n apparatus, 300 MHz (IH
frequency), 5 m m tubes. IH - The samples were d i s s o l v e d in C~96 at a c o n c e n t r a t i o n
of 1%. The spectra were obtained using a 30 o pulse, I000 t r a n s i e n t s and 75~
13C - (frequency of 75.4 MHz). The concentration was 20-30% in CDCI 3. We have used
45 ~ p u l s e and 12.0 s b e t w e e n pulses. The decoupler m o d e was gated to avoid NOE
and about 1800 pulses were accumulated at ambient temperature.

* Corresponding author, present address: Polymer Science and Engineering, University of Massachusetts, Amherst,
MA 01003, USA
 558

RESULTS AND DISCUSSION

Figures 1 and 2 show the hydroxyl region of the ~H and 13C N M R spectra of
L i q u i f l e x H samples.

Figure 1 - 3.2 to 4.2 ppm region of the IH NMR (300 MHz) for Liquiflex H.

Figure 2 - 54 to 74 p p m region of the 13C NMR (75.4 MHz) for Liquiflex H.

The assigments of olefinic and C ~ resonances in HTPB NMR spectra are well
established 3,t0:i. In addition to these olefinic and C ~ resonances, the N M R
spectra of HTPB yielded other peaks related to three m a i n alcoholic funnctions.
These peaks were assigned differently in the literature 341 (Table 1).
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TABLE 1

N M R a s s i g n m e n t s for t h e t h r e e m a i n a l c o h o l i c fucntions
in H T P B a n d m o d e l c o m p o u n d s

Resonance 6 (ppm) Structures Author

Assigned
IH 13c

4.00 58.1 "C" R a m e y I0

4.05 "C" B r a s l e r ~j
4.05 58.1 "G" p h a m 3~
4.03 58.1 "C" This work

3.90 62.89 "T" R a m e y ~o

3.95 "T" B r e s l e r 11
3.95 63.2 "H" P h a m ~9
3.91 63.2 "T" This work

3.40 64.83 "V" R a m e y Is

3.37 "V" Bresler n
3.3 - 3.5 64.8 "V" Pham ~9
3.42 64.8 "V" This work

H /H - - ~H-CH2OH --C-CH 2
/C=C "C" | "V" Ii "G"
-- H2C ~CH2OH CH=CH 2 CH-C_H2OH

::2c\
/C=C "T" ~ CH2-CH=CH-CH2OH "H"
N \CH2OH

T a b l e 1 s u m m a r i z e s t h e r e p o r t e d r e s u l t s so far, a n d it c a n b e s e e n t h a t
o u r r e s u l t s as w e l l as B r e s l e r ' s u a g r e e w i t h R a m e y ' s ~~ a s s i g n m e n t s . T h e l a t t e r
w a s t h e f i r s t t o u s e N M R s p e c t r o s c o p y t o e l u c i d a t e t h e n a t u r e of O H g r o u p s in
HTPB. He showed that these hydroxyls are predominantly primary and allylic,
b a s e d o n t h e f a c t t h a t w h e n t h e O H g r o u p s of H T P B r e a c t e d w i t h CF3COOH , o n e
s i n g l e r e s o n a n c e r e l a t i v e t o -CH2OOCCF 3 w a s s e e n in t h e 19F N M R s p e c t r u m . A s t h e
derivatives from primary and secondary alcohols show resonances within a
d i f f e r e n c e o f a b o u t 0.5 ppm, it w a s c o n c l u d e d t h a t t h e p r e d o m i n a n c e o f p r i m a r y
a l c o h o l s w a s g r e a t e r t h a n 95%. A s a m a t t e r of f a c t it w a s f o u n d (see P a r t II o f
this series) t h a t a s i g n i f i c a n t a m o u n t of h i g h e r a l c o h o l i c functions are
p r e s e n t . R a m e y ' s a s s i g n m e n t s w e r e s u b s t a n t i a t e d b y t h e c h e m i c a l s h i f t s o f cis
and trans 3-methyl allyl alcohols. The cis and trans 3-methyl allyl
isomers r e s o n a t e at 6 = 57.9 p p m and 6 = 62.9 ppm r e s p e c t i v e l y 14, w h i c h
were correlated t o 6 = 58.1 p p m a n d 6 = 6 2 . 8 9 p p m r e s o n a n c e s in t h e 13C N M R
s p e c t r a o f H T P B . T h e p o l y m e r p e a k at 6 = 6 4 . 8 3 p p m w a s a s s i g n e d t o t h e v i n y l
hydroxyls, based on the fact that saturated alcohols show a peak aproximately
at 6 = 62 ppm, a n d t h e v i n y l i c d o u b l e b o n d in t h e v i c i n i t y s h o u l d s h i f t t h i s
r e s o n a n c e d o w n f i e l d I~
P h a m 3"9 d i d n o t d i s t i n g u i s h b e t w e e n "C" a n d "T" s t r u c t u r e s , a s s u m i n g t h a t
b o t h f o r m s s h o u l d h a v e t h e s a m e p e a k s at 6 = 63.2 p p m ( c a l l e d "H" s t r u c t u r e ) .
H e a g r e e s w i t h t h e a s s i g n m e n t at 6 = 64.8 p p m for t h e v i n y l h y d r o x y l s ( c a l l e d
"V" s t r u c t u r e ) a n d a s s i g n e d t h e 6 = 58.1 p p m t o t h e s t r u c t u r e c a l l e d "G" b y
c o r r e l a t i n g w i t h t h e r e s o n a n c e of g e r a n i o l , as t h e -CH2OH o f t h i s c o m p o u n d s h o w s
a p e a k at 5 = 5 8 . 6 p p m 12.
M o s t o f t h e w o r k d o n e b y B r e s l e r u et al. w a s d o n e at 2 7 0 M H z *H NMR, a n d
o u r w o r k is b a s e d m o s t l y o n 13C NMR. In t h i s w o r k , w e u s e d cis a n d t r a n s - b u t e n e -
2 - o 1 - 1 a n d ci___ssa n d t r a n s - h e x e n e - 2 - o l - i as m o d e l c o m p o u n d s . T h e '3C N M R s p e c t r a
of t h e s e m o d e l c o m p o u n d s w e r e o b t a i n e d b y u s i n g t h e S P E C I N F O d a t a b a s e f r o m S T N
( S c i e n t i f i c a n d T e c h n i c a l N e t w o r k ) d a t a bank. It has in its m e m o r y N M R d a t a f r o m
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the l i t e r a t u r e (as ci__~sand t r a n s - b u t e n e - 2 - o l - i and t r a n s - h e x e n e - 2 - o l - l ) and un-

p u b l i s h e d (as cis-hexene-2-ol-l) 13. We found for ci___~s-butene-2-ol-i a p e a k at
6 = 57.90 p p m and for ci___ss-hexene-2-ol-I another at 6 = 58.12 ppm. For trans-
b u t e n e - 2 - o l - i the chemical shifts varied according to the references, and were
located at ~ = 63.22 ppm, 6 = 63.00 ppm, 6 = 62.90 p p m and 6 = 61.60 ppm. For
t r a n s - h e x e n e - 2 - o l - i a peak was found at 6 = 63.20 ppm. All these peaks were
assigned to the -CH2OH resonance, leading us to attribute the r e s o n a n c e s at
= 58.1 ppm and 6 = 63.2 ppm in the HTFB spectrum to s t r u c t u r e s "C" and "T"
respectively, as Ramey and Bresler did, and not to "G" or "H" as P h a m (Table 3).
Our assignment is further supported by the f o l l o w i n g reasoning: results
from f r a c t i o n a t i o n of HTPB by preparative GPC, and s u b j e c t e d to polarity-
c o n t r o l l e d a d s o r p t i o n t h i n - l a y e r chromatography to d e t e r m i n e the f u n c t i o n a l i t y
d i s t r i b u t i o n of each fraction, showed that: the low m o l e c u l a r weight fractions
(400 < Mn < 2000) of R 4 5 M and R45HT are composed mainly by di- and m o n o f u n c i o n a l
species; the i n t e r m e d i a t e (2000 < Mn < 7000) by d i f u n c t i o n a l species; and the
high m o l e c u l a r weight fractions (7000 < Mn < 30000) by p o l y f u n c t i o n a l species 15.
This was t a k e n as an indication that the higher f u n c t i o n a l i t i e s of HTPB were due
to b r a n c h i n g and c r o s s l i n k i n g reactions, and not by the p r e s e n c e of hydroxyl
groups r a n d o m l y d i s t r i b u t e d along the chains. On the other hand, it was shown
by P h a m 6 that fractions of R45M with 3000 < Mn < 30000 and f u n c t i o n a l i t y (fn)
b e t w e e n 1.9 and 3.5 had p r a t i c a l l y the same amount of "G" structures. Taking
into account that "G" structure corresponds to a hydroxyl group in the m i d d l e
of the chain 3, this finding is in c o n t r a d i c t i o n w i t h the f u n c t i o n a l i t y increase
w i t h m o l e c u l a r weight and indicates that probaly the r e s o n a n c e o b s e r v e d at 6 =
58,1 ppm is "C" structure and not "G". This however does not d i s c a r d t h e
p o s s i b i l i t y of the e x i s t e n c e of small amounts of "G" s t r u c t u r e in HTPB.
Tables 2 (IH) and 3 ('3C) show the corresponding q u a n t i t a t i v e data for
microstructure and types of hydroxyl end groups of HTPB's samples. The
m i c r o s t r u c t u r e results were calculated from the IH and 13C NMR s p e c t r a a c c o r d i n g
to the l i t e r a t u r e 3.

TABLE 2

IH NMR data for HTPB samples

Structures % R45M R45HT Liq.P Liq.H

Double b o n d 1,2 (vinyl)" 21.6 21.3 21.1 20.6

Double b o n d 1,4 (trans)' 57.8 56.7 57.9 57.0
Double b o n d 1,4 (cis)" 20.7 22.0 21.0 22.3
Double bond 1,4 (total)' 78.5 78.7 78.9 79.3
"T" 52.3 51.1 53.4 52.7
"C" 14.3 14.1 13.6 14.0
"V" 33.4 34.7 32.9 33.2
F u n c t i o n a l i t y fn ' 1.6 2.0 1.7 2.0
9 c a l c u l a t e d a c c o r d i n g to ref. 3

TABLE 3

Hydroxyl end groups in HTPB - t3C NMR data

Structures % 6 (ppm) R45M R45HT Liq. P Liq.H

"V" 64.8 24.3 24.2 26.2 25.2

"T" 63.2 45.3 45.8 48.5 48.6

"C" 58.1 17.5 18.1 16.0 16.6

F r o m Tables 2 and 3 it can be seen that r e g a r d i n g to microstructure,

L i q u i f l e x and R45 samples have comparable amounts of cis, trans and vinyl
components. These samples have also comparable amounts of the three main
h y d r o x y l a t e d end group functions, namely "C", "T" and "V", w h i c h are in the
v i c i n i t y of the cis, trans and vinyl groups of the m o n o m e r i c units. R45M and
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L i q u i f l e x P h a v e l o w e r f u n c t i o n a l i t i e s a n d a r e p r o d u c t s u s e d for r o c k e t f u e l
binders. The functionality values reported here were calculated by a NMR based
method which takes into account only the primary hydroxyl groups 3 and are
s o m e w h a t l o w e r t h a n t h e t r u e o n e s (see P a r t II of t h i s s e r i e s ) .

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Received: 20 July 1994/Revised version: 31 August 1994/

Accepted: 6 September 1994