Synthesis details of
Transesterification of HMS with PBA ad PTMEG:
products were prepared analogously to ɛ-polycaprolactone samples in Experimental, but at higher
reaction temperature of 180°C. The final products are high viscous liquids at RT.
Transesterification of HMS with polybutylene adipate
131.4 g HMS (0.4 mol), 200 g PBA, 0.82 g Tegokat 233
Reaction time: 3.25 hours, Catalyst deactivation: 1.64 g Hypophosphorous acid
Transesterification of HMS with PTMEG:
164.3 g HMS (0.50 mol), 81.30 g PTMEG, 0.82 g Tegokat 233, Reaction time: 3 hours, Catalyst
deactivation: 1.64 g Hypophosphorous acid.
Supplementary analytical information on synthesised polyols of this research.
SEC/RI chromatogram of ε-polycaprolactone SEC (Mw/Mn): 1430/1040.
2.0
Response
1.5
1.0
0.5
0.0
10
11
12
13
14
Minutes
2101a.001
15
16
17
18
SEC/RI chromatogram of copolymer HMS/ ε-polycaprolactone , SEC (Mw/Mn): 1750/935.
2.0
Response
1.5
1.0
0.5
0.0
10
11
12
13
14
15
16
17
18
Minutes
2301a.001
SEC/RI chromatogram of copolymer ε-polycaprolactone (blue line), poly-HMS (green), εpolycaprolactone-pHMS-copolymer (red) copolymer Mw/Mn = 4300/2400
Example high throughput well configuration. PCAP = ɛ-polycaprolactone, F44-111 and F44-56 are
polybutylene adipate 1000 and 2000 g/mol respectively, T2000 is 2000 g/mol PTMEG, V222-056 is a
2000 g/mol 11/89 EO/PO triblock copolymer (Voranol 222-056). X/Y Numbers are volume ratios
1
2
3
4
5
6
7
8
9
10
11
12
A
A
B
C
D
E
F
G
H
1
75/25
PCAP/28-140
75/25 28-140/T2000
75/25
T2000/28-140
75/25 28-140/PCAP
75/25 28-140/F44-111
75/25 28-140/F11-56
75/25 V222056/F44111
75/25
F44111/V222056
75/25 F1156/28-1-40
75/25
PCAP/V222056
75/25 28-140/T2000
75/25 V222056/PCAP
75/25 28-140/PCAP
75/25 F44111/28-1-40
75/25 28-140/T2000
75/25
PCAP/28-140
2
3
4
5
6
7
8
9
10
11
B
C
D
E
F
G
H
12
EXPERIMENTAL METHOD
1) Samples mixed at 180 C in rotational oven for 1.5 hrs
2) Samples were then place on a heating block preheated to 180 C and allowed to equilibrate for 1 hr
3) Samples were then analyzed visually for number of phases, phase clarity, and approximate volume fraction of
x:y = bottom:top approx. volume fraction (obtained visually)
4) Samples were then cooled at 10 C increments and allowed to equilibrate for 1 hr (180 to 150 C)
5) Samples kept at 150 C overnight (~17 hrs) - no phase changes observed
6) Samples were then cooled at 10 C increments, but equilibration decreased to 30 min (140 to 50 C)
GENERAL
OBSERVATIONS
1) Only clear and 2 phase (clear over clear) samples were observed from 180 to 50 C.
2) No changes in phase behavior were observed from 180 to 50 C
Therefore, measurements of phase height for vol. fraction at 50 C are typical of what was observed
listed
3) Solidification of some polyols was observed after weekend equilibration at room temp.
equilibrated
Well Position at 180 C - 1 hr
2 phase (6:1) B2
clear
B5
1 phase clear
B8
D5
1 phase clear
2 phase (1:5) clear
2 phase (1:5) clear
2 phase (1:3) clear
D8
1 phase clear
D11
F2
1 phase clear
2 phase (5:1) clear
F5
1 phase clear
F8
1 phase clear
F11
1 phase clear
2 phase (1:5) clear
2 phase (4:1) clear
B11
D2
H2
H5
H8
H11
1 phase clear
2 phase (6:1) clear
equilibrated
at 170 C - 1 hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 160 C - 1 hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 150 C - 2 hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 140 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 130 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 120 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 110 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 100 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 90 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 80 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 70 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 60 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
equilibrated
at 50 C - 0.5
hr
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
no observable
change
vol fration
bottom phase
meausred at
50 C
0.90
room
temperature
over
weekend
cloudy over
white solid
1.00
clear
1.00
0.20
white solid
clear over
cloudy
clear over
cloudy
0.24
clear over clear
1.00
white solid
1.00
white solid
0.86
clear
1.00
white solid
1.00
clear
1.00
white solid
clear over
cloudy
clear over
white solid
0.14
0.16
0.85
1.00
0.86
clear
cloudy over
white solid
Supplementary Information.
Calculation of the polyol binary phase diagrams
The free energy of mixing is described using Flory-Huggins expression,
g  v ref
G

1

ln  
ln 1      1   
V
N1
N2
(A1)
where the interaction parameter  is given by,
      .
b
 a   a  vref
T
RT
2

(A2)
The spinodal boundaries are obtained by setting the second derivative of g to zero,
1
1

 2  0
N1 N 2 1   
(A3)
Thus, spinodal boundaries are given by,
1, 2 


2 N  p  p 1  D
4 N
where N  N1 N 2 
1/ 2

, p
N2
(A4)
N
, and D is given by,

D  2N  p  p 1  8Np
2
(A5)
If D < 0, the blend is fully miscible at this temperature; D = 0 corresponds to the critical temperature, and
for D > 0, the two components are only partially miscible, and there are two spinodal branches.
To compute the binodals (miscibility limits), we use the double-tangent construction, i.e.,
 dg 
 dg 
  
 
 d  1  d   2
(A6)
 dg 
 dg 
g 1   1  
 g 2   2  
 d  1
 d  2
(A7)
After substituting the expression for g, we obtain,
p ln 1  p 1 ln 1  1   2N1  p ln 2  p 1 ln 1  2   2N2




p 1 ln 1  1   p  p 1 1  N12  p 1 ln 1  2   p  p 1 2  N22
(A8)
(A9)
The equations (A8)-(A9) are solved iteratively, with starting points 1  1 , 2  2 . We use simple
Excel macros, and perform iterations until the difference between the “old” and “new” values becomes
less than 10-4.
30% Hard MDI-BDO hard segment in 2000 molecular weight ɛ-polycaprolactone
1.0E+09
0.8
G' Pa
0.7
G" Pa
0.6
tanδ
0.5
1.0E+07
0.4
G"/G'
G',G' Pa
1.0E+08
0.3
1.0E+06
0.2
0.1
1.0E+05
0
-50
0
50
100
150
200
Temperature oC
30% Hard MDI-BDO hard segment in 2000 molecular weight PTMEG. The transition between ca -20 and
5 oC is soft segment crystalline melting.
1.0E+09
0.8
G' Pa
0.7
G" Pa
1.0E+08
0.6
0.5
1.0E+07
0.4
1.0E+06
0.3
0.2
1.0E+05
0.1
1.0E+04
0
-100
-50
0
50
100
Temperature (oC)
150
200
G"/G'
G', G" Pa
tanδ
30% MDI-BDO hrd segment in 50/50 blend of pHMS and ɛ- polycaprolactone.
1.0E+10
0.5
0.45
G" Pa
0.4
tan_delta
0.35
1.0E+08
0.3
0.25
1.0E+07
G"/G'
G',G" Pa
1.0E+09
G' Pa
0.2
0.15
1.0E+06
0.1
0.05
1.0E+05
0
-70
-20
30
80
Temperature (oC)
130
30% Hard segment in blend of 50/50 Voranol 222-056/pHMS. Note that while the phase separation of
this blend is quite good based on narrow and low temperature Tg and flat plateau modulus, the
modulus of the elastomer is relatively low.
30% HS 50/50 NOP/Vor 222-056
1.E+11
1.5
1.E+09
1
1.E+07
0.5
1.E+05
-60
40
140
Temp (C)
0
240
G"/G'
dyn/cm2
G' dyn/cm2
G" dyn/cm2
tan_delta
30% HS MDI-BDO in 2000 g/mol PTMEG
30% MDI-BDO hard segment in 50/50 blended pHMS/ɛ-polycaprolactone
30% MDI-BDO in a soft segment prepared by copolymerizing polybutylene adipate with pHMS in a
mole[OH] ratio 2/1 HMS/PBA Equiv wt 993 g/mole [OH]
30% MDI-BDO in a soft segment prepared by copolymerizing PTMEG with HMS in a mole [OH] ratio of
4/1 HMS/PTMEG Equiv wt 874 g/mole [OH]
Table of properties from 30% (vol) hard segment polyurethane elastomers based on indicated soft
segment compositions. FWHM is calculated from the peak of the tan delta envelope and the center of
the baseline defining the bottom of the tan delta envelope. The full width is merely the chord across the
envelope taken at the tan delta value at the peak minus the baseline value
Soft segment composition Soft segment
Blend/transesterifiied/hybrid)
pHMS
Single soft segment
PBA
Single soft segment
ɛ-polycaprolactone
Single soft segment
Soft segment
Tg (oC)
-50
-34
-28
FWHM of Tg (oC)
PTMEG
Voranol 222-056
Single soft segment
Single soft segment
-53
-31
20
17
pHMS/Voranol 222-056
pHMS/PBA
pHMS/PBA
pHMS/ɛ-pcap
pHMS/ɛ-pcap
pHMS/ɛ-pcap
pHMS/PTMEG
pHMS/PTMEG
blend
blended
transesterified
blended
transesterified
hybrid
blended
transesterified
-37
-31
-38
-20
-32
-29
-50
-42
20
36
21
34
23
21
15
22
18
19
15