Chapter IV Structure-Property Relationships for Hetero- Complementary Hydrogen-Bonding Partners
4.6 Figures, Schemes, and Tables
Figure 4.1 Representative examples of directional noncovalent bondings. (a) Directional hydrogen bonding (Left: hetero-complementary thymine (THY)/diamidopyridine (DAP) interaction;11 Right: carboxyl/tertiary amine charge-assisted hydrogen bonding.2 (b) Metal coordination interaction (palladated-pincer complex/pyridine interaction).9
Figure 4.2 (a) Structures of polymers PA, PB, PC and step-wise self-assembly of supramolecular triblock copolymer. (b) Plot of specific viscosity versus concentration for PB and supramolecular block copolymers (Adapted from Yang et al.21 and reproduced with permission).
22 24 26 28 30 32 34 36 38 40
Elution Time (Min)
Di-THY 1,4-PB Di-THY macro CTA
Figure 4.3 GPC-LS traces of di-THY macro CTA and the corresponding 288K di-THY 1,4-PB. Note that the superposition indicates complete consumption of di-THY macro CTA in the synthesis of 288K di-THY 1,4-PB.
22 24 26 28 30 32 34 36 38 40
Elution Time (Min)
Di-DAAP 1,4-PB Di-DAAP macro CTA
Figure 4.4 GPC-LS traces of di-DAAP macro CTA and the corresponding 219K di- DAAP 1,4-PB. Note that the superposition indicates complete consumption of di-DAAP macro CTA in the synthesis of 219K di-DAAP 1,4-PB.
20 22 24 26 28 30 32 34 36 38
Elution Time (Min)
Di-CA 1,4-PB Di-CA macro CTA
Figure 4.5 GPC-LS traces of di-CA macro CTA and the corresponding 200K di-CA 1,4- PB. Note that the superposition indicates complete consumption of di-CA macro CTA in the synthesis of 200K di-CA 1,4-PB.
20 22 24 26 28 30 32 34 36 38 40
Elution Time (Min)
Di-HR 1,4-PB Di-HR macro CTA
Figure 4.6 GPC-LS traces of di-HR macro CTA and the corresponding 240K di-HR 1,4- PB. Note that the superposition indicates complete consumption of di-HR macro CTA in the synthesis of 240K di-HR 1,4-PB.
Figure 4.7 Expanded 1H NMR (500 MHz) spectra of CDCl3 solutions of telechelic polymers that have a 10 kg/mol 1,4-PB backbone with end groups that are (a) THY, (b) DAAP, and (c) a mixture of the two polymers with a mass ratio of 1:2, which represents a stoichiometric ratio of approximately 1:2. The concentration of polymer in solution is approximate 1wt%.
Figure 4.8 Expanded 1H NMR (500 MHz) spectra of CDCl3 solutions of telechelic polymers that are (a) 1,4-PB of Mw = 50 kg/mol with CA end groups, (b) 1,4-PB of Mw = 24 kg/mol with HR end groups, and (c) a mixture of the two polymers with a mass ratio of 1:1.4, which represents a stoichiometric ratio of CA:HR of approximately 1:2. The concentration of polymer in solution is approximate 1wt%.
(a)
(b)
2 1 H1
H1
H2
H2
BHT
2 1
Figure 4.9 Expanded 1H NMR (500 MHz) spectra of CDCl3 solutions of telechelic polymers that are (a) 1,4-PB of Mw = 22 kg/mol with TB end groups, (b) a mixture of 1,4-PB of Mw = 22 kg/mol with TB end groups and 1,4-PB of Mw = 22 kg/mol with TA end groups two polymers with a mass ratio of 1:1. The concentration of polymer in solution is approximate 1wt%.
Figure 4.10 Expanded 1H NMR (500 MHz) spectra of CDCl3 solutions of telechelic polymers that are (a) 1,4-PB of Mw = 288 kg/mol with THY end groups, (b) 1,4-PB of Mw = 219 kg/mol with DAAP end groups, and (c) a mixture of the two polymers with a mass ratio of 1:2. The concentration of polymer in solution is approximate 1wt%.
Figure 4.11 Expanded 1H NMR (500 MHz) spectra of CDCl3 solutions of telechelic polymers that are (a) 1,4-PB of Mw = 200 kg/mol with CA end groups, (b) 1,4-PB of Mw
= 240 kg/mol with HR end groups, and (c) a mixture of the two polymers with a mass ratio of 1:2. The concentration of polymer in solution is approximate 1wt%.
BHT
-CH=CH2-
-CH=CH2-
2 1
H
1H2
1 2
Figure 4.12 Expanded 1H NMR (500 MHz) spectra of CDCl3 solutions of telechelic polymers that are (a) 1,4-PB of Mw = 250 kg/mol with TB end groups, (b) a mixture of 1,4-PB of Mw = 250 kg/mol with TB end groups and 1,4-PB of Mw = 230 kg/mol with TA end groups two polymers with a mass ratio of 1:1. The concentration of polymer in solution is approximate 1wt%.
Figure 4.13 Specific viscosity (25oC) of 1wt% 1-chlorododecane (CDD) and dodecane solutions of 288K di-THY 1,4-PB, 219K di-DAAP 1,4-PB, and 1:2 (w/w) mixture of 288K di-THY 1,4-PB and 219K di-DAAP 1,4-PB.
0 0.5 1 1.5 2 2.5
Di- THY Di- DAAP THY:DAAP
= 1:2
Di-THY Di-DAAP THY:DAAP
=1:2
Specific V iscosity
0 0.5 1 1.5 2 2.5
Di-HR Di-CA HR:CA
=2:1
HR:CA
=1:2
Di-HR Di-CA HR/CA 2:1
HR/CA 1:2
S pecif icV isco sity (- )
Figure 4.14 Specific viscosity (25oC) of 1wt% 1-chlorododecane (CDD) and Jet-A solutions of 240K di-HR 1,4-PB, 200K di-CA 1,4-PB, and 1:2 and 2:1 (w/w) mixtures of 240K di-HR 1,4-PB and 200K di-CA 1,4-PB.
1 10 100 1000 0
2 4 6 8 10 12
Speci fi c V is cos ity (-)
Shear Rate (s
-1)
1:1 mixture of 230K di-TA/250K di-TB 1,4-PBs 230K di-TA 1,4-PB
250K di-TB 1,4-PB 230K di-TE 1,4-PB
Figure 4.15 Specific viscosity (25oC) of 1wt% CDD solutions of 230K di-TE 1,4-PB, 230K di-TA 1,4-PB, 250K di-TB 1,4-PB, and the 1:1 (w/w) mixture of 230K di-TA 1,4- PB and 250K di-TB 1,4-PB at shear rates 1-3000 s-1.
1 10 100 1000 0
2 4 6 8 10 12
Sp ec if ic V isc os ity ( -)
Shear Rate (s
-1)
1:1 mixture of 230K di-DA/204K di-DB 1,4-PBs 230K di-DA 1,4-PB
204K di-DB 1,4-PB 230K di-DE 1,4-PB
Figure 4.16 Specific viscosity (25oC) of 1wt% CDD solutions of 230K di-DE 1,4-PB, 230K di-DA 1,4-PB, 204K di-DB 1,4-PB, and the 1:1 (w/w) mixture of 230K di-DA 1,4- PB and 204K di-DB 1,4-PB at shear rates 1-3000 s-1.
1 10 100 1000 0
5 10 15 20 25 30
Sp ec ific V isc osity (-)
Shear Rate (s
-1)
1:1 mixture of 430K di-TA/430K di-TB 1,4-PBs 430K di-TB 1,4-PB
430K di-TA 1,4-PB 430K di-TE 1,4-PB
Figure 4.17 Specific viscosity (25oC) of 1wt% Jet-A solutions of 430K di-TE 1,4-PB, 430K di-TA 1,4-PB, 430K di-TB 1,4-PB, and the 1:1 (w/w) mixture of 430K di-TA 1,4- PB and 430K di-TB 1,4-PB at shear rates 1-3000 s-1.
N N Br
HN O NH
NH H
O Ph
Ph N NH
NH
N O
HN
O O
O
N N N NH
O2N NH
H O EtO
O EtO NH
H
Figure 4.18 Secondary-electrostatic-interaction (SEI) analysis of all possible hydrogen- bond donor (D) and acceptor (A) site arrangements for triple-hydrogen-bonding hetero- complementary associative pairs and their representative examples. (a) ADA-DAD;76 (b) AAD-DDD;71 (c) AAA-DDD.8
O
O O
N N
N N
N O
R
N
O R H
H
H H
N
O N O
N H O
H
N N
N N
O O R
N N N N
O
N
O N R' O H O O
H H
H
H
N N
N N
tBu
tBu NH
N NH
NH NH N
H H
N
Figure 4.19 SEI analysis of D/A site arrangements for multiple-hydrogen-bonding hetero-complementary associative pairs. (a)HR/CA (ADAADA-DADDAD); (b) UG/DAN (ADDA-DAAD); (c) AAAA-DDDD.
Scheme 4.1 Synthesis of Di-DB and Di-TB 1,4-PBs via Two-Stage, Post-Polymerization End-Functionalization
Scheme 4.2 Synthesis of THY-Functional Acid, Di-THY Macro CTA, and Di-THY 1,4- PB of Mw ~ 200 kg/mol
N H O N
O O
OH N
H O O N
O
O N
H O O N
O
O S
O OH
O O
n O O
n
OH
HO
N O H O N O O S O O
N N O O H O
O S
O O
1 2 3
3 c 4
5
a b
Grubbs III/DCM @ 40oC 4 min.
O O
m
N O H O N O O S O O
N O NH
O O
O S
O O
6 m>>n
Key: a) allyl alcohol, pTSA·H2O, bulk, reflux, overnight; b) 3MPA, hv, R.T., 4 h; c) DIC, DMAP, THF, 40oC, overnight.