Table 1 Experimental conditions and macromolecular characteristics of P(AAm-co-MPDL) and P(AAm-co-MDO) copolymers synthesized by RAFT-mediated copolymerization of AAm and MPDL (or MDO) in anhydrous DMSO at 70 °C for 16 h.

From: Vinyl copolymers with faster hydrolytic degradation than aliphatic polyesters and tunable upper critical solution temperatures

Entry

CKA

fCKA,0

FCKAa

Open CKA (%)a

AAm conv. (%)b

Tcp from UV (°C)c

Mn, NMR d (g mol−1)

Mn, exp.e (g mol−1)

Đ exp.e

Mn, deg. theo..f (g mol−1) (% Mn loss)

Mn, deg.g (g mol−1) (% Mn loss)

Cooling

Heating

P0

-

0

0

0

>98

-h

-h

8200

28,300

1.2

-

27,500 (−2.8%)

P1

MPDL

0.2

0.038

51

>98

-h

-h

6600

22,300

1.3

3800 (−83%)

22,900 (+2%)

P2

MPDL

0.4

0.043

50

>98

15

-i

6500

17,800

1.2

3400 (−81%)

15,600 (−12%)

P3

MPDL

0.6

0.067

37

   98

18

-i

6100

12,500

1.2

3000 (−76%)

10,000 (−20%)

P4

MPDL

0.8

0.108

44

   87

38

38

8200

8300

1.2

1600 (−81%)

5700 (−31%)

P5

MDO

0.2

0.095

76

>98

-h

-h

16,000

29,300

1.7

1000 (−97%)

13,500 (−54%)

P6

MDO

0.4

0.18

43

   93

-h

-h

5600

37,900

2.3

960 (−97%)

7500 (−80%)

P7

MDO

0.6

0.27

53

   95

-h

-h

8500

53,700

3.3

540 (−99%)

6200 (−88%)

P8

MDO

0.8

0.44

43

   76

-j

-j

7100

14,000

4.4

420 (−97%)

1700 (−87%)

  1. aDetermined by 1H NMR after precipitation by: (i) integrating the 2H (–NH2) of AAm, the 5H (aromatic protons) of open and closed MPDL (6.5–7.5 ppm), the 2H of open MPDL (4.0–4.4 ppm) and the 1H of closed MPDL (5.0–5.2 ppm) for MPDL and (ii) by integrating the 2H (–NH2) of AAm (6.5–7.5 ppm), the 2H of open MDO (3.9–4.1 ppm) and the 4H of closed MDO (3.4–3.8 ppm) for MDO. bDetermined by 1H NMR by integrating the 2H of AAm (6.02–6.24 ppm) at t = 0 and 16 h. cDetermined from the maximum of the first derivative of the cooling/heating curves obtained by UV-vis temperature ramp (1 °C min−1) at 10 mg mL−1 in deionized water. dDetermined by 1H NMR after precipitation by integrating the 3H from the CH3 moiety of the RAFT agent C12 alkyl chain (0.86 ppm), the 1H of AAm (2.1 ppm) and: (i) the 2H of open MPDL (4.0–4.4 ppm) and the 1H of closed MPDL (5.0–5.2 ppm) or (ii) the 2H of open MDO (3.9–4.1 ppm) and the 4H of closed MDO (3.4–3.8 ppm). Note that this method is only accurate for high-living chain fractions. eDetermined by SEC in DMSO with 100 mM LiBr. fDetermined according to Mn, deg. theo = ([1/(open CKA × FCKA)]–1) × MWAAm + MWCKA, with MW being the molecular weight of the considered monomer. gDetermined by SEC in DMSO with 100 mM LiBr after hydrolytic degradation using KOH 5 wt.% solution. hSamples were water-soluble at any temperature. iLoss of the UCST behavior due to precipitation occurring below the UCST. jSamples were insoluble in water at any temperature.