Macromolecules
ARTICLE
1
H NMR(400 MHz, DMSO-d
6
, TMSint). Repeating units δ= 3.27ꢀ3.39
dissolved in dimethylformamide (100 mL) and sodium azide (5.006 g,
77 mmol) was added to the solution. The reaction mixture was stirred at
100 °C for 12 h. After completion of the reaction the amount of solvent
was reduced and the salts filtered off. The remaining dimethylformamide
was removed under reduced pressure. The product was isolated as
yellowish oil with a yield of 96%.
(
CH N , 1H), 3.40ꢀ3.51 (CH N , 1H), 3.55ꢀ3.72 (CH CHO, 3H) ppm.
2
3
2
3
2
1
3
C NMR(100 MHz, DMSO-d
6
, TMSint). Repeating units δ = 51.04
(
CH
2
N
3
), 68.58 (CH O), 78.05 (CHO) ppm.
2
Mn,SEC,DMF = 21400, M /M = 1.26.
Synthesis of Poly(glycidyl amine). Poly(glycidyl azide) (9.904 g, 100
w
n
1
mmol), was dissolved in dimethylformamide (220 mL) and triphenyl-
phosphine (28.850 g, 110 mmol) was added. The reaction mixture was
stirred for 2 h and subsequently water (5 mL) was added. The solvents
were removed under reduced pressure. The polymer was dissolved in
water, triphenylphosphine oxide was filtered off and finally the polymer
was washed with toluene. The product was isolated as yellowish oil with
H NMR(400 MHz, DMSO-d , TMS ). Repeating units δ = 3.23ꢀ
6
int
3.87 (polymer backbone, 10H), 4.43ꢀ4.78 (OH) ppm.
1
3
C NMR(100 MHz, DMSO-d , TMS ). Repeating units δ = 50.95
6
int
(CH N ), 60.57 (CH OH), 68.56, 69.29 (CH CH(CH OH)O, CH CH-
2
3
2
2
2
2
(CH Cl)O), 77.95 (CH CH(CH OH)O), 80.30 (CH CH(CH N )O)
2
2
2
2
2
3
ppm.
Mn,SEC,DMF = 10000, M /M = 1.32.
a yield of 96%.
w
n
1
H NMR(400 MHz, DMSO-d
6
, TMSint). Repeating units δ = 2.41ꢀ
Reaction of Poly(glycidol-co-glycidyl azide) with Propargyl Alcohol.
Poly(glycidol-co-glycidyl azide) (866 mg, 5.0 mmol azide groups) and
propargyl alcohol (280 mg, 5.0 mmol) were dissolved in DMF (10 mL)
and copper(I)bromide (72 mg, 0.5 mmol) was added to the reaction
mixture. After overnight stirring, the copper bromide was filtered off and
the solvent was removed under reduced pressure. The product was
isolated as yellowish oil with a yield of 99%.
2
.69 (CH NH , 2H) 3.09ꢀ3.70 (CH CHO, 3H) ppm.
2
2
2
13
C NMR(100 MHz, DMSO-d , TMS ). Repeating units δ = 42.64
NH ), 69.83 (CH ), 80.07 (CHO) ppm.
2 2 2
6
int
(
CH
Synthesis of Poly(glycidyl acetamide). To a solution of poly(glycidyl
amine) (73 mg, 1 mmol glycidyl amine groups) in dry DMF, N,
N-diisopropyethylamine (1.292 g, 10 mmol) and acetic anhydride (1.021 g,
1
1
0 mmol) were added. The solution was stirred for 3 h and solvent and
H NMR(400 MHz, DMF-d , TMS ). Repeating units δ = 3.32ꢀ
7
int
excess of amine and anhydride were removed under reduced pressure.
3.71 (CH CHO, 3H), 4.09ꢀ4.20 (CH N, 2H), 5.23 (triazoleꢀCH ꢀ
2
2
2
1
H NMR(400 MHz, DMF-d , TMS ). Repeating units δ = 1.88ꢀ1.97
OH, 2H), 8.00 (triazole, 1H) ppm.
7
int
(
4
H
3
H) ppm.
CON, 3H), 3.32ꢀ3.42 (CH
2
N, 1H), 3.43ꢀ3.74 (CH
2
CH(CH
2
N)O,
Synthesis of Poly(glycidol-co-glycidyl amine). Poly(glycidol-co-gly-
cidyl azide) (9.156 g, 70 mmol) was dissolved in DMF (75 mL) and
triphenylphosphine (20.196 g, 77 mmol) was added to the solution
which was stirred at room temperature until gas formation stopped.
Subsequently, water was added and the solvents were removed under
reduced pressure. The polymer was washed with toluene and dried
M
Synthesis of Poly(ethoxyethyl glycidyl ether-co-epichlorohydrin).
n,SEC,DMF = 21500, M
w
/M
n
= 1.21.
Tetraoctylammonium bromide (0.374 g, 0.684 mmol) was dissolved in
dry toluene (2 mL) under nitrogen atmosphere. Epichlorohydrin (4.430
g, 47.9 mmol) and ethoxyethyl glycidyl ether (3.000 g, 20.5 mmol) were
added. The polymerization was started by adding the triisobutylalumi-
nium while cooling with an ice bath. The reaction mixture was allowed to
warm up to room temperature and stirred overnight. The monomer
ꢀ2
under reduced pressure (10 mbar). The product was isolated as
yellowish oil with a yield of 95%.
1
H NMR(400 MHz, DMSO-d
6
, TMSint). Repeating units δ = 3.27ꢀ
3.68 (polymer backbone) ppm.
1
13
conversion was monitored via H NMR spectroscopy. After polymer-
C NMR(100 MHz, DMSO-d
NH ), 60.39 (CH OH), 69.24 (CH
OH)O), 80.33 (CH CH(CH NH )O) ppm.
6
, TMSint). Repeating units δ = 42.39
ization, toluene was removed under reduced pressure. The colorless
polymer was dissolved in tetrahydrofuran and precipitated in an aqueous
solution of sodium hydroxide (5 wt %). The product was isolated as
(CH
(CH
2
2
2
2
CHO), 79.98 (CH CH-
2
2
2
2
2
Synthesis of Poly(glycidol acetyl-co-glycidyl acetamide). To a
solution of poly(glycidol-co-glycidyl amine) (74 mg, 0.7 mmol glycidyl
amine groups, 0.3 mmol glycidol groups) in dry DMF and N,
N-diisopropyethylamine (1.292 g, 10 mmol) acetic anhydride (1.021 g,
10 mmol) was added. The solution was stirred for 3 h and solvent and excess
colorless oil with a yield of 96%.
1
H NMR(400 MHz, DMSO-d
CH
, 3H), 1.15ꢀ1.23 (CHCH
O)O, CH CH , CH CH(CH
Cl)O, 12H), 4.57ꢀ4.74 (OCHO,
H) ppm.
, TMSint) Repeating units δ = 15.10
), 44.09 (CH Cl), 60.13 (CH CH ), 64.39,
OH)O), 68.71 (CH CH(CH OH)O), 69.53
Cl)O), 78.57ꢀ79.15 (CH CHO), 99.07 (CHCH ) ppm.
/M = 1.35.
Synthesis of Poly(glycidol-co-epichlorohydrin). Poly(ethoxyethyl
6
, TMSint). Repeating units δ = 1.05ꢀ
1
(
1
.13 (CH
CH
2
3
3
, 3H), 3.42ꢀ3.87 (CH CH-
2
2
2
3
2
2
of amine and anhydride were removed under reduced pressure.
1
3
1
C NMR(100 MHz, DMSO-d
CH CH ), 19.62 (CHCH
4.59 (CH CH(CH
CH CH(CH
6
H NMR(400 MHz, DMF-d
CON, 3H), 1.98ꢀ2.02 (H
N, 1H), 3.50ꢀ3.77 (CH CH(CH N)O, CH
H), (CH OCO, 1H) ppm.
/M
7
, TMSint). Repeating units δ =
COO, 3H), 3.13ꢀ3.33
CH(CH O)O, 9
(
6
(
2
3
3
2
2
3
1.86ꢀ1.90 (H
(CH
3
3
2
2
2
2
2
2
2
2
2
2
2
2
3
2
M
n,SEC,DMF = 10200, M
w
n
M
n,SEC,DMF = 8400, M
w
= 1.38.
n
Synthesis of Poly(epichlorohydrin)-block-poly(ethoxyethyl glycidyl
ether). Tetraoctylammonium bromide (196 mg, 0.360 mmol) and epi-
chlorohydrin (1.667 g, 18.000 mmol) were dissolved in toluene (1.000 mL)
under nitrogen atmosphere. The polymerization was started by adding a
solution of triisobutylaluminium (700 μL, 0.77 mmol) at a constant
temperature of 0 °C. The reaction mixture was kept overnight at this
glycidyl ether-co-epichlorohydrin) (10.941 g, 30 mmol EEGE) was
dissolved in THF (25 mL) and an appropriate amount of hydrochloric
acid (5 wt %) was added. The solution was stirred for 30 min. After
stirring the solution for 30 min it was neutralized with sodium bicar-
bonate. The solvents were removed under reduced pressure, the
polymer dissolved in dimethylformamide and the salts filtered off. The
remaining dimethylformamide was removed under reduced pressure.
1
temperature. Complete monomer conversion was confirmed by H NMR
spectroscopy. Ethoxyethyl glycidyl ether (2.631 g, 18 mmol) was added to
the solution at a constant temperature of 0 °C, the reaction mixture was
allowed to warm up to room temperature and kept overnight. Monomer
The product was isolated as colorless oil with a yield of 96%.
1
H NMR(400 MHz, DMSO-d
6
, TMSint). Repeating units δ = 3.36ꢀ
1
3
.93 (polymer backbone, 10H), 4.46ꢀ4.64 (OH) ppm.
conversion was again monitored via H NMR spectroscopy. The colorless
1
3
C NMR(100 MHz, DMSO-d , TMS ). Repeating units δ = 44.23
polymer obtained after removal of the solvent was dissolved in tetrahy-
drofuran and precipitated in an aqueous solution of sodium hydroxide
6
int
(
(
CH Cl), 60.77 (CH OH), 68.51, 69.46 (CH CH(CH OH)O, CH CH-
CH
Mn,SEC,DMF = 8700, M /M = 1.39.
Synthesis of Poly(glycidol-co-glycidyl azide). Poly(glycidol-co-
epichlorohydrin) (8.698 g, 70 mmol methylene chloride groups) was
2
2
2
2
2
2
Cl)O),78.21(CH
2
CH(CH
2
OH)O),80.21(CH
2
CH(CH
2
Cl)O) ppm.
(5 wt %). The product was isolated as colorless oil with a yield of 97%.
1
H NMR(400 MHz, CDCl
CH
, TMSint). Repeating units δ = 0.99ꢀ1.13
w
n
3
(CH
2
3
,3H),1.12ꢀ1.23 (CHCH
3
,3H),3.17ꢀ3.96 (CH CH(CH O)O,
2
2
CH CH , CH CH(CH Cl)O, 12H), 4.43ꢀ4.79 (OCHO, 1H) ppm.
2
3
2
2
4
084
dx.doi.org/10.1021/ma200757v |Macromolecules 2011, 44, 4082–4091