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Differential scanning calorimetry (DSC) data were collected with a
Netzsch DSC 214 Polyma between temperatures of 08C and 3008C
under nitrogen atmosphere. The first cycle involved heating sam-
ples to 3008C followed by rapid cooling to 08C before the second
and third cycles conducted with a heating rate 108Cmin . The
second heating cycle was used to determine the glass temperature
Preparation of poly(methylenephosphine) homopolymers
(
PMPs)
In a glove box, benzyllithium initiator was prepared by adding
sBuLi (1.4m in cyclohexane) dropwise to a stirred solution of
TMEDA dissolved in toluene for 30 mins at 508C. The color of solu-
tion was orange. The concentration of benzyllithium initiator was
subsequently determined by titration following previously reported
ꢀ1
(Tg), taken at the middle point of the heat capacity change.
[18]
procedure. To the stirred benzyllithium initiator solution at 508C
was added dropwise PA in toluene. The color of solution was
changing from orange to deep red. Polymerization progress was
Preparation of PhCH Li initiator
2
To a stirred solution of TMEDA (0.84 mL, 0.65 g, 5.6 mmol) in tolu-
ene (100 mL) was added sBuLi solution in cyclohexane (3.12 mL,
31
monitored by P NMR. Upon complete consumption of the PA
monomer half of the reaction mixture were withdrawn and
quenched by degassed MeOH (2 drops). The deep red color of the
reaction mixture became pale yellow. The solvent was removed in
vacuo leaving a yellow residue. To the residue was added degassed
methanol (3ꢁ50 mL) and the suspension was filtered, and the sol-
vent removed in vacuo leaving white solid product.
1
1
.4m, 4.37 mmol). The red orange solution was heated to 508C for
h. Subsequently, the solution was cooled to room temperature
and the solvent was removed in vacuo. Addition of 50 mL hexanes
followed by cooling to ꢀ788C, resulted in the precipitation of
PhCH Li. The product was isolated as a yellow powder after filtra-
2
tion, washing with hexanes (2ꢁ10 mL at ꢀ788C) and drying in
vacuo. Following a modification of the reported procedure to ti-
PMP : Toluene (1 mL), TMEDA (2 drops, ca. 0.009 mL, 0.060 mmol),
1
0
[18]
trate nBuLi,
the yellow PhCH Li (0.289 g, 2.95 mmol) was dis-
sBuLi (in 1.4m cyclohexane solution) (31.21 mL, 43.69 mmol)/PA
(0.100 g, 0.316 mmol) in toluene (1 mL). Yield=33.1%.
2
solved in THF (5 mL) to afford dark red solution. This solution is ti-
trated against N-benzylbenzamide requiring (0.623 g, 2.95 mmol)
PMP : Toluene (1 mL), TMEDA (2 drops, ca. 0.009 mL, 0.060 mmol),
1
5
to equivalence. Therefore, the concentration of the PhCH Li solu-
2
sBuLi (in 1.4m cyclohexane solution) (31.21 mL, 43.69 mmol)/PA
0.150 g, 0.474 mmol) in toluene (1 mL). Yield=31.7%.
PMP : Toluene (1 mL), TMEDA (2 drops, ca. 0.009 mL, 0.060 mmol),
tion was 0.059 m.
(
General procedure for kinetic study of the anionic polymerization
of PA: To a stirred solution of PA (0.1 g, 0.32 mmol) in toluene
2
0
sBuLi (in 1.4m cyclohexane solution) (31.21 mL, 43.69 mmol)/PA
0.200 g, 0.632 mmol) in toluene (1 mL). Yield=34.1%.
PMP : Toluene (1 mL), TMEDA (2 drops, ca. 0.009 mL, 0.060 mmol),
(
1 mL) was added a solution of sBuLi (10.40 mL, 14.56 mmol) in tolu-
(
ene (1 mL) with TMEDA (1 drop, ca 0.003 mL, 0.020 mmol) in the
glovebox. The reaction mixture was transferred to an NMR tube
after stirring for 1 min. The sample was transferred to Bruker
Avance 400dir NMR spectrometer which was maintained at the de-
sired temperature (i.e. 323.15 K, 328.15 K, 333.15 K, 338.15 K,
2
5
sBuLi (in 1.4m cyclohexane solution) (31.21 mL, 43.69 mmol)/PA
0.250 g, 0.791 mmol) in toluene (1 mL). Yield=45.2%.
PMP : Toluene (1 mL), TMEDA (2 drops, ca. 0.009 mL, 0.060 mmol),
(
3
0
3
1
sBuLi (in 1.4m cyclohexane solution) (31.21 mL, 43.69 mmol)/PA
0.300 g, 0.949 mmol) in toluene (1 mL). Yield=40.1%.
3
43.15 K, 348.15 K). P NMR spectra were recorded in every 15 min
(
interval with 72 scans for each spectrum until the polymerization
3
1
1
was complete. The delay time (d1) for PMP was set to 10 s. The ac-
P NMR (161.9 MHz, CDCl
(400 MHz, CDCl
-CHPh ), 3.41 (br, 2H, o-CH
(100.6 MHz, CDCl , 298 K): d=146.7 (br, Mes-C), 143.1 (br, Mes-C),
138.5 (br, Mes-C), 135.2–125.1 (br, Ph-C), 52.0 (br, -CHPh ), 32.5 (br,
-CH -), 23.5 (br, -CH ), 21.1 (br, -CH ). The M and ꢀ for PMP are
given in Table 1.
,
3
298 K): d=ꢀ7.10 (br). H NMR
31
curacy of integration in the P NMR spectra was controlled by inte-
grating the same region (between 220–240 ppm) for the PA and
, 298 K): d=7.11 (br, 12H, aryl H), 4.74 (br, 1H,
3
13
1
), 2.02 (br, 6H, o, p-CH ), C{ H} NMR
2 3
2
the PMP (between +10 and ꢀ40 ppm). Two drops of degassed
3
n
methanol were added to the reaction mixture to terminate the
living polymer. After precipitation from concentrated solution mix-
ture with dry hexanes (2ꢁ50 mL), the white polymer solid was iso-
lated by filtration and dried in vacuo. The isolated yields are be-
tween 40% to 50%. The reproducibility of the kinetic study was
confirmed by repeating every experiment twice at each tempera-
2
2
3
3
n
n
ture. M , ꢀ were estimated by triple detection gel permeation
chromatography (GPC-LLS).
Preparation of poly(methylenephosphine)-block-poly-
methylmethacrylate)s (PMP -b-PMMA )
n
(
n
m
The other half of the deep red solution of PMP carbanion was
cooled at ꢀ788C for 10 mins and LiCl solution in THF was slowly
added to the reaction mixture followed by the second monomer,
MMA, dissolved in THF. After 1 min, the color of solution was from
deep red to light yellow. The reaction mixture was stirred at
Refractive index increments of PMP -b-PMMA block copoly-
mers
n
m
The refractive index increment of a copolymer is a linear function
[20]
of its composition according to equation 1 where (dn/dc) , (dn/
A
ꢀ
788C then slowly warmed up to room temperature. 2 drops of
dc) are the refractive index increments of PMP , PMMA homo-
B
n
m
degassed MeOH were used to quench the polymerization. The
yellow color of the reaction mixture became much paler, towards
colorless. The solvent was removed in vacuo leaving a pale yellow
residue. To the residue was added degassed MeOH (3ꢁ50 mL)
with vigorous stirring and the suspension was filtered and the sol-
vent removed in vacuo leaving white solid product.
polymer, respectively and W , W are the weight fractions of PMP,
A
B
PMMA components. The values of (dn/dc) =0.2387 and (dn/dc) =
A
B
0
.0445 were determined from Cauchy plot. The measurements of
Cauchy plots of the polymer solutions were performed by using a
Wyatt Optilab T-rEx differential refractometer at l0 =658 nm
[
Eq. (1)]:
Bn-PMP -PMMA400: Toluene (1 mL), TMEDA (2 drops, ca.
1
0
(
.009 mL,0.06 mmol), sBuLi (in 1.4m cyclohexane solution)
31.21 mL, 43.69 mmol)/PA (0.010 mg, 0.032 mmol) in toluene
(1 mL)/LiCl (0.012 g, 0.28 mmol) in THF (1 mL)/MMA (0.10 mL,
.10 g, 1.00 mmol) in THF (1 mL). Yield=59.1%.
ꢀ
ꢁ
ꢀ
ꢁ
dn
dc
dn
dc
dn
dc
¼
WA
þ WB
ð1Þ
A
B
0
&
&
Chem. Eur. J. 2018, 24, 1 – 9
6
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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