5
mol of trimethyl orthoformate and 0.2 mol of diphenylphosphoric
acid at 110 oC for 48 h. The reaction mixture was cooled to room
temperature, and the excessed orthoformate was evaporated
under reduced pressure. The obtained residue was recrystallized
with dichloromethane and ethyl acetate, and washed with ethyl
acetate and petroleum ether. The product was dried in a vacuum
oven at 60 °C overnight to obtain 3n in 69% yield. 1H NMR (500
MHz, CDCl3) δ 7.72–7.69 (m, 3H), 7.63–7.56 (m, 12H), 7.23 (d,
J = 8.0 Hz, 4H), 7.10 (t, J = 7.7 Hz, 4H), 6.87 (t, J = 7.3 Hz, 2H),
2.96 (d, J = 13.3 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 153.96,
153.90, 134.75, 134.72, 132.93, 132.85, 130.19, 130.08, 128.54,
121.62, 120.17, 120.13, 119.33, 118.63, 9.14, 8.69; 31P NMR
(162 MHz, CDCl3) δ 22.75, -9.17; HRMS (ESI-MS): Calcd. for
C19H18P+: 277.1140, Found: 277.1120. Calcd. for C12H10O4P-
:249.0317, Found:249.0303.
4.21. Propane-1,3-diylbis(methyldiphenylphosphonium) 4-
methylbenzenesulfonate (3s)
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1
Yield: 78%; white solid; 155-157 C; H NMR (500 MHz,
CDCl3) δ 7.90–7.79 (m, 12H), 7.66–7.54 (m, 12H), 7.12 (d, J =
8.2 Hz, 4H), 3.72–3.66 (m, 4H), 2.62 (d, J = 13.3 Hz, 6H), 2.33
(s, 6H), 2.06 – 2.02 (m, 2H); 13C NMR (125 MHz, CDCl3) δ
143.90, 139.03, 134.38, 132.44, 132.40, 132.36, 130.29, 130.24,
130.19, 130.18, 130.14, 130.09, 128.56, 128.54, 125.87, 125.85,
119.46, 118.77, 22.82, 22.67, 22.38, 22.23, 21.25, 16.30, 6.86,
6.41; 31P NMR (202 MHz, CDCl3) δ 23.45; HRMS (ESI-MS):
Calcd. for C29H32P22+:442.1968, Found: 221.0994. Calcd. for
C7H7O3S-: 171.0121, Found: 171.0123.
4.22. [1,1'-binaphthalene]-2,2'-diylbis
(methyldiphenylphosphonium) 4-methylbenzenesulfo-nate (3t)
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4.17. Methyltriphenylphosphonium dinaphtho[2,1-d:1',2'-
f][1,3,2]dioxaphosphepin-4-olate 4-oxide (3o)
Yield: 51%; light yellow solid; 138-140 C; H NMR (500
MHz, CDCl3) δ 8.48–8.30 (m, 2H), 8.06 (d, J = 8.3 Hz, 2H),
7.80–7.45 (m, 20H), 7.34 (td, J = 7.8, 3.6 Hz, 4H), 7.11–6.96 (m,
8H), 6.81 (t, J = 7.7 Hz, 2 H), 6.60 (d, J = 8.6 Hz, 2H), 2.30 (s,
6H), 2.25 (d, J = 12.9 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ
144.17, 138.74, 135.31, 135.29, 135.11, 134.78, 133.56, 133.47,
132.56, 132.46, 132.28, 132.20, 130.75, 130.70, 130.64, 130.28,
130.18, 129.11, 129.01, 128.92, 128.47, 128.38, 126.28, 126.05,
119.71, 119.00, 118.83, 118.31, 118.13, 117.63, 21.27, 10.62,
10.18; 31P NMR (202 MHz, CDCl3) δ 21.48; HRMS (ESI-MS):
Calcd. for C46H38P22+: 652.2438, Found: 326.1223. Calcd. for
C7H7O3S-: 171.0121, Found: 171.0123.
1
Yield: 81%; White solid; 143-145 oC; H NMR (500 MHz,
CDCl3) 1H NMR (500 MHz, Chloroform-d) δ 7.81–7.78 (m,
4H), 7.60–7.56 (m, 3H), 7.47–7.41 (m, 14H), 7.32–7.28 (m, 4H),
7.14–7.11 (m, 2H), 2.67 (d, J = 13.2 Hz, 3H); 13C NMR (125
MHz, CDCl3) δ 150.55, 150.48, 134.88, 134.86, 133.22, 133.13,
133.12, 132.81, 130.92, 130.36, 130.26, 129.81, 128.22, 127.18,
125.59, 124.21, 122.94, 122.92, 122.60, 122.58, 119.74, 119.03,
9.20, 8.75; 31P NMR (202 MHz, CDCl3) δ 21.80, 21.77, 6.34;
HRMS (ESI-MS): Calcd. for C19H18P+: 277.1141, Found:
277.1140. Calcd. for C20H12O4P-:347.0479, Found:347.0476.
4.23. Tributyl(methyl)phosphonium 4-methylbenzenesulfonate
(3u)
4.18. Ethyltriphenylphosphonium 4-methylbenzenesulfonate (3p)
Yield: 91%; light pink solid; 104-107 oC; 1H NMR (500 MHz,
CDCl3) δ 7.78–7.72 (m, 11H), 7.67–7.64 (m, 6H), 7.05 (d, J =
7.9 Hz, 2H), 3.58–3.51 (m, 2H), 2.29 (s, 3H), 1.30 (dt, J = 20.1,
7.4 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 144.39, 138.25,
134.79, 134.77, 133.39, 133.31, 130.41, 130.34, 130.24, 128.09,
125.98, 118.25, 117.56, 21.13, 16.06, 15.65, 6.53, 6.48; 31P NMR
(202 MHz, CDCl3) δ 26.04; HRMS (ESI-MS): Calcd. for
C20H20P+: 291.1297, Found: 291.1297. Calcd. for C7H7O3S-
:171.0121, Found:171.0132.
1
Yield: 76%; colorless liquid; H NMR (500 MHz, CDCl3) δ
7.74 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 7.9 Hz, 2H), 2.33 (s, 3H),
2.25–2.19 (m, 6H), 1.90 (dd, J = 13.5, 5.1 Hz, 3H), 1.45–1.41 (m,
12H), 0.91 (t, J = 6.8 Hz, 9H); 13C NMR (125 MHz, CDCl3) δ
142.91, 139.44, 139.42, 128.48, 125.94, 125.92, 23.75, 23.63,
23.48, 23.44, 21.19, 19.92, 19.53, 13.35; 31P NMR (202 MHz,
CDCl3) δ 31.79; HRMS (ESI-MS): Calcd. for C13H30P+:
217.2080, Found: 217.2079. Calcd. for C7H7O3S-: 171.0121,
Found: 171.0107.
4.19. Triphenyl(propyl)phosphonium 4-methylbenzenesulfonate
(3q)
4.24. PC/phosphonium salt composites preparation
PC, phosphonium salts and anti-dripping agent (Ethylene
tetrafluoro-ethylene ,ETFE) were dried in vacuum heating drying
oven before processing. PC, phosphonium salts and ETFE were
mixed in a weight ratio of 100:2:0.1 [2 phr (parts of per hundreds
of rubber or resin)] in a Haake Rheocord 90 internal mixer
(Haake, Bersdorff, Germany) at 210 oC for 10 min. The obtained
mixtures were subsequently pressed into sheets of 3 mm which
could be easily processed into desired sample shape.
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1
Yield: 77%; light yellow solid; 130-132 C; H NMR (500
MHz, CDCl3) δ 7.78–7.74 (m, 11H), 7.68–7.64 (m, 6H), 7.05
(dd, J = 8.1, 2.0 Hz, 2H), 3.54–3.48 (m, 2H), 2.30 (s, 3H), 1.68–
1.58 (m, 2H), 1.15 (td, J = 7.2, 1.9 Hz, 3H); 13C NMR (125 MHz,
CDCl3) δ 144.12, 138.53, 134.81, 134.79, 133.57, 133.54, 133.49,
133.46, 130.42, 130.39, 130.32, 128.23, 126.15, 126.12, 118.78,
118.09, 23.66, 23.26, 21.25, 16.48, 16.44, 15.20, 15.06; 31P NMR
(202 MHz, CDCl3) δ 23.90; HRMS (ESI-MS): Calcd. for
C21H22P+:305.1454, Found:305.1454. Calcd. for C7H7O3S-
:171.0121, Found:171.0123.
4.25. Thermal behaviour of PC/phosphonium salt composites
The thermogravimetric analysis (TGA) of PC/phosphonium
salt composites was performed with a NETZSCH TG 209
thermal analyzer at a heating rate of 20 oC/min and the
temperature ranged from 50 oC to 800 oC. TGA was carried out in
N2 atmosphere, and specimen mass for TGA was 5 mg.
4.20. Isopropyltriphenylphosphonium 4-methylbenzenesulfonate
(3r)
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Yield: 82%; white solid; 191-193 C; H NMR (500 MHz,
CDCl3) δ 7.94–7.88 (m, 8H), 7.75–7.64 (m, 9H), 7.12 (d, J = 7.8
Hz, 2H), 5.03–4.96 (m, 1H), 2.32 (d, J = 3.1 Hz, 3H), 1.31 (dd, J
= 19.0, 6.8 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 144.44,
138.54, 134.55, 134.53, 133.83, 133.75, 130.40, 130.31, 128.33,
126.17, 118.04, 117.38, 21.26, 20.46, 20.09, 16.21, 16.19; 31P
NMR (202 MHz, CDCl3) δ 31.90; HRMS (ESI-MS): Calcd. for
C21H22P+: 305.1454, Found: 305.1453. Calcd. for C7H7O3S-:
171.0121, Found: 171.0124.
4.26. Flame retardancy of PC/ phosphonium salt composites
The limiting oxygen index (LOI) values were tested by using
an HC-2 type instrument (Nanjing Jiangning Analytical
Instrument Factory, China) on the sheets of 120×6.5×3 mm3
according to ASTM D2863-77. The vertical burning rating (UL-
94) was tested by using a CZF-1 type instrument (Nanjing
Analytical Instrument Factory, China) on the sheets of
127×12.7×3 mm3 according to ANSI/UL-94.