Mark James E. (ed.). Physical Properties of Polymers Handbook
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TABLE 11.1. Thermodynamic quantities determined by use of diluent equation [Eq. (11.6)].
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
[CH
2
]
n
Ethylene
418.7 4,142 295.8 9.9 [26–28]
CH
3
Isot.-propylene
a
[CH
2
−CH]
n
a
b
485.2
465.2
8,786
8,201
208.8
194.9
18.1
17.6
[29–36]
CH
3
CH
2
Isot.-butene-1
[CH
2
−CH]
n
(I)
(II)
(III)
408.7
397.2
379.7
6,318
6,276
6,485
112.5
111.9
115.6
15.5
15.8
17.1
[37–38]
CH
2
CH
CH
3
CH
3
[CH − CH
2
]
n
4-Methyl pentene-1
523.2 5,297 63.7 10.1 [39]
CH
3
[CH − (CH
2
)
6
− CH
2
]
n
1-Methyl octamer
268.2 10,857 86.2 40.5 [40]
[ CH
2
− CH ]
n
Isot.-styrene
⎯⎯
>516.2
b
8,682
c
83.4 16.8 [41–44]
Synd.-styrene
[ CH
2
− CH ]
n
⎯⎯
>560.5
d
8,577 82.4 15.3 [45–47]
Vinyl alcohol
[CH
2
− CH]
n
OH
523.2 6,862 156.1 13.1 [48–50]
Acrylonitrile
[CH
2
− CH]
n
C≡N
593.2 5,021 94.7 8.5 [51,52]
Isot.-iso -propyl
acrylate
[CH
2
− CH]
n
C
O
OCH
CH
3
CH
3
450.2 5,857 51.4 13.0 [53]
Butadiene
H
H
trans-1,4
[CH
2
− C
=
C− CH
2
]
n
(I)
(II)
369.2
421.2
13,807
4,602
255.7
85.2
37.4
10.9
[54]
cis-1,4 Butadiene
H
[CH
2
− C
=
C − CH
2
]
n
H
273.2 9,205 170.4 33.7 [55]
THERMODYNAMIC QUANTITIES GOVERNING MELTING / 169
TABLE 11.1. Continued.
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
trans-1,4 Isoprene
H
CH
3
[CH
2
− C
=
C − CH
2
]
n
(a)
(b)
360.2
354.2
12,719
10,544
187.0
155.1
35.3
29.8
[56–58]
cis-1,4 Isoprene
HH
3
C
[CH
2
− C
=
C − CH
2
]
n
308.7 4,393 64.6 14.2 [59,60]
trans-1,4 Chloroprene
H
CI
[CH
2
− C
=
C − CH
2
]
n
380.2 8,368
e
94.6 22.0 [61–63]
trans-Pentenamer
[CH
=
CH − CH
2
− CH
2
− CH
2
]
n
307.2 12,008 176.3 39.1 [64,65]
trans-Octenamer
e
[CH
=
CH
− (CH
2
)
5
− CH
2
]
n
350.2 23,765 215.7 67.9 [66]
cis-Octenamer
[
CH
=
CH
− (CH
2
)
5
− CH
2
]
n
311.2 21,000 190.9 67.5 [67]
trans-Decenamer
e
[CH
=
CH
− (CH
2
)
7
− CH
2
]
n
353.2 32,844 237.6 92.9 [66]
trans-Dodecenamer
[CH
=
CH
− (CH
2
)
9
− CH
2
]
n
357.2 41,171 247.6 115.3 [66,68]
Methylene oxide
[CH
2
− O)
n
479.2 7,012 233.7 14.6 [69–72]
Ethylene oxide
[CH
2
− CH
2
− O]
n
353.2 8,703 197.8 24.6 [73–75]
Isot.-propylene
oxide
[CH
2
− CH
− O]
n
CH
3
355.2 7,531
8,368
f
129.8 21.2 [76,77]
Trimethylene
oxide
[(CH
2
)
3
− O]
n
323.2 8,786 151.5 27.2 [78]
Tetramethylene
oxide
[(CH
2
)
4
− O]
n
330.2 15,899 220.8 48.2 [79]
Hexamethylene
oxide
[(CH
2
)
6
− O]
n
346.7 23,640 236.4 68.2 [80]
1,3 Dioxolane
[O
− CH
2
− O − (CH
2
)
2
]
n
366.2 15,481 209.2 42.3 [81]
1,3 Dioxepane
[
O− CH
2
− O − (CH
2
)
4
]
n
303.0 14,454 141.7 47.7 [82]
1,3 Dioxocane
[O
− CH
2
− O − (CH
2
)
5
]
n
319.2 7,740 75.9 24.3 [83]
3,3 Dimethyl
oxetane
CH
3
CH
3
[O
− CH
2
− C − CH
2
]
n
II
III
349.2
329.2
9,205
7,448
107.0
86.6
26.3
22.6
[84]
170 / CHAPTER 11
TABLE 11.1. Continued.
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
3-Ethyl 3-methyl
oxetane
C
2
H
5
CH
3
[O − CH
2
− C
− CH
2
]
n
334.2 6,276 62.8 18.8 [85]
3,3 Diethyl oxetane
Monoclinic
Orthorhombic
C
2
H
5
C
2
H
5
[O − CH
2
− C
− CH
2
]
n
373.2
353.2
10,460
10,042
91.8
88.1
28.0
28.4
[86]
[86]
3,3-bis Ethoxy methyl
[O
− CH
2
− C
− CH
2
]
n
Oxetane
CH
2
−O−CH
2
−CH
3
CH
2
−O−CH
2
−CH
3
398.2 9,414 54.1 23.6 [87]
CH
2
N
3
CH
2
N
3
[O − CH
2
− C
− CH
2
]
n
3,3-bis Azido methyl
Oxetane
401.2 53,555 318.8 133.5 [87]
2,6 Dimethyl,1,4
phenylene oxide
CH
3
CH
3
[]
O
n
548.2 5,230 43.6 9.5 [88,89]
2,6 Dimethoxy,1,4
phenylene oxide
OCH
3
CH
3
[]
O
n
560.2 3,184 20.9 5.7 [90]
[(CH
2
)
3
− S]
n
Trimethylene sulfide
363.2 10,460 141.4 28.8 [91]
[ CH
2
− CH
2
−C
]
n
Propanone-1
=
O
>528.2 12,600 225.0 <23.8 [92]
Ethylene azelate
=
O
=
O
[O−C−(CH
2
)
7
−C−O−(CH
2
)
2
]
n
338.2 43,095 138.1 127.6 [93]
Decamethylene adipate
=
O
=
O
[O−C−(CH
2
)
4
−C−O−(CH
2
)
10
]
n
352.7 42,677 150.3 121.0 [94]
THERMODYNAMIC QUANTITIES GOVERNING MELTING / 171
TABLE 11.1. Continued.
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
=
O
=
O
[O−C−(CH
2
)
7
−C−O−(CH
2
)
10
]
n
Decamethylene azelate
342.2 41,840 129.7 121.3 [93]
=
O
=
O
[O−C−(CH
2
)
8
−C−O−(CH
2
)
10
]
n
Decamethylene sebacate
353.2 50,208 147.7 142.2 [95]
Ethylene terephthalate
=
O
=
O
[O−C−−C−O(CH
2
)
2
]
n
−−
613.2 23,430 122.0 38.2 [96–98]
Tetramethylene
terephthalate
=
O
=
O
[O−C−−C−O(CH
2
)
4
]
n
−−
503.2 31,798 144.5 63.2 [99]
Hexamethylene
terephthalate
=
O
=
O
[O−C−−C−O(CH
2
)
6
]
n
−−
433.7 35,564 143.4 82.0 [93]
Decamethylene
terephthalate
=
O
=
O
[O−C−−C−O(CH
2
)
10
]
n
−−
411.2 46,024 151.4 111.9 [93]
Tetramethylene
isophthalate
=
O
=
O
[O−C−−C−O(CH
2
)
4
]
n
−−
425.7 42,258 192.1 99.3 [99,100]
terephthalate
Diethylene glycol
=
O
=
O
[O−C−−C−O−(CH
2
)
2
−O−(CH
2
)
2
]
n
−−
373.2 39,748 168.4 106.5 [101]
β-propiolactone
[C−O−(CH
2
)
2
]
n
O
=
357 8,577 119.1 24.0 [102]
ε-caprolactone
[C−O−(CH
2
)
5
]
n
O
337 16,297 142.9 48.3 [102]
α,α' Dimethyl
propiolactone
[C−O−CH
2
−C]
n
O
=
CH
3
CH
3
542.2 14,853 148.5 27.4 [103–105]
172 / CHAPTER 11
TABLE 11.1. Continued.
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
α,α' Dimethyl
propiolactone
[C−O−CH
2
−C]
n
O
=
H
5
C
2
C
2
H
5
531.2 20,920 163.4 39.4 [106]
α-Methyl, α- N propyl,
β−propiolactone
[C
−
O
−
CH
2
−
C]
n
O
=
CH
3
C
3
H
7
425.2 14,602 114.1 34.3 [107]
Decamethylene
azelamine
N−
(CH
2
)
10
N
−
C
−
(CH
2
)
7
−
C
−
HHO O
=
=
n
487.2 36,819 112.9 75.3 [93]
Decamethylene
sebacamide
N−
(CH
2
)
10
N−
C
−
(CH
2
)
8
−
C
−
HHO O
=
=
n
489.2 34,727 102.7 71.0 [93]
N,N' sebacoyl
piperazine
CH
2
−CH
2
CH
2
−CH
2
N
OO
n
N−C(CH
2
)
8
C
=
=
453.2 25,941 102.9 57.2 [108]
[C
−
(CH
2
)
5
−
N]
n
O
=
H
Caprolactam
g
g
502.2 17,949 158.8 35.7 [109]
Ester amide
h
6-6 526 92,885 188.3 176.6 [110]
Ester amide
h
12-2 517 102,522 194.6 198.3 [110]
Ester amide
h
12-6 487 116,315 200.8 238.8 [110]
Ester amide
h
12-12 470 140,164 211.3 298.2 [110]
Urethane
i
n ¼ 2 440.2 44,267 192.5 100.6 [111]
n ¼ 5 428.2 45,522 167.4 106.3 [111]
n ¼ 10 427.2 61,505 179.8 144.0 [111]
THERMODYNAMIC QUANTITIES GOVERNING MELTING / 173
TABLE 11.1. Continued.
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
Urethane
j
n ¼ 5 462.2 54,810 154.8 118.6 [111]
n ¼ 10 465.2 70,961 167.4 152.5 [111]
Vinyl fluoride
F
[CH
2
− CH]
n
470.2 7,531 163.7 16.0 [112]
Vinylidene
fluoride
F
F
[CH
2
− C]
n
⎯
⎯
(a) 532.2 6,694 104.6 12.6 [113–115]
Chloro trifluoro
ethylene
F
Cl
F
F
[C
− C]
n
483.2 5,021 43.1 10.4 [116]
Vinylidene chloride
Cl
Cl
[CH
2
− C]
n
468.2 5,623 58.6 12.0 [117]
Dimethyl siloxane
k
n
CH
3
CH
3
− Si − O −
233 2,767 36.7 11.9 [118]
Tetramethyl-p -silphenylene siloxane
n
CH
3
CH
3
CH
3
CH
3
− Si Si − O −
433.2 11,340 54.4 26.2 [119]
2,2'-bis 4,4'(Oxyphenyl)
propane carbonate
CH
3
CH
3
COOC
n
O
=
590.2 34,008 133.9 57.6 [120,121]
O
Cellulose tributyrate
l
X= −
O − C − (CH
2
)
2
CH
3
480.2 12,552 33.7 26.1 [122]
174 / CHAPTER 11
TABLE 11.1. Continued.
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
Cellulose trinitrate
l
X= −
O − NO
2
>973 3,765–6,276 12.6–21.1 3.9–6.4 [123]
Cellulose (2.44) nitrate
l
Cellulose [O
− NO
2
]
2.44
890.2 5,648 21.5 6.3 [124]
O
Cellulose tricaprylate
l
X= −
O − C − (CH
2
)
6
CH
3
389.2 12,970 24.0 33.3 [125]
Collagen 418.2
m
9,414 100.4 22.5 [126]
a
The equilibrium melting temperature of isotactic polypropylene is still debated between values ranging from 458 to 493 K. See
for example refs [200, 201, 202].
b
516.2 K is the highest T
m
observed [44]. Therefore, T
0
m
should be greater.
c
Average value of references cited.
d
Extrapolated equilibrium melting temperatures of the a and b forms are very close to one another. Depending on the method
used they are close to 545 or 573 K [203].
e
Extrapolated to all trans.
f
Obtained by direct determination of activity coefficients in polymer-diluent mixtures.
g
That these data belong to the g form is deduced from the reported specific volumes (V
g
c
) and the heat of fusion data of Fig. 13 of
von K-H Illers et al. ref [166].
h
Ester-amide (n–m)
− C − N − (CH
2
)
6
N − C − O(CH
2
)
n
− O −
=
=
=
=
O
O
O
i
O
C
C
N
H
HH
N
O
C
H
O
x
O
O
C
(CH
2
)
m
(CH
2
)
n
x
OH
−C−N−−CH
2
−
−N−C−O−(CH
2
)
n
−O−
OH
x
j
k
The value of DH
u
was determined with only one diluent. It was originally reported in terms of calories per mole of chain atoms
and misinterpreted. The value in joules per gram was subsequently clarified by M. I. Arangurem [204].
O
O
H
H
CH
2
X
l
H
H
X
n
X
m
Extrapolated from the melting point of glycol mixtures.
THERMODYNAMIC QUANTITIES GOVERNING MELTING / 175
TABLE 11.2. The
`
rmodynamic quantities determined by the use of Clapeyron equation [Eq. (11.7)]
Polymer
T
0
m
a
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
Ethylene
[CH
2
]
n
414.6 4,059 289.9 9.8 [127]
Isot.-propylene (γ)
[CH
2
− CH]
n
CH
3
460.2 6,300
b
7,980
b
150
190
13.7
17.3
[128]
[128]
Isot.-butene-1 (I)
(II)
[CH
2
− CH]
n
CH
3
CH
2
406.2
392.9
7,782
c
7,531
c
138.7
134.2
19.2
19.2
[129,130]
[CH
− CH
2
]
n
CH
3
CH
3
4-Methyl pentene-1
CH
2
CH
506.2 5,205 61.9 10.3 [131]
[CH
2
− O]
n
Methylene oxide
456.2 11,673 389.1 25.6 [132]
[CH
2
− CH
2
− O]
n
Ethylene oxide
339.2 9,037 205.4 26.6 [133]
[(CH
2
)
4
− O]
n
Tetramethylene oxide
315.9 14,728 204.6 46.6 [133]
[ C
− O − (CH
2
) ]
n
Glycolic acid
O
−−
504.6 10,626 183.2 21.1 [134]
[O
− C − (CH
2
)
4
− C − O − CH
2
]
n
Ethylene adipate
OO
326.2 20,150 127.5 61.8 [135]
[O
− C − (CH
2
)
5
− C − O − CH
2
]
n
Ethylene pimelate
OO
309.2 27,489 159.8 88.9 [135]
[O
− C − (CH
2
)
6
− C − O − CH
2
]
n
Ethylene suberate
OO
336.2 24,451 131.4 72.8 [135]
176 / CHAPTER 11
TABLE 11.2. Continued.
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) References
Ethylene azelate
OO
[O−C−(CH
2
)
7
−C−O−CH
2
]
n
320.2 40,488 202.4 126.4 [135]
Ethylene terephthalate
O
[ O
O
−C
−−
−C
−−O(CH
2
)
2
]
n
535.2 26,150 136.2 48.9 [136]
OOH
Hexamethylene
Adipamide α
2
[−N−(CH
2
)
6
−N− C−(CH
2
)
4
−C−]
n
H
542.2 43,367 191.9 79.9 [137]
Tetrafluoro ethylene (virgin) 619.2 5,105 102.1 8.2 [138]
Tetrafluoro ethylene
(melt cured)
[C]
n
F
F
601.2 4,632 92.6 7.7 [138]
aryl-ether−ether−
ketone
O
−O
−
−O
−
−C −
−
n
611.2 47,359 164.4 77.5 [139]
2,2'bis(4,4' Oxyphenyl)
propane carbonate
O
−O −C
−
−O −C−
−
n
CH
3
CH
3
506.2 39,497 155.5 78.0 [140]
a
Melting temperature actually used in calculation.
b
Both values are quoted.
c
Average values.
THERMODYNAMIC QUANTITIES GOVERNING MELTING / 177
TABLE 11.3. Unique values of thermodynamic parameters determined by indirect methods.
Polymer
T
0
m
(K)
DH
u
(J=mol)
DH
u
=M
0
(J=g)
DS
u
(J=K mol) Method References
Synd.-propylene
[CH
2
− CH]
n
CH
3
455.2
a
8,274 196.7 18.2 DSC-x ray [141,142]
Methyl methacrylate
[CH
2
− C]
n
CH
3
CH
3
C
=
O
Isot.
Synd.
411.2
>397.5
5,021 50.2 12.2 DSC-x ray
DSC-Mn
[143]
[144]
Synd.-vinyl chloride
[CH
2
− CH]
n
CI
538.2
b
658.2
c
4,937
6,694
79.0
107.1
9.2
10.2
DSC-x ray
DSC-x ray
[145]
Octamethylene oxide
[(CH
2
)
8
− O]
n
356.2 32,401 253.1 91.0 DSC-density [146]
3-Tertbutyl oxetane
H
CH
3
− C − CH
3
[O − CH
2
− C − CH
2
]
n
CH
3
350.2 5,021 45.2 14.3 DSC-x ray [147]
1,4 Phenylene ether
[]
O
n
535.2 7,824 85.0 14.6 DSC-x ray [148]
2,6 diphenyl
1,4 phenylene ether
[]
O
n
757.2 12,201 50.0 16.1 DSC-x ray [149]
Ethylene sulfide
[CH
2
− CH
2
− S]
n
489.2 14,226 237.1 29.1 (T
m
-mol. wt)
d
[150]
3,3’-Dimethyl thietane
CH
3
CH
3
S − CH
2
− C − CH
2
n
−−
286.2 5,442 56.7 19.0 DSC-x ray [151]
p-Phenylene sulfide
S
[
]
n
621.7 12,092 112.0 19.4 DSC-x ray [152–154]
Ethylene sebacate
OO
[O − C − (CH
2
)
8
− C − O − (CH
2
)
2
]
n
356.2 36,765 161.2 103.2 DSC-density [155]
178 / CHAPTER 11