Polyurethane

L. S. RAMANATHAN, S. SIVARAM, AND MUNMAYA K. MISHRA

ACRONYMS PU, PUR
CLASS Polyurethanes
STRUCTURE O O
= =
O[( R
/
)
x
OCNHRNHCO[
n

R = isocyanate unit
R
/
= polyol segment
MAJOR APPLICATIONS Polyurethane exible foams nd applications in protective
packaging, gaskets, textile laminates, protective cushioning in automobiles, and
two component injection-grouting resins. Rigid polyurethane foams are used as
thermal insulating materials in refrigerators, freezers, and water heaters. It is also
used as a roof proong material.
PROPERTIES OF SPECIAL INTEREST Excellent dampening property, good mechanical and
physical properties even at low temperatures, high combustion resistance, and low
thermal conductivity.
PROPERTY UNITS CONDITIONS VALUE REFERENCE
Density g cm
3
4,4
/
-Diphenylmethane diisocyanate
(MDI)/1,4-butane diol (BD)
1.297 (1)
Flory-Huggins polymer solvent
interaction parameter
TDI/1,4-BD (DMF) 0.122 (2)
Unit cell dimensions
Sample Lattice Cell dimensions (A

) Cell angles (degrees) Reference

a b c
Hexamethylene diisocyanate (HMDI)/
Ethylene glycol (EG)
Triclinic 4.59 5.14 13.9 90 90 119 (3)
HMDI/1,3-propane diol (PD) Monoclinic 4.70 8.36 33.9 115 (3)
HMDI/BD Triclinic 4.98 4.71 19.4 116 105 109 (3)
HMDI/1,5-pentane diol (PtD) Monoclinic 4.70 8.36 39.0 115 (3)
HMDI/1,6-hexane diol (HD) Triclinic 5.05 4.54 21.9 112 108 108 (3)
Trimethylene diisocyanate (TMDI)/BD Triclinic 5.06 5.04 30.1 112 113 110 (4)
TMDI/HD Triclinic 5.04 5.04 34.6 111 111 111 (4)
MDI/BD Triclinic 5.2 4.8 35 115 121 85 (5, 6)
MDI/BD Triclinic 4.92 5.66 38.4 124 104 86 (7)
870 Polymer Data Handbook. Copyright #1999 by Oxford University Press, Inc. All rights reserved.
Conformational characteristics
Sample Solvent Mark-Houwinck parameters [R
2
)aM[
1a2
10
9
Reference
K 10
4
(ml g
1
) a
Toluene diisocyanate
(TDI)/BD
5.4 0.74 (2)
MDI/EG 100 DMF 3.64 0.71 10.11 (8)
95/5 DMF/acetone 6.29 0.65 10.19 (8)
90/10 DMF/acetone 7.19 0.63 10.25 (8)
85/15 DMF/acetone 10.02 0.59 10.04 (8)
79/21 DMF/acetone 14.19 0.56 9.97 (8)
71/29 DMF/acetone 30 0.50 (8)
MDI/BD DMA (at 258C) 870 1.43 (9)
Refractive index gradient
Sample Condition dnadc (ml g
1
) Second virial
coefcient
Reference
Solvent ! (nm) Temp (8C) A
2
10
4
TDI/BD DMF 546 0.14 (2)
MDI/1,6-HD DMF/acetone 0.1590.203
+
3.04.5
+
(10)
DMF/toluene 0.1230.154
+
2.38.0
+
(10)
+
Variable with respect to DMF volume fraction.
PROPERTY UNITS CONDITIONS VALUE REFERENCE
Heat of fusion kJ mol
1
MDI/BD 5.3 (9)
Heat capacity cal g
1
8C
1
HMDI/BD (11)
50 to 108C 0.422
451208C 0.495
1952108C 0.665
HMDI/DEG
50 to 58C 0.422
501008C 0.512
1401608C 0.623
Crystallization half time min HMDI/BD 6 (12)
HMDI/diethylene glycol (DEG) 10.5
Crystallization enthalpy cal cm
3
HMDI/BD 40 (12)
HMDI/DEG 45
Glass transition K HMDI/BD 295 (12)
temperature HMDI/DEG 272 (12)
HMDI/octauoro1,6-hexane diol (OFHD) 271 (13)
MDI/EG 363 (14)
Desmodur/1,6-HD 322 (15)
Desmodur/cyclohexane dimethanol (CHDM) 302 (15)
Polymer Data Handbook. Copyright # 1999 by Oxford University Press, Inc. All rights reserved. 871
Polyurethane
PROPERTY UNITS CONDITIONS VALUE REFERENCE
Melting temperature K HMDI/BD 476 (12)
HMDI/DEG 396 (12)
HMDI/OFHD 399 (13)
TDI/EG 453 (14)
MDI/EG 498 (14)
Optical properties
System Temp. (8C) Solvent Optical rotation [[
D
Reference
MDI/(1S,2S)-diphenyl propane diol 25 DMSO 71.6 (16)
HMDI/(1S,2S)-diphenyl propane diol 25 DMSO 14.7 (16)
HMDI/(2R,4R)-pentanediol 25 DMSO 80.6 (16)
MDI/(1S,2S)-()-2-acetamido-1-phenyl-1,3-propanediol 25 DMF 24.6 (17)
TDI/(1S,2S)-()-2-acetamido-1-phenyl-1,3-propanediol 25 DMF 20.6 (17)
PROPERTY UNITS CONDITIONS VALUE REFERENCE
Photoconductivity ohms
1
cm
1
Polyurethane with pendant
chromophore
1X3 10
13
(18)
Refractive index Polyurethane with pendant
chromophore
(18)
At 532 nm 1.879
At 690 nm 1.812
At 1,064 nm 1.763
Water vapor absorption % MDI/EG 2.5 (14)
Solubility parameter (MPa)
1a2
MDI/BD 27 (1)
MDI/EG 21 (19)
Elongation % MDI/EG 36 (14)
Adhesion strength psi Desmodur/1,6-HD 220 (15)
Desmodur/CHDM 220
REFERENCES
1. Camberlin, Y., and J. P. Pascaut. J. Polym. Sci., Polym. Phys. Ed. 22 (1984): 1,835.
2. Malichenko, B. F., et al. Polym. Sci. USSR 9 (1967): 2,975.
3. Sato, Y., S. Nansai, and S. Kinoshita. Polym. J. 3 (1972): 113.
4. Sato, Y., K. Hara, and S. Kinoshita. Polym. J. 14 (1982): 19.
5. Blackwell, J., and K. H. Gardner. Polymer 20 (1979): 13.
6. Blackwell, J., and M. Ross. J. Polym. Sci., Polym. Lett. Ed., 17 (1979): 447.
7. Born, L., et al. J. Polym. Sci., Polym. Phys. Ed., 22 (1984): 163.
8. Beachell, H. C., and J. C. Peterson. J. Polym. Sci., Part A-1, 7 (1969): 2,021.
872 Polymer Data Handbook. Copyright #1999 by Oxford University Press, Inc. All rights reserved.
Polyurethane
9. Hwang, K. K. S., et al. J. Polym. Sci., Polym. Chem. Ed., 22 (1984): 1,677.
10. Tuzar, Z., and H. C. Beachell. J. Polym. Sci., Polym. Lett. Ed., 9 (1971): 37.
11. Godovskii, Y. K., and Y. S. Lipatov. Polym. Sci. USSR 10 (1968): 34.
12. Godovskii, Y. K., and G. C. Slomimsky. J. Polym. Sci., Polym. Phys. Ed., 12 (1974): 1,053.
13. Malichenko, B. F., Y. V. Sheludks, and Y. Y. Kercha. Polym. Sci. USSR 9 (1967): 2,808.
14. Lyman, D. J. J. Polym. Sci. 45 (1960): 49.
15. Chung, F. H. J. Appl. Polym. Sci. 42 (1991): 1,319.
16. Kobayashi, T., M. Kakimoto, and Y. Imai. Polym. J. 25 (1993): 969.
17. Chen, Y., and J. Tsay. Polym. J. 24 (1992): 263.
18. Chen, M., et al. Appl. Phys. Lett. 64 (1994): 1,195.
19. Nishimura, H., et al. Polym. Eng. and Sci. 26 (1986): 585.
Polymer Data Handbook. Copyright # 1999 by Oxford University Press, Inc. All rights reserved. 873
Polyurethane