Polyethylene

1.	Introduction
2.	Properties of Polyethylenes
2.1.	Molecular Structure and Morphology
2.2.	General Properties
2.3.	High Molecular Mass (Bimodal) Polyethylene (HMWPE)
2.4.	Ultra High Molecular Mass Polyethylene (UHMWPE)
2.5.	Properties of Ethylene Copolymers
3.	Polymerization Chemistry
3.1.	Free-Radical Catalysis
3.1.1.	Introduction
3.1.2.	Copolymerization
3.2.	Coordination Catalysis
3.2.1.	Phillips Catalysts
3.2.2.	Ziegler Catalysts
3.2.3.	Single-Site Catalysts (Metallocenes)
3.2.4.	Copolymerization
4.	Raw Materials
4.1.	Ethylene
4.2.	Comonomers
4.3.	Other Materials
5.	Production Processes
5.1.	High-Pressure Process
5.1.1.	Autoclave Reactor
5.1.2.	Tubular Reactor
5.1.3.	High-Pressure Copolymers
5.1.4.	Linear Low-Density Polyethylene (LLDPE)
5.2.	Suspension (Slurry) Process
5.2.1.	Autoclave Process
5.2.2.	Loop Reactor Process
5.3.	Gas-Phase Process
5.4.	Solution Process
6.	Uses
6.1.	Film
6.2.	Extrusion Coating
6.3.	Blow Molding
6.4.	Injection Molding
6.5.	Pipe
6.6.	Wire and Cable Insulation
6.7.	Ethylene Copolymers
6.8.	Ultra High Modulus Polyethylene Fibers
6.9.	Joining Polyethylene
7.	Chemically Modified Polyethylenes
7.1.	Cross-Linked Polyethylene
7.2.	Chlorinated Polyethylene
7.3.	Fluorinated Polyethylene
8.	Environmental Aspects
8.1.	Manufacture
8.2.	Polymer Disposal and Recycling

General References

1 Golden Jubilee Conference, Polyethylenes 1933 – 1983, Preprints, The Plastics and Rubber Institute, London 1983.
Google Scholar
2 Golden Jubilee Conference, Polyethylenes 1933 – 1983, Plenary Papers, The Plastics and Rubber Institute, London 1983.
Google Scholar
3 R. B. Seymour, T. Cheng (eds.): History of Polyolefins, Reidel Publ. Co., Dordrecht 1986.
Google Scholar
4 F. M. McMillan: The Chain Straighteners, Macmillan, London 1981.
Google Scholar
5 R. A. V. Raff, K. W. Doak: Crystalline Olefin Polymers, parts I and II, Interscience Publishing, London 1965.
Google Scholar
6 A. Renfrew, P. Morgan (eds.): Polythene, 2nd ed., Iliffe, London 1960.
Google Scholar
7 S. van der Ven: Polypropylene and other Polyolefins, Elsevier, Amsterdam 1990.
Google Scholar
8 Aufbereiten von Polyolefinen, VDI-Verlag, Düsseldorf 1984.
Google Scholar
9 P. Ehrlich, G. A. Mortimer: “Fundamentals of the Free Radical Polymerization of Ethylene,” Adv. Polym. Sci. 7 (1970) 386 – 448.
10.1007/BFb0051053
CAS Google Scholar
10 Papers and Proceedings, Polycon '84 LLDPE, Plastics and Rubber Institute, London 1984.
Google Scholar
11 Conference Papers, Polyethylene — The 1990s and Beyond, Plastics and Rubber Institute, London 1992.
Google Scholar
12 G. W. Gilby: Ethylene-Vinyl Acetate Copolymers, in A. Whelan, K. S. Lee (eds.): Developments in Rubber Technology-3, Applied Science Publishers, Barking 1983, chap. 4.
Google Scholar
13 J. Boor Jr. Ziegler-Natta Catalysis and Polymerization, Academic Press, New York 1979.
Google Scholar
14 W. Kaminsky, H. Sinn (eds.): Transition Metals and Organometallics as Catalysts for Olefin Polymerization, Springer Verlag, Berlin 1988.
10.1007/978-3-642-83276-5
Google Scholar
15 R. P. Quirk (ed.): Transition Metal Catalyzed Polymerizations, Cambridge University Press, Cambridge 1988.
Google Scholar
16 F. J. Karol, Catal. Rev.-Sci. Eng. 26 (1984) no. 3, 4, 557 – 595.
Web of Science® Google Scholar
17 P. J. T. Tait: Ziegler-Natta and Related Catalysts, in R. N. Haward (ed.): Developments in Polymerization-2, Applied Science Publishers, London 1979, chap. 3.
Google Scholar
18 Papers presented at MetCon 96, Worldwide Metallocene Conference, Houston, TX, USA 1996.
Google Scholar
19 A. D. Horton: “Metallocene Catalysis: Polymers by Design?”, Trends Polym. Sci. 2 (1994) no. 5, 158 – 166.
CAS Google Scholar
20 M. Bochmann: Cationic Group 4 Metallocene Complexes and their Role in Polymerisation Catalysis: the Chemistry of Well-Defined Ziegler Catalysts. Chem. Soc. Dalton Trans., 1994 ,255 – 270.
Google Scholar

Specific References

21 W. L. Mattice, F. C. Stehling, Macromolecules 14 (1981) 1479.
10.1021/ma50006a066
CAS ADS Web of Science® Google Scholar
22 see General Ref. (7).
Google Scholar
23 F. M. Mirabella, E. A. Ford, J. Polym. Sci. Polym. Phys. Ed. 25 (1987) 777.
10.1002/polb.1987.090250407
CAS ADS Web of Science® Google Scholar
24 A. Keller, Philos. Mag. 2 (1957) 1171.
10.1080/14786435708242746
CAS ADS Web of Science® Google Scholar
Prog. Phys. 31 (1968) 623
10.1088/0034-4885/31/2/304
CAS ADS Web of Science® Google Scholar
See General Ref. (1), paper D1.
Google Scholar
25 K. Bergmann, K. Nawotki, Kolloid Z. 219 (1967) 132.
10.1007/BF02086201
CAS Web of Science® Google Scholar
26 S.-D. Clas, D. C. McFaddin, K. E. Russell, J. Polym. Sci. Part B 25 (1987) 1057.
10.1002/polb.1987.090250507
CAS ADS Web of Science® Google Scholar
27 R. S. Stein, R. Prud'homme, J. Polym. Sci. Part B 9 (1971) 595.
10.1002/pol.1971.110090808
CAS ADS Web of Science® Google Scholar
28 H. Schonhorn, H. L. Frisch, R. V. Albarino, J. Polym. Sci. Polym. Phys. Ed. 11 (1973) 1013.
10.1002/pol.1973.180110516
CAS Web of Science® Google Scholar
29 L. Wild, T. Ryle, D. Knobeloch, J. Polym. Sci. Polym. Phys. Ed. 20 (1982) 441.
10.1002/pol.1982.180200307
CAS ADS Web of Science® Google Scholar
G. Glöckner, J. Appl. Polym. Sci.: Appl. Polym. Symp. 45 (1990) 1 (review).
10.1002/app.1990.070450002
Google Scholar
30 M. Aroca Hervás, Revista de Plásticos Modernos (1996) no. 481, 61 – 68.
Google Scholar
31 Du Pont, US 4 076 698, 1957 (A. W. Anderson, G. S. Stamatoff).
Google Scholar
32 M. Philip, I. M. Ward, B. Parsons, J. Mat. Sci. 21 (1986) 879.
10.1007/BF01117368
CAS ADS Web of Science® Google Scholar
33 L. C. E. Struik, Polymer 28 (1987) 1521.
10.1016/0032-3861(87)90353-3
CAS Web of Science® Google Scholar
34 P. C. Powell: Engineering with Polymers, Chapman and Hall, London 1983, p. 130.
Google Scholar
35 Exxon Chemicals, Escorene Ultra EVA Copolymers, company brochure, Kraainem, Belgium.
Google Scholar
36 J. Scheirs, L. L. Böhm, J. C. Boot, P. S. Leevers, Trends Polym. Sci. 4 (1996) no. 12, 408 – 415.
CAS Web of Science® Google Scholar
37 Y-L. Huang, N. Brown, J. Polym. Sci. Part B 29 (1991) 129 – 137;
10.1002/polb.1991.090290116
CAS ADS Web of Science® Google Scholar
38 Hoechst, Hostalen GUR Ultra High Molecular Weight Polyethylene, company brochure, Frankfurt 1989.
Google Scholar
39 K. S. Whiteley in General Ref. (1), paper B2.
Google Scholar
40 L. J. Young in Brandrup and Immergut (eds.): Polymer Handbook, 2nd ed., Wiley, New York 1975, Section II, p. 105.
Google Scholar
41 L. J. Young, J. Polym. Sci. 54 (1961) 411.
10.1002/pol.1961.1205416011
CAS ADS Web of Science® Google Scholar
42 DSM, Teamex Octene based VLDPE, company brochure, Geleen, The Netherlands, 1990.
Google Scholar
43 R. J. Statz in General Refs. (1), paper B5 and (3), chap. 11.
Google Scholar
44 W. J. MacKnight, T. R. Earnest, Macromol. Rev. 16 (1981) 41.
10.1002/pol.1981.230160102
CAS Web of Science® Google Scholar
45 P. Mapleston, Modern Plastics International, June 1996, 56 – 61.
Google Scholar
46 Shell, US 4 808 699, 1987 (J. A. M. Van Broekhoven, M. J. Doyle).
Google Scholar
47 Hoechst, US 5 610 253, 1995 (W. Hatke, F. Osan).
Google Scholar
48 A. Gilchrist (ICI): unpublished work, 1965.
Google Scholar
49 R. Spahl, G. Luft, Ber. Bunsenges. Phys. Chem. 86 (1982) 621.
10.1002/bbpc.19820860709
CAS Web of Science® Google Scholar
G. Jungermann, G. Luft, Ber. Bunsenges. Phys. Chem. 91 (1987) 541.
10.1002/bbpc.198700008
CAS Web of Science® Google Scholar
50 K. E. Weale: Chemical Reactions at High Pressures, Spon, London 1967.
Google Scholar
51 P.-C. Lim, G. Luft, Makromol. Chem. 184 (1983) 849.
10.1002/macp.1983.021840419
CAS Web of Science® Google Scholar
52 M. J. Roedel, J. Am. Chem. Soc. 75 (1953) 6110.
10.1021/ja01120a005
CAS Web of Science® Google Scholar
53 M. E. A. Cudby in General Ref. (1), paper D6.
Google Scholar
54 G. Luft, R. Kämpf, H. Seidl, Angew. Makromol. Chem. 108 (1982) 203.
10.1002/apmc.1982.051080113
CAS Web of Science® Google Scholar
55 L. Nicolas, J. Chim. Phys. 55 (1958) 185.
CAS Web of Science® Google Scholar
56 H. Tobita, J. Polym. Sci. Polym. Phys. 33 (1995) 841 – 853.
10.1002/polb.1995.090330513
CAS ADS Web of Science® Google Scholar
57 R. A. Jackson, P. A. Small, K. S. Whiteley, J. Polym. Sci. Polym. Chem. Ed. 11 (1973) 1781.
10.1002/pol.1973.170110802
CAS ADS Web of Science® Google Scholar
58 P. Ehrlich et al., A. I. Ch. E. Journal 22 (1976) no. 3, 463.
Web of Science® Google Scholar
59 Y. Tatsukami, T. Takahashi, H. Yoshioka, Makromol. Chem. 181 (1980) 1107.
10.1002/macp.1980.021810515
CAS Web of Science® Google Scholar
60 Peroxid Chemie, Organic Peroxides P 3.2.1 (Half-Lifetimes), A 3.7.4 (Ethylene Polymerization I, II), company brochure, München.
Google Scholar
61 W. W. Lawrence, S. E. Cook: Loss Prevention S.10, Chemical Engineering Progress Technical Manual, A.I.Ch.E. 1967.
Google Scholar
62 D. G. H. Ballard et al., Polymer 15 (1974) 169.
10.1016/0032-3861(74)90196-7
CAS Web of Science® Google Scholar
63 M. P. McDaniel, M. B. Welch, J. Catal. 82 (1983) 98.
10.1016/0021-9517(83)90121-5
CAS Web of Science® Google Scholar
64 C. E. Marsden: Paper 4A3 in General Ref. (11).
Google Scholar
65 M. P. McDaniel, M. B. Welch, M. J. Dreiling, J. Catal. 82 (1983) 118.
10.1016/0021-9517(83)90123-9
CAS Web of Science® Google Scholar
66 M. P. McDaniel, M. M. Johnson, Macromolecules 20 (1987) 773.
10.1021/ma00170a012
CAS ADS Web of Science® Google Scholar
67 F. J. Karol in General Ref. (16), p. 573.
Google Scholar
68 V. A. Zakharov, Yu. I. Yermakov, Cat Rev.-Sci. Eng. 19 (1979) no. 1, 67.
10.1080/03602457908065101
CAS Web of Science® Google Scholar
69 W. L. Carrick et al., J. Polym. Sci. A1, 10 (1972) 2609.
10.1002/pol.1972.150100909
CAS ADS Web of Science® Google Scholar
70 L. M. Baker, W. L. Carrick, J. Org. Chem. 35 (1970) 714.
10.1021/jo00828a051
Web of Science® Google Scholar
71 F. J. Karol et al., J. Polym. Sci. A1, 10 (1972) 2621.
10.1002/pol.1972.150100910
CAS ADS Web of Science® Google Scholar
72 Union Carbide, NL 68 16149, 1968.
Google Scholar
73 Standard Oil (Indiana), US 2 692 257, 1951 (A. Zletz).
Google Scholar
74 B. Diedrich, Appl. Polym. Symp. 26 (1975) 1.
CAS Google Scholar
75 Hoechst, DE 1 595 666, 1966 (B. Diedrich, K. D. Keil).
Google Scholar
76 Solvay, BE 650 679, 1963.
Google Scholar
77 Union Carbide, US 4 293 673, 1979 (A. D. Hamer, F. J. Karol).
Google Scholar
78 Stamicarbon, BE 751 315, 1969.
Google Scholar
79 ICI, GB 1 253 046, 1968 (J. C. Greaves, W. G. Oakes).
Google Scholar
80 Du Pont, GB 1 209 825, 1967.
Google Scholar
81 G. Henrici-Olivé, S. Olivé, Adv. Polym. Sci. 15 (1974) 1 – 30.
10.1007/3-540-06910-0_1
CAS Google Scholar
82 J. Herwig, W. Kaminsky, Polym. Bull. 9 (1983) 464.
10.1007/BF00265329
CAS Web of Science® Google Scholar
83 W. Kaminsky: Paper 5.1 in General Ref. (1).
Google Scholar
84 For a review of earlier work, see General Ref. (20).
Google Scholar
85 BASF, US 4 404 344, 1981 (H. W. Sinn, W. O. Kaminsky, H. C. Vollmer, R. O. H. H. Woldt)
Google Scholar
86 L. Resconi, S. Bossi, L. Abis, Macromolecules 23 (1990) 4489 – 4491.
10.1021/ma00222a029
CAS ADS Web of Science® Google Scholar
87 P. J. Tait, M. G. K. Monteiro, M. Yang, J. L. Richardson: “Some Recent Advances in Supported Metallocene Catalysts,” in General Ref. (20).
Google Scholar
88 M. Arndt, I Beulich, W. Kaminsky: “C1 Symmetric Metallocenes for Olefin Copolymerization: Catalytic Performance and Polymer Properties,” in General Ref. (18).
Google Scholar
89 Dow, US 5 064 802, 1990 (J. C. Stevens, D. R. Neithamer).
Google Scholar
Exxon, US 5 026 798, 1990 (J. A. M. Canich).
Google Scholar
90 Dow, EP 416 815, 1990 (J. C. Stevens, F. J. Timmers, D. R. Wilson, G. F. Schmidt, P. N. Nickias, R. K. Rosen, G. W. Knight, S. Lai).
Google Scholar
91 M. Galimberti, T. Dall'Occo, F. Piemontesi, I. Camurati, G. Collina: “Metallocenes and Alumoxanes: Do they determine the Copolymer's Fingerprint,” in General Ref. (18).
Google Scholar
92 Exxon, US 4 752 597, 1987 (H. W. Turner).
Google Scholar
93 Dow, US 5 064 802, 1990 (J. C. Stevens, D. R. Neithamer).
Google Scholar
94 P. Mapleston, Modern Plastics International 21 (1991) no. 3, 63;
Google Scholar
19 (1989) no. 11, 36.
Google Scholar
95 N. Baron: “A New Polyolefin Product Family Based on EXPOL Catalyst Technology”, paper presented at 2nd International Symposium on High Pressure Chemical Engineering, Erlangen 1990.
Google Scholar
96 Exxon, US 4 530 914, 1983 (J. A. Ewen, H. C. Welborn).
Google Scholar
97 Phillips, US 5 594 078, 1994 (M. B. Welch, R. L. Geerts, S. J. Palackal, T. M. Pettjohn).
Google Scholar
98 G. A. M. Diepen, M. A. de Zeeuw in S. A. Miller (ed): Ethylene and its Industrial Derivatives, Ernest Benn, London 1969.
Web of Science® Google Scholar
99 D. Commereuc et al., Hydrocarbon Process. 63 (1984) no. 11, 118.
CAS Web of Science® Google Scholar
100 A. Chauvel, Y. Chauvin, J. Gaillard, J. Leonhard: LLDPE in Europe, Preprints to Conference, Madrid 1986, Plastics and Rubber Institute.
Google Scholar
101 ICI, GB 1 456 841, 1973 (R. R. Cooper, K. S. Whiteley).
Google Scholar
102 Y. V. Kissin, D. L. Beach, J. Polym. Sci., Polym. Chem. Ed. 24 (1986) 1069.
10.1002/pola.1986.080240601
CAS ADS Web of Science® Google Scholar
103 W. R. D. Manning, S. Labrow: High Pressure Engineering, Chemical and Process Engineering Series, Leonard Hill, London 1971.
Google Scholar
104 B. C. Crossland: “Philosophical Thoughts on Standards for High Pressure Systems,” ASME Conference on Pressure Vessels and Piping, Chicago 1986.
Google Scholar
105 K. E. Bett, B. C. Crossland, H. Ford, A. K. Gardner in General Ref. (1), paper B1.
Google Scholar
106 Esso, Research and Engineering, DT 2 151 649, 1970 (K. L. O'Hara).
Google Scholar
107 J. P. Machon in Ref. (15) p. 344.
Google Scholar
108 Charbonnages de France, GB 2 141 491, 1983 (D. Grasset).
Google Scholar
109 Charbonnages de France, US 4 105 609, 1978 (J. P. Machon, B. Levresse, P. Gloriod).
Google Scholar
110 K. Ziegler, GB 799 392, 1953.
Google Scholar
111 J. P. Hogan in General Ref. (1), paper B3.
Google Scholar
112 Hydrocarbon Process 62 (1983) no. 11;
Google Scholar
64 (1985) no. 11.
Google Scholar
113 L. Böhm, Chem.-Ing.-Tech. 56 (1984) 674.
10.1002/cite.330560904
Web of Science® Google Scholar
114 Hoechst, DE 1 720 611, 1967 (B. Diedrich, K. D. Keil).
Google Scholar
115 Ullmann, 4th ed., 19 p. 185.
Google Scholar
116 Phillips Petroleum, US 3 405 109, 1960 (R. G. Rohlfing).
Google Scholar
117 R. B. Staub in General Ref. (1), paper 5.4.
Google Scholar
118 R. B. Staub: LLDPE in Europe, Preprints to Conference, Madrid 1986, Plastics and Rubber Institute, paper 1.
Google Scholar
119 Union Carbide, US 4 003 712, 1975 (A. R. Miller).
Google Scholar
120 D. E. James in Ref. (116), paper 2.
Google Scholar
Union Carbide, US 4 543 399, 1984 (J. M. Jenkins et al.).
Google Scholar
121 T. K. Moynihan in General Ref. (1), paper 5.3.1.
Google Scholar
122 Mod. Plast. Int. 27 (1997) no. 1 .
Google Scholar
123 C. Krumm: Polycon '84, Papers and Proceedings, Plastics and Rubber Institute, London 1984, paper D.
Google Scholar
124 Miller et al., Plast. Eng. 42 (1986) 37.
Google Scholar
125 S. Bork, Kunststoffe 74 (1984) 474.
CAS Web of Science® Google Scholar
126 G. R. Chapman, D. E. Priester, R. D. Souffie: RETEC Polyolefins V, Houston 1987, Society of Plastics Engineers, Brookfield, Conn., p. 271.
Google Scholar
127 D. F. Klein in Ref. (126), p. 285.
Google Scholar
128 W. A. Fraser, W. B. Herdle in Ref. (126) p. 301.
Google Scholar
129 R. D. Leaversuch, Modern Plastics International 20 (1990) no. 9, 55.
Google Scholar
130 J-M. Yernaux: Paper S3B in General Ref. (11).
Google Scholar
131 D. W. Woods, I. M. Ward, Plastics, Rubber and Composites Processing and Applications 18 (1992) no. 4, 255 – 261.
CAS Web of Science® Google Scholar
132 A. B. Brennan: “Surface Modification of Polyethylene Fibres for Enhanced Performance in Composites”, Trends Polym. Sci. 3 (1995) no. 1, 4 – 11.
Google Scholar
133 I. M. Ward: “A Review of Recent Developments in the Processing and Properties of Oriented Polyethylene”, Plastics, Rubber and Composites Processing and Applications 19 (1993) no. 1, .
Google Scholar
134 D. C. Prevorsek: “Preparation, Structure, Properties and Applications of Gel-spun Ultrastrong Polyethylene Fibers”, Trends Polym. Sci. 3 (1995) no. 1, 12 – 21.
Google Scholar
135 Rigidex HDPE Technical Manual No. 22 (BP).
Google Scholar
136 Loctite Data Sheets: Primer 770 and Adhesive 406.
Google Scholar
137 B.-A. Sultan, M. Palmlöf in General Ref. (11), paper 4B/3
Google Scholar
138 B. E. Roberts, S. Verne in General Ref. (1), paper C3.1.
Google Scholar
139 B. J. Lyons in General Ref. (1), paper C3.2.
Google Scholar
140 L. Panzer: ANTEC '88, Conference Proceedings Society of Plastics Engineers, Brookfield, Conn., p. 1421.
Google Scholar
141 D. C. Eagles, Wire Technology International 18 (1990) no. 6, 15.
Google Scholar
Mitsubishi, US 4 413 066, 1981 (T. Isaka, M. Ishioka, T. Shimada, T. Inoue).
Google Scholar
142 Hoechst, Hostapren Chlorinated Polyethylene, company brochure, Frankfurt 1986.
Google Scholar
143 D. A. Buck, F. A. Milcetich, P. D. Marsh, K. J. Kallish: ANTEC '86, Conference Proceedings, Society of Plastics Engineers, p. 803.
Google Scholar
Air Products, US 3 862 242, 1972 (R. C. Terrell).
Google Scholar
144 G. Scott in S. A. Barenberg, J. L. Brash, R. Narayan, A. E. Redpath (eds.): Degradable Materials, CRC Press, Boca Raton 1990, p. 143.
Web of Science® Google Scholar
145 W. J. Maddever, P. D. Campbell in Ref. (144), p. 237.
Google Scholar
146 I. Dent, S. Hardman: “Plastics Waste Recycling — an Alternative Approach”, I.Chem.E. Environmental Protection Bulletin Issue 044, 1996.
Google Scholar

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