Acrylic Elastomers, Survey
Abstract
Acrylic elastomers have the ASTM designation ACM for polymers of ethyl acrylate and other acrylates, and ANM for copolymers of ethyl or other acrylates with acrylonitrile. In both cases, the M indicates a polymer having a saturated chain of the polymethylene type. The combination of a saturated backbone with polar side chains results in a class of polymers with very good resistance to heat and oil, including oils containing hypoid additives. Acrylic elastomers also have good resistance to sunlight and ozone. Ethylene–acrylic elastomers are discussed in a separate article.
The first acrylic elastomers were homopolymers of either ethyl acrylate or methyl acrylate. Because these had limited utility, particularly for vulcanized applications, various copolymer modifications were developed to improve performance, and there evolved a division of monomers into two types: backbone monomers, which comprise the principal proportion of the monomers and determine the physical and chemical properties of the polymer, and cure-site monomers, which are incorporated to the extent of 1–5% to introduce reactive sites for subsequent cross-linking reactions.
Emulsion and suspension polymerization are the important methods for preparing the elastomers. Their rheological characteristics require processing that addresses contamination more than for other types. Fairly rigid processing is required. The monomers from which these elastomers are prepared have varying degrees of toxicity. Because of the wide property range, the acylic elastomers have many application, eg, coatings, textiles, automotive products, adhesives, paper, and agriculture.
Bibliography
“Acrylic Elastomers” in EPST 1st ed., Vol. 1, pp. 226–246, by Pail Fram, Minnesota Mining and Manufacturing Company.; in EPST 2nd ed., Vol. 1, pp. 306–325, by P. H. Starmer and F. R. Wolf, The BF Goodrich Company
Cited Publications
- 1 ASTM D 1418–81, American Society for Testing and Materials, Philadelphia, Pa., 1981.
- 2 C. H. Fisher, W. C. Mast, C. E. Rehberg, and L. T. Smith, Ind. Eng. Chem. 36, 1032 (1944).
- 3 E. H. Riddle, Monomeric Acrylic Esters, Reinhold Publishing Corp., New York, 1954.
- 4 C. H. Fisher, G. S. Whitby, and E. M. Beavers in G. S. Whitby, ed., Synthetic Rubber, John Wiley & Sons, Inc., New York, 1954, p. 900.
- 5 S. Mottram and P. H. Starmer, Rubber Plast. Age 39(2), 120 (1958).
- 6 H. A. Tucker and A. H. Jorgensen in J. P. Kennedy and E. G. Tornqvist eds., Polymer Chemistry of Synthetic Elastomers, Part I, Wiley-Interscience, New York, 1968, p. 253.
- 7 F. Ducci and A. Croci, Ind. Gomma 12(10), 55 (1968).
- 8 M. Maini and A. Croci, Mater. Plast. Elastomeri 36, 1062 (1970).
- 9 T. M. Vial, Rubber Chem. Technol. 44, 344 (1971).
- 10 F. V. Baez, Caucho (Madrid) 341, 13 (1978).
- 11 F. R. Wolf and R. D. DeMarco in R. O. Babbit, ed., Vanderbilt Rubber Handbook, 12th ed., R. T. Vanderbilt, Norwalk, Conn., 1978, p. 188.
- 12 R. V. Sloan, “Acrylic Ester Polymers', in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 1, 5th ed., Wiley Hoboken, N. J., 2004.
- 13 G. C. Sweet in A. Whelan and co-workers, eds., Developments in Rubber Technology, Vol. 1, Applied Science, Barking, UK, 1979, p. 45.
- 14 R. D. DeMarco, Rubber Chem. Technol. 52(1), 173 (1979).
- 15 R. B. Seymour, Aust. Plast. Rubber 31(11), 12 (1980).
- 16 W. Hofmann, Kautsch. Gummi Kunstst. 35, 378 (1982).
- 17 S. T. Semegen and J. H. Wakelin, Rubber Age (N.Y.) 71, 57 (1952); Rubber Chem. Technol. 25, 582 (1952).
- 18 U.S. Pat. 3,284,421 (Nov. 8, 1966), D. S. Breslow (to Hercules, Inc.)
- 19 A. R. Schultz and F. A. Bovey, J. Polym. Sci. 22, 485 (1956).
- 20 R. H. Hansen, W. M. Martin, and T. deBenedictio, Trans. Inst. Rubber Ind. 39, 301 (1963).
- 21
R. M. Thomas,
Rubber Chem. Technol.
42,
G.90
(1969).
10.5254/1.3539292 Google Scholar
- 22 R. H. Yocum and E. B. Nyquist, eds., Functional Monomers: Their Preparation, Polymerization and Application, Vol. 2, Marcel Dekker, Inc., New York, 1974.
- 23 R. M. Murray and D. C. Thompson, The Neoprenes, E. I. du Pont de Nemours & Co., Inc., Wilmington, Del., 1963, Appendix I, p. 93.
- 24 W. C. Mast, L. T. Smith, and C. H. Fisher, Ind. Eng. Chem. 36, 1027 (1944).
- 25 W. C. Mast and C. H. Fisher, India Rubber World 119, 596, 727 (1949).
- 26 U.S. Pat. 3,497,571 (Feb. 24, 1970), P. Tellier and E. Grimand (to Ugine Kuhlman).
- 27 U.S. Pat. 4,228,265 (Oct. 14, 1980), T. Ohishi, K. Handa, and H. Ueno (to Nippon Zeon Co., Ltd.).
- 28
R. Hank,
Rubber Chem. Technol.
40,
936
(1967).
10.5254/1.3539110 Google Scholar
- 29 J. E. Capito, F. Innes, and R. D. Allen, J. Inst. Rubber Ind. 2, 228 (1968).
- 30 U.S. Pat. 3,396,152 (Aug. 6, 1968), J. C. W. Hemming (to Firestone Co.).
- 31 U.S. Pat. 3,402,158 (Sept. 17, 1968), A. F. Santaniello and M. N. Gillis (to Thiokol).
- 32 U.S. Pat. 3,487,054 (Dec. 30, 1969), H. E. Minnerly and A. H. Jorgensen (to BFGoodrich Co.).
- 33 M. Kakei and co-workers, Nippon Gomu Kyokaishi 49(3), 178 (1976).
- 34 T. Fukumori, E. Okuya, and H. Enyo, paper presented at the Division of Rubber Chem. of the ACS, Toronto, Ontario, Canada, May 10–12, 1983, Paper 41.
- 35 Jpn. Pat. Kokoku 72, 7893 (March 6, 1972), E. Shiratuchi and S. Terashima (to J. S. R.).
- 36 D. D. Berry and co-workers, Rubber World 170(3), 42 (1974).
- 37 M. A. Mendelsohn, Rubber Age 95, 403 (1964).
- 38 Hycar 2121 x 38 Technical Data, BFGoodrich Co., Cleveland, Ohio, Feb. 14, 1966.
- 39
L. S. Chuiko,
N. M. Geinenko,
and A. V. Krut,
Polym. Sci. USSR
18,
563
(1976).
10.1016/0032-3950(76)90247-1 Google Scholar
- 40 W. C. Mast, T. J. Dietz, R. L. Dean, and C. H. Fisher, India Rubber World 116, 355 (1947).
- 41 W. C. Mast and C. H. Fisher, Ind. Eng. Chem. 40, 107 (1948).
- 42 H. P. Owen, Rubber Age 66, 544 (1950).
- 43 Diak # 1 Bulletin, Report #58-7, E. I. du Pont de Nemours & Co., Inc., Wilmington, Del., 1958.
- 44 U.S. Pat. 3,335,117 (Aug. 8, 1967), M. B. Berenbaum and G. A. Kanavel (to Thiokol).
- 45 D. W. Yochum, Thioureas in Polyacrylic Rubber, Pennwalt Report R147, Pennwalt, King of Prussia, Pa., Oct. 14, 1963.
- 46 W. G. Lloyd, CHEMTECH 1, 391 (1971).
- 47 U.S. Pat. 3,201,373 (Aug. 15, 1965), S. Kaizerman (to American Cyanamid Co.).
- 48 Bel. Pat. 647,927 (Nov. 16, 1964), T. F. Waldron (to American Cyanamid Co.).
- 49 H. W. Holly, F. F. Mihal, and I. Starer, Rubber Age 96, 565 (1965).
- 50 U.S. Pat. 3,458,461 (July 29, 1969), F. F. Mihal (to American Cyanamid Co.).
- 51 U.S. Pat. 3,622,547 (Nov. 23, 1971), N. P. Ermidis (to American Cyanamid Co.).
- 52 U.S. Pat. 4,092,303 (May 30, 1978), R. A. Behrens (to American Cyanamid Co.).
- 53 U.S. Pat. 3,624,058 (Nov. 30, 1971), A. H. Jorgensen (to BFGoodrich Co.).
- 54 U.S. Pat. 3,536,681 (Oct. 27, 1970), R. E. Morris (to BFGoodrich Co.).
- 55 Brit. Pat. 1,169,955 (Nov. 11, 1969), M. Troussier and E. Grimand (to Ugine Kuhlman).
- 56 U.S. Pat. 3,493,548 (Feb. 3, 1970), D. C. Chalmers (to Polysar).
- 57 U.S. Pat. 3,763,119 (Oct. 2, 1973), R. D. DeMarco and H. A. Tucker (to BFGoodrich Co.).
- 58 Jpn. Pat. 76, 144,484 (Dec. 11, 1976), Y. Ebina and co-workers (to Nippon Oil Seals).
- 59 Eur. Pat. 1-843 (May 5, 1979), R. D. DeMarco (to BFGoodrich Co.).
- 60 Brit. Pat. 920,809 (Mar. 13, 1963), R. M. Christenson and co-workers (to Pittsburgh Plate Glass Co.).
- 61 Brit. Pat. 960,743 (June 17, 1964), E. Muller and K. Dinges (to Bayer).
- 62 U.S. Pat. 3,315,012 (Apr. 18, 1967), A. H. Jorgensen, P. H. Starmer, and J. F. Stuesse (to BFGoodrich Co.).
- 63 U.S. Pat. 3,445,403 (May 20, 1969), H. A. Tucker and H. J. Essig (to BFGoodrich Co.).
- 64 U.S. Pat. 2,772,251 (Nov. 27, 1956), J. E. Hansen and T. J. Dietz (to U.S. Dept. of Agriculture).
- 65 H. P. Brown, Rubber Chem. Technol. 30, 1347 (1957).
- 66
J. A. Sims,
J. Appl. Polym. Sci.
5,
58
(1961).
10.1002/app.1961.070051309 Google Scholar
- 67 P. K. Dhal, M. S. Ramakrishna, and G. N. Babu, J. Polym. Sci. Polym. Chem. Ed. 20, 1581 (1982).
- 68 U.S. Pat. 3,335,118 (Aug. 8, 1967), G. A. Kanavel and G. Rosen (to Thiokol).
- 69 Jpn. Kokai 78, 24,352 (Mar. 7, 1978), H. Fukushima and R. Tsuchiya (to Nippon Zeon Co., Ltd.).
- 70 P. Bernstein, G. A. Kanavel, A. F. Santaniello, and R. S. Walker, paper presented at the Division of Rubber Chemistry of the ACS, New York, Sept. 14–16, 1966, Paper 26.
- 71 Jpn. Kokai 78, 88,853 (Aug. 4, 1978), T. Iida, T. Imoto, and T. Nishikubo (to Nippon Oil Seal Industry Co., Ltd.).
- 72 U.S. Pat. 3,038,886 (June 12, 1962), R. A. Hayes (to Firestone Co.).
- 73 R. Saxon and F. C. Lestienne, J. Appl. Polym. Sci. 8, 475 (1964).
- 74 U.S. Pat. 3,146,215 (Aug. 25, 1964), G. B. Sterling and R. L. Zimmerman (to The Dow Chemical Co.).
- 75 U.S. Pat. 4,069,180 (Jan. 17, 1978), D. C. Chalmers (to Polysar).
- 76 U.S. Pat. 3,875,092 (Apr. 1, 1975), R. E. Morris (to BFGoodrich Co.).
- 77 U.S. Pat. 3,919,143 (Nov. 11, 1975), R. E. Morris (to BFGoodrich Co.).
- 78 U.S. Pat. 3,912,672 (Oct. 14, 1975), R. E. Morris and H. Tucker (to BFGoodrich Co.).
- 79 U.S. Pat. 3,925,281 (Dec. 9, 1975), A. H. Jorgensen (to BFGoodrich Co.).
- 80 Jpn. Kokai Tokkyo Koho 79, 83,047 (July 2, 1979), Y. Ebina (to Nippon Oil Seal Industry Co., Ltd.).
- 81 Jpn. Kokai Tokkyo 80, 112,212 (Aug. 29, 1980, (to Nippon Oil Seal Industry Co., Ltd.).
- 82 E. Gianetti, R. Mazzorchi, L. Fiore, and E. Crespi, Rubber Chem. Technol. 56(1), 21, (1983).
- 83 U.S. Pat. 2,729,625 (Jan. 3, 1956), M. D. Hurwitz (to Rohm and Haas Co.).
- 84 U.S. Pat. 4,237,258 (Dec. 2, 1980), G. Cantalupo, S. de Servi, and A. Lepori (to Montedison).
- 85 C. E. Rehberg and C. H. Fisher, J. Am. Chem. Soc. 66, 1203 (1944).
- 86 C. E. Rehberg, W. A. Faucette, and C. H. Fisher, J. Am. Chem. Soc. 66, 1723 (1944).
- 87 H. A. Tucker, BFGoodrich Research Center, Brecksville, Ohio, unpublished results, Aug. 14, 1962.
- 88 U.S. Pat. 3,326,868 (June 20, 1967), H. A. Tucker (to BFGoodrich Co); Fr. Pat. 1,426,950 (Dec. 27, 1965), H. A. Tucker (to BFGoodrich Co.).
- 89 U.S. Pat. 2,839,511 (June 17, 1958), J. O. Harris and M. H. Wilt (to Monsanto).
- 90 U.S. Pat. 3,488,331 (Jan. 6, 1970), A. H. Jorgensen (to BFGoodrich Co.).
- 91 U.S. Pat. 3,525,721 (Aug. 25, 1970), A. H. Jorgensen (to BFGoodrich Co.).
- 92 U.S. Pat. 3,510,442 (May 5, 1970), D. C. Chalmers (to Polysar).
- 93 U.S. Pat. 3,697,490 (Oct. 10, 1972), P. H. Starmer (to BFGoodrich Co.).
- 94 U.S. Pat. 3,450,681 (June 17, 1969), R. H. Gobran and P. Bernstein (to Thiokol).
- 95 U.S. Pat. 3,397,193 (Aug. 13, 1968), R. R. Alsia and S. Kaizerman (to American Cyanamid Co.).
- 96 Acrylate Monomers, Rohm and Haas Co., Philadelphia, Pa., 1965.
- 97 Acrylate Product Information Union Carbide Corp. New York, 1965.
- 98 J. Brandrup and E. H. Immergut, eds., Polymer Handbook, 2nd ed., John Wiley & Sons, Inc., New York, 1975.
- 99 R. G. Gilbert, Emulsion Polymerization: A Mechanistic Approach, Academic Press. New York, 1955.
- 100 H. Warson, Polym. Paint Colour J. 178, 625 (1988).
- 101 H. Warson, Polym. Paint Colour J. 178, 865 (1988).
- 102 Hycar Bulletin HPA-1 (Revised), BFGoodrich Co., Cleveland, Ohio, 1979.
- 103 N. S. Steck and W. F. Bartoe, paper presented at Delaware Valley, ACS, Jan. 25, 1962; SPE Trans. 4(1), 34 (1964).
- 104 G. P. Mikhailov and L. L. Burshtein, Vysokomol. Soedin. 4, 270 (1962).
- 105 D. Mangaraj, S. Patra, and S. B. Rath, Makromol. Chem. 67, 84, 1963.
- 106 Hycar Polyacrylic Rubber, Manual HM-3, BFGoodrich Co., Cleveland, Ohio, Mar. 1959.
- 107 K. S. V. Srinivasan and M. Santappa, Polymer 14(1), 5 (1973).
- 108
T. Ina,
T. Kurosawa,
T. Komatsu, and
T. Takaota,
Nippon Gomu Kyokaishi
47,
107
(1970).
10.2324/gomu.43.107 Google Scholar
- 109 R. Steele and H. Jacobs, J. Appl. Polym. Sci. 2, 86 (1959).
- 110 R. T. Conley and P. L. Valint, J. Appl. Polym. Sci. 9, 785 (1965).
- 111 N. Grassie, J. G. Speakman, and T. I. Davis, J. Polym. Sci. Part A-1 9, 931 (1971).
- 112 Hycar Data Sheet, PA-81-6, BFGoodrich Co., Cleveland, Ohio, 1981.
- 113 Ibid., PA-81-7, BFGoodrich Co., Cleveland, Ohio, 1981.
- 114 Ibid., PA-81-8, BFGoodrich Co., Cleveland, Ohio, 1981.
- 115 Ibid., PA-81-9, BFGoodrich Co., Cleveland, Ohio, 1981.
- 116 Hycar Bulletin, E-5, BFGoodrich Co., Cleveland, Ohio, 1979.
- 117 The General Chemical Resistance of Various Elastomers, The Los Angeles Rubber Group, Inc., Los Angeles, Calif., 1970.
- 118 Hycar Bulletin E-7, BFGoodrich Co., Cleveland, Ohio, 1975.
- 119 D. A. Seil, BFGoodrich Technical Center, Avon Lake, Ohio, unpublished results, 1978.
- 120 Hycar Laboratory Report Summary E–335, BFGoodrich Co., Cleveland, Ohio, 1977.
- 121 Hycar Data Sheet, PA-80-6, BFGoodrich Co., Cleveland, Ohio, 1980.
- 122 R. J. Mayers and D. A. Seil, paper presented at the Division of Rubber Chemistry of the ACS, Cleveland, Ohio, Oct. 13–16, 1981, Paper 4.
- 123 Hycar Manual HM-1, BFGoodrich Co., Cleveland, Ohio, 1980.
- 124 Hycar Data Sheet, PA-79-28, BFGoodrich Co., Cleveland, Ohio, 1979.
- 125 Ibid., PA-82-2, BFGoodrich Co., Cleveland, Ohio, 1982.
- 126 General Motors Procedure No. 9003-P, G. M. Research Center, Warren, Mich., 1965.
- 127 R. D. DeMarco, BFGoodrich Technical Center, Avon Lake, Ohio, unpublished results, June 1977).
- 128 H. E. Minnerly in G. G. Winspear ed., ref. 12, 11th ed., R. T. Vanderbilt, Norwalk, Conn. 1968, p. 156.
- 129 U. S. Pat. 3,386,868 (June 9, 1966), J. R. Gimler and S. E. Jurman (to Hercules, Inc.).
- 130 H. J. Fabris and J. G. Sommer, Rubber Chem. Technol. 50(3), (1977).
- 131 Hycar Technical Supplement, No. 8, BFGoodrich Co., Cleveland, Ohio, 1980.
- 132 A. E. Juve, BFGoodrich Research and Development Center, Brecksville, Ohio, unpublished results, 1962.
- 133 Hycar Technical Supplement, No. 19 (Revised), BFGoodrich Co., Cleveland, Ohio, 1979.
- 134 G. J. Van Amerongen, J. Polym. Sci. 5(3), 307 (1950).
- 135 W. H. Heinlen, BFGoodrich Technical Center, Avon Lake, Ohio, unpublished results, 1971.
- 136 D. E. Jablonski, BFGoodrich Technical Center, Avon Lake, Ohio, unpublished results, 1981.
- 137 American Cyanamid Co., Bound Brook, N.J., 1981.
- 138 Curative C-50 Manual, American Cyanamid Co., Bound Brook, N.J., 1975.
- 139 U. S. Pat. 7,087,696 (Aug. 8, 2006), R. Wiedenanger and M. Resinger (to Huntsman Advanced Materials America).
- 140 U. S. Pat. 6,673,851 (Jan. 6, 2004), T. M. May and R. S. Harvey (to Ashland Inc).
- 141 Hycar Data Sheet, PA-79-3, BFGoodrich Co., Cleveland, Ohio, 1979.
- 142 N. R. Choudhuri, Rubber News 14(10), 36 (1975).
- 143 Hycar Data Sheet, PA-81-5, BFGoodrich Co., Cleveland, Ohio, 1981.
- 144 Hycar Laboratory Report Summary E-52, BFGoodrich Co., Cleveland, Ohio, 1966.
- 145 Ibid., E-320, BFGoodrich Co., Cleveland, Ohio, 1974.
- 146 U. S. Pat. 3,337,492 (Aug. 22, 1967), T. F. Waldron and F. F. Mihal (to American Cyanamid Co.).
- 147 U.S. Pat. 3,445,413 (May 20, 1969), A. H. Jorgensen and P. H. Starmer (to BFGoodrich Co.).
- 148 Ger. Pat. 1,808,484 (June 4, 1969), P. H. Starmer and A. H. Jorgensen (to BFGoodrich Co.).
- 149 Hycar Data Sheet PA-79-10, BFGoodrich Co., Cleveland, Ohio, 1979.
- 150 Ibid, PA-79-24, BFGoodrich Co., Cleveland, Ohio, 1979.
- 151 Hycar Laboratory Summary E-185, BFGoodrich Co., Cleveland, Ohio, 1972.
- 152 Ibid, E-170, BFGoodrich Co., Cleveland, Ohio, 1971.
- 153 J. D. Hutchison, Elastomerics 110(4), 35 (1978).
- 154 Adhesives Red Book, Communication Channels, Inc., Atlanta, Ga., 1983.
- 155 J. Glauser, M. Blgoev, and K. Fujita, “Acrylic Acid and Esters,” Chemical Economics Handbook, SRI Consulting, Menlo Park, Calif., July 2007.
- 156 M. Kirschner, Chem. Market Rept., 50 (April 18–24, 2005).
- 157 Annual Book of ASTM Standards, Volumes 09.01 and 09.02, American Society for Testing and Materials, Philadelphia, Pa., 1983.
- 158 SAE Handbook Society of Automotive Engineers, Inc., Warrendale, Pa., 1983.
- 159 R.J. Lewis, ed., Sax's Dangerous Properties of Industrial Materials, Wiley-online, 2006.
- 160 D. W. Aubrey in D. E. Packham. Handbook of Adhesion, Wiley, Chichester, UK, 2005.