Sept. 12, Formulating (Meth)Acrylic Structural Adhesives for Modern Vehicle Assembly Al DeCato Technical Manager TT-Automotive Product Development Henkel Corp Trout Brook Crossing Rocky Hill, CT Presented at a meeting of the Thermoset Resin Formulators Association at the Hyatt Regency Montreal in Montreal, Quebec, Canada, September 11 through 12, 2006.

Sept. 12, Presentation Outline History of formulations Goals of formulating Components of formulations –desired properties Acknowledgements

Sept. 12, History of formulations From rubber cement beginnings Significant developments –monomer:polymer ratio –redox curing system

Sept. 12, Goals of formulating Cure activity versus stability Fixture time versus open time Strength versus toughness

Sept. 12, Formulation components Monomer (Meth)acrylic esters –Methyl methacrylate, ethyl methacrylate, 2- ethylhexyl methacrylate, cyclohexyl methacrylate, ethyl acrylate Effects –Solvency, stiffness, odor, cure speed

Sept. 12, Formulation components Polymeric elastomer/liquid rubber – Polychloroprene,polybutadiene, chlorosulfonated polyethylene, copolymers of butadiene or isoprene with styrene, acrylonitrile, copolymers of ethylene and acrylate esters, homopolymers of epichlorohydrin, copolymers of epichlorohydrin and ethylene oxide, nitrile Effects –Toughening, low temperature flexibility, vibration damping

Sept. 12, Formulation components Graft co-polymer/core shell – methyl methacrylate/1,3-butadiene/styrene (MBS) –acrylonitrile/butadiene/styrene (ABS) – styrene/butadiene/styrene (SBS) Effects –Impact modifier, thixotropy

Sept. 12, Formulation components Inhibitors –2,6-di-t-butyl-4-methylphenol (BHT), hydroquinone (HQ), methylhydroquinone (MHQ) Effects –stability, cure speed, heat of exotherm

Sept. 12, Formulation components Carboxylic acid – acrylic acid, methacrylic acid Effects –Fast cure, adhesion

Sept. 12, Formulation components Initiators –Organic peroxides, organic hydroperoxide, peresters, peracids, and azo compounds Effects –Cure speed, heat of exotherm, open time, and stability

Sept. 12, Formulation components Activators –N,N-dimethylaniline, diethyl aniline, N,N- dimethyl-p-toluidine, aldehyde-amine reaction products, dihydropyridine Effects –cure speed, open time, heat of exotherm, and stability

Sept. 12, Formulation components Catalysts –oxidizable heavy metal salts, such as the naphthenates, octoates, acetylacetonates, and hexoates of transition metals such as copper, cobalt, nickel, and iron Effects –cure speed, heat of exotherm, open time, and stability

Sept. 12, Formulation components Additives –Adhesion promoters Carboxylic acid, phosphorus compounds –Wax Effects –adhesion, cure speed –reduce odor, extend open time

Sept. 12, Acknowledgements To Henkel Corp. for the opportunity, encouragement, and support to develop this chemistry To my family which has supported me, always To Paul Rachielles who has always had the faith that I could succeed