Methacrylate-based adhesives

Briggs, P. C., Bonding Method Employing Novel Methacrylate Based Adhesive Compositions Chlorinated or Chlorosulfonated Polyethylene as Adhesion Promoter, U.S. Patent No. 4,773,957, 1988. 

The use of methacrylate-based adhesives has been a great success in orthopedics, for the purpose of anchoring hip socket implants to the bone. There are currently no other types of adhesive used for this application. The adhesive products are comprised of (a) a powder component (a mixture of polymethyl methacrylate and a polymerization initiator) and (b) a liquid component [whose main components are methyl methacrylate (MMA) and a polymerization... 

The use of methacrylate-based adhesives has been a great success in orthopedics for the purpose of anchoring hip socket implants to the bone. There are currently no other types of adhesive used for this application. 

Chrome complexes have been developed as adhesion promoters by the reaction of chromium chloride with methacrylic acid. The chromium oxide portion of the adhesion promoter reacts with a substrate while the methacrylic portion reacts with a free radical curing outer layer. Chrome-based adhesion promoters are commonly used as a primer for aluminum foil to increase the strength and durability of aluminum/polyethylene interfaces.26... 

To avoid inner tensions through thermal stress, it is recommended to use only adhesives that cure at room temperature. The adhesive selection is limited by the fact that many applications require an invisible glueline. In such cases, adhesives with fillers are excluded, cyanoacrylates and in particular radiationcuring products (Section 9.3.3) are the suitable choice. If the visual appearance of the bonded joint is not important, two-component reactive adhesives based on expoxides, polyurethanes, methacrylates, contact adhesives and, if required, adhesive tapes are recommended. 

Solvent-based adhesives, two-component epoxy resin adhesives, two-component methacrylates for assembly purposes (priming, filling, smoothing, sealing, etc.) For these applications, a multitude of so-called building/ construction adhesives is commercially available. 

Chem. Descrip. Ethyl methacrylate-based resin Uses Acrylic for solv.-applied coatings for wood, metal, and plastics, aerosol paints, inks/toners, adhesives, specialty coatings tor masonry, and reproduction papers and films, temporary binders Elvacite 2044,2045,2046 [Ludte Int l.j... 

Sodium magnesium silicate base, adhesives Isobutyl methacrylate base, alcohol ethoxylates C12-13 alcohols C12-15 alcohols base, antiperspirant sticks Stearamide MEA base, antistats... 

For 193 nm applications, evaluation of a series la) of cholate based dissolution inhibitors suggested that the dissolution inhibition of methacrylate-based resins by these derivatives is largely a function of the hydrophobicity of the cholates employed. The observed relative order of hydrophobicity and dissolution inhibition was lithocholate (1 pendant hydroxyl) > deoxycholate == ursocholate (2 pendant hydroxyls) > cholate (3 pendant hydroxyls). Experiments using monomeric dissolution inhibitors such as t-butyl cholate (la), t-butyl deoxycholate (lb), t-butyl lithocholate (Ic), t-butyl lithocholate acetate (2) with the P(NB/MA) acrylate resins afforded resist systems that exhibited low contrast, poor adhesion, dark erosion (unexposed resist film loss) and were incompatible with industry standard 0.26 N TMAH developers. 

The use of adhesives/sealants in both the industrial and consumer spheres has increased dramatically in the past 20 years. In the industrial segment, both reactive and nonreactive systems are used in a wide variety of applications. The increasing use of reactive systems has, however, tended to overshadow that of the nonreactive systems. Most prominent amongst the reactive systems favored in industrial applications are anaerobic sealants (methacrylate ester based), instant adhesives (alkyl cyanoacrylate ester based), acrylic (toughened) adhesives, epoxy resin adhesives, polyurethane/isocyanate-based adhesives, silicone adhesives/sealants, and phenolic resin adhesives. 

Dental Cements. Polymeric matrices used in formulating cements are similar to those used in methacrylate-based composites and sealants. BisGMA or some other dimethacrylate is blended with monomers snch as MMA, along with fillers and other additives, to make the formulated adhesive useful in the oral cavity. They may be of the VLC type and/or chemically cnred type. They may also contain additives such as inorganic fluoride salts, which may result in redncing recurrent decay. 

Acrylic- and methacrylic-based polymers. Poly(methyl methacrylate) (PMMA), due to its transparency and weatherability, is used extensively in signs, lighting fixtures, and windows. Polyacrylates and copolymers are used extensively in the adhesives and coatings markets, and are also combined with acrylonitrile to make acrylic fibers. 

Solvent adhesives and reactive adhesives are made from homo- and copolymers of methacrylates, generally methyl and ethyl methacrylate and, occasionally, butyl methacrylate. Monomeric (meth)acrylates are also used in reactive adhesive systems (polymerization adhesives). Poly(ethyIene glycol) dimethacrylates are the basis of anaerobically curing liquid resins (reactive adhesives). They also are added as adhesion promoters to plastisol adhesives. Acrylate-ethylene copolymers, in some cases with a small content of carboxyl groups, are used instead of ethylene-vinyl acetate copolymers as fusible polymers for special hot-melt adhesives. Salts of polyacrylate and acrylate - acrylic acid copolymers are used as thickeners for aqueous adhesive solutions and emulsion-based adhesives. 

AFM has been used in studies of adhesion in the cases of PS/polymethl methacrylate (PMMA) [47], PET/PP [48], and poljmrethane- and epoxy-based adhesives [49]. General discussions of the use of this technique in adhesion studies have been reported [50]. 

Lord Corporation introduced adhesives containing methacrylated phosphate monomers that gave much-improved thermal and atmospheric durability, and Dymax Corporation introduced their aerobic acrylics that were less sensitive to inhibition by atmospheric oxygen. Dow Automotive, 3M, and Loctite recently introduced two-part acrylic-based adhesives that can bond many low-surface-energy plastics, including many grades of polypropylene, polyethylene, and thermoplastic polyolefins without special surface preparation (see Section 4.2.2 for a description of this technology). 

Park, J., Eslick, J., Ye, Q., Misra, A., Spencer, R The influence of chemical structure on the properties in methacrylate-based dentin adhesives. Dent. Mater. 27,1086—1093 (2011)... 

The most widely used emulsion based additives are the all-acrylic or MBS coreshell polymers. Methacrylate-based shell compositions are generally not highly miscible with the various engineering resin compositions, creating a challenge for proper impact modifier dispersion and adhesion. Common approaches to this problem... 

Other commercially snccessful reactive acrylic-based adhesives are mixtures of methacrylate polymers dissolved in methyl methacrylate (MMA) monomers. Extensive research and development of these adhesives first introduced in the 1960s have led to what is termed high-performance acrylic adhesives. These products are supplied as two separate components to be mixed prior to an application. A peroxide in one component and an amine or metal salt (reducing agent) in the other initiate a free-radical polymerization of the MMA upon mixing [16]. 

Heteroatom functionalized terpene resins are also utilized in hot melt adhesive and ink appHcations. Diels-Alder reaction of terpenic dienes or trienes with acrylates, methacrylates, or other a, P-unsaturated esters of polyhydric alcohols has been shown to yield resins with superior pressure sensitive adhesive properties relative to petroleum and unmodified polyterpene resins (107). Limonene—phenol resins, produced by the BF etherate-catalyzed condensation of 1.4—2.0 moles of limonene with 1.0 mole of phenol have been shown to impart improved tack, elongation, and tensile strength to ethylene—vinyl acetate and ethylene—methyl acrylate-based hot melt adhesive systems (108). Terpene polyol ethers have been shown to be particularly effective tackifiers in pressure sensitive adhesive appHcations (109). 

AH-acryHc (100%) latex emulsions are commonly recognized as the most durable paints for exterior use. Exterior grades are usuaHy copolymers of methyl methacrylate with butyl acrylate or 2-ethyIhexyl acrylate (see Acrylic ester polymers). Interior grades are based on methyl methacrylate copolymerized with butyl acrylate or ethyl acrylate. AcryHc latex emulsions are not commonly used in interior flat paints because these paints typicaHy do not require the kind of performance characteristics that acryHcs offer. However, for interior semigloss or gloss paints, aH-acryHc polymers and acryHc copolymers are used almost exclusively due to their exceUent gloss potential, adhesion characteristics, as weU as block and print resistance. 

C. R. Cuervo and A. J. Maldonado, Solution Adhesives Based on Graft Polymers of Neoprene and Methyl Methacrylate, Du Pont Informal Bulletin, Wilmington, Del., Oct. 1984 K. Itoyama, M. Dohi, and K. Ichikawa, Nippon Setchaku Kyokaishi 20, 268 (1984). 

Polystyrene-PDMS block copolymers4l2), and poly(n-butyl methacrylate-acrylic acid)-PDMS graft copolymers 308) have been used as pressure sensitive adhesives. Hot melt adhesives based on polycarbonate-PDMS segmented copolymers 413) showed very good adhesion to substrates with low surface energies without the need for surface preparation, such as etching. 

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