Acrylate monomer adhesive

Caprolactone acrylate monomer adhesion promoter, EB-curable metal coatings... 

Synthetic emulsion polymers account for approximately 70% of the U.S. consumption of acrylate monomers. Major end uses for these latex polymers are coatings (32%), textiles (17%), adhesives (7%), paper (5%), and floor poHshes (3%). The U.S. producers of acryflc copolymer emulsions include Rohm and Haas, Reichhold, National Starch, Union Carbide, Air Products, Unocal, B. F. Goodrich, and H. B. Fuller. 

The reluctance of acrylic monomers to polymerise in the presence of air has been made a virtue with the anaerobic acrylic adhesives. These are usually dimethacrylates such as tetramethylene glycol dimethacrylate. The monomers are supplied with a curing system comprising a peroxide and an amine as part of a one-part pack. When the adhesive is placed between mild steel surfaces air is excluded, which prevents air inhibition, and the iron present acts as a polymerisation promoter. The effectiveness as a promoter varies from one metal to another and it may be necessary to use a primer such as cobalt naphthenate. The anaerobic adhesives have been widely used for sealing nuts and bolts and for a variety of engineering purposes. Small tube containers are also available for domestic use. 

Liquid organic rubbers with reactive functionality can be prepared by several methods. End-functional oligomers are preferred. Chains attached to the network at only one end do not contribute as much strength to the network as those attached at both ends [34], Urethane chemistry is a handy route to such molecules. A hydroxy-terminated oligomer (commonly a polyester or a polyether) can be reacted with excess diisocyanate, and then with a hydroxy methacrylate to form a reactive toughener [35]. The methacrylate ends undergo copolymerization with the rest of the acrylic monomers. The resulting adhesive is especially effective on poIy(vinyl chloride) shown in Scheme 2. 

Because they are acrylic monomers, alkyl cyanoacrylate esters still require the addition of radical polymerization inhibitors, such as hydroquinone or hindered phenols, to prevent radically induced polymerization over time [3j. Since basic initiation of alkyl cyanoacrylate monomers is the predominant polymerization mechanism, large quantities of free radical inhibitors can be added, with little or no effect on adhesive performance. 

Suspension polymerization also is used When acrylic monomers or their mixtures with other monomers are polymerized while suspended (usually in aqueous system), the polymeric product is obtained m the form of small beads, sometimes called pearls or granules. Bead polymers are the basis of the production of molding powders and denture materials. Polymers derived from acrylic or methacrylic acid furnish exchange resins of the carboxylic acid type. Solutions in organic solvents furnish lacquers, coatings and cements, while water-soluble hydrolysates are used as thickeners, adhesives, and sizes. 

Structural adhesives are formulated from epoxy resins, phenolic resins, acrylic monomers and resins, high temperature-resistant resins (e.g., polyimidcs), and urethanes. Structural adhesive resins arc often modified by elastomers. 

Another class of acrylic sealants arc the solvent-releasing acrylics. Acrylic monomers are polymerized in a solvent. The natural adhesion of most of the solvent-releasing acrylics produces some of the best unprimed adhesion in the sealant industry. However, slow, continual cure generally produces large compression sets and limits their use to low movement applications. Also, the relatively high amounts of solvent and traces of acrylic monomer in these formulations limits their use to outdoor applications, usually in construction,... 

Acrylics. Many acrylic monomers are capable of being formulated into adhesives. Methyl or lower alkyl methacrylates often are used, although they have a strong odour which frequently is said to be objectionable. 

Radiation curing adhesives are generally applied as solvent-free liquids. High-solids EB and uv curing liquid adhesives have been formulated from a variety of resins and elastomers. They include epoxy acrylates, epoxies, other acrylates, polyesters, blends of acrylate monomers with elastomers, and other compositions. 

MIL-A-8576 MIL-A-9117 MIL-A-12850 MIL-C-14064 MIL-C-15705 MIL-C-18255 MIL-C-18969 MIL-C-23092 MIL-C-27315 MIL-C-27725 MIL-C-5539 MIL-C-7438 Adhesive, Acrylic Monomer Base Synthetic Elastomeric Sealant Natural Liquid Rubber Cement Grinding Disk Cement Caulking Compound Caulking Compound with Synthetic Rubber Base Caulking Compound—Watertight Exterior Hull Seams of Vessels Cement, Natural Rubber Coating Systems, Elastomeric Coating, Corrosion, Preventative, Air Fuel Tanks Natural Rubber Cement Core Material, Aluminum, for Sandwich Construction... 

Polymerizing acrylic monomers in the presence of oil-modified polyurethane leads also to a grafting onto the polyacrylics, resulting in dispersions suitable for stable water-borne latexes with good adhesion properties and fair hardness properties [103]. 

All acrylic structural adhesives consist basically of a solution or a mixture of polymers and unsaturated, low-molecular-weight, free-radical-polymerizable monomers with other materials added as needed for the particular intended use. In addition, some precursor of the polymerization initiator will be present. 

The choice of monomers that are useful in acrylic structural adhesives is rather limited. Cost always is an important factor, and because acrylic structural adhesives consume only a very small portion of the world s output of acrylic monomer, the formulator usually must rely on acrylic monomers that are made in large quantity for other uses. In addition, the monomers must polymerize readily at room temperature. If a mixture of monomers is to be used, the monomers must copolymerize easily. Finally, the monomers must be good solvents or dispersants for the polymers used in formulating the adhesive. The acrylic monomers finding most use in acrylic structural adhesives are methyl methacrylate and tetrahydrofurfuryl methacrylate. The later, albeit more expensive, has a much higher flashpoint and a generally perceived low odor, yet maintains good solvency. 

The curing reaction of an acrylic structural adhesive is the chain-growth polymerization of the acrylic monomer. The monomer units are not reactive with each other but react only with a growing chain having an active site on one end. In order to begin a chain, one must generate an initiator in the monomer solution. In the case of acrylic structural adhesives, this initiator nearly always is a free radical, a species having an unpaired, reactive electron. 

A technology developed at Du Pont75 combines the use of reactive sites on the oligomers with the initiation reaction. The resulting family of acrylic structural adhesives has become popularly known as second generation acrylics. They consist essentially of solutions of chlorosulfonated polyethylene (Du Pont Hypalon ) in acrylic or methacrylic monomers. The chlorosulfonyl groups present on the polymer will react with... 

Other acrylic structural adhesives can be used on poorly prepared metal surfaces. Inclusion of reactive monomers having phosphate groups can lead to significant improvements in primary bonds to many unprepared metals.76 Kowa American supplies one such monomer, 2-hydroxyethylmethacrylate acid phosphate. 

It is common in acrylic structural adhesives to use oligomers that have a desirable backbone and are terminated with free-radical-polymerizable bonds. A variety of isocyanate-terminated polyurethanes can be adapted to use in acrylic structural adhesives by reacting the terminal isocyanates with a hydroxy functional acrylic monomer such as 2-hydroxyethyl methacrylate.76,92 93... 

The fundamental chemistry of the structural adhesives described here can change very little. Vinyl and acrylic monomers polymerize by chain growth polymerization initiated by free radicals or ions. Isocyanate and epoxy compounds react with compounds containing active hydrogen in step growth polymeriza-... 

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