Polymerisation adhesives

The field of solvent-free pressure-sensitive adhesives is an upcoming industrial technology. Such products find application as self-adhesive technical and medical products. The main aim is to manufacture solvent-free acrylic PSAs (A-PSAs), which have excellent performance and provide a good balance between adhesive and cohesive strengths. PSAs can act as extruder adhesives or UV-polymerised adhesives. Such adhesives, through their viscoelastic fluid state, can build joints without any requirement to change this flow state during or after application. 

The polymers of the 2-cyanoacryhc esters, more commonly known as the alkyl 2-cyaiioacrylates, are hard glassy resins that exhibit excellent adhesion to a wide variety of materials. The polymers are spontaneously formed when their Hquid precursors or monomers are placed between two closely fitting surfaces. The spontaneous polymerisation of these very reactive Hquids and the excellent adhesion properties of the cured resins combine to make these compounds a unique class of single-component, ambient-temperature-curing adhesives of great versatiUty. The materials that can be bonded mn the gamut from metals, plastics, most elastomers, fabrics, and woods to many ceramics. 

Type AD-G is used in an entirely different sort of formulation. The polymer is designed for graft polymerisation with methyl methacrylate. Typically, equal amounts of AD-G and methyl methacrylate are dissolved together in toluene, and the reaction driven to completion with a free-radical catalyst, such as bensoyl peroxide. The graft polymer is usually mixed with an isocyanate just prior to use. It is not normally compounded with resin. The resulting adhesive has very good adhesion to plasticised vinyl, EVA sponge, thermoplastic mbber, and other difficult to bond substrates, and is of particular importance to the shoe industry (42,43). 

Poly(vinyl alcohol) will function as a non-ionic surface active agent and is used in suspension polymerisation as a protective colloid. In many applications it serves as a binder and thickener is addition to an emulsifying agent. The polymer is also employed in adhesives, binders, paper sizing, paper coatings, textile sizing, ceramics, cosmetics and as a steel quenchant. 

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. 

Hydroxy propyl cellulose, like methyl cellulose, is soluble in cold water but not in hot, precipitating above 38°C. It was introduced by Hercules in 1968 (Klucel) for such uses as adhesive thickeners, binders, cosmetics and as protective colloids for suspension polymerisation. The Dow company market the related hydroxypropylmethyl cellulose (Methocel) and also produce in small quantities a hydroxyethylmethyl cellulose. 

These effects have been found by Creton et al. [79] who laminated sheets of incompatible polymers, PMMA and PPO, and studied the adhesion using a double cantilever beam test to evaluate fracture toughness Fc. For the original laminate Fc was only 2 J/m, but when interface reinforced with increasing amounts of a symmetrical P.M.M.A.-P.S. diblock copolymer of high degree of polymerisation (A > A e), the fracture toughness increased to around 170 J/m, and then fell to a steady value of 70 J/m (Fig. 9). 

Methylpropene can be made to continue the process to yield high polymers—cationic polymerisation—but most simple alkenes will go no further than di- or tri-meric structures. The main alkene monomers used on the large scale are 2-methyIpropene (— butyl rubber ), and vinyl ethers, ROCH=CH2 (— adhesives). Cationic polymerisation is often initiated by Lewis acid catalysts, e.g. BF3, plus a source of initial protons, the co-catalyst, e.g. traces of HzO etc. polymerisation occurs readily at low temperatures and is usually very rapid. Many more alkenes are polymerised by a radical induced pathway, however (p. 320). 

Transparency is often required. This is achieved by arranging that the particle size of the modifier to be below that of the wavelength of visible light (0.4-0.8 pm). This can normally be achieved by emulsion polymerisation, e.g., polybutadiene, polystyrene. Adhesion and surface compatibility between the polymer and modifier can be achieved by surface grafting of polar groups, e.g., acrylonitrile, various acrylates, onto the impact modifier surface before blending. 

Tertiary amines such as benzyldimethylamine, 2-(dimethyl aminoethyl) phenol, etc. form an anion with epoxide which leads to their polymerisation. These are used mainly for adhesives and surface coating applications. 

Both acrylic acid and methacrylic acid polymerise to give water soluble hard resins. The viscous solutions so formed have been used as emulsifying agents, adhesives and as thickening agents for inks and dyes. Polymers of esters of these acids are of greater commercial importance. Esters can be prepared from cyanhydrins by reaction with an alcohol ... 

Hill, C.A.S. and etin, N.S. (2000). Surface activation of wood for graft polymerisation. International Journal of Adhesion and Adhesives, 20, 71-76. 

Unlike bulk plastics and paper where unwanted substances can be removed by vacuum stripping (e.g. vinylchloride monomer from polyvinylchloride, styrene from polystyrene) or by washing (e.g. organic and metallic residues in mass-polymerised plastics), adhesives by their gummy nature are difficult to clean-up. Residues of incomplete polymerisation and reaction by-products could be effectively retained and may subsequently migrate. On the other hand, adhesives are generally not used in direct contact with the packaged foods. Rather, they are applied at seams and pack ends and any contact with the food is likely to be incidental and limited in area. 

Transparent hydrogels useful for adhesion inhibitors, tissue adhesives, wound dressings, hemostatics and embolisation materials are obtained from dextran methacrylates via polymerisation with N-isopropylacrylamide in DMSO in the presence of azobisisobutyronitrile [176]. A broad variety of new hydrogels with different sensitivities and tunable degradation behaviour is accessible by grafting L-lactide onto 2-hydroxyethyl methacrylate (HEMA) and binding this polymerisable group on dextran via activation with N,N -carbonyldiimidazole (CDI, Sect. 4.2.2) [177]. 

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