Cyanoacrylates polyolefin

Primers for cyanoacrylate adhesives, chlorinated polyolefin primers... 

Cyanoacrylate adhesives cure by anionic polymerization. This reaction is catalyzed by weak bases (such as water), so the adhesives are generally stabilized by the inclusion of a weak acid in the formulation. While adhesion of cyanoacrylates to bare metals and many polymers is excellent, bonding to polyolefins requires a surface modifying primer. Solutions of chlorinated polyolefin oligomers, fran-sition metal complexes, and organic bases such as tertiary amines can greatly enhance cyanoacrylate adhesion to these surfaces [72]. The solvent is a critical component of these primers, as solvent swelling of the surface facilitates inter-... 

Fig. 11. Effect of polyolefin primers on bond strength of ethyl cyanoacrylate to plastics. All assemblies tested in accordance with ASTM D 4501 (block shear method). ETFE = ethylene tetrafluoroethylene copolymer LDPE = low-density polyethylene PFA = polyper-fluoroalkoxycthylene PBT = polybutylene terephthalate, PMP = polymethylpentene PPS = polyphenylene sulfide PP = polypropylene PS = polystyrene PTFE = polytetrafluoroethylene PU = polyurethane. From ref. [73].

Low surface energy substrates, such as polyethylene or polypropylene, are generally difficult to bond with adhesives. However, cyanoacrylate-based adhesives can be effectively utilized to bond polyolefins with the use of the proper primer/activa-tor on the surface. Primer materials include tertiary aliphatic and aromatic amines, trialkyl ammonium carboxylate salts, tetraalkyl ammonium salts, phosphines, and organometallic compounds, which are initiators for alkyl cyanoacrylate polymerization [33-36]. The primer is applied as a dilute solution to the polyolefin surface, solvent is allowed to evaporate, and the specimens are assembled with a small amount of the adhesive. With the use of primers, adhesive strength can be so strong that substrate failure occurs during the course of the shear tests, as shown in Fig. 11. 

The mechanism by which the primers are thought to work is relatively straightforward. The primer first diffuses into the polyolefin surface, and subsequently becomes entangled in the polyolefin. The primer molecule can then act as an anchor in the substrate surface for the adhesive polymer, which forms after the primer initiates polymerization of the alkyl cyanoacrylate monomer [37]. 

This difference in reactivity between the different classes of amines explains the difference in the primer performance on polyolefin substrates with ethyl cyanoacrylate-based adhesives [37J. Since primary and secondary amines form low molecular weight species, a weak boundary layer would form first, instead of high molecular weight polymer. Also, the polymer, which does ultimately form, has a lower molecular weight, which would lower adhesives strength [8,9]. 

The new technical developments have made possible quick bonding to woods, papers, and porous surfaces. Polyolefins, which comprise approximately 50% of the U.S. thermoplastic production, are now bondable with the cyanoacrylic ester adhesives. These new capabilities are sure to provide for continued market growth in the years ahead. 

Polyolefin bonding has been advanced using cyanoacrylates through the use of surface primers. These primers promote adhesion to untreated polyethylene (PE), polypropylene (PP), and EPDM rubber. Table 7 shows comparison bonds using standard industrial-grade cyanoacrylates. 

The use of synthetic adhesives in the past twenty-five years (1) has grown/ particularly the use of eight classes of polymers polyvinyl acetate/ polyolefins/ styrenic block copolymerS/ acrylicS/ cyanoacrylates/ anaerobicS/ polyurethanes/ and epoxy resins. Some of these polymers are Still in high demand as specialty adhesives (2). During the last several yearS/ however / other polymers have been added to this list/ e.g. / polyamides/ polyimideS/ and polyesters. Today/ synthetic adhesives account for 75% of the adhesives produced and 85% of the sales/ while the market share of natural products has steadily declined. 

Cyanoacrylate adhesives will bond a wide variety of substrates with the exception of polyolefins (unless pre-treated). Teflon and highly acidic surfaces. Porous substrates such as wood, paper and leather require the use of products containing accelerators. Formulations are now appearing that when used in conjunction with a so-called primer can give high bond strength on polyethylene and polypropylene. See Industrial applications of adhesives. 

A new primer (see Primers for adhesive bonding) has been developed that enables a cyanoacrylate to be used to bond polyolefins. The primer is applied to one surface, adhesive to the other - the bond is virtually instantaneous. This will allow the designers flexibility in choice of plastics, enabling less costly polyolefins to be selected. 

Cyanoacrylate adhesives will bond most substrates to themselves and to each other. The few adherends which do not bond well with standard adhesives are polyethylene, polypropylene, EPDM rubber, plasticized PVC, teflon, and acidic surfaces. A few manufacturers sell modified adhesives which will bond some of these materials, such as EPDM and flexible PVC. Adhesion to low surface energy plastics like polyolefins and Teflon can be improved by an etching or oxidizing treatment. 

Water vapor from the atmosphere is the curing agent for some silicone and isocyanate adhesives. Adsorbed surface water causes the cure of cyanoacrylates. Such adhesives are often packed in polyolefin containers, which are naturally permeable to water. Hence, the passage of water through the container wall has the possibility to shorten shelf life. 

Epoxies generally have excellent adhesion to metals, ceramics and glass, although on most amorphous thermoplastics epoxies will usually he outperformed by MMA, UV adhesives or cyanoacrylates. Epoxies will bond well to thermoset plastics and are widely used for bonding sheet moulding compound door and body panels in the transportation industries. Epoxies do not adhere well to elastomers, fluoropolymers or polyolefin plastics. 

In the late 1980s primers were introduced that considerably enhance the adhesion of cyanoacrylates to polyolefins. 

The primer changes the surface condition of the plastic, creating bond sites for the cyanoacrylate adhesive. The effect of a polyolefin primer when used with a cyanoacrylate on polypropylene should not be underestimated. Bond strengths are often 25 to 40 times higher than those achieved when using the same adhesive without primer (Figure 6.4). Note that these polyolefin primers are only suitable for cyanoacrylate adhesives and are not compatible with other technology adhesives. 

Loctite Polyolefin Primer used with Prism 406 cyanoacrylate adhesive on top PTFE tape, centre Polythene, lower Nylon. The thin PTFE tape broke before the Joint separated, but the adhesive failed with the thicker specimens. 

Natural rubber butt joint made with Loctite Polyolefin Primer and Prism 406 cyanoacrylate adhesive. Joint could not be broken by hand. 

Products obtained by pyrolysis of other polymers is reviewed in Table 4.5. Some specific applications of the chromatography-MS technique to various types of polymers include the following PE [34,35], poly(l-octene) [29], poly(l-decene) [29], poly(l-dodecene) [29], CPE [36], polyolefins [37, 38], acrylic acid-methacrylic acid copolymers [39, 40], polyacrylate [41], nitrile rubber [42], natural rubbers [43, 44], chlorinated natural rubber [45, 46], polychloroprene [47], PVC [48-50], polysilicones [51, 52, 53], polycarbonates [54], styrene-isoprene copolymers [55], substituted olystyrene [56], PP carbonate [57], ethylene-vinyl acetate [58], Nylon 66 [59], polyisopropenyl cyclohexane-a-methyl styrene copolymers [60], cresol-novolac epoxy resins [61], polymeric flame retardants [62], poly(4-N-alkyl styrenes) [63], polyvinyl pyrrolidone [64], polybutyl-cyanoacrylate [65], polysulfides [66], poly(diethyl-2-methacryl-oxy) ethyl phosphate [67, 68], polyetherimide [69], bisphenol-A [70], polybutadiene [71], polyacenaphthalene [72], poly(l-lactide) [73], polyesterimide [74], polyphenylene triazine [75], poly-4-N-vinyl pyridine [76], diglycidylether-bisphenol-A epoxy resins [77], polyvinylidene chloride [78] and poly-p-chloromethyl styrene [79]. 

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