Polymerization cyanoacrylates

For closing parenchymatous renal hemorrhages, a needleless injector was used [468]. This method consists in obtaining a hemostatic infiltrate on the wound surface, which is achieved by introducing easily polymerized cyanoacrylate adhesives into the organ parenchyma using a needleless injector. A thin adhesive film that is formed... 

Initiators, accelerators, and inhibitors of cyanoacrylate polymerization are used to modify the cure speed and storage stability of these adhesives. They can also be used to broaden the range of materials which can be bonded with cyanoacrylates. Initiators are those materials which are capable of polymerizing cyanoacrylate esters upon contact. These are, therefore, applied either to the substrate surface ( surface primers ), or mixed with the adhesive just prior to application. Accelerators are materials which do not cause polymerization on contact with monomer, but which increase the cure rate once the adhesive is applied. These chemicals are most often compounded with the monomer in the adhesive formulation. The distinction between these two classes can be blurred, as some additions will not cause immediate polymerization on contact but will shorten shelf life in the long run. Anionic polymerization inhibitors are Lewis or Bronsted acids which retard or completely inhibit anionic polymerization. Radical inhibitors prevent polymerization by adventitious, radical sources and are used to prolong the storage stability of the adhesive they generally do not affect cure speed. 

Monomeric and polymeric cyanoacrylates are clear and colorless. Most of the time this is a desirable characteristic, though occasionally an applica-... 

The polymerized cyanoacrylate is then heated to a temperature of 140-260°C, forcing the de-polymerization of the polycyanoaciylate back to a cyanoacrylate ester ... 

Studies carried out on polymerized cyanoacrylates revealed that oral doses of 6400 mg/kg failed to kill laboratory rats." While the adhesive did cause mild irritation of the skin of guinea pigs after 24 hours exposure, there was no evidence of skin sensitization or absorption through the skin. 

The amount of stabilizer molecules in cyanoaerylate is very small—measured in parts per million—and very little moisture moleeules are required to eause rapid polymerization. Cyanoacrylates begin to form polymer ehains immediately on contact with the water vapor on the surface of the part. If parts are moved during initial eontaet, the polymerization proeess and polymer ehains are stopped. The process must start again at a new eatalyzed site. ... 

Table 3. Adhesive Bond Properties of 2-Cyanoacrylic Esters with Metals and Various Polymeric Materials...

Cyanoacrylate adhesives (Super-Glues) are materials which rapidly polymerize at room temperature. The standard monomer for a cyanoacrylate adhesive is ethyl 2-cyanoacrylate [7085-85-0], which readily undergoes anionic polymerization. Very rapid cure of these materials has made them widely used in the electronics industry for speaker magnet mounting, as weU as for wire tacking and other apphcations requiring rapid assembly. Anionic polymerization of a cyanoacrylate adhesive is normally initiated by water. Therefore, atmospheric humidity or the surface moisture content must be at a certain level for polymerization to take place. These adhesives are not cross-linked as are the surface-activated acryhcs. Rather, the cyanoacrylate material is a thermoplastic, and thus, the adhesives typically have poor temperature resistance. 

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

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-... 

Since amines initiate cyanoacrylate polymerization, the monomer cannot be isolated directly, because a polymer is generated immediately after formation of the monomer. An acid is then added to the polymer, and heat (140-180°C) is applied to the reaction mixture. Because of the relatively low ceiling temperature of the polymer, the pure monomer can be isolated, in greater than 80% yield, by the thermal reversion of the polymer back to the free monomer [4,5]. 

To prevent premature polymerization, a strong protic or a Lewis acid is added to the distilled monomer and to adhesive formulations. A wide variety of materials have been utilized as acidic stabilizers in the alkyl cyanoacrylate monomers. A list of some of these materials is shown in Table 1 [2,11-14]. 

These acids can be used alone or as mixtures. It is especially advantageous to use a mixture of liquid and gaseous acids. The gaseous acid will stabilize free monomer in the headspace of a container, while the liquid acid will prevent premature polymerization of the bulk monomer or adhesive. However, it is important to use only a minimum amount of acid, because excess acid will slow initiation and the formation of a strong adhesive bond. It can also accelerate the hydrolysis of the alkyl cyanoacrylate monomer to 2-cyanoacrylic acid, which inhibits the polymerization of the monomer and reduces molecular weight of the adhesive polymer. While carboxylic acids inhibit the polymerization of cyanoacrylate monomer, they do not prevent it completely [15]. Therefore, they cannot be utilized as stabilizers, but are used more for modifying the reactivity of instant adhesives. 

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. 

Alkyl cyanoacrylate monomers have been copolymerized with a variety of monomers, both by radical and anionic initiation. The radical-initiated copolymerization with acrylic monomers was performed with a sufficient amount of an acid stabilizer present to suppress polymerization by anionic means [19]. This investigation has been covered extensively elsewhere. 

The molecular weights of the polymers are much larger than would be predicted from the monomer/initiator ratio, as seen in Fig. 4. However, this effect is most evident for the polymerization of ethyl cyanoacrylate alone. 

An example of this improvement in toughness can be demonstrated by the addition of Vamac B-124, an ethylene/methyl acrylate copolymer from DuPont, to ethyl cyanoacrylate [24-26]. Three model instant adhesive formulations, a control without any polymeric additive (A), a formulation with poly(methyl methacrylate) (PMMA) (B), and a formulation with Vamac B-124 (C), are shown in Table 4. The formulation with PMMA, a thermoplastic which is added to modify viscosity, was included to determine if the addition of any polymer, not only rubbers, could improve the toughness properties of an alkyl cyanoacrylate instant adhesive. To demonstrate an improvement in toughness, the three formulations were tested for impact strength, 180° peel strength, and lapshear adhesive strength on steel specimens, before and after thermal exposure at 121°C. 

Eihyl cyanoacrylate formulations with and without polymeric additives... 

The data also demonstrate that the addition of the thermoplastic, PMMA, does not have the significant effect on the toughness or adhesion properties as does the addition of the rubber, Vamac B-124. Clearly, the physical properties of the polymeric additive determine the magnitude of the adhesive physical property modifications, which result from their addition to an alkyl cyanoacrylate monomer. 

Care must also be taken in the choice of rubber to insure that the rubber, or one of its additives, does not initiate the premature polymerization of the monomer. Even very low concentrations of a basic or nucleophilic material in the rubber or elastomer will cause the premature polymerization of an alkyl cyanoacrylate adhesive formulation. 

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]. 

For surfaces which do not readily polymerize alkyl cyanoacrylate monomers, the adhesive monomer can be applied, a part assembled and repositioned, if... 

While alkyl cyanoacrylate-based adhesives are used globally in a large variety of domestic and commercial settings, their physical and toxicological properties must be considered. Alkyl cyanoacrylate polymerization is a very exothermic reaction, so care must be taken to prevent the contamination of large quantities with any materials, which might initiate a very rapid, runaway reaction. Also, alkyl cyanoacrylate monomers and the polymers which they form, will burn, and users should avoid their use near sparks or open flames. 

Polymeric ethyl cyanoacrylate exhibits very low toxicity properties. In tests with laboratory rats, oral administration of 6400 mg/kg of the polymer failed to harm the test animals. Some skin irritation did occur in tests on guinea pigs, but skin sensitization or absorption through the skin was not observed [45]. 

Synthetic polymers can be classified as either chain-growth polymen or step-growth polymers. Chain-growth polymers are prepared by chain-reaction polymerization of vinyl monomers in the presence of a radical, an anion, or a cation initiator. Radical polymerization is sometimes used, but alkenes such as 2-methylpropene that have electron-donating substituents on the double bond polymerize easily by a cationic route through carbocation intermediates. Similarly, monomers such as methyl -cyanoacrylate that have electron-withdrawing substituents on the double bond polymerize by an anionic, conjugate addition pathway. 

Figure 14.5.3 The overall polymerization process for forming the cyanoacrylate polymer.

Polymeric materials are commonly used for bonding materials. Impact or contact adhesives are mainly based on highly crystalline polychloroprene (Neoprene), NR latex is used as a flexible adhesive very suitable for use with fabrics. Rigid adhesives based on materials such as polystyrene cement, epoxy resin or cyanoacrylates are suitable for bonding of rigid materials. The bond is provided by intramolecular forces between the adhesive and the adherend. Adiabatic... 

M. Gallardo, L. Roblot-Treupel, J. Manhuteau, I. Genin, P. Couvreur, M. Plat, and F. Puisieux, Nanocapsules et nanospheres d alkyl-cyanoacrylate, interactions principe actif/polymere, in 1989 Proc. 5th Int. Conf. Pharm. Tech. pp. D36-D45. 

In many cases, homopolymerization can be initiated by the anion-radicals of the monomers themselves. Of course, such monomers must have pronounced electron affinity (EA) and be stabilized by delocalization of an unpaired electron. Typical examples are represented by the anion-radicals of 1,1-dicyanoethylene (EA = 1.36 eV) and methyl or ethyl 2-cyanoacrylates (EA = 1.08 eV). In all of these anion-radicals, an unpaired electron is primarily localized on C atom of the CH2 segment and characterized by appreciable resonance stabilization (Brinkmann et al. 2002). These anion-radicals are nucleophilic and attack the neutral monomers to initiate polymerization. 

Cyanoacrylate adhesives, the famous consumer Super glue , is a monomer that polymerizes when it comes in contact with moisture, even with atmospheric moisture. 

Reactive adhesives Reactive adhesives are either low molecular weight polymers or monomers that solidify by polymerization and/or cross-linking reactions after application. Cyanoacrylates, phenolics, silicon rubbers, and epoxies are examples of this type of adhesive. Plywood is formed from impregnation of thin sheets of wood with resin, with the impregnation occurring after the resin is placed between the wooden sheets. 

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