Acrylate monomers polymerization

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-... 

Photosensltlzers or Photolnltlators. The primary component In the UV-curable coating system Is the photosensitizer or photolnltlator (a light sensitive catalyst that upon absorption of energy results In a free radical species that can initiate acrylic monomer polymerization). C2.)... 

The acrylate monomers polymerize because of the C=C double bond contained in the molecule under the influence of a hardener characterized by an oxygen-oxygen bond, a so-called peroxide. (Even the hydrogenperoxide, a known bleaching agent, shows such a 0-0 bond). The triggering of the polymerization requires an accelerator already incorporated into the resin component by the manufacturer. 

Statistical copolymers of uBA and IBA with different molecular weights and compositions were synthesized under ATRP conditions, as described in detail earlier (26). In all ATRP reactions, a CuBr/PMDETA complex was used since it is commercially available and well mediates controlled polymerization of acrylate monomers. Polymerizations were performed at 50°C in acetone/anisole mixture using EtBrIB as the initiator. The schematic representation of all prepared materials is shown in Scheme 2. The solid line represents a series of polymers with similar DP but systematically increasing IBA content. Another such group of copolymers is indicated with a dashed line. Copolymers with similar IBA/nBA ratio but different degree of polymerization (DP), i.e., the dotted line, were also synthesized. When comparing the thermo-mechanical properties of acrylate homopolymers and P(IBA-co-nBA) copolymers, the first important question is whether the copolymer system is isotropic in the bulk state or rather exhibits a micro-phase separation. To answer this question, the DSC thermograms for all samples shown in Scheme 2 were measured. 

J of the acrylic monomer polymerizes to form acrylic copolymer,... 

Complexes 61-63 may also be used to polymerize acrylates " in a living manner, although, unlike the thiolate complexes, the methyl initiator again requires photoexcitation. Acrylate monomers polymerize faster than methacrylates, with even sterically encumbered tert-hu y acrylate being consumed more rapidly than MMA. As for MMA, no information concerning the stereoselectivity of these polymerizations has been disclosed. 

In normal practice, inhibitors such as hydroquinone (HQ) [123-31 -9] or the monomethyl ether of hydroquinone (MEHQ) [150-76-5] are added to acrylic monomers to stabilize them during shipment and storage. Uninhibited acrylic monomers should be used prompdy or stored at 10°C or below for no longer than a few weeks. Improperly iahibited monomers have the potential for violent polymerizations. HQ and MEHQ require the presence of oxygen to be effective inhibitors therefore, these monomers should be stored in contact with air and not under inert atmosphere. Because of the low concentration of inhibitors present in most commercial grades of acrylic monomers (generally less than 100 ppm), removal before use is not normally required. However, procedures for removal of inhibitors are available (67). 

Hie common acrylic ester monomers are combustible liquids. Commercially, acrylic monomers are shipped with DOT red labels in bulk quantities, tank cars, or tank tmcks. Mild steel is the usual material of choice for the constmction of bulk storage facilities for acrylic monomers. Moisture must be excluded to avoid msting of the tanks and contamination of the monomers. Copper or copper alloys must not be allowed to contact acrylic monomers intended for use in polymerization because copper is an inhibitor (67). 

Usually, free-radical initiators such as azo compounds or peroxides are used to initiate the polymerization of acrylic monomers. Photochemical (72—74) and radiation-initiated (75) polymerizations are also well known. At a constant temperature, the initial rate of the bulk or solution radical polymerization of acrylic monomers is first order with respect to monomer concentration and one-half order with respect to the initiator concentration. Rate data for polymerization of several common acrylic monomers initiated with 2,2 -azobisisobutyronittile (AIBN) [78-67-1] have been determined and are shown in Table 6. The table also includes heats of polymerization and volume percent shrinkage data. 

The free-radical polymerization of acrylic monomers follows a classical chain mechanism in which the chain-propagation step entails the head-to-tail growth of the polymeric free radical by attack on the double bond of the monomer. 

In general, acryUc ester monomers copolymerize readily with each other or with most other types of vinyl monomers by free-radical processes. The relative ease of copolymerization for 1 1 mixtures of acrylate monomers with other common monomers is presented in Table 7. Values above 25 indicate that good copolymerization is expected. Low values can often be offset by a suitable adjustment in the proportion of comonomers or in the method of their introduction into the polymerization reaction (86). 

Peioxydicaibonates are efficient polymerization initiators for most vinyl monomer polymerizations, especially for monomers such as acrylates, ethylene, and vinyl chloride. They are particularly good initiators for less reactive monomers such as those containing aHyl groups. They are also effective for curing of unsaturated polyester mol ding resins. 

Group-Transfer Polymerization. Living polymerization of acrylic monomers has been carried out using ketene silyl acetals as initiators. This chemistry can be used to make random, block, or graft copolymers of polar monomers. The following scheme demonstrates the synthesis of a methyl methacrylate—lauryl methacrylate (MMA—LMA) AB block copolymer (38). LMA is CH2=C(CH2)COO(CH2) CH2. 

Acrylic PSAs are obtained by polymerizing acrylate monomers having the following general structure ... 

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. 

Group of plastics based on resins generated from the polymerization of acrylic monomers (e.g., ethyl acrylate and methyl methacrylate). 

The free radical initiators are more suitable for the monomers having electron-withdrawing substituents directed to the ethylene nucleus. The monomers having electron-supplying groups can be polymerized better with the ionic initiators. The water solubility of the monomer is another important consideration. Highly water-soluble (relatively polar) monomers are not suitable for the emulsion polymerization process since most of the monomer polymerizes within the continuous medium, The detailed emulsion polymerization procedures for various monomers, including styrene [59-64], butadiene [61,63,64], vinyl acetate [62,64], vinyl chloride [62,64,65], alkyl acrylates [61-63,65], alkyl methacrylates [62,64], chloroprene [63], and isoprene [61,63] are available in the literature. 

A substantial number of photo-induced charge transfer polymerizations have been known to proceed through N-vinylcarbazole (VCZ) as an electron-donor monomer, but much less attention was paid to the polymerization of acrylic monomer as an electron receptor in the presence of amine as donor. The photo-induced charge-transfer polymerization of electron-attracting monomers, such as methyl acrylate(MA) and acrylonitrile (AN), have been recently studied [4]. In this paper, some results of our research on the reaction mechanism of vinyl polymerization with amine in redox and photo-induced charge transfer initiation systems are reviewed. 

The well-known photopolymerization of acrylic monomers usually involves a charge transfer system with carbonyl compound as an acceptor and aliphatic tertiary amine, triethylamine (TEA), as a donor. Instead of tertiary amine such as TEA or DMT, Li et al. [89] investigated the photopolymerization of AN in the presence of benzophenone (BP) and aniline (A) or N-methylaniline (NMA) and found that the BP-A or BP-NMA system will give a higher rate of polymerization than that of the well-known system BP-TEA. Still, we know that secondary aromatic amine would be deprotonated of the H-atom mostly on the N-atom so we proposed the mechanism as follows ... 

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