Methacrylate esters copolymerization

A substantial fraction of commercially prepared methacrylic polymers are copolymers. Monomeric acryUc or methacrylic esters are often copolymerized with one another and possibly several other monomers. Copolymerization greatiy increases the range of available polymer properties. The aH-acryhc polymers tend to be soft and tacky the aH-methacryhc polymers tend to be hard and brittie. By judicious adjustment of the amount of each type of monomer, polymers can be prepared at essentially any desired hardness or flexibiUty. Small amounts of specially functionalized monomers are often copolymerized with methacrylic monomers to modify or improve the properties of the polymer directiy or by providing sites for further reactions. Table 9 lists some of the more common functional monomers used for the preparation of methacrylic copolymers. 

Table 9. Common Functional Monomers for Copolymerization with Acrylic and Methacrylic Esters...

Various methacrylate esters have been disclosed as modifiers of DADC. Thus methyl methacrylate polymer may be dissolved in DADC and the sheets cast (22). When DADC is copolymerized with methyl methacrylate, a silane derivative may be added to control the release from the mold (23). 

Small amounts of TAIC together with DAP have been used to cure unsaturated polyesters in glass-reinforced thermo sets (131). It has been used with polyfunctional methacrylate esters in anaerobic adhesives (132). TAIC and vinyl acetate are copolymerized in aqueous suspension, and vinyl alcohol copolymer gels are made from the products (133). Electron cure of poly(ethylene terephthalate) moldings containing TAIC improves heat resistance and transparency (134). 

The major applications of catalytic chain transfer are in molecular weight control and in synthesis of macromonomcrs based on methacrylate esters. However, they have also been shown effective in polymerizations and copolymerizations of MAA, MAM, MAN, AMS, S and some other monomers. 

Copolymerizations of other monomers may also be subject to similar effects given sufficiently high reaction temperatures (at or near their ceiling temperatures - Section 4.5.1). The depropagation of methacrylate esters becomes measurable at temperatures >100 °C (Section 4.5.1).96 O Driseoll and Gasparro86 have reported on the copolymerization of MMA with S at 250 °C. 

Recently it has been shown that anionic functionalization techniques can be applied to the synthesis of macromonomers — macromolecular monomers — i.e. linear polymers fitted at chain end with a polymerizable unsaturation, most commonly styrene or methacrylic ester 69 71). These species in turn provide easy access to graft copolymers upon radical copolymerization with vinylic or acrylic monomers. 

Grafting from method, 7 652-653 Grafting onto method, 7 654 Grafting process, 73 537 Grafting through method, 7 653 Graft polymerization. See also Graft copolymerization ABS, 7 419, 421 acrylic ester monomers, 7 386 of methacrylic ester polymers, 76 289-290... 

Methacrylates Methacrylic ester polymers copolymerization with acrylic monomers, l 380t... 

In this paper, we report an alternative approach to the design of deep UV resist systems combining the desired properties, which involves copolymerization of methacrylic ester with styrenic comonomer and the use of the acid-catalyzed deprotection chemistry. 

Scheme 8.12 Preparation of the diblock copolymer 57 by random copolymerization of PMMA block prepared by ATRP, methacrylic esters containing alkoxyamine nnits 55 and 56 [44],...

Syntheses of Self-Sensitized Polymers by Cationic Copolymerizations. The cationic polymerizations of several vinyl ethers containing pendant ester groups such as cinnamic ester 12), methacrylic ester 16), acrylic ester (77), and crotonic ester 18) have been reported. Based on these reports, cationic copolymerizations of CEVE with photosensitizer monomers such as NPVE, NNVE, VNP and NPEVE were carried out using TFB as a catalyst in toluene at — 65 °C. Each copolymer was obtained with high yield except in the case of copolymerization of CEVE with VNP as summarized in Table I. 

Berlin, and Makarova (85) took up this approach ten years later and prepared the methacrylic esters of cellulose which could be polymerized to cross-linked products. They also descibed the graft copolymerization with methyl methacrylate, although, they did not recognize at that time their products as graft copolymers. 

Comparing the reactivity ratios of the DADMAC/AAM copolymerization with results of the copolymerization of other cationic monomers with AAM, significant differences can be identified. The differences between rx and r2 are much lower, and the cationic monomer even reacts preferentially during the copolymerization. As an example, for cationic methacrylic esters and methacrylamid derivatives, 1 nonideal copolymerization preferring the cationic component. For the cationic analogs of acrylic acid and acrylamide, 0.34azeotropic copolymerization, preferring the cationic monomer only at low content in the comonomer mixture. 

Polymerizations via the hydroxyl group of 3,3-bis(hydroxymethyl) thietane have been used to prepare polyurethanes " and polyethers. " Tin derivatives are stabilizers for poly(vinyl chloride) as well as being used in polyurethane formation. Cyclic carbonate derivatives are homo- or copolymerized to high-molecular-weight solids. The methacrylate ester of 3-hydroxythietane has been copolymerized with methyl methacrylate. ... 

A macroporous reactive polymer was prepared by copolymerization of the methacrylate esters 75 and 76, using the methacrylate ester 77 as crosslinking agent. After removal of the benzylidene protecting groups the polymer could be diazotized and used for immobilizing phenolic analytes by a coupling reaction. The azo dye formed on the polymer was split by hydrolysis of the ester and quantitatively determined by LC. ... 

The chemistry is dependent on the particular substituents. Oxygen analogs of 31, a-alkoxyacylates (32), do not inhibit polymerization but readily polymerize and copolymerize with reactivity ratios similar to methacrylate esters. ... 

Flame retardants are usually halogen-containing materials. 2,4,6-Tribromophenyl, pentabromopheuyl, and 2,3-dibromopropyl derivatives of acrylate and methacrylate esters can be readily polymerized or copolymerized with styrene, methyl methacrylate, and acrylonitrile to produce polymers with improved flame retardancy (Equation 5.20). 

Chem. Descrip. Methyl methacrylate CAS 80-62-6 EINECS/ELINCS 201-297-1 Uses Polymerization/copolymerization plastics, leather, paint, paper, and textile industries base material for other methacrylic esters dental prods. Properties 0.01 /o max. water < 0.005% acid MHT 60 S [Dow]... 

Styrene was also copolymerized with many aciylic and methacrylic esters. Products with better weatherability often form. Copolymerizadon with some acrylates lowers the value of Tg ... 

Solvents influence the rate of free-radical homopolymerization of acrylic acid and its copolymerization with other monomers. Hydrogen-bonding solvents slow down the reaction rates. Due to the electron-withdrawing nature of the ester groups, acrylic and methacrylic ester polymerize by anionic but not by cationic mechanisms. Lithium alkyls are very effective initiators of a-methyl methacrylate polymerization yielding stereospecific polymers.Isotactic poly(methyl methacrylate) forms in hydrocarbon solvents. Block copolymers of isotactic and syndiotactic poly(methyl methacrylate) form in solvents of medium polarity. Syndiotactic polymers form in polar solvents, like ethylene glycol dimethyl ether, or pyridine. This solvent influence is related to Lewis basicity in the following order ... 

When copolymerized, the acrylic ester monomers typically randomly incorporate themselves into the polymer chains according to the percentage concentration of each monomer in the reactor initial charge. Alternatively, acrylic ester monomers can be copolymerized with styrene, methacrylic ester monomers, acrylonitrile, and vinyl acetate to produce commercially significant polymers. 

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