Acrylic and methacrylic derivatives

Other efforts based on the macromonomer approach to homopolymers having dendritic side chains, include the work of Draheim and Ritter on acrylate and methacrylate derived structures having dendritic chiral side chains based on L-aspartic esters [17a], and of Xi and coworkers with poly(methacrylate) structures containing very small benzyl ether dendritic side-chains [17b]. Unfortunately, both of these approaches met with limited success due to a significant drop in degree of polymerization (DP) when the size of the dendron used as pendant group in the macromonomers increased from G-l to G-2. 

Some of the most important critical points in RAFT polymerizations are the relative concentrations of the free radical initiator, the CTA, and the monomer, since these will establish the delicate balance between the dormant and active species. Acrylate and methacrylate derivatives can be successfully polymerized using 2-cyano-2-butyl dithio benzoate (CBDB) as a CTA. However, the amount of free radical initiator (a, a-azobisisobutyronitrile (AIBN) is used in general) compared to CTA determines the rate of control over the polymerization. Therefore, eight different acrylates or methacrylates were polymerized with different ratios of CTA to AIBN [54]. The structures of the monomers and the design of the experiment are shown in Fig. 6. 

With thioglycolic acid as a chain-transfer agent, macromonomers are prepared from dimethylaminoethyl methacrylate and other acrylate and methacrylate derivatives (539). lodoacetic acid is used as the transfer agent for polystyrene macromonomers (540). 

Yin, M., Krause, T., Messerschmidt, M., Habicher, W.D. and Voit, B. (2005) Nitroxide-mediated homo- and block copolymerization of styrene and multifunctional acryl- and methacryl derivatives./. Polym. Sci. Part A, Polym. Chem., 43,1873-1882. 

Results obtained in the many copolymerizations of carbazole-containing monomers with different chiral comonomers may be summarized as follows i) real copolymer macromolecules are obtained in the cationically and free radically initiated polymerization with alkyl vinyl ethers, acrylic and methacrylic derivatives, and butene-dioic acid diesters ii) homopolymer mixtures are obtained in copolymerization runs with a-olefms in the presence of Ziegler-Natta catalysts, indicating that the conventional anionic coordinate mechanism is not effective in the polymerization of carbazole monomers... 

The largest volume commercial derivatives of 1-butanol are -butyl acrylate [141-32-2] and methacrylate [97-88-1] (10). These are used principally ia emulsion polymers for latex paints, ia textile appHcations and ia impact modifiers for rigid poly(vinyl chloride). The consumption of / -butanol ia the United States for acrylate and methacrylate esters is expected to rise to 182,000—186,000 t by 1993 (10). 

Radical copolymerization is used in the manufacturing of random copolymers of acrylamide with vinyl monomers. Anionic copolymers are obtained by copolymerization of acrylamide with acrylic, methacrylic, maleic, fu-maric, styrenesulfonic, 2-acrylamide-2-methylpro-panesulfonic acids and its salts, etc., as well as by hydrolysis and sulfomethylation of polyacrylamide Cationic copolymers are obtained by copolymerization of acrylamide with jV-dialkylaminoalkyl acrylates and methacrylates, l,2-dimethyl-5-vinylpyridinum sulfate, etc. or by postreactions of polyacrylamide (the Mannich reaction and Hofmann degradation). Nonionic copolymers are obtained by copolymerization of acrylamide with acrylates, methacrylates, styrene derivatives, acrylonitrile, etc. Copolymerization methods are the same as the polymerization of acrylamide. 

MMA, styrene, 2-hydroxy ethyl methyacrylate, 2-hy-droxypropyl methacrylate, acrylic and methacrylic acids, acrylamide and N-vinyl pyrrolidone (NVP) [64]. By this process, polyurethane is partially converted to N-chloro or N-bromo derivatives by a short immersion... 

Kammerer ei aL1(n m have conducted extensive studies on the template polymerization of acrylate or methacrylate derivatives of polyphenolic oligomers 22 with X n < 5 (Scheme 8.14). Under conditions of low "monomer" and high initiator concentration they found that X n for the daughter polymer was the same as X n for the parent. The possibility of using such templates to control microstructure was considered but not reported. 

Sawamoto et al. have revealed that the ruthenium complex induces the living radical polymerization of MMA [30,273-277]. For example, RuCl2(PPh)3 provided poly(MMA) with Mw/Mn 1.1 and the block copolymers. This system has a unique characteristic in that it is valid not only for MMA and other methacrylates, but also for acrylates and St derivatives. 

Alkyl derivatives of the alkaline-earth metals have also been used to initiate anionic polymerization. Organomagnesium compounds are considerably less active than organolithiums, as a result of the much less polarized metal-carbon bond. They can only initiate polymerization of monomers more reactive than styrene and 1,3-dienes, such as 2- and 4-vinylpyridines, and acrylic and methacrylic esters. Organostrontium and organobarium compounds, possessing more polar metal-carbon bonds, are able to polymerize styrene and 1,3-dienes as well as the more reactive monomers. 

Was used in prepn of acrylate resins and of other copolymers and polymers. Acrylate resins are thermoplastic polymers or polymers of acrylic and methacrylic acid, esters of these acids or acrylonitrile. Acrylic acid acrylonitrile and their derivatives are described in Vol 1 of Encycl, pp A96-R A97. Methacrylic acid is a-methylacrylic acid,... 

Acrylic Polymers. Although considerable information on the plasticization of acrylic resins is scattered throughout journal and patent literature, the subject is complicated by the fact that acrylic resins constitute a large family of polymers rather than a single polymeric species. An infinite variation in physical properties may be obtained through copolymerization of two or more acrylic monomers selected from the available esters of acrylic and methacrylic acid (30) (see Acrylic esterpolya rs Methacrylic acid and derivatives). 

Hie largesl-volume conmiercial derivatives of 1-bulanol are n-bulyl acrylate and methacrylate. These are used principally iu emulsion polymers... 

The highest volume oxo chemical in the United States, n-butyraldehyde, is converted mainly into u-butanol, employed chiefly to produce butyl acrylate and methacrylate. In contrast, the principal -butyraldehyde derivative in Europe and Japan is 2-ethylhexanol, the precursor to the polyi vinyl chloride) (PVC) plasticizer, DOP. 

Another type of important linear polymers are the acrylates and methacrylates. In Figure 2.35, the repeating unit with two side groups from which these polymer types are derived is shown [195,197]. In Table 2.3, three examples of this type of polymers, specifically, poly (ethyl acrylate), which is applied in paints poly (methyl methacrylate), which is applied fundamentally as a construction material in place of glass and poly (ethyl methacrylate), which is applied as adhesives, are reported. 

The majority of radiation curable materials are derived from or consist of acrylic and methacrylic unsaturated monomers, oli-gonomers, and polymers (including unsaturated polyethers) which cure through free radical addition-propagation reactions. 

A new family of perfluoroacrylate and methacrylate based positive and negative tone photoresist compositions activated at 193 run has been prepared by free radical homo-or co-polymerization of acrylate or methacrylate derivatives. Polymeric agents prepared in this manner had Mn s between 5,000 and 50,000 daltons and were readily soluble in organic solvents. 

Several optically active polymers of acrylates and methacrylates have been obtained by enantioselective polymerization of a racemic monomer initiated by a Grignard compound complexed with chiral reagent. Complexing agents for the polymerization of (K,S)-a-methylbenzyl methacrylate include chiral alcohols, such as quinine and cinchonine [63], (— )-sparteine and its derivatives [64-67], and other axially disymmetric biphenyl compounds [68,69]. Other racemic monomers used include (/ ,S)-a-methylbenzyl acrylate [70], (K,S)-l-phenylethyl acrylate, methacrylate and a-ethylacrylate [71], and 1,2-diphenylethylmethacrylate [72]. 

The third type of composition is exemplified acrylate- and methacrylate-ester derivatives of epoxy resins combined with a photoinitiator 1. Epo prepolymers (e. g., glycidyl methacrylate-allyl glycidyl ether copolymers or Ciba ECN 1299) combined with a photosensitive aryldiazonium compound (e.g.,... 

Vinyl derivatives are frequently used to obtain copolymers. Some of the copolymers containing vinyl comonomers are discussed in other sections of this book in connection with the pairing comonomer, or in the sections dealing with halogenated copolymers or the copolymers of acrylates and methacrylates. 

The carboxyl group in acrylates and methacrylates can be esterified with various other alcohols, including diols such as ethylene glycol, diethyleneglycol, etc. In addition to the free acids and their esters, to this class can be added other derivatives of acrylic acid such as poly(acrylonitrile) [-CH2-CH(CN)-]n, poly(acrylamide) [-CH2-CH(CONH2)-]n,... 

Probably the first polymerizable ultraviolet absorbers for general use were acryloyl or methacryloyl derivatives of the 1-hydroxy group of 2,1-dihydroxybenzophenone (7). Acrylic and methacrylic esters have also been prepared from 2(2-hydroxyphenyl)2H-benzotria-zoles with a phenolic hydroxyl group in the carbocyclic ring of a benzotriazole group (8). 

Polymerizable Ultraviolet Stabilizers — Miscellaneous Types. In our research on polymerizable ultraviolet stabilizers, we have decided to prepare styrene-type monomers in which the vinyl (or isopropenyl) group is directly attached to the phenyl group of the stabilizer, which might be polymerized similarly to styrene. These monomers can indeed be polymerized and copolymerized successfully with styrene, acrylic and methacrylic acid derivatives with azobisisobutyronitrile (AIBN) as the radical initiator (12-Ut-). 

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