Methacrylate-ester derivatives

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.,... 

The second type of composition is exemplified by a wide variety of acrylate- or methacrylate-ester derivatives of conventional ink vehicles combined with a photoinitiator 1. The reaction product of tung oil fatty acids, glycidyl methacrylate, -benzoquinone, and 2-methyl-imidazole mixed with tung oil and treated with tolylene diisocyanate, combined with benzoin methyl ether (26) 2. Glycerol-linseed oil-isophthalic acid alkyd reacted with isocyanate-containing prepolymer (formed by reaction of tolylene diisocyanate, -henzoquinone, 2-hydroxypropyl acrylate in ethyl acetate solution) using dibutyltin diacetate catalyst, combined with tung oil, synthetic varnish, and benzoin methyl ether (27) 3. Epoxidized... 

The third type of composition is exemplified by acrylate- and methacrylate-ester derivatives of epoxy resins combined with a photoinitiator 1. Epoxy prepolymers (e. g., glycidyl methacrylate-allyl glycidyl ether copolymers or Ciba ECN 1299) combined with a photosensitive aryldiazonium compound (e.g., -nitrobenzenediazonium hexaflourophosphate) (38,39) 2. Epoxy prepolymers (e.g., a diglycidyl ether of disphenol A-(3,4-epoxycyclohexyl)-methyl-3,4-epoxycyclohex-anecarboxylate-alkyl glycidyl ether mixture) combined with a photosensitive aryldiazonium compound (e.g., -chlorobenzenediazonium hexaflourophosphate) and l-methyl-2-pyrrolidone gelation inhibitor (40) ... 

The tetrakis-sulphoxides (67) have been reported as a new type of PT catalyst in a solid-liquid mode, for example in 5n reactions of 1-bromo-octane. Nucleophilic substitutions of 1-bromo-octane and benzyl bromide are again the test reactions in a report on the use of the sucrose-ethylene oxide adducts (68a) as PT catalysts in both solid-liquid and liquid-liquid modes. The methacrylate ester derivative (68b) has been polymerized to a cross-linked gel that acts in a TC capacity for the same reactions. In a related approach some modified dextran anion exchangers carrying lipophilic substituents, such as the modified hydroxypropylated dextran gel shown in (69), have been synthesized and shown to catalyse displacement reactions including the alkyl bromide to iodide transformation under TC conditions. ... 

An additive that was a mixture of esters of methacrylic acid and 60% C12-15 branched alcohols, methyl methacrylate, methacrylic esters derived from 23% C12 15 branched alcohols, and Cie-is linear alkyl methacrylates... 

Selected physical properties of various methacrylate esters, amides, and derivatives are given in Tables 1—4. Tables 3 and 4 describe more commercially available methacrylic acid derivatives. A2eotrope data for MMA are shown in Table 5 (8). The solubiUty of MMA in water at 25°C is 1.5%. Water solubiUty of longer alkyl methacrylates ranges from slight to insoluble. Some functionalized esters such as 2-dimethylaniinoethyl methacrylate are miscible and/or hydrolyze. The solubiUty of 2-hydroxypropyl methacrylate in water at 25°C is 13%. Vapor—Hquid equiUbrium (VLE) data have been pubHshed on methanol, methyl methacrylate, and methacrylic acid pairs (9), as have solubiUty data for this ternary system (10). VLE data are also available for methyl methacrylate, methacrylic acid, methyl a-hydroxyisobutyrate, methanol, and water, which are the critical components obtained in the commercially important acetone cyanohydrin route to methyl methacrylate (11). 

Methacryhc acid and its ester derivatives are Ctfjy -unsaturated carbonyl compounds and exhibit the reactivity typical of this class of compounds, ie, Michael and Michael-type conjugate addition reactions and a variety of cycloaddition and related reactions. Although less reactive than the corresponding acrylates as the result of the electron-donating effect and the steric hindrance of the a-methyl group, methacrylates readily undergo a wide variety of reactions and are valuable intermediates in many synthetic procedures. 

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). 

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). 

Theses polymers are made from acrylic acid, its homologues and their derivatives. Glass like resins were made from esters of aerylic acid in 1877 by Fitting and Peter by Kahlbaum. In 1928, Rohm and Hass, a German Company started commercial development of methacrylic esters. Limited production started in 1933. The rapidly expanding air-force used this plastic in place of glass in the aeroplanes. Most of the early production of "Plexiglass was used up by air-force planes. In 1936, ICI marketed methyl methacrylate sheets as "Perspex". 

Both CO2 activation and enolate formation are combined in the preparation of malonic acid derivatives. The reaction of CO2 with methacrylic esters or methacry-lonitrile and under visible light irradiation produced the corresponding aluminum porphyrin malonate complex. When diethylzinc was added to this system, Al(TPP)Et could be regenerated by axial ligand exchange reactions, and the malonic acid derivatives were formed catalytically with respect to the aluminum porphyrins in a one-pot photosynthetic route (Scheme 1). The first step in this... 

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. 

Some interesting resins have been obtained from the dianhydrides through their acrylic or methacrylic esters. Thus, 2,5-dimethacrylyl-l,4 3,6-dianhydro-mannitol (XIX) was formed by treating dianhydro-mannitol with methacrylyl chloride in the presence of sodium hydroxide. The product, a crystalline compound, polymerized extremely rapidly to a colorless, transparent, infusible resin. The corresponding sorbitol derivative, however, was an oil which polymerized to a softer resin. On the other hand, 2,5-diacrylyl-l,4 3,6-dianhydro-sorbitol (XX) was a crystalline compound, which polymerized to a hard, infusible, glass-like resin. 

Table V. Lithographic Properties of Ester Derivatives of Methacrylate — Based Electron Resists... 

Methacrylic esters of poly hydroxy compounds, like glucose (SO, 51, 136), maltose (136), dextrin (136), starch (136), sorbitol (47, 50, 51) and mannitol (47) derivatives, have also been polymerized however the polymers obtained are mostly insoluble and have not been investigated from the point of view of the relationships between optical activity and structure. 

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. 

Epoxy acrylate resins or vinyl esters are made from the esterification of epoxy resin via their terminal group with an unsaturated acid, such as methacrylic acid derived from epoxy resin. A typical reaction sequence is illustrated in Fig. 4.3. The resultant polymer is usually dissolved in a reactive monomer such as styrene. 

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. ... 

The contribution of the homolytical substitution to the total sum of reactions occuning in free-radical polymerization in the presence of anthracene of its derivatives depends on the nature of the monomer and the anthracene-containing compound and on the polymerization conditions. It has been diown that the macroradicals of the methacrylic esters do not interact with anthracene under usual conditions On the other hand, in the polymerization of styrene, substitution with the formation of terminal LM of type II (Scheme 1) proceeds only if one or both meso-positions of the anthracene ring are free ... 

Screening of an impressive series of polymers derived from different bulky methacrylate esters, e.g., 42 (Chart 8), and using a variety of chiral ligands has revealed the scope of the process of forming helical poly(methacrylate ester)s and their applicability in, for example, the separation of chiral compounds.151 These polymers were prepared not only by anionic polymerization, but also by cationic, free-radical, and Ziegler—Natta techniques. Recently, Nakano and Okamoto reported the use of a co-balt(II)—salophen complex (43) in the polymerization of methacrylate ester 41.155 The free-radical polymerization in the presence of this optically active metal complex resulted in the formation of an almost completely isotactic polymer with an excess of one helical sense. 

Acrylic resins are the materials of choice for almost all dental applications wherever synthetic plastics are favored for the restoration of missing teeth or tooth structures. This is not surprising because polymers derived from methacrylate esters fulfill most requisites of a restorative adequate strength, resilience and abrasion resistance dimensional stability during processing and subsequent use translucency or transparency simulating the visual appearance of the oral tissue that it replaces satisfactory color stability after fabrication resistance to oral fluids, food or other substances with which it may come Into contact satisfactory tissue tolerance low toxicity, and ease of fabrication into a dental appliance. 

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). 

Acrylic and methacrylic esters Vinylidene esters Derivatives of acrylonitrile... 

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