Acrylic alkyl esters, copolymer

Polymer PolyactyUc acid Acryl alkyl ester copolymer SIS block copolymer... 

A typical acrylic adhesive is a copolymer of acrylic alkyl esters and polar vinyl monomers. Acrylic alkyl ester, whose homopolymer T is lower than — 40°C,... 

Standard-grade PSAs are usually made from styrene-butadiene rubber (SBR), natural rubber, or blends thereof in solution. In addition to rubbers, polyacrylates, polymethylacrylates, polyfvinyl ethers), polychloroprene, and polyisobutenes are often components of the system ([198], pp. 25-39). These are often modified with phenolic resins, or resins based on rosin esters, coumarones, or hydrocarbons. Phenolic resins improve temperature resistance, solvent resistance, and cohesive strength of PSA ([196], pp. 276-278). Antioxidants and tackifiers are also essential components. Sometimes the tackifier will be a lower molecular weight component of the high polymer system. The phenolic resins may be standard resoles, alkyl phenolics, or terpene-phenolic systems ([198], pp. 25-39 and 80-81). Pressure-sensitive dispersions are normally comprised of special acrylic ester copolymers with resin modifiers. The high polymer base used determines adhesive and cohesive properties of the PSA. 

Tphis paper is concerned with the effect of ionizing radiation on the physical and mechanical properties of copolymers of ethylene with alkyl acrylates, such as ethyl acrylate, butyl acrylate, and 2-ethvlhexyl acrylate (J, 2, 3). These polymers are made by the free radical copolymerization of ethylene under high pressure with alkyl esters of acrylic acid (9). They are more flexible than polyethylene and because of the polar nature of the comonomer, they are more compatible with fillers and with other polymers than is polyethylene. 

VCap alkyl(methyl)acrylate ester Copolymers contain short-chain alkyl methacrylates, such as methyl... 

In ASA terpolymer acrylic acid brings more flexibility and the material has very good mechanical properties and weather resistance. For these reasons ASA is extensively used in automotive industry and in the fabrication of various appliances. Even more frequently than acrylic acid itself, various acrylates are used in copolymers. Among these can be mentioned the copolymers of acrylic acid esters with methacrylic acid esters such as poly(methyl methacrylate-co-methyl acrylate), poly(methyl methacrylate-co-ethyl acrylate), poly(methyl methacrylate-co-butyl acrylate), poly(ethyl methacrylate-co-ethyl acrylate), poly(acrylonitrile-co-methyl acrylate), poly(alkyl acrylate-co-methyl methacrylates), and poly(alkyl acrylate-co-hydroxyethyl methacrylates) where alkyl can be methyl, ethyl, butyl, etc. Some literature information regarding thermal decomposition of copolymers including acrylic acid and acrylic acid esters is given in Table 6.7.8 [6],... 

Acenaphthalene 119-122, 128, 134 Acrylates, activated 1, 3 -, reactivity ratios 7 -, -, suspension copolymerization 13 Acrylic groups 49, 53 A-Acryloxy derivatives 37 Active ester method, graft copolymers 29 Alkyl esters, aminolysis 14 Aminolysis, alkyl esters 14 Amphigels, polymer-solvent compatibility 24... 

Hydrophobic regions can be one or two small, well-defined blocks of pendant hydrophobic moieties in an otherwise water-soluble polymer (2-4). An example is a water-soluble sulfonated BAB triblock copolymer where B is hydrophobic f-butylstyrene and A is vinyltoluene (2). However, hydro-phobic regions can also be less well-defined as well as more numerous in a polymer molecule than is the case for a triblock copolymer (5-22). For example, pendant alkyl esters appear to have been randomly incorporated in styrene-maleic anhydride (5) and vinyl benzyl ether-styrene-maleic anhydride (6-ii) copolymers. Also, alkyl polyoxyethylene acrylate monomers can be copolymerized with acrylamide to yield copolymers with pendant hydrophobic chains (12-15). More recently it was found (16-22) that small amounts of water-insoluble monomers that are solubilized by surfactants into aqueous solutions of a hydrophilic monomer produce copolymers with pendant hydrophobic chains, but the size, number, and nature of the hydro-phobic regions has not been determined. 

Copolymers containing allyl methacrylate have found application as an additive to other resin to enhance the properties of the system. For example, in one patent disclosure, an aqueous emulsion polymer was formed in water using 0.03 gm of sodium carbonate, 50 gm of methyl methacrylate, 2.0 gm of ethyl acrylate, and 0.1 gm of allyl methacrylate, and 0.40 gm of the sodium salt of an allyl Ci3-alkyl ester of sulfosuccinic acid. The polymerization was initiated with sodium persulfate and heated at 83°C for 1 hr. To this latex, 40 gm of butyl acrylate, 10 gm of styrene, 1.0 gm of allyl methacrylate, and another 0.40 gm of the above surfactant were added while polymerization continued. In a third... 

All vinyl polymers are addition polymers. To differentiate the, the homopolymers have been classified by the substituents attached to one carbon atom of the double bone. If the substituent is hydrogen, alkyl or aryl, the homopolymers are listed under polyolefins. Olefin homopolymers with other substituents are described under polyvinyl compounds, except where the substituent is a nitrile, a carboxylic acid, or a carboxylic acid ester or amide. The monomers in the latter cases being derivatives of acrylic acid, the derived polymers are listed under acrylics. Under olefin copolymers are listed products which are produced by copolymerization of two or more monomers. 

Synonyms AA/AM Acrylamide/acrylic acid copolymer Acrylic acid/ acrylamide copolymer Propenamide, polymer with propenoic acid, butenoic acid, and/or alkyl propenoates Definition Polymer of acrylamide and one or more monomers of acrylic acid, methacrylic acid or one of their simple esters Properties Nonionic... 

The poly alkyl acrylates and poly cyano acrylates generally resist biodegradation. In soil-burial tests, weight loss has been reported for copolymers of ethylene and propylene with acrylic acid, acrylonitrile, and acrylamide. The rapidly polymerizable systems such as poly(alkyl-2-cyanoacrylate)s adhered to moist surfaces have been examined in biomedical applications. Poly(methyl-2-cyanoacrylate) is the most degradable among the alkyl esters, and its degradability decreases as alkyl size increases (Holland etal., 1990). 

Additives acting on the pour point also modify the crystal size and, in addition, decrease the cohesive forces between crystals, allowing flow at lower temperatures. These additives are also copolymers containing vinyl esters, alkyl acrylates, or alkyl fumarates. In addition, formulations containing surfactants, such as the amides or fatty acid salts and long-chain dialkyl-amines, have an effect both on the cold filter plugging point and the pour point. 

Higher alkyl acrylates and alkyl-functional esters are important in copolymer products, in conventional emulsion appHcations for coatings and adhesives, and as reactants in radiation-cured coatings and inks. In general, they are produced in direct or transesterification batch processes (17,101,102) because of their relatively low volume. 

Unlike most crystalline polymers, PVDF exhibits thermodynamic compatibiUty with other polymers (133). Blends of PVDF and poly(methyl methacrylate) (PMMA) are compatible over a wide range of blend composition (134,135). SoHd-state nmr studies showed that isotactic PMMA is more miscible with PVDF than atactic and syndiotactic PMMA (136). MiscibiUty of PVDF and poly(alkyl acrylates) depends on a specific interaction between PVDF and oxygen within the acrylate and the effect of this interaction is diminished as the hydrocarbon content of the ester is increased (137). Strong dipolar interactions are important to achieve miscibility with poly(vinyhdene fluoride) (138). PVDF blends are the object of many papers and patents specific blends of PVDF and acryflc copolymers have seen large commercial use. 

The earliest study describing vulcanised polymers of esters of acryUc acid was carried out in Germany by Rohm (2) before World War I. The first commercial acryUc elastomers were produced in the United States in the 1940s (3—5). They were homopolymers and copolymers of ethyl acrylate and other alkyl acrylates, with a preference for poly(ethyl acrylate) [9003-32-17, due to its superior balance of properties. The main drawback of these products was the vulcanisation. The fully saturated chemical stmcture of the polymeric backbone in fact is inactive toward the classical accelerators and curing systems. As a consequence they requited the use of aggressive and not versatile compounds such as strong bases, eg, sodium metasiUcate pentahydrate. To overcome this limitation, monomers containing a reactive moiety were incorporated in the polymer backbone by copolymerisation with the usual alkyl acrylates. 

In 1950, Dahlquist et al. [82] reported the use of polyvinyl A -alkyl carbamates as PSA release materials. Since then, many other types of alkyl side chain polymers have been patented for use as release coatings, including copolymers based on higher alkyl acrylates or methaci ylates [83-86], polyvinyl esters of higher aliphatic fatty acids [87], higher alkyl vinyl esters or ethers and a maleic... 

Aqueous, removable, pressure-sensitive adhesive compositions, useful for high-performance applications, comprise a mixture of a copolymer of alkyl (meth)acrylate and N-substituted (poly)amide of (meth)acrylic acid and a copolymer of alkyl (meth)acrylate and ethylenically unsaturated carboxylic acid, where at least one of the copolymers is an emulsion copolymer. Polyoxyalkyl-enes and phosphate esters may be used as surfactants [234]. 

By employing anionic techniques, alkyl methacrylate containing block copolymer systems have been synthesized with controlled compositions, predictable molecular weights and narrow molecular weight distributions. Subsequent hydrolysis of the ester functionality to the metal carboxylate or carboxylic acid can be achieved either by potassium superoxide or the acid catalyzed hydrolysis of t-butyl methacrylate blocks. The presence of acid and ion groups has a profound effect on the solution and bulk mechanical behavior of the derived systems. The synthesis and characterization of various substituted styrene and all-acrylic block copolymer precursors with alkyl methacrylates will be discussed. 

Although the potassium superoxide route can be universally applied to various alkyl methacrylates, it is experimentally more difficult than simple acid hydrolysis. In addition, limited yields do not permit well-defined hydrophobic-hydrophilic blocks. On the other hand, acid catalyzed hydrolysis is limited to only a few esters such as TBMA, but yields of carboxylate are quantitative. Hydrolysis attempts of poly(methyl methacrylate) (PMMA) and poly(isopropyl methacrylate) (PIPMA) do not yield an observable amount of conversion to the carboxylic acid under the established conditions for poly(t-butyl methacrylate) (PTBMA). This allows for selective hydrolysis of all-acrylic block copolymers. 

Suspension of water soluble solids in oil can be achieved by a variety of chemical additives. Chemical suspension additives that have been suggested include alkyl mercaptophosphonic acids(174), organophylic clay plus hydroxypropyl cellulose(175), polyols(176), aluminum stearate(177), organophylic clay plus surfactant(178-181), aluminum phosphate esters(182), and acrylate copolymers(183-184). 

In this instance the thermal stability of vinylidene chloride /alkyl acrylate copolymers in which the alkyl groups are isomeric butyl units has been examined by thermogravimetry. The butyl ester comonomers incorporated are shown below (scheme 7). 

By polymerization of mixtures of monomers of ethylene and the acid in a tubular reactor, and hydrolysis of copolymers of ethylene and alkyl acrylates, which converts the ester groups to carboxylic acid groups. 

Granular starch and copolymers of ethylene and acrylic esters and alkyl(meth)acr-ylates or vinylacetate are produced as master batches for the production of mulch films, geotextiles and molded articles.146 The polar copolymers act as compatibilizers by lowering the interfacial energy between starch and the polyolefin and eliminate the need to coat granules. Processing via a vented twin-screw extruder also eliminates the need for anhydrous starch. 

The long side chains of the acrylate ester group can apparently act as internal plasticizers. Substitution of a carboxyl group on the polymer chain increases brittleness. A more polar substituent, eg, an /V-alkyl amide group, is even less desirable. Copolymers of VDC with N- alkyl a c ryl ami d e s are more brittle than the corresponding acrylates even when the side chains are long (87). Side-chain crystallization may be a contributing factor. 

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