Carboxylated olefin copolymer

The compositions consist of a heat-plastified mixture of an ethylene homopolymer or copolymer, about 3 to 30 pbw of an elastomer, a stability control agent, which is a partial ester of a long chain fatty acid with a polyol, higher allyl amine, fatty acid amide or olefinically unsaturated carboxylic acid copolymer, and a hydrocarbon blowing agent having from 1 to 6 carbon atoms and a boiling point between -175 and 50C. 

In the latter, the undecenoic acid termonomer, with a hydrophilic carboxylic acid moiety, can function as a copolymerizable stabilizer. By comparison to terpo-lymerization in non-aqueous polymerizations in methanol, the high local concentration of the liquid termonomer in droplets in the aqueous polymerization is beneficial for its incorporation. The 1-olefin copolymers exhibit glass transition temperaUires of Tg+10 to -55 °C, and thus can form films upon drying of a latex at room temperature. 

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. 

ADHESION WITH NONELASTOMERIC, CARBOXYL FUNCTIONAL, OLEFIN COPOLYMERS... 

ATBN - amine terminated nitrile rubber X - Flory Huggins interaction parameter CPE - carboxylated polyethylene d - width at half height of the copolymer profile given by Kuhn statistical segment length DMAE - dimethyl amino ethanol r - interfacial tension reduction d - particle size reduction DSC - differential scanning calorimetry EMA - ethylene methyl acrylate copolymer ENR - epoxidized natural rubber EOR - ethylene olefin rubber EPDM - ethylene propylene diene monomer EPM - ethylene propylene monomer rubber EPR - ethylene propylene rubber EPR-g-SA - succinic anhydride grafted ethylene propylene rubber... 

Ionic copolymers are composed from an a-olefin with an olefin content of 80 mol-% and an ethylenically unsaturated carboxylic acid (6). Suitable olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, etc. 

Ionomers of practical interest have been prepared by two synthetic routes (a) copolymerization of a low level of functionalized monomer with an olefinically unsaturated monomer or (b) direct functionalization of a preformed polymer. Typically, carboxyl containing ionomers are obtained by direct copolymerization of acrylic or methacrylic acid with ethylene, styrene and similar comonomers by free radical copoly-merization. Rees (22) has described the preparation of a number of such copolymers. The resulting copolymer is generally available as the free acid which can be neutralized to the degree desired with metal hydroxides, acetates and similar salts. Recently, Weiss et al.(23-26) have described the preparation of sulfonated ionomers by copolymerization of sodium styrene sulfonate with butadiene or styrene. 

The preparation of ionomers involves either the copolymerization of a functionalized monomer with an olefinic unsaturated monomer or direct functionalization of a preformed polymer. Typically, free-radical copolymerization of ethylene, styrene, or other a-olefins with acrylic acid or methacrylic acid results in carboxyl-containing ionomers. The copolymer, available as a free acid, is then neutralized partially to a desired degree with metal hydroxides, acetates, or similar salts. The second route for the preparation of ionomers involves modification of a preformed polymer. For example, sulfonated polystyrene is obtained by direct sulfonation of polystyrene in a homogeneous solution followed by neutralization of the acid to the desired level. Some commercially available ionomers are listed in Table 15.17. 

Potassium castor oil sulfate Potassium stearate PPG-5-ceteth-10 phosphate PPG-10 cetyl ether PPG-10 cetyl ether phosphate PPG-9 diethylmonium chloride PPG-40 diethylmonium chloride PPG-1 hydroxyethyl caprylamide PPG-2 hydroxyethyl cocamide PPG-3 hydroxyethyl linoleamide Ricinoleamidopropyl trimonium methosulfate Silicone glycol copolymer Silicone quaternium-2 Sodium C12-15 alkoxypropyl iminodipropionate Sodium C8-10 all l sulfate Sodium carboxyethyl tallowpolypropylamine Sodium cetearyl sulfate Sodium C14-16 olefin sulfonate Sodium C12-15 pareth-3 sulfonate Sodium C12-15 pareth-7 sulfonate Sodium C12-15 pareth-15 sulfonate Sodium laureth-4 carboxylate Sodium laureth-7... 

Photoconductive Lithographic Printing Plate Assembly. NVK has been copolymerized with olefinic monomers possessing carboxylic acid, such as acrylic acid, methacrylic acid, fumaric acid, and, maleic anhydride, or carboxylic anhydride [7]. The acid functionality yields copolymers that are soluble in aqueous alkaline media. The copolymers are intended... 

Pickton[73] reported impact modified nylon blends of poly(2-methyl pentamethylene terephthalamide) and an ionomer such as a partially neutralized copolymer of -olefin and, -ethylenically unsaturated carboxylic acid as minor component. Melt blending of poly(2-methyl pentamethylene terephthalamide) and 1 wt% Du Pont Surlyn 8527 at 290 °C gave tensile modulus 68.4 g/d, tensile strength 7.4 g/d, and elongation at break 18.2%. 

A broad variety of difunctional allylic olefins have been used for the synthesis of amino-, carboxyl-, and halide-terminated polybutadienes by means of the Grubbs catalyst I (396-398). With the same catalyst, commercially interesting hydroxy telechelic polybutadienes could be obtained by the cleavage of the acetyl end-capped polymer or the copolymer, as depicted in Figure 14 (399,400). 

There has been a slight increase in activity in this area compared with that in the previous two year period. For the polymeric esters of acrylic, methacrylic acids, and related polymers the simplest reaction, apart from thermal depolymerization, is hydrolysis, and one or two papers on this subject have appeared. One of these concerns a comparison of the kinetics of hydrolysis of a number of methacrylate esters and a further two deal with the formation of copolymers containing carboxylic acid functions. Methyl trifluoroacrylate forms alternating copolymers with cE-olefins (ethylene, propylene, isobutylene) and these are readily hydrolysed in boiling aqueous methanolic sodium hydroxide to yield hydrophilic fluoropolymers. Hydrolysis is reported to be nearly quantitative with no chain scission. An alternating copolymer is also formed by radical polymerization of maleic anhydride with A-vinyl succinimide. On hydrolysis this copolymer is... 

In the absence of hydrogen, metallocene-based catalyst systems produce well-defined polymers which are olefin- or aluminum-terminated. Miilhaupt has polymerized propylene with a chiral metallocene and MAO under conditions where P-hydrogen elimination was the predominant chain transfer process. In a post-polymerization functionalization, the olefin endgroups of the highly isotactic polypropylene chains were converted to bromo-, epoxy-, anhydride-, ester-, amine-, carboxylic acid-, silane-, borane-, hydroxy-, thiol-terminated polymers as intermediates for the preparation of block copolymers. Using olefin-terminated atactic and isotactic polypropylene formed with MAO-activated Cp2ZrCl2 and (EBTHI)ZrCl2 Shiono has synthesized amine- and aluminum-terminated polymers." ... 

A wide range of dithioester RAFT agents has been reported. Common examples of mono-RAFT agents and their application are provided in Tables 11 (Z = aryl) and 13 (Z = alkyl or aralkyl). RAFT agents can contain various unprotected functionality on the R fragment of dithiobenzoate including hydroxy, carboxylic acid/carboxylate, sulfonic acid/sulfonate, olefin, and siloxane. Examples of bis- and multi-dithioester RAFT agents (Z=aryl) that may be used for triblock or star synthesis are shown in Tables 12 and 22, respectively. Bis-dithioesters can be used to synthesize triblock copolymers in a two-step process. 

In principle, such protection using the carboxylate salt is feasible, but an exchange of the metal cation coordinated to the carboxylate salt has to be taken into account. This would lead to a transfer of the protected olefin between the titanocene and the active catalyst. Copolymerization experiments of Tim/Iia with ethene lead to the desired titanocene-protected copolymers in yields comparable to ethene homopolymerization. Hydrochlorination of the protected polymer regenerates the protecting Cp2TiCl and the free carboxylic acid of the polymer (Scheme 19). 

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