Methacrylate graft polyolefins

The first LDPE/HDPE blends were patented by du Pont de Nemours before Z-N polymers became available (Roedel 1961). The blend comprised an experimental HOPE (p = 0.939-1.096 g mL Tm 120 °C) obtained by polymerizing C2 in its own medium at T 0 °C and P 31 MPa, using, e.g., a hydroxy-cyclohexyl-L-hydroperoxide catalyzed by ferrous chloride tetrahydrate. The blend showed 50 % moisture permeabDity of that by LDPE. In 1958 Phillips Petroleum patented PE/PE blends, either cross-linked in electron accelerator or not (Canterino and Martinovich 1963 Nelson 1964). Mitsubishi disclosed PO blends comprising vinyl-trimethoxysUane-grafted polyolefin (PP, LDPE, EPR, or EVAc) and ethylene-acryloyloxy tetramethylpiperidine copolymer. These water-cross-linkable resins were used for the manufacture of weather-resistant cross-linked PO pipes in outdoor applications (Ohnishi and Fukuda 1993). Thermally reversible cross-links (based on ionic interaction between maleated- and glycidyl methacrylate-grafted polyolefins) were also proposed (Okada 1994 Okada and Masuyama 1994). 

Some authors combined the IPN concept with the use of compatibi-lizers similar to that mentioned in Section 2. These may be a coupling agent such as epoxy-functionalized polysiloxane, polysiloxane copolymers or an organofunctional grafted polyolefin such as poly(ethylene-co-methacrylate) or MA-g-EPDM (maleic anhydride grafted EPDM) [124,125, 133]. Knaub et al. [150] studied a poly(urethane-ureas)/PDMS semi-IPN in... 

Examples of acid modified polyolefins are the copolymers of ethylene with acrylic acid or methacrylic acid. Variations include the partially neutralised acid copolymers with metal ions (ionomers) or terpolymers of ethylene, an acid and an acrylate such as methyl acrylate or isobutyl acrylate. Acid-containing extrudable adhesives are widely used to bond to aluminium foil. Examples of anhydride-modified polyolefins include terpolymers of ethylene, maleic anhydride and acrylates such as ethyl acrylate or butyl acrylate and the anhydride-grafted polyolefins. Some typical applications and stmctures of a variety of multilayer materials with extruded polymer tie-layer adhesives, as described in Du-Pont trade literature, are detailed in Table 16.2. 

Dow has prepared a compatibilized blend of PC and linear PE. The compati-bilizer used was EPDM grafted with SAN. The product has high impact strength and good melt processability. Polymer alloys with S-AMS copolymer and PP with styrene-grafted polyolefin copolymer have been reported. Triax 1000 of Monsanto is a blend of nylon and ABS compatibilized with styrene-acrylonitrile and glycidyl methacrylate terpolymer. The compatibilizer often improves the property balance of an immiscible blend. Reactive compatibilization is an emerging technique. 

Epoxy groups are introduced by grafting glycidyl methacrylate onto polyolefins. They react readily with carboxylic acid, amine, and other active hydrogen groups on other polymers. 

Various (meth)acrylic monomers have been successfully grafted onto polyolefins. Most studies deal with functional monomers. Grafting yields obtained with PP are usually low (<20%) and are dependent on the particular monomer. Liu et al.jM carried out a comparative study on the grafting of various functional methacrylates onto PP. The experiments were performed in a batch mixer at 180 °C with 7 wt% monomer and 0.05 wt% 22 as an initiator. Grafting levels (wt%) obtained under these conditions were as follows HPMA (I), TBAEMA (1), GMA (0.8), IIEMA (0.4), DMAEMA (0.3), 32 (0.2). Grafting yields to PE appear generally higher. 

Chung and coworkers have reported on the use of stable borinale or boroxyl radicals (e.g. 114) to mediate radical polymerization." Methacrylates (MMA) and acrylates (trifluoroelhyl acrylate) have been polymerized at ambient temperature to yield polymers with relatively narrow molecular weight distributions.231233 The method has been used to prepare block copolymers and polyolefin graft copolymers.2 4 37... 

In addition, borane-containing POs can be prepared by copolymerization of olefin with borane monomers or by hydroboration of polyolefins including unsaturated groups, such as olefin-divinylbenzene copolymer and olefin-diene copolymers. Many kinds of graft copolymers, such as poly-elhylene-gra/f-poly( vinyl alcohol), PE-g-PMMA, polypropylcnc-gra/f-poly-(maleicanhydride-co-styrene), polypropylene-gra/f-poly(methacrylic acid), polypropylene-gra/f-poly(vinyl alcohol), polypropylene-gra/f-polycaprolac-tone (PP-g-PCL), polypropylcnc-gra/f-poly(methyl methacrylate) (PP-g-PMMA), poly( ethylene-co-propylene)-gra/f-poly(methyl methacrylate) (EPR-g-PMMA), and poly(ethylene-co-propylene)-gra/f-poly(maleic anhydride-costyrene), have been synthesized by such a method resulting in controllable composition and molecular microstructures [63-66]. 

Interchain copolymer formation Copolymers of reactive polystyrene and polymers with amide, mercaptan, epoxy, hydroxy, anhydride or carboxylic acid groups, copolymer of polypropylene grafted with maleic anhydride and nylon-6, copolymer of polyolefines and polystyrene, copolymer of EVA grafted with methacrylates and grafted polystyrene... 

PVC can be blended with numerous other polymers to give it better processability and impact resistance. For the manufacture of food contact materials the following polymerizates and/or polymer mixtures from polymers manufactured from the above mentioned starting materials can be used Chlorinated polyolefins blends of styrene and graft copolymers and mixtures of polystyrene with polymerisate blends butadiene-acrylonitrile-copolymer blends (hard rubber) blends of ethylene and propylene, butylene, vinyl ester, and unsaturated aliphatic acids as well as salts and esters plasticizerfrec blends of methacrylic acid esters and acrylic acid esters with monofunctional saturated alcohols (Ci-C18) as well as blends of the esters of methacrylic acid butadiene and styrene as well as polymer blends of acrylic acid butyl ester and vinylpyrrolidone polyurethane manufactured from 1,6-hexamethylene diisocyanate, 1.4-butandiol and aliphatic polyesters from adipic acid and glycols. 

The same technique can be used to dye a material that is otherwise difficult to dye. An ethylene-propylene copolymer rubber was reacted first with maleic anhydride, then with an aromatic amine dye in an extruder to produce a dyed rubber.81 Dye sites can also be inserted into polyolefins by grafting them with dimethylaminoethyl methacrylate, using azo or peroxide catalysts in an extruder.82 jV-Vinylimidazole has been grafted to polyethylene in an extruder with the help of dicumylperoxide.83 The product was mixed with an acrylic acid-modified polypropylene and used to compatibilize polyethylene and polypropylene. This could be helpful in the recycling of mixed polyolefins from municipal solid waste. Recycling of cross-linked (thermoset) polymers is more of a problem because they cannot be remelted in an extruder. However, they can be if... 

Polyolefin films have been post-irradiation grafted with materials such as trifluorostyrene or methacrylic acid followed by sulfonation to control ion flow through nickel-cadmium batteries [8, 9], Investigation is underway to use crosslinked films grafted with selected monomers to develop lower cost membranes for fuel cells. A major commercial use of EB grafting has been to modify the surfaces of plastic films and paper with low molecular weight silicones to impart adhesive or release properties. 

Monomers, such as n-vinyl pyrrolidinone and hydroxy ethyl methacrylate, have been used to enhance the biocompatibility of films and to control the air permeation and hydrophilicity of microporous films and of non-woven polyolefin materials [10], Significant opportunities exist to pursue other uses in the bio-materials area [11, 12], Attempts to produce grafted films to control gas permeation for use in food packaging applications have not met with success [13], Co-extruded films have proven to be more acceptable in this food packaging area. The modification of films and non-woven materials rely upon low-voltage, self-shielded electron beams. The development of lower cost, low-voltage EB equipment reduces the economic barriers to further development in this area (Fig. 4) [14, 15],... 

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