Styrenics impact modifiers

R.R. Clikeman, D.H. Jones, T.J. Shortridge, and E.J. Troy, Methyl methacrylate-butadiene-styrene impact modifier polymers, polyvinyl chloride, compositions and methods, US Patent 4 379 876, assigned to Rohm and Haas Company (Philadelphia, PA), April 12,1983. 

Effects of additives in the matrix were observed by substituting for methyl methacrylate a poly (methyl methacrylate) homopolymer with a solution molecular weight of 950,000, a vinylidene fluoride copolymer (Pennwalt s Kynar 7201), and a methacrylate-butadiene-styrene impact modifier (Marbon s Blendex BTA IIIN). Concentrations were 2% on the total dispersion volume. The same additives were studied at the same volume concentration in the dispersed phase. Barium sulfate (Whittaker, Clark, and Daniels Barytes No. 91), a commonly used additive for radiopacity, was also studied in the dispersed phase. Responses were observed by the test methods described below. 

Methyl methacrylate-butadiene-styrene, impact modifier 20... 

Impact modifiers are often added to BPAPC to counteract this effect (Cheng et al. 1992 Tan et al. 2005) and a few studies have been conducted to investigate the effect of thermal annealing on the mechanical performance of BPAPC. Eor example, blends of BPAPC with several core-shell methacrylate-butadiene-styrene impact modifiers have been studied after aging at 125 °C, 130 °C, and 135 °C (Cheng et al. 1992). 

The principal monomer of nitrile resins is acrylonitrile (see Polyacrylonitrile ), which constitutes about 70% by weight of the polymer and provides the polymer with good gas barrier and chemical resistance properties. The remainder of the polymer is 20 to 30% methylacrylate (or styrene), with 0 to 10% butadiene to serve as an impact-modifying termonomer. 

Acrylics. Acetone is converted via the intermediate acetone cyanohydrin to the monomer methyl methacrylate (MMA) [80-62-6]. The MMA is polymerized to poly(methyl methacrylate) (PMMA) to make the familiar clear acryUc sheet. PMMA is also used in mol ding and extmsion powders. Hydrolysis of acetone cyanohydrin gives methacrylic acid (MAA), a monomer which goes direcdy into acryUc latexes, carboxylated styrene—butadiene polymers, or ethylene—MAA ionomers. As part of the methacrylic stmcture, acetone is found in the following major end use products acryUc sheet mol ding resins, impact modifiers and processing aids, acryUc film, ABS and polyester resin modifiers, surface coatings, acryUc lacquers, emulsion polymers, petroleum chemicals, and various copolymers (see METHACRYLIC ACID AND DERIVATIVES METHACRYLIC POLYMERS). 

MBS polymers are prepared by grafting methyl methacrylate and styrene onto a styrene—butadiene mbber in an emulsion process. The product is a two-phase polymer useful as an impact modifier for rigid poly(vinyl chloride). 

There is extensive Hterature on PC blends with ABS, and blends of PC with related materials such as SAN, methacrylate-butadiene—styrene (MBS) emulsion-made core-shell mbber modifiers (297—299), and other impact modifiers. One report reviews some of these approaches and compares PC blends based on emulsion vs bulk ABS (229). In PC—ABS blends, no additional compatihili er is used, because of the near-miscihility of the SAN matrix of ABS and PC. 

Not only ate ABS polymers useful engineering plastics, but some of the high mbber compositions are excellent impact modifiers for poly(vinyl chloride) (PVC). Styrene—acrylonitrile-grafted butadiene mbbers have been used as modifiers for PVC since 1957 (87). 

Styrene-based plastics are used somewhat in blow mol ding but not as much as linear polyethylene and PVC. HIPS and ABS are used in specialty botdes, containers, and furniture parts. ABS is also used as one of the impact modifiers for PVC. Clear, tough bottles with good barrier properties are blow-molded from these formulations. 

At one time butadiene-acrylonitrile copolymers (nitrile rubbers) were the most important impact modifiers. Today they have been largely replaced by acrylonitrile-butadiene-styrene (ABS) graft terpolymers, methacrylate-buta-diene-styrene (MBS) terpolymers, chlorinated polyethylene, EVA-PVC graft polymers and some poly acrylates. 

There are various requirements for impact-modified PVC. The most demanding is for outdoor sidings and window frames, where lifetimes of 20 years are expected. Because butadiene polymers or copolymers (e.g., acrylonitrile/butadiene/styrene (ABS), methyl methacrylate/butadiene/styrene (MBS)) are susceptible to UV degradation these polymers are usually not employed instead acrylate polymers are used for these applications. 

Impact modifiers Polybutadiene rubber, methacrylate-butadiene-styrene terpolymers, acrylic rubber... 

SEM and transmission electron microscopy (TEM) are employed to examine materials for the presence and distribution of impact modifiers such as polybutadiene rubber in high impact polystyrene (HIPS) and methacrylate butadiene styrene terpolymer in PVC. Quantification is either by transmission IR spectroscopy against standards or nuclear magnetic resonance (NMR) spectroscopy. 

Properties Poly(methyl methacrylate) Cast sheet Impact- modified Heat- resistant Alkyd, molded Acrylic poly(vinyl chloride) alloy styrene-poly(vinyl chloride) alloy... 

Figure 14.9 Effect of various impact modifiers (25wt%) on the notched Izod impact strength of recycled PET (as moulded and annealed at 150°C for 16 h) E-GMA, glycidyl-methacrylate-functionalized ethylene copolymer E-EA-GMA, ethylene-ethyl acrylate-glycidyl methacrylate (72/20/8) terpolymer E-EA, ethylene-ethyl acrylate EPR, ethylene propylene rubber MA-GPR, maleic anhydride grafted ethylene propylene rubber MBS, poly(methyl methacrylate)-g-poly(butadiene/styrene) BuA-C/S, poly(butyl acrylate-g-poly(methyl methacrylate) core/shell rubber. Data taken from Akkapeddi etal. [26]...

MBS (methyl methacrylate-butadiene-styrene) graft copolymers are known as one of the most efficient non-reactive impact modifiers for PET and also poly(vinyl chloride) (PVC). MBS is used commercially as an effective impact modifier for PET recyclate [27], Typical MBS rubber particles contain an elastomeric core of... 

Impact modifiers improve the resistance of materials to stress. Most impact modifiers are elastomers such as ABS, BS, methacrylate-butadiene-styrene, acrylic, ethylene-vinyl acetate, and chlorinated PE. 

Such materials essentially contain PS as the matrix polymer and uniformly dispersed in this matrix are elastomeric types of particles, which form the soft phase (3). The soft phase is essentially composed of poly(butadiene) or of block copolymers of butadiene and styrene. This soft phase can be also addressed as the impact modifier for PS. 

H. Keskkula, D.R. Paul, K.M. McCreedy, and D.E. Henton, Methyl methacrylate grafted rubbers as impact modifiers for styrenic polymers, Polymer, 28(12) 2063-2069, November 1987. 

Methyl methacrylate-butadiene-styrene (MMBS) types are rarely used as such, but rather in blends as impact modifiers (1). Styr-enic copolymers such as acrylonitrile-butadiene-styrene (ABS) and MMBS make up the largest category of impact modifiers, with about 45% of the impact modifier market (2). The field of polymer blends and the reasons for the addition of impact modifiers have been reviewed (3). 

Core-shell emulsion polymers with a core or rubbery stage based on homopolymers or copolymers of butadiene are used as impact modifiers in matrix polymers, such as ABS, for styrene acrylonitrile copolymer methyl methacrylate (MMA) polymers, poly(vinyl chloride) (PVC), and in various engineering resins such as polycarbonate) (PC) poly(ester)s, or poly(styrene)s, further in thermosetting resins such as epoxies. 

Such impact modifiers containing copolymers of butadiene and styrene and at least one stage or shell of poly(methyl methacrylate) are known MMBS core-shell polymers. 

Besides MMBS, also related copolymers, such as methyl meth-acrylate/acrylonitrile/butadiene/styrene and acrylonitrile/ethylene/ propylene/diene/styrene are impact modifiers for PC compositions (16). 

STYRENE-MALEIC ANHYDRIDE. A thermoplastic copolymer made by the copolymerization of styrene and maleic anhydride. Two types of polymers are available—impact-modified SMA terpolymer alloys (Cadon ) and SMA copolymers, with and without rubber impact modifiers (Dylark ). These products are distinguished by higher heat resistance than the parent styrenic and ABS families. The MA functionality also provides improved adhesion to glass fiber reinforcement systems. Recent developments include lerpolymer alloy systems with high-speed impact performance and low-temperature ductile fail characteristics required by automotive instrument panel usage. 

Further evidence of the heat stability of the PTHF blends with PVC and CPVC was obtained in an oven aging test at 350°F. Samples were removed from the oven at 10-minute intervals and compared with similarly treated blends containing the impact modifier, a styrene/acrylonitrile/butadiene terpolymer. The blends containing PTHF were outstanding in their resistance to discoloration at elevated temperature. The blends containing the terpolymer showed some darkening at 90 minutes and were brown at 370 minutes. The PTHF blends did not discolor at all until 190 minutes, and 920 minutes were required for the... 

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