Styrene Containing Terpolymers

The styrene-MA monomer pair has been combined with a variety of 

In terpolymerizations with MA, where two azeotropic copolymer pairs can be formed, Slocombe described an azeotropic copolymer index. In the method, the monomer-terpolymer composition plots take the form of a triangular coordinate graph. A line connecting the points that represented the composition along the azeotropic line have unique properties, i.e., give clear terpolymers, whereas compositions removed from the line gave increasingly turbid polymers as their distance from the azeotropic line increased. 

Such efforts to refine concepts dealing with predicting homogeneous terpoly-merizations have continued/  

Jenner and Kellou recently studied the pressure effect on azeotropy in free-radical terpolymerization of MA with acrylonitrile, dielthyl fumarate, methyl acrylate, methyl methacrylate, methyl vinyl ketone, vinylidene chloride, norbornene, a-methylstyrene, indene, and vinyl acetate, with styrene as the second comonomer common in all cases. It was found that ternary azeotropes were only possible for those systems where the first comonomers had positive e values, i.e., diethyl fumarate, acrylonitrile, methyl acrylate, methyl methacrylate, methyl vinyl ketone, and vinylidene chloride. Surprisingly, the coordinates of the ternary azeotropes were very little affected by variations of the pressure from 1-3,000 bars. Since reactivity ratios in multi-component polymerizations are sensitive to pressure, causing terpolymer composition to also be pressure dependent, a shift of the ternary azeotropic point would be expected. Why this occurs awaits further clarification. 

Styrene-MA-divinylbenzene terpolymers have been prepared in kerosene,aromatic naphtha, dioxane, and benzene. The terpolymers have also been prepared in benzene/methyl alcohol mixtures at 100°C, with BPO initiator.The fine powdery terpolymers are easily dispersed in poly(propylene), functioning both as a modifier and dye-assist agent. These products are also proposed as ion-exchange resins, membranes, and absorbents. Attempts to prepare the terpolymer from styrene, divinylben-zene, and monomethyl maleate failed to work as well, due to different copolymerization reactivity ratios.Addition of a small amount of 2-vinyl-pyridine to the styrene-MA-divinylbenzene termonomer mixture provided improved ion-exchange resins.The exchange capacity, i.e., metal-ion selectivity, was demonstrated and compared for a number of cations, including Fe , AP, nP, Co, Cu Na, and 

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As of 1992, the first specialty platable plastic, acrylonitrile—butadiene—styrene (ABS) terpolymer (see Acrylonitrile polymers, ABS resins), is used ia over 90% of POP appHcatioas. Other platable plastics iaclude poly(pheayleae ether) (see PoLYETPiERs), ayloa (see Polyamides), polysulfoae (see Polymers CONTAINING sulfur), polypropyleae, polycarboaate, pheaoHcs (see Pphenolic resins), polycarboaate—ABS alloys, polyesters (qv), foamed polystyreae (see Styrene plastics), and other foamed plastics (qv). 

Blending of the high heat resistant terpolymer with ABS to form a miscible matrix phase, as defined in Figure 4, is of course, expected to increase the heat resistance of the ABS. The data in Table II, taken from references (2-4), provide a systematic representation of the variation of DTUL with terpolymer/ABS blend composition for the AN, IB, and MM-containing terpolymers (both glassy and rubber-modified). In some of these cases, as noted, a copolymer of a-methyl styrene/acrylonitrile was added to the formulation. From these data it is apparent that DTUL does, indeed, increase with increasing terpolymer concentration in the blends. Moreover, the effect of the terpolymer composition on DTUL of the blends is... 

Acrylonitrile-styrene-acrylate terpolymers, known as either ASA or AAS, constitute another class of ABS resins, viz. Centrex , Luran S, Richform , etc. These materials may also contain reactive groups, viz. maleic anhydride or glycidyl methacrylate. 

HIPS polymers consist of a matrix of polystyrene containing approximately spherical particles of rubbery polybutadiene ranging in size from about 0.1 to 10 pm depending on the precise composition and method of polymerisation. The rubber particles may themselves contain small regions of PS as shown in fig. 12.7. Another series of rubber-toughened blends is the acrylonitrile-butadiene-styrene (ABS) terpolymers, which are basically... 

Calculated from both epoxy equivalent and H-NMR spectroscopy in Styrene (St)-containing terpolymers and from both epoxy equivalent weight and elemental analysis ... 

Nitrile rubber (NBR), a copolymer of 1,3-butadiene with 20-40% acrylonitrile, is noted for its oil resistance. More than 150 million pounds are produced annually in the United States. Applications include fuel tanks, gasoline hoses, and creamery equipment. Nitrile resin is made by copolymerizing acrylonitrile with about 20-30% styrene or methyl methacrylate in the presence of NBR or SBR rubber to yield a blend of the graft terpolymer and homocopolymer. Applications include extruded and blow-molded containers for household, automotive, and other products as well as some nonbeverage foods (spices, vitamins, candy). 

Calculate the composition of the initial terpolymer that would be produced from the radical polymerization of a solution containing acrylonitrile, styrene, and 1,3-butadiene in mole fractions of 0.47, 0.47, and 0.06, respectively. 

Copolymers of itaconic esters with butadiene have not yet been used technically. On the other hand, acrylonitrile containing copolymers with other components have been studied from several points of view. Standard Oil Co. has claimed a terpolymer of isobutylene, butadiene, and acrylonitrile, and BASF a similar product of butadiene, acrylonitrile, and styrene. The films from these combinations are said to have high flexibility and cold resistance. However, all butadiene containing copolymers are not light fast. Copolymers of butadiene, acrylonitrile, and unsaturated dicarboxylic esters are suggested for plasticizing PVC, but they must be thermally degraded before they are combined with the polymer. 

Copolymers of acrylonitrile and methyl acrylate and terpolymers of acrylonitrile, styrene, and methyl methacrylate are used as bamer polymers. Acrylonitrile copolymers and multipolymers containing butyl acrylate, ethyl aciylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methaciylate. vinyl acetate, vinyl ethers, and vinylidene chlonde are also used in bamer films, laminates, and coatings. Environmentally degradable polymers useful in packaging are prepared from polymerization of acrylonitrile with styrene and methyl vinyl ketone. 

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... 

Typical mechanical properties for transparent injection-molded polymers, designated MBAS, having a compositional range of from 11-18%, 1,3-butadiene, 34-39% styrene, and 23-25% each of acrylonitrile and methyl methacrylate are given in Table IV. This polymer is closely akin to the polyblend described previously, differing by containing a butadiene-styrene elastomer backbone, with a terpolymer resin graft consist-... 

Copolymerizing VBT with either cationic or anionic substituted styrenes allowed us to obtain a fully water-processable photoresist [36]. Extension of polymeric structures is possible through backbone and side-chain modifications, especially terpolymers. Three-component systems containing the photoreactive monomer, the solubilizing monomer, and a functional monomer open the door to a virtually infinite set of physical and chemical parameters to be exploited and optimized. 

Conventional ABS polymers are blends of poly (styrene-coacrylonitrile) with either poly (butadiene-coacrylonitrile) or a graft of poly-(styrene-coacrylonitrile) onto a rubbery spine. To confer flame-resistance on either ABS system using DBPF as a fourth monomer, the major component should be a styrene-acrylonitrile-DBPF terpolymer since the resinous component is the major one. The composition of such a terpolymer is restricted by two considerations (1) it should contain sufficient acrylonitrile to impart the resistance to solvent attack which is characteristic of ABS polymers, and (2) the amount of DBPF should be sufficient to give a useful level of flame resistance. 

In the recent miscibility studies with a-methyl styrene/acrylonitrile copolymer and a a-methyl styrene/methyl methacrylate/acrylonitrile terpolymer (8), it was found that almost all miscible second components contain amides, imides, nitriles, or esters, each of which contains lone-pair electrons capable of donor-acceptor complexation—a state which... 

Table 6.10 Comparison of experimental (Xf1) and theoretical (Xf1) values of compositions of terpolymers (styrene (M,) + acrylonitrile (M2) + bromine-containing monomer (M3)) prepared in dimethylformamide at low conversions (p < 0.1) and at various monomer feed compositions (xf) [312, 313]. 2,4,6-Tribromine phenyl ether of acrylic (I) [312] and methacrylic (II) [313] acids were used as M3...

Additional block terpolymers containing propyl acrylate and star block terpo-lymers containing styrene were previously prepared by the author [2] and used in hot-melt pressure-sensitive and heat-activatable adhesives. 

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