Styrene, copolymers with methacrylate

Perfluoroalkyl groups are also introduced into block copolymers with methacrylates, acrylates, and styrene (B-46 to B-53), which can be synthesized in scCC>2 or in the bulk.95,315 Amphiphilic block copolymers based on glycopolymer segments (B-54 and B-55) are synthesized by copper-catalyzed polymerizations.321,322 Comonomers with a polyhedral oligomeric silsesquioxane unit afforded hybrid polymers between organic and inorganic components (B-56 and B-57).326... 

Figure 1. Olefinic proton resonances of styrene-methacrylic anhydride copolymers containing both uncycttzed methacrylic anhydride units and absorbed monomer (top), and uncyclized methacrylic anhydride units but little absorbed monomer (bottom). This sample was prepared by reacting a styrene-methacrylic acid copolymer with methacrylic anhydride.

In the copolymerization of styrene (S) with methacrylic anhydride (Anh), three structures are incorporated into the resulting copolymers styrene units (S), uncyclized methacrylic anhydride units (U), and cyclized methacrylic anhydride units (C). 

Free-radical suspension polymerization, originally developed by Hoffman and Delbruch in 1909 [1] is commonly employed for producing a wide variety of commercially important polymers such as poly(vinyl chloride) (PVC), polystyrene (PS), expandable polystyrene (EPS), high-impact polystyrene (HIPS) and various styrene copolymers with acrylonitrile (SAN) and acrylonitrile-polybutadiene (ABS), poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), etc. [2],... 

Blending methyl methacrylate-butadiene-styrene copolymer with poly(vinyl chloride) for instance was shown to decelerate the dehydrochlorination (leading to discoloration). The gel content, surface energy, and the spectroscopic characteristics of the blend was altered by the presence of the seccHid polymer [158]. In ethylene-propylene-diene rubber EPDM where the third monomer is ethylene-2-norbomene (NB), the photo-oxidation rate as measured by the accumulation of typical products such as hydroperoxides, varied linearly with the NB content [159]. The same held true for peroxide-crosslinked compounds of the same EPDM except that the linear relationship was found between the relative carbonyl absorbance on photoxidation and the amoiuit of peroxide used to crosslink the material... 

Alkanolamines are used as cross-linking and hardener accelerators in epoxy resins applications. Improved thermal and oxidative stability of polyvinyl alcohol, poly(phenylene ether), polystyrene, polypropylene, and polyethylene polymers are achieved by the addition of small amounts of the alkanolamines. Diethanolamine and morpholine act as initiators for the preparation of poly (alkyl methacrylate) in bulk or solution polymerization. The ethanolamines are efficient initiators for the preparation of polyvinyl chloride. Alkanolamines promote cross-linking of styrene copolymers with polystyrene or polyvinyl alcohol. Addition of alkanolamines to phenolic formaldehyde or urea formaldehyde resins affords improved electrical properties and increased water solubility. 

Methylthiophene/styrene copolymers Methyl methacrylate does not homopolymerize or copolymerize if present in the monomer feed during the oxidation of 3-methylthiophene. This is the reason that its copolymer with 3-MT is prepared indirectly as described above. Its homopolymerization is generally initiated by anions or free radicals. Styrene, however, undergoes a random copolymerization when present during the chemical oxidation of 3-methylthiophene initiated with anhydrous FeCls [73]. Monomer reactivity ratios for the copolymerizations in methylene chloride and nitrobenzene at 5°C are reported, but there is considerable scatter in the Fineman-Ross plots. The proposed structure of the 3-MT/stryrene copolymer is shown in Figure 11.16, where R = H. 

Emulsion polymerization is similar to suspension polymerization in the sense that the reaction also takes place in the presence of a water phase and the applied monomer forms a second liquid phase. However, in this case the added radical initiator is not soluble in the monomer droplets but in the water phase. To allow the monomer to come into contact with the initiator an emulsifier is added to the reaction mixture that creates micelles in the systems. By diffusion processes both monomer molecules and initiator molecules reach the micelle. Polymerization takes places and a polymer particle suspended in the water phase forms that is much smaller than the original monomer droplet (see Figure 5.3.12 for a graphical illustration of these steps). At the end of the overall emulsion polymerization process, all monomer droplets have been consumed by the polymerization reaction in the micelles. Typical emulsifiers for emulsion polymerization are natural or synthetic detergents, such as, for example, sodium palmitate or sodium alkyl sulfonates. Emulsion polymerization is very versatile and is applied for many polymers [e.g., PVC, styrene copolymers, poly(methacryl esters)] in batch, semi-continuous, and continuous processes. In some cases, the obtained polymer particles in water are directly applied as technical products for coatings, lacquer applications, or as adhesives. In other cases the formed product is further treated to obtain the dry polymer. Note that the aqueous phase in emulsion polymerization always contains some isolated emulsifier and also some monomer. Moreover, the formed polymer contains the emulsifier as impurity. 

Fig. 10. Arrhenius plots of rotational parameters/fs (fuU symbols) and/ [ (empty symbols) in determined in the random copolymer of styrene witb spin-labeled methacrylic acid nnits in four solvents and their best fits to Eq. 4. The X-band data for the styrene copolymer with spin-labeled acryhc acid nnits in toluene (TOL ) are given for comparison. (From Ref 43, with permission.)...

Y., and Okamoto, Y. (2011) Synthesis and characterization of trifluoromethyl substituted styrene polymers and copolymers with methacrylates effects of trifluoromethyl substituent on styrene. Polymer, 52 (4), 949 —953. 

Polystyrene, expandable polystyrene (containing a volatile C4-C6 hydrocarbon), high impact polystyrene, styrene copolymers with acrylonitrile (SAN) and ABS, and poly(methyl methacrylate) are the main products of the suspeusion bead polymerization. PVC is the main polymeric material produced by suspension powder polymerization. 

An adipic acid-diethylene glycol copolymer, by treatment with a THF polymer or polypropylene glycol in the presence of chlorosulfonic acid, afforded polyether polyesters useful for the preparation of thermoplastic block copolyester rubbers and polyurethans. Strongly acid sulfonate derivatives of hydrophilic polymers may be prepared by reacting glycidyl methacrylate-ethylene dimethacrylate copolymer or ethylene dimethacrylate-glycidyl methacrylate-styrene copolymer with chlorosulfonic acid or oleum at 0-60 °C. ... 

A covalently bound photoisomerizable chromophore is expected to give a more direct effect on the deformation of the swollen gels. Matejka et al. [13] studied cross-linked systems with azo side groups copolymers of 2-hydroxyethyl methacrylate and azonaphthol methacrylate [P(HEMA-MAN)] swollen in water, and maleic anhydride-styrene copolymers with covalently bound aminoazobenzene [P(MAH-STY-AAB)] swollen in diethyl phthal-ate. They carefully estimated the contribution of the thermal effect during the photomechanical conversion. 

Fig. 11.46 Plot of spherulite radius as a function of time for poly(ethylene oxide) in blends with either ethylene-methacrylic acid or styrene-hydroxy styrene copolymer. With ethylene-methacrylic acid poly(ethylene oxide)/ethylene-methacrylic acid A 80/20, = 52.5 °C X 70/30, = 48 °C. With styrene-hydroxy styrene ...

Figure 9.17 Plot of log [i ]M versus retention volume for various polymers, showing how different systems are represented by a single calibration curve when data are represented in this manner. The polymers used include linear and branched polystyrene, poly(methyl methacrylate), poly(vinyl chloride), poly(phenyl siloxane), polybutadiene, and branched, block, and graft copolymers of styrene and methyl methacrylate. [From Z. Grubisec, P. Rempp, and H. Benoit, Polym. Lett. 5 753 (1967), used with permission of Wiley.]...

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

Many synthetic latices exist (7,8) (see Elastomers, synthetic). They contain butadiene and styrene copolymers (elastomeric), styrene—butadiene copolymers (resinous), butadiene and acrylonitrile copolymers, butadiene with styrene and acrylonitrile, chloroprene copolymers, methacrylate and acrylate ester copolymers, vinyl acetate copolymers, vinyl and vinyUdene chloride copolymers, ethylene copolymers, fluorinated copolymers, acrylamide copolymers, styrene—acrolein copolymers, and pyrrole and pyrrole copolymers. Many of these latices also have carboxylated versions. 

I ew Rubber-Modified Styrene Copolymers. Rubber modification of styrene copolymers other than HIPS and ABS has been useful for specialty purposes. Transparency has been achieved with the use of methyl methacrylate as a comonomer styrene—methyl methacrylate copolymers have been successfully modified with mbber. Improved weatherability is achieved by modifying SAN copolymers with saturated, aging-resistant elastomers (88). 

A waterborne system for container coatings was developed based on a graft copolymerization of an advanced epoxy resin and an acryHc (52). The acryhc-vinyl monomers are grafted onto preformed epoxy resins in the presence of a free-radical initiator grafting occurs mainly at the methylene group of the aHphatic backbone on the epoxy resin. The polymeric product is a mixture of methacrylic acid—styrene copolymer, soHd epoxy resin, and graft copolymer of the unsaturated monomers onto the epoxy resin backbone. It is dispersible in water upon neutralization with an amine before cure with an amino—formaldehyde resin. 

The toughness of interfaces between immiscible amorphous polymers without any coupling agent has been the subject of a number of recent studies [15-18]. The width of a polymer/polymer interface is known to be controlled by the Flory-Huggins interaction parameter x between the two polymers. The value of x between a random copolymer and a homopolymer can be adjusted by changing the copolymer composition, so the main experimental protocol has been to measure the interface toughness between a copolymer and a homopolymer as a function of copolymer composition. In addition, the interface width has been measured by neutron reflection. Four different experimental systems have been used, all containing styrene. Schnell et al. studied PS joined to random copolymers of styrene with bromostyrene and styrene with paramethyl styrene [17,18]. Benkoski et al. joined polystyrene to a random copolymer of styrene with vinyl pyridine (PS/PS-r-PVP) [16], whilst Brown joined PMMA to a random copolymer of styrene with methacrylate (PMMA/PS-r-PMMA) [15]. The results of the latter study are shown in Fig. 9. 

Polymerization of styrene or methyl methacrylate by macroazoinimers having two vinyl groups (MIM-2v) resulted in crosslinked block copolymers, while macroazoinimers with one vinyl end (MIM-1 v) group to polymerize vinyl monomers yielded branched block copolymers. 

The reaction of ACPC with linear aliphatic amines has been investigated in a number of Ueda s papers [17,35,36]. Thus, ACPC was used for a interfacia] polycondensation with hexamethylene diamine at room temperature [17] yielding poly(amide)s. The polymeric material formed carried one azo group per repeating unit and exhibited a high thermal reactivity. By addition of styrene and methyl methacrylate to the MAI and heating, the respective block copolymers were formed. 

A variety of ionomers have been described in the research literature, including copolymers of a) styrene with acrylic acid, b) ethyl acrylate with methacrylic acid, and (c) ethylene with methacrylic acid. A relatively recent development has been that of fluorinated sulfonate ionomers known as Nafions, a trade name of the Du Pont company. These ionomers have the general structure illustrated (10.1) and are used commercially as membranes. These ionomers are made by copolymerisation of the hydrocarbon or fluorocarbon monomers with minor amounts of the appropriate acid or ester. Copolymerisation is followed by either neutralisation or hydrolysis with a base, a process that may be carried out either in solution or in the melt. 

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

II. B polyethylene glycol, ethylene oxide, polystyrene, diisocyanates (urethanes), polyvinylchloride, chloroprene, THF, diglycolide, dilac-tide, <5-valerolactone, substituted e-caprolactones, 4-vinyl anisole, styrene, methyl methacrylate, and vinyl acetate. In addition to these species, many copolymers have been prepared from oligomers of PCL. In particular, a variety of polyester-urethanes have been synthesized from hydroxy-terminated PCL, some of which have achieved commercial status (9). Graft copolymers with acrylic acid, acrylonitrile, and styrene have been prepared using PCL as the backbone polymer (60). 

With regards to the copolymerization, a recent kineuc study by Gruber and KneU (10 has indicated that styrene n-butyl methacrylate obeys the cla ical kinetic theory with regards to composition and sequence length to complete conversion. This theory is applied to high conversion to charau terize copolymer samples for GPC analysis. 

Brown and White employed this approach to prepare block copolymers of styrene and mcthacrylic acid (6). They were able to hydrolyze poly(styrene-b-methyl methacrylate) (S-b-MM) with p-toluenesulfonic acid (TsOH). Allen, et al., have recently reported acidic hydrolysis of poly(styrene-b-t-butyl methacrylate) (S-b-tBM) (7-10). These same workers have also prepared potassium methacrylate blocks directly by treating blocks of alkyl methacrylates with potassium superoxide (7-10). 

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