POLY-N-BUTYL

A number of higher n-alkyl methacrylate polymers have found commercial usage. The poly-(n-butyl-), poly-(n-octyl-) and poly-(n-nonyl methacrylate)s have found use as leathering finishes whilst polyflauryl methacrylate) has become useful as a pour-point depressant and improver of viscosity temperature characteristics of lubricating oils. 

Polystyrene-PDMS block copolymers4l2), and poly(n-butyl methacrylate-acrylic acid)-PDMS graft copolymers 308) have been used as pressure sensitive adhesives. Hot melt adhesives based on polycarbonate-PDMS segmented copolymers 413) showed very good adhesion to substrates with low surface energies without the need for surface preparation, such as etching. 

Since this pioneering work a number of IPNs have been prepared. Poly(styrene) has been used as the second network polymer in conjunction with several other polymers, including poly(ethyl acrylate), poly(n-butyl acrylate), styrene-butadiene, and castor oil. Polyurethanes have been used to form IPNs with poly(methyl methacrylate), other acrylic polymers, and with epoxy resins. 

Fig. 145.—Osmotic pressure-concentration ratios ( in g./cm and c in g./lOO ml.) for poly-(4-vinylpyridine) in alcohol, O, coordinates left and below poly-(N-butyl-4-vinylpyridinium bromide) in alcohol, coordinates right and above and the same polymer in alcoholic 0.61 N lithium bromide, 3 coordinates left and below. °> ...

Polystyrene standards used were narrow molecular weight distribution sample produced by anionic polymerization and available from Pressure Chemical Co. Also sample NBS7C from the National Bureau of Standards was used. The sample of poly n-butyl methacrylate was obtained from Aldrich Chemical. It was produced by free radici polymerization with an Mw of 320,(XK) and an Mn of 73,500 (Cat. No. 18,153-6). 

Figure 21 shows the result of sampling a 50 50 blend of NBS706 and poly n-butyl methacrylate using Column Codes A4 and B4 (Table I) injecting a total of 1.5 mg into GPC 1. 

Methyl and ethyl methacrylate polymers, although extensively used in Industry, do not possess the solubility characteristics (low polarity) that would make them appropriate for use over traditional oil paintings and other organic-based museum objects that might be sensitive to polar solvents such as alcohols, ketones and esters. Poly(n-butyl methacrylate), offered as an artists varnish in the late 1930 s, did not become widely accepted in the war-disrupted decade that followed. Accordingly, early in 1951, our laboratory began a detailed study of the higher alkyl methacrylate polymers for potential use as picture varnishes (1). 

ARGET ATRP has been successfully applied for polymerization of methyl methacrylate, ft-butyl acrylate and styrene in the presence of Sn(EH)2 (10 mol% vs. alkyl halide initiator or 0.07 mol% vs. monomer) [164,165]. For all monomers, polymerizations were well controlled using between 10 and 50 ppm of copper complexes with highly active TPMA and Me6TREN ligands. ARGET ATRP has also been utilized in the synthesis of block copolymers (poly(n-butyl acrylate)— -polystyrene and polystyrene-Z -poly(n-butyl acrylate) [164,165] and grafting... 

C Spin-Lattice Relaxation-Times and n.O.e. Values of Resonance of Poly(n-butyl methacrylate) as 50% (w/w) Solution in Toluene-2H8... 

Fig. 57. Gladstone - Dale plots [Eq. (110)] for solutions of (a) polystyrene, (b) poly-n-butyl methacrylate, (c) polymethyl methacrylate165 = 436 nm)...

The two examples of adsorbed side chain substituted macromolecules, i.e., the poly(n-butyl acrylate) brush and the tris(p-undecyloxybenzyloxo) benzoate jacketed polystyrene, demonstrate two rather complementary aspects of the interaction of such molecules with a planar surface. In the first case the two-dimension to three-dimension transition results in a cooperative collapse of an extended coil conformation to a globule. The second case shows a rather high degree ordering with a distinct orientation of the backbone in the substrate plane. Combination of both effects and partial desorption can lead to a repta-tion-hke directed motion as depicted schematically in Fig. 36. 

The variation of the domain sizes with crosslink density was recognized by Yeo et al. [28], investigating cross-poly(n-butyl acrylate)-inter-cross-polystyrene. Figure A shows the morphology of 50/50 compositions as a function of network I crosslinking level. The cellular structures are gradually transformed to finer, and more obviously cylindrical or worm-like shapes with increasing crosslink density. 

A comparison of the theoretical and experimental results for the IPN system cross-poly(n-butyl acrylate) inter-cross polystrene is given in Table II [18,21]. The agreement between theory and experiment for this system as well as other systems was better than expected, noting the approximations required to obtain a usable result. It must be pointed out that Yeo et al. had to use spherical shapes for their mathematical treatment, even though it was already recognized that most of the domains were cylindrical. 

Yeo, et al. [23,24] went on to make more complete studies of modulus-composition data using cross-poly(n-butyl acrylate)-Inter-cross-polystyrene, PnBA/PS, see Figure 6. Both the Davies and the Budlansky models fit reasonably well over wide ranges of composition, especially the Budlansky model. Other models, which in one form or another assume one continuous and one disperse phase, fit much less well. 

Table II. Experimental and theoretical domain sizes for cross-poly(n-butyl acrylate)-Inter-cross-polystyrene IPN s... 

Figure 6. Modulus-composition behavior of cross-poly(n-butyl acrylate)-/ iter-cross-polystyrene IPNs and semi-I IPNs at 25 C. (Reproduced with permission from ref. 23. Copyright 1981 Polymer Engineering and Science.)...

Figure 7. High magnification scanning electron micrograph of decrosslinked and extracted cross-poly(n-butyl acrylate)-inter-cross-polystyrene IPN (80/20). The poly(n-butyl acrylate) phase was extracted. (Reproduced from Ref. 2 . Copyright 1982 American Chemical Society.)...

The temperature optimization for the RAFT polymerization of EAA revealed an optimum reaction temperature of 70 °C. Block copolymers with a poly(methyl acrylate) (PMA), a poly(n-butyl acrylate) (PnBA), a PMMA, or a poly(A,A-dimethyl aminoethyl methacrylate) (PDMAEMA) first block and a poly(l-ethoxyethyl acrylate) (PEEA) second block were successfully synthesized in an automated synthesizer. The synthesis robot was employed for the preparation of 16 block copolymers consisting of 25 units of the first block composed of PMA (exp. 1 ), PnBA (exp. 5-8), PMMA (exp. 9-13), and PDMAEMA (exp. 13-16) and a second block of PEEA consisting of 25, 50, 75, or 100 units, respectively. The first blocks were polymerized for 3 h and a sample from each reaction was withdrawn for SEC analysis. Subsequently, EAA was added and the reactions were continued for 12 h. The molar masses and PDI values of the obtained block copolymers are shown in Fig. 15. 

The correlation of residence time to reaction time is critical in the ability to treat the volume of the channel as a continuous gradient in molecular mass. ATRP is particularly well-suited to this type of device because the reaction can be initiated at a fixed mixing element at the head of the channel where a catalyst and initiator can be brought together. By replacing a small molecule initiator with a polymer chain capable of being reinitiated, copolymers could be prepared. This was done in the thiolene/glass devices with a poly(n-butyl methacrylate) block... 

Figure 10.8 Stress-strain curves for 6% crosslinked poly(n-butyl acrylate) elastomer for the sample and control specimen (strain rate= lOOmm/min, room temperature). Adapted from Kushner et al. (2007). Copyright 2007 American Chemical Society.

Figure 8 (1., 6) shows the fractionation obtained by analyzing a mixture of polystyrene, poly(styrene co-n-butyl methacrylate) and poly(n-butyl methacrylate) with various n-heptane concentrations. 

Figure 8 Two series of Orthogonal Chromatography runs showing the effec of % n-hept me in the mobile phase of SEC 2 on the fractionation (AA polystyrene, AB poly(styrene co-n-butyl methacrylate) BB poly n-butyl methacrylate). (Reproduced fran Ref. 6. Copyright 1983, American Chemical Society.)...

Figure 12 Effect of column reordering on polystyrene (AA) and poly (n-butyl methacrylate) (BB) retention in SBC 2. Key top, small pore size column last and bottom, small pore size column first. (Reproduced from Ref. 6. Copyright 1983,...

Figure 15. Influence of the Polyester Yellow dye film absorbance and polymer binder material on the marking threshold energy. PnBMA = poly(n-butyl methacrylate) PiBMA = poly(isobutyl methacrylate) PS = polystyrene PsBMA = poly (sec-butyl methacrylate) PVB = polyvinylbutyl PMMA = polymethyl methacrylate PVAC = polyvinylacetate, S-iBMA = poly(styrene-co-isobutyl methacrylate), PC = polycarbonate S-AN — poly(styrene-co-...

ASA structural latexes have been synthesized in a two stage seeded emulsion polymerization. In the first stage, partially crosslinked poly(n-butyl acrylate) and poly( -butyl acrylate-sfaf-2-ethylhexyl acrylate) rubber cores are synthesized. In the second stage, a hard styrene acrylonitrile copolymer (SAN) shell is grafted onto the rubber seeds (16). 

Table 2.2. Extents of reaction in acetone between alcohol and isocyanate functions on different poly(n-butyl acrylate) molecules, extrapolated to 0% reactive functions...

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