Methacrylates from ethylene

One of the calculation results for the bulk copolyroerization of methyl methacrylate and ethylene glycol dimethacrylate at 70 C is shown in Figure 4. Parameters used for these calculations are shown in Table 1. An empirical correlation of kinetic parameters which accounts for diffusion controlled reactions was estimated from the time-conversion curve which is shown in Figure 5. This kind of correlation is necessary even when one uses statistical methods after Flory and others in order to evaluate the primary chain length drift. 

Most of the polymers are better known by their trivial names or trade names. Polymers prepared from single polymers are denoted by prefixing poly- to the name of the monomer, e.g., polyethylene, polypropylene, Polyacrylonitrile, polystyrene, etc. If the monomer has substituents or has a multi-worded name, the name of the monomer is enclosed in parenthesis after the prefix poly-, e.g., poly (methyl methacrylate), poly (vinyl alcohol), etc. Condensation polymers like that derived from ethylene glycol and terephthalic acid are named as poly (ethylene terephthalate). 

Fig. 3. Effect of dodecanol in the porogenic solvent on the differential pore size distribution of molded poly(glycidyl methacrylate-co-ethylene dimethacrylate) monoliths (Reprinted with permission from [62]. Copyright 1996 American Chemical Society). Conditions polymerization time 24 h, temperature 70 °C, polymerization mixture glycidyl methacrylate 24%, ethylene dimethacrylate 16%, cyclohexanol and dodecanol contents in mixtures 60/0 (curve 1), 57/3 (curve 2), 54/6 (curve 3), and 45/15 vol.% (4)...

Fig. 8. Effect of linear flow velocity of an L-benzoyl arginine ethylester solution (0.2 mol/1) on the enzymatic activity of trypsin immobilized on poly(glycidyl methacrylate-co-ethylene dimethacrylate) beads (curve 1) and monolith (curve 2) (Reprinted with permission from [90]. Copyright 1996 Wiley-VCH). Reactor 50 mm x 8 mm i.d., temperature 25 °C...

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]...

EMA ionomers (see Figure 4.30) are speciality thermoplastics copolymerized from ethylene and a small fraction of methacrylic acid, which is then transformed into the salt of sodium, zinc, lithium or another metal randomly distributed along the backbone. The backbone is identical to that of the polyolefins but the pendant groups are different, with a polar and ionic character. 

There are various speciality polyethylene copolymers developed from ethylene and acrylic acid, methylacrylate, butylacrylate, ethylacrylate, maleic anhydride, glycidyl methacrylate, acrylic esters, acrylic ester-maleic anhydride. .. 

The vast majority of commercial polymers based on the vinyl group (H2C=CHX) or the vinylidene group (H2C=CX2) as the repeat unit are known by their source-based names. Thus, polyethylene is the name of the polymer synthesized from the monomer ethylene poly(vinyl chloride) from the monomer vinyl chloride, and poly(methyl methacrylate) from methyl methacrylate. 

FIGURE 1.6 Influence of the polymerization temperature on the porosity of polyfglycidyl methacrylate-co-ethylene dimethacrylate) monoliths determined by MIP. (a) Differential pore size distribution curves of the polyfglycidyl methacrylate-co-ethylene dimethacrylate) rods, prepared by 22 h polymerization at a temperature of 55°C ( ), 12 h at 70°C ( ), and a temperature increased during the polymerization from 50°C to 70°C in steps by 5°C lasting 1 h each and kept at 70°C for another 4h ( ). (Reprinted with permission from Svec, F. and Frechet, Chem. Mater., 1, 707, 1995. Copyright 1995, American Chemical Society.) (b)... 

Ethylene-Based (C-2> Routes. MMA and MAA can be produced from ethylene as a feedstock via propanol, propionic acid, or melhyl propionate as intermediates. Propanal may be prepared by hydrofonnylalion of ethylene over cobalt or rhodium catalysts. The propanal then reads in the liquid phase with formaldehyde in the presence of a secondary amine and. optionally, a carboxylic acid. The reaction presumably proceeds via a Mannich base intermediate which is cracked to yield methacrolcin. Alternatively, a gas-phase, crossed akin I reaelion with formaldehyde cataly zed by molecular sieves [Pg.988]

Further studies were directed to examine different SCBs and the effect of different counterions. Potassium counterions provide improved efficiency as compared to lithium or sodium counterions. The most efficient system in terms of formation of carbanions was achieved with diphenylsilacyclobutane in combination with potassium tert-butoxide and diphenylethylene <2004MI856>. Di-block copolymers from ethylene oxide and methyl methacrylate (or styrene) were synthesized by this method with 85% efficiency (Scheme 14) <2004MI856>. 

Fig. 6.24. Electrochromatographic separation of aromatic acids (a) and anilines (b) on monolithic capillary columns. (Reprinted with permission from [14]. Copyright 2000 Elsevier). Conditions monolithic poly(butyl methacrylate-co-ethylene dimethacrylate) stationary phase with 0.3 wt. % 2-acrylamido-2-methyl-l-propanesulfonic acid pore size, 750 nm UV detection at 215 nm voltage, 25 kV pressure in vials, 0.2 MPa injection, 5 kV for 3 s. (a) capillary column, 100 pm i.d. x 30 cm (25 cm active length) mobile phase, 60 40 vol./vol mixture of acetonitrile and 5 mmol/L phosphate buffer pH 2.4. Peaks 3,5-dihydroxybenzoic acid (1), 4-hydroxybenzoic acid (2), benzoic acid (3), 2-toluic acid (4), 4-chlorobenzoic acid (5), 4-bromobenzoic acid (6), 4-iodobenzoic acid (7). (b) capillary column, 100 pm i.d. x 28 cm (25 cm active length) mobile phase, 80 20 vol./vol mixture of acetonitrile and 10 mmol/L NaOH pH 12. Peaks 2-aminopyridine (1), 1,3,5-collidine (2), aniline (3), N-ethylaniline (4), N-butylaniline (5).

Fig. 6.27. Electrochromatographic size-exclusion chromatography of polystyrene standards (Reprinted with permission from [64], Copyright 1998 American Chemical Society). Conditions monolithic poly(butyl methacrylate-co-ethylene dimethacrylate-co-2-...

Fig. 6.31. Effect of mode pore diameter on flow velocity of the mobile phase through monolithic capillary columns. (Reprinted with permission from [55], Copyright 1999 Wiley-VCH). Conditions stationary phase poly(butyl methacrylate-co-ethylene dimethacrylate) with 0.3 wt. % 2-acrylamido-2-methyl-l-propanesulfonic acid Column 100 pm i.d. x 28 cm mobile phase, 75 25 vol/vol mixture of acetonitrile and 5 mmol/L phosphate buffer pH 7, marker thiourea. The line represents linear fit of experimental data.

Fig. 6.34. CEC separation of drugs using a capillary column packed with 5 mm ODS silica beads and entrapped in porous poly(butyl methacrylate-co-ethylene dimethacrylate-co-2-acrylamido-2-methyl-l-propanesulfonic acid). (Reprinted with permission from [63]. Copyright 2000 American Chemical Society). Conditions column 26 cm (active length 17 cm) x 75 pm i.d, mobile phase 70 30 acetonitrile-10 mmol/L acetate buffer solution pH 3, 20 kV, detection at 2 different wavelengths shown.

Figure 29 Separation of the nonsteroidal anti-inflammatory drugs ibuprofen (peak 1), naproxen (2), ketoprofen (3), and suprofen (4) in anion-exchange CEC mode using a strong anion-exchange monolithic column. Conditions on-column alkylated monolith prepared from mixtures consisting of 8% 2-dimethylaminoethyl methacrylate, 24% 2-hydroxyethyl methacrylate, 8% ethylene dimethacrylate, 20% cyclohexanol, 40% 1-dodecanol UV-initiated polymerization at room temperature for 16 h cfpmode= 1423 nm. Column dimensions inner diameter 0.1 mm, total length 335 mm, effective length 250 mm. Mobile phase 0.4 mol/L acetic acid and 4 mmol/L triethylamine in acetonitrile/methanol (60/40), voltage -25 kV, injection -5 kV for 5 s, temperature 50°C, UV detection at 250 nm. (Reprinted from Ref. 127, with permission.)...

Fig. 24 Experimental results for the weight-average molecular weight development during the emulsion crosslinking copolymerization of styrene (St)/divinylbenzene (DVB) and methyl methacrylate (MMA)/ethylene glycol dimethacrylate (EGDMA). Data from [323]...

Chiral polymer-supported thiiranes 401 were prepared by free radical copolymerization of TMA ((3)-thiiranylmethyl-methacrylate) and ethylene glycol dimethacrylate (EDMA) (Equation 60) <2006TA1944>. These chiral thiiranes were transformed into polymer-supported aminothiols by the facile ring opening of the thiirane group with benzylamine and methylamine. These derivatives, complexed with [RuCl2(p-cymene)]2, were used in assymmetric reduction of acetophenone to gave (A)-l-phenylethanol (39% ee from methylamine and 50% ee from benzylamine derivatives). 

Physical incorporation of different porphines (9) and also phthalocyanines (2) into polymer matrices were done by pearl polymerisations of glyddyl or 2-hydroxyethyl methacrylate and ethylene dimethacrylate -The amount of inorrporated dtielate is 0,05 to 0.4 wt %(50-70% of the inserted porphyrine). The surface hole is small enough to prevent diffusion of N4-chelates from the interior of the matrix. Also polymers, sudi as polystyrene or polyvinylalcohole, were directly used to incorporate porphyrines or phthalocyanines. ... 

Podual K, Doyle F, and Peppas NA. Modeling of water transport in and release from glucose-sensitive swelling-controlled release systems based on poly(diethylaminoethyl methacrylate-g-ethylene glycol). Industrial engineering chemistry research 2004 43 7500-7512. 

Kanerva L, Jolanki R, Leino T, Estlander T. Occupational allergic contact dermatitis from 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate in a modified acrylic structural adhesive. Contact Dermatitis 1995 33(2) 84-9. 

Problem 27.4 The following compounds are of great industrial importance for the manufacture of polymers acrylonitrile (for Orion), methyl acrylate (for Acryloid), methyl methacrylate (for Lucite and Plexiglas). Outline a possible industrial synthesis of (a) acrylonitrile from ethylene (b) methyl acrylate from ethylene (c) methyl methacrylate from acetone and methanol. 

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