Copolymerization of MMA with

In contrast to /3-PCPY, ICPY did not initiate copolymerization of MMA with styrene [39] and AN with styrene [40]. However, it accelerated radical polymerization by increasing the rate of initiation in the former case and decreasing the rate of termination in the latter case. The studies on photocopolymerization of MMA with styrene in the presence of ICPY has also been reported [41], /8-PCPY also initiated radical copolymerization of 4-vinylpyridine with methyl methacrylate [42]. However, the ylide retarded the polymerization of N-vinylpyrrolidone, initiated by AIBN at 60°C in benzene [44]. (See also Table 2.)... 

Copolymerizations of other monomers may also be subject to similar effects given sufficiently high reaction temperatures (at or near their ceiling temperatures - Section 4.5.1). The depropagation of methacrylate esters becomes measurable at temperatures >100 °C (Section 4.5.1).96 O Driseoll and Gasparro86 have reported on the copolymerization of MMA with S at 250 °C. 

The block copolymerization of MMA with ethylene was recently described using (202)/ B(C6F5)3.499 The olefin must be polymerized first (as observed with (188) and (190)) and the diblock nature of the product was inferred from solubility behavior. 

A is also used in conjunction with other plastics to achieve translucent or transparent qualities. Transparent bottles, made by copolymerization of MMA with vinyl chloride, are gradually replacing glass containers. MMA is used in many of the same applications as acrylic latices and is also used as a comonomer with acrylonitrile to make acrylic fibers. 

In the polymerization of MMA by BuLi the initiator was reported to react first with many more carbonyl groups than with vinyl double bonds at low temperatures O). Therefore, the butyl carbonyl group must be incorporated through the copolymerization of MMA with butyl isopropenyl ketone formed by the former reaction. 

The copolymerization of MMA with a large number of alkyl methacrylates has been studied by Bevington et al. (39), Ito et... 

Fig. 3.4. Time-conversion plot of the copolymerization of MMA with 7 in emulsion at 25 °C...

The homopolymerization of MMA with the soluble catalyst was found to exhibit the characteristic of living polymerization at the initial stage of polymerization ( 5 h) giving poly(MMA) with a narrow molecular weight distribution (Mw/IVln = 1.2, Mn = 2400), at 25 °C. To elucidate the mechanism of the MMA polymerization, the copolymerization of MMA with styrene was carried out. The observed reactivity ratios (rs = 0.5, rMMA = 0.4) indicated that the living polymerization of MMA occurred via a radical intermediate. 

Haddleton determined the reactivity ratios for copolymerization of MMA with BMA by classical anionic as 1.04 0.81 by alkyllithium/trialkylalu-minum initiation, 1.10 0.72 by GTP, 1.76 0.67 by ATRP, 0.98 1.26 by catalytic chain transfer, 0.75 0.98 by classical free radical, 0.93 1.22 [39]. The difference in reactivity ratios between GTP and classical anionic polymerization seems to indicate GTP is an associative process. However, Jenkins has also measured reactivity ratios for the same pair by GTP and reports different results rMMA=0.44 and rBMA=0.26 [40]. 

Muller et al. [53] prepared similar PMMA-g-PMMA by radical copolymerization of MMA with methacrylate-terminated PMMA macromonomer, 29, and characterized the samples by SEC-multiangle laser fight scattering (MALLS). The power law exponent, a, in the equation, 1/2°cMa, was found to be 0.36. In remarkable contrast to the result of Ward et al. [51], the shrinking factor decreased with increase of MW. This may imply that the difference in graft copolymerization method, anionic or radical, results in the graft copolymers with very different branch distribution. 

Since the decay behaviors of polymer radicals is mainly governed, by molecular motions of the polymer matrix (79, 81), the fact that the decay behandor rather resembles to that of the pure PTFE suggests that the imdecular motion rtf this I IMA radicals is rather same to that of PTFE polymer. TMs is also good support for the copolymerization of MMA with PTFE. Moreover, this PTFE-PMMA copolymer radicid decays more rapidly than either one of the hcmopolymers does. This rapid decay seems to be interpreted as that the PMMA branch of the cc Kdymer is not so long as to retard the molecular motion in the range of lower temperature. 

The thermodynamic excluded volume effect should be also reflected as a solvent effect on gelation. That is, a more delayed gelation is expected in a good solvent than in a poor solvent this was the case in the solution polymerization of DAP in various solvents [75,76]. In this connection, Walling [3] has reported the solvent effect on the gelation in the copolymerization of MMA with EDMA, but the result was contrary to our expectations. So, we will discuss this subject in more detail later. 

Fig. 15. Dependence of Mw on conversion in the solution copolymerizations of MMA with 1 mol% of ( ) EDMA, (A) PEGDMA-2, ( ) PEGDMA-3, (A) PEGDMA-9, and ( ) PEGDMA-23, along with (o) MMA homopolymerization (volume ratio total monomer/1,4-dioxane = 1/ 4, [AIBN] = 0.04 mol K at 50 °C)...

A similar solvent effect was also observed in the gelation behavior of the copolymerization of MMA with nonaethylene glycol dimethacrylate [104] The delay between the actual gel point and the theoretical one was much larger in... 

Random copolymerization of MMA with other polar monomers proceeds in a living fashion with relative monomer reactivity ratios in the order BuA > MMA = EtMA > /-PrMA when mediated by 4(Sm Me)/THF [60, 89]. Block polymerization of MMA with other polar monomers as lactone yields ideal living copolymers (PDI = 1.11-1.34) under these conditions. Similarly, ABA triblock copolymers were obtained by sequential addition of MMA, BuA, and MMA [89]. AB block copolymers could be obtained by sequential addition of (L,L)-lactide and (D,D)-lactide (PDI = 1.38) as well as -caprolactone and (l,l)- lactide monomers (PDI = 1.36) in the presence of Y(OCH2CH2NMe2) [82]. 

Branched polymers can also be obtained by copolymerization of MMA with dimethacrylates based upon the condensation product of hexamethylenedi-isocyanate with two hydroxyethyl methacrylates.335... 

The copolymerization of MMA with nBA was also studied using different catalytic systems. The calculated reactivity ratios were close to those for a conventional radical polymerization and similar for different Cu-based catalytic systems (bpy, PMDETA, and Me6TREN) [92]. The distribution of triads and the polymer stereochemistry was as in any other free radical system [93]. 

RAFT has also been used to prepare copolymers. The copolymerization of MMA with nBA in the presence of cumyl dithiobenzoate as the transfer agent resulted in a polymer with a gradient of composition along the backbone, well-defined molecular weights, and low polydispersities [53]. Several copolymers were made by degenerative transfer with alkyl iodides [133]. 

Simultaneous copolymerization of MMA with MMA terminated po-ly(dimethylsiloxane) macromonomers results in the formation of a gradient of composition of PDMS units along the backbone due to a lower macromonomer reactivity which additionally decreases at lower temperatures [139]. 

ATRP can also be carried out in water under homogeneous [208] or under bi-phasic conditions [209-211]. Block and statistical copolymers have also been prepared in water-borne systems. Matyjaszewski et al. demonstrated that a copolymerization of MMA with either BA or nBMA proceeded in a controlled fashion, resulting in copolymers with Mn=26,850 (Mw/Mn=1.22) or Mn=33,550 (Mw/Mn=1.25), respectively [121]. A pnBA macroinitiator prepared in a bulk... 

Anionic block copolymerizations of MMA with lactones proceeded smoothly to give copolymers with Mw/Mn=1.11-1.23 when the monomers were added in this order (Fig. 13). 

Anionic block copolymerizations of MMA with lactones proceeded smoothly by... 

Whereas polymethylacrylate (PMA) is within its main plasticization range at room temperature (Tg at 5 °C), polymethylmethacrylate (PMMA) is still in the vitreous state at this temperature (Tg at 105 °C). Because of the statistical copolymerization of MMA with MA, there a downward shift of the glass transition... 

Fig. 22 CuBr-HMTETA-silica gel packed column reactor for the atom transfer radical block copolymerization of MMA with butyl methacrylate ( BMA) initiated by methyl a-bromoacetate...

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