AIBN initiator

Assuming that no other transfer reactions occur, calculate the values missing from the table. Criticize or defend the following proposition The v values obtained from the limit [SX]/[M] 0 show that the AIBN initiates polymerization identically in all solvents. 

Continuous porous polymer rods have been prepared by an in situ polymerization within the confines of a chromatographic column. The column is filled with glycidyl methacrylate and ethylene dimethacrylate monomer mixtures, cyclo-hexanol and dodecanol diluents, and AIBN initiator. They are then purged with nitrogen, stopped, and closed with a silicon rubber septum. The polymerization is allowed to proceed for 6 hr at 70°C with the column acting as a mold (47). 

Figure 5.3 Conversion-time profile for bulk MMA polymerization at 50 °C with AIBN initiator illustrating the three conversion regimes. Data are taken from...

Hensley ei al.,n reported the only direct experimental observation of head-to-head linkages in PS by 2D INADEQUATE NMR on, 3C-enriched PS. The method did not enable these groups to be quantified with sufficient precision for evaluation of W tc- Zammit el a/.130 studied chain distribution of low molecular weight PS prepared with AIBN initiator by MALDI-TOF. Separate distributions of chains formed by combination and disproportionation were observed. They estimated kJkK. at 90 °C to be 0.057. 

These examples show how initiator selection can be critical in determining the properties of PS prepared by radical polymerization. If thermal stability were of importance, then, since some initiator-derived ends cannot be avoided, a preferred initiator would be one which gives rise to end groups that do not readily eliminate or dissociate. End groups formed with AIBN initiator appear stable with respect to the polymer backbone,19 Many other systems remain to be studied. 

Copolymerizations were performed at 70 C using an ampoule technique similar to that used for MMA. Monomers were purified by distillation. Most of the runs had an initial weight fraction styrene of 0.767 and 1.45 mole % AIBN initiator. Also utilized is one run using 0.235 wt. fraction styrene (0.350 mole % AIBN) and one at 0.557 (1.45 mole % AIBN). Gruber and Knell (10) used both the former compositions. The latter one is the calculated azeotropic composition using their values of the reactivity ratios. 

Free radical copolymerizations of the alkyl methacrylates were carried out in toluene at 60°C with 0.1 weight percent (based on monomer) AIBN initiator, while the styrenic systems were polymerized in cyclohexane. The solvent choices were primarily based on systems which would be homogeneous but also show low chain transfer constants. Methacrylate polymerizations were carried out at 20 weight percent solids... 

Due to the low solubility of the monomer 1III) in benzene, the polymerization had to be carried out at less than 10% (w/v) monomer concentration. A yield of 92% was obtained by AIBN initiation at 60°C. Ammonium persulfate and benzoyl peroxide initiators were found to be ineffective. The solubility characteristics of poly(N-pheny1-3,4-dimethylenepyrroline) are listed in Table I. The polymer was insoluble in most common solvents except for formic acid and trifluoroacetic acid. The polymer was characterized by C,H elemental analysis, IR and NMR. 

The DIS monomer, unlike its iron analogue, did not homopolymerize with SnCl initiator even on heating. A plausible reason for this result is that this monomer contains a lone pair of elec-trons available for donation to Lewis acids.JU Thus side reactions similar to those of the previous two monomers would prevent propagation. However, the DIS monomer also underwent a free radical copolymerization reaction with styrene and AIBN initiation. 

In 1994, we reported the dispersion polymerization of MM A in supercritical C02 [103]. This work represents the first successful dispersion polymerization of a lipophilic monomer in a supercritical fluid continuous phase. In these experiments, we took advantage of the amphiphilic nature of the homopolymer PFOA to effect the polymerization of MMA to high conversions (>90%) and high degrees of polymerization (> 3000) in supercritical C02. These polymerizations were conducted in C02 at 65 °C and 207 bar, and AIBN or a fluorinated derivative of AIBN were employed as the initiators. The results from the AIBN initiated polymerizations are shown in Table 3. The spherical polymer particles which resulted from these dispersion polymerizations were isolated by simply venting the C02 from the reaction mixture. Scanning electron microscopy showed that the product consisted of spheres in the pm size range with a narrow particle size distribution (see Fig. 7). In contrast, reactions which were performed in the absence of PFOA resulted in relatively low conversion and molar masses. Moreover, the polymer which resulted from these precipitation... 

Homolytic hydrostannation can also be initiated at room temperature by thiophenols, when a trace of oxygen may oxidize the thiol to the ArS radical, which abstracts hydrogen from the stannane to give the stannyl radical (Equation (15)).93 With azoisobutyronitrile (AIBN) initiation, alkynes undergo only monohydrostannation, but with the thiol, simple alkynes show bis(hydrostannation) or bis(stannation). 

It was noted by Ohto et al. (1977b) that PBN inhibits the AIBN-initiated autoxidation of hydrocarbons, and that in the course of these inhibited... 

The use of appropriate functionalized oligomers is a key to the success of this synthesis. The necessary functionalized oligomers were prepared by polymerization of ferf-butyl acrylate (n = ca. 120) with a functional AIBN initiator (Eq. 1). Since... 

The value of kd is then found from the slope of a plot of the left side of Eq. 3-94 versus time. Figure 3-4 shows the plot for the AIBN-initiated polymerization of isoprene at three temperatures [Gobran et al., I960]. Since kd is determined, / can be obtained from either Eq. 3-32 or 3-93 if the ratio kp/kis known from other studies. 

AIBN is, however, virtually unaffected by the presence of dithio-phosphates (Table II). Further, with specific reference to the oxidation of the disulfide in Table I, which has no effect on the rate of AIBN-initi-ated autoxidation of cumene (6), it is unlikely that the efficiency of radical production from AIBN increases since this would produce a prooxidant effect in cumene. Thus, the zinc salt inhibitor is being oxidized in competition with the main chain reaction. 

Table I. AIBN-Initiated Oxidation of Organic Phosphorus Compounds in ferf-Butylbenzene at 70°C.

By far the most studied PolyHIPE system is the styrene/divinylbenzene (DVB) material. This was the main subject of Barby and Haq s patent to Unilever in 1982 [128], HIPEs of an aqueous phase in a mixture of styrene, DVB and nonionic surfactant were prepared. Both water-soluble (e.g. potassium persulphate) and oil-soluble (2,2 -azo-bis-isobutyronitrile, AIBN) initiators were employed, and polymerisation was carried out by heating the emulsion in a sealed plastic container, typically for 24 hours at 50°C. This yielded a solid, crosslinked, monolithic polymer material, with the aqueous dispersed phase retained inside the porous microstructure. On exhaustive extraction of the material in a Soxhlet with a lower alcohol, followed by drying in vacuo, a low-density polystyrene foam was produced, with a permanent, macroporous, open-cellular structure of very high porosity (Fig. 11). 

Polymer-bound dinitrogen complexes containing Mn have been prepared [8] directly from the polymer bound (n5-vinylmethyl-cyclopentadienyl) tricar-bonylmanganese (VCM) and molecular nitrogen in THF/benzene. The metal-containing base polymer may be readily prepared by AIBN initiated radical polymerization of VCM with styrene or /V-vinylpyrrolidone (Fig. 4). 

RCOOH - RH. Another method for degradation of carboxylic acids to the noralkane involves conversion to the phenyl carboselenoate 1, which is then reduced with Lri-n-bulyllin hydride (AIBN initiation) (equation 1). Reduction can result in... 

In 1979, Maciejewski et al. also explored Method 3 for the preparation of main-chain poly(vinylidene chloride-/ -CD rotaxane) 35 [74, 75]. Radiation polymerization and AIBN-initiated solution polymerization of the complex of vinyli-dene chloride with 21 gave products with min = 0.34 and 0.49, respectively. However, the polyrotaxane via Method 1 had a much lower min (0.087) with much lower CD/monomer feed ratio than for those via the polymerization of the complex (1 1 ratio). Therefore, the reported min values are not comparable, so the difference between the two methods in terms of threading efficiencies cannot be distinguished. Although the authors did not see any threading via Method 2 for the same polyrotaxanes, Ogino and coworkers prepared a true CD-based polyrotaxane of Type 5 using metal complexes as stoppers [76]. It was also found that... 

It has been deduced from the order of reaction with respect to monomer that the rate of initiation is not independent of monomer (122). One could assume that initiator and monomer may form a complex from which the actual initiator is derived, or else that the AIBN and its radical products are in equilibrium within a cage of solvent. Although kinetic data are consistent with such assumptions, it appears that the results can be explained reasonably on the grounds of termination by primary radicals (21). The order of reaction with respect to AIBN initiator in nearly all of these studies is the expected 0.50 or possibly slightly higher (0.55 to 0.59). 

The radiotracer method for estimating efficiency of initiation was applied by Bevington and Eaves (32) to polymerization in benzene and in carbon tetrachloride. Whereas they had calculated that about 47% of the radicals from AIBN initiate polymer chains in DMF solvent, efficiency in benzene was about 50% and in carbon tetrachloride about 30%. This low efficiency in carbon tetrachloride is attributed to attack of radicals from AIBN on the carbon tetrachloride solvent, especially at high concentrations of solvent. Chains initiated by secondary radicals derived in this way from the solvent would not be detected by the tracer method. 

Physical entrapment or chemical coupling is a well-established procedure for MIP preparation. First, a complex is formed between a functional monomer and template in an appropriate solvent solution. Then the complex is immobilized by polymerization in excess of a cross-linker. Predominantly, free-radical polymerization thermally launched with a 2,2-azobis(isobutyronitrile) (AIBN) initiator, is performed. In the case of photo-radical polymerization, a benzophenone or acetopho-none derivative is also used as the initiator [101]. Next, the template is extracted by rinsing the resulting MIP block with a suitably selected solvent solution. The bulk... 

An MIP-QCM chemosensor has been devised for determination of thymine [141]. A new functional monomer, vis. methacryloylamidoadenine (MA-Ade), as well as the EDGMA cross-linker and AIBN initiator have been used for preparation of the thymine-imprinted polymer film by photo-induced polymerization. This film was deposited on the QCM resonator, featuring homogeneous binding sites for... 

A biomimetic MIP recognition material was devised for determination of a paracetamol (also known as acetominphen) pain reliever using a QCM transducer [109]. To this end, MIP was prepared with two different functional monomers, namely VPD and MAA. An EGDMA cross-linker and AIBN initiator were also present in the solution. The thermo-radical polymerization was performed at 60 °C. The resulting MIP powder was dispersed in a PVC matrix and then drop coated onto a quartz resonator. A linear decrease of the resonant frequency change with the increase of the paracetamol concentration ranged from 50 nM to 10 mM at LOD of 50 nM paracetamol. The chemosensor was successfully applied for the paracetamol determination in real samples, such as human serum and urine. 

A histamine selective MIP chemosensor, based on impedimetric transduction, has been devised [136]. Its preparation involved immobilization of the histamine imprinted MIP particles in apoly[2-methoxy-5-(3,7-dimethyloctyloxy)-l-4-pheny-lene vinylene] (OCiCi0-PPV) film deposited on aluminium electrodes. Preparation of these particles comprised thermally induced co-polymerization of MAA (functional monomer), EGDMA (cross-linker) and AIBN (initiator) in the presence of histamine. This film efficiently rebound histamine in the presence of histidine and... 

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