VDC-Zonyl

Fig. 3.2.9 DSC/TGA of the RBl-200 product, which contains segments from VDC, Zonyl methacrylate, methyl methacrylate (MMA), and glycidyl methacrylate(GMA). The run includes a heat-up step to 200°C, then a cool-down step to room temperature, followed by a final heatup step. Both heat-up and cool-down steps are at 10°C/min rate. Note that exotherm is up in the vertical axis...

The FRRPP polymerization of VDC-Zonyl TA-N was carried out in parallel pressure tubes and in a Stage 1 stirred-tank reactor system. The reaction process was done at 120°C for about 8 h reaction yield was about 80%. A high-throughput polymerization reaction using a robotic dispensing system containing VDC and Zonyl TA-N was undertaken by varying the amounts of VDC and Zonyl TA-N for 24 samples. 

The second high-throughput polymerization reaction was the use of VDC, Zonyl TA-N, Zonyl TM, and Zonyl PFBE. The Zonyl concentration for the three reactions was higher than the VDC concentration ranging from 62 to 83% Zonyl . No polymers were formed in the reaction possibly due to low reactivities of the Zonyl monomers. An FRRPP recipe of 36 g VDC, 3.6 g Zonyl TA-N, AIBN 1 wt% initiator in the solvent mixture (methyl ethyl ketone 66%, t-butanol 34%) at 110°C was commenced for our first-stage reaction with a 9% conversion. Sometimes during the first-stage reaction additional Zonyl TA-N was added 3.6 g after the initial monomer, AIBN, and solvent injection. PolyZonyl TA-N was synthesized with a 15 wt% solution in t-butanol, methyl ethyl ketone, and 0.5 wt%... 

Product VDC-Zonyl TA-N copolymers are in the form of fine particulate (Fig. 3.2.6), which were removed from the reactor through a 1/8 in. copper or stainless steel line that is immersed in ice-water bath. This kept the polymer radicals active for block multipolymer formation. 

Fig. 4.1.12 DSC/TGA heating curves for a VDC-Zonyl copolymer generated via the FRRPP process. Since the exotherm is up, the melting transitions are minima at 100, 150, and 200°C in the DSC curve...

After the Stage 1 and Stage 2 polymerization runs, products were separated from the reactor solvents (1-butanol, MEK, and NMP), unreacted monomers (VDC, Zonyl -TAN, Zonyl -TM, MMA, GMA, and BA), and unreacted initiator (AIBN... 

DSC/TGA analysis of RBI-215 product has been shown to be even more thermally stable than the Stage 1 VDC-Zonyl intermediate product (Fig. 4.1.5). As shown in Fig. 4.3.5, the weight of the RBl-215 material decreased to only 80% of its original value at 300 C, even after two heating cycles. Curing of the GMA segments is also evident at 100-275°C. 

An example product is a diblock called RBI-232 made of a VDC copolymer (96 wt% VDC, 6 wt% Zonyl TA-N) block with a butyl acrylate-Vaf-glycidyl methacrylate block. The reactor product solution was fractionally precipitated, and... 

Radicalized VDC statistical copolymer with Zonyl has been shown to be capable of formation of various block copolymers, which in turn can also be reactive intermediates. This is true with the RBl-200 and RBI-232 products described in Section 4.2, in which the second block contains epoxide groups from glycidyl methacrylate. Another product, called RBI-201, was similar to RBl-200 but contained Zonyl TM segments in the second block (see synthesis procedure in Table 4.3.1). 

The A-block contains the VDC segments, while its B and C blocks contain both GMA and MMA segments. The B-block also contains BA segments. What makes the C-block unique is the presence of the Zonyl TA-N or Zonyl TM segments, which have a melting transition of 50-80 C (Caneba et al 2008). 

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