Polyolefin soluble polyisobutylene oligomer-bound metallophthalocyanine and azo dye additives

Abstract

Metallophthalocyanines prepared with polyisobutyl (PIB) substituents have very high solubility in organic solvents including saturated hydrocarbons, toluene, and other low polarity organic solvents. In heptane, PIB-bound metallophthalocyanines have solubility of about 0.1 g/mL at 25 C, solubility values that are significantly higher than other substituted metallophthalocyanines. PIB terminally functionalized with metallophthalocyanines as well as PIB containing terminal azo dye groups also dissolve in molten hydrocarbon polymers like polyethylene or polypropylene. Thus, these highly chromogenic PIB-bound dyes can be incorporated uniformly into the polyolefins to form colored polymer solids on cooling. Because only a low concentration of a highly hydrocarbon compatible dye is used, the crystallinity and thermal properties of the colored polyolefin products are not significantly affected.

Sustainable Hydrocarbon Oligomer Solvent Systems for Sequestration of Trace Organics from Water

“…To address the issue of insufficient sequestration levels for polar organics, we explored modifying PAO with a PAO‐phase‐anchored cosolvent to generate a sequestering phase that contained molecular‐recognition elements. Our experience with PIB‐bound dyes, ligands, catalysts, and polar nanoparticles is that hydrocarbon oligomeric solvents are very effective at phase‐anchoring PIB‐bound polar species . Thus, we reasoned that a PIB with a hydrogen‐bonding terminal catechol group (Figure ) could be phase‐anchored in PAO and could be used to facilitate sequestration of polar groups in PAO because the ability of catechol to form H‐bonds.…”

“…Our experience with PIB-bound dyes, ligands, catalysts, and polar nanoparticles is that hydrocarbon oligomeric solvents are very effective at phase-anchoring PIB-bound polar species. [9,[16][17][18] Thus, we reasoned that aP IB with ah ydrogen-bonding terminal catecholg roup ( Figure 2) could be phase-anchored in PAOa nd couldb eu sed to facilitate sequestration of polar groups in PAOb ecause the ability of catechol to form H-bonds. This benzene( 900) [a] 7.0 99 hexane (800) [a,d] < 0.1 > 99 benzene( 24) [b] < 0.1 > 99 dichloromethane (1450) [b] 72 95 benzene( 550) [c] 3.4 99 benzene( 450) [d] 8.1 98 1,2-dichloroethane (650) [c] 40 94 1,4-dichlorobenzene (17) [c] < 0.1 > 99 dichloromethane (7000) [c] 350 > 99 THF (11100) [c] 7700 (2820) [e] 30 (76) [e] THF (2820) [c] 330 [e] 88 [e] triethylamine (15 000) [c] 4500 (600) [ [a] Sequestration was performedb ym ixing the D 2 Os olution (3.5 g) containingt he organic impurity with the PAO 432 (1.5 g) with av ortexm ixer for 1min.…”

“…ChemSusChem 2019, 12,416 -419 www.chemsuschem.org property would be enhanced in ah ydrocarbon such as PAOi n which there are no competing H-bond acceptors, ap remise that has precedent in water separation with membranes. [7] Thus, we prepared ac atechol derivative from alkene-terminated PIB 450 (450 Da M n )b yu sing the chemistry detailed below [18] and used this PIB derivative as aP AO-phase-anchorable Hbondinga gent. Ap reliminary experiment with PAO, 1 m PIB 450 -catechol, and an aqueous solution of p-methyl red suggested this strategy would be effective because the methyl red visually transferred from water to the PAOp hase, forming ar ed PAOs olution consistent with strong H-bonding of the PIB 450 -catechol tot he methyl red dye.…”

Block copolymers derived from polyisobutylene oligomers

“…However, the synthesis of PIB block copolymers whose polar block has a degree of polymerization that is less than that of the polyisobutylene block that are alkane soluble has not been described. Based on other work, we believe such materials could be used as cosolvents with alkane oligomers, as fully miscible polyolefin additives, or as polyvalent ligands to solubilize nanoparticles …”

“…However, the synthesis of PIB block copolymers whose polar block has a degree of polymerization that is less than that of the polyisobutylene block that are alkane soluble has not been described. Based on other work, we believe such materials could be used as cosolvents with alkane oligomers, 9 as fully miscible polyolefin additives, 18 or as polyvalent ligands to solubilize nanoparticles. 8 In this work, we examined three different synthetic routes to block copolymers from PIB oligomers with terminal alkene groups (Scheme 1): hydroboration/oxygen initiation; atom transfer radical polymerization (ATRP); and reversible addition/fragmentation chain transfer polymerization (RAFT).…”