Ring‐Opening Metathesis Polymerization‐Derived Materials for Separation Science, Heterogeneous Catalysis and Tissue Engineering

Abstract

Summary: The chemistry of ring‐opening metathesis polymerization‐ (ROMP) derived monolithic materials is summarized. Since ROMP triggered by well‐defined transition metal alkylidenes is a living polymerization method, it allows for the controlled and highly reproducible synthesis of monolithic media in terms of total porosity, pore size distribution and specific surface area. In addition, the high functionality tolerance of ROMP allows for creating monolithic supports with an unprecedented diversity in terms of functional groups that may be introduced. Selected applications in the areas of separation science, heterogeneous catalysis and tissue engineering are presented and discussed within the context of ROMP.

Synthesis of Soluble Star-Shaped Polymers via In and Out Approach by Ring-Opening Metathesis Polymerization (ROMP) of Norbornene: Factors Affecting the Synthesis

“…were applied as fluorescent materials [19], supported catalysts [20], and as controlled release and drug delivery systems [24,26,27]. In this method, related examples for synthesis of cross-linked ROMP polymers (insoluble in common organic solvents) were also known [31][32][33][34][35], especially in terms of application as monolith materials. Two major approaches shown in Scheme 1, such as the "in and out" (core first) approach using a molybdenum-alkylidene catalyst [17][18][19][20][21], and arm (brush) first approach using a ruthenium-carbene catalyst [23][24][25][26][27][28], have been known for synthesis of 'soluble' star-shaped ROMP polymers.…”

Mono‐ and Bisionic Mo‐ and W‐Based Schrock Catalysts for Biphasic Olefin Metathesis Reactions in Ionic Liquids

“…Yield:6 5mg( 63 %). 1 H-NMR (400 MHz, CD 2 Cl 2 ): d = 11.29 (s, 1H,M o= CH), 7.65 (s, 2H,A r), 7.63-7.55, 7.41-7.30 (m, 6H,A r), 7.20-7.15 (m, 2H,A r), 7.11-7.05 (m, 4H, Ar), 7.03-6.98 (m, 2H,A r), 6.98-6.92 (m, 2H,A r), 5.77 (s, 2H,p yr), 2.89 (sept, 3 27;H ,5 .98;N ,4.15. Found:C,64.89;H ,5.955;N,4.14. Synthesis of 9b: 5a (330 mg, 5.577 mmol) was dissolved in 5mL of THF.T he solution was cooled to À35 8C.…”

“…Today, olefin metathesis is considered one of the most useful C−C coupling reactions . Its enormous potential, whether in Organic or in Polymer Chemistry, assures for a constantly high interest in the further development of this reaction as well as in olefin metathesis polymerization‐derived materials . Until now, many issues with regards to catalyst stability, productivity, activity and technical applicability have been investigated in great detail.…”

“…[2] Its enormous potential, whether in Organico ri nP olymer Chemistry,a ssuresf or ac onstantly high interesti nt he furtherd evelopmento ft his reaction as well as in olefin metathesis polymerization-derived materials. [3] Until now,many issuesw ith regards to catalyst stability,productivity, activity and technical applicabilityh ave been investigated in great detail. More recent, fundamental achievements relate to E/Z selectivity [4] or the tolerance of polar or even protic functional groups.…”

“…Me), 1.29 (s, 3H,C Me 2 Ph), 1.28 (s, 3H,C Me 2 Ph), 0.77 (d,3 J HH = 6.2 Hz, 6H, iPr), 0.64 ppm (d,3 J HH = 6.2 Hz, 6H, iPr); 13 C-NMR (100 MHz, CDCl 3 ): d = 293.7 (Mo = CH), 161.8 (q, 1 J CB = 49.8 Hz, (BAr F ) 4 ), 160.7 (Ar), 158.2 (Ar), 157.5 (Ar), 153.7 (Ar), 147.7 (Ar), 136.8 (Ar), 134.9 (s, br, o-CH B(Ar F ) 4 ), 134.3 (Ar), 133.9 (Ar), 132.8 (Ar), 132.3 (Ar), 131.4 (Ar), 130.6 (Ar), 130.5 (Ar), 129.5 (Ar), 129.4 (Ar), 129.3 (Ar), 129.2 (Ar), 129.0 (qq, 2 J CF = 31.6 Hz, 3 J CB = 2.7 Hz, C-CF 3 B(Ar F ) 4 ), 128.8 (Ar), 128.7 (Ar), 128.5 (Ar), 128.1 (Ar), 128.1 (Ar), 126.3 (Ar), 125.9 (Ar), 125.8 (Ar), 124.7 (q, 1 J CF = 272.8 Hz, CF 3 B(Ar F ) 4 ), 123.0 (Ar), 117.6 (sept, 3 J CF = 3.8 Hz, p-CH B(Ar F ) 4 ), 109.1 (pyr), 56.1 (CMe 2 Ph), 31.5 (CMe 2 Ph), 30.1 (CMe 2 Ph), 28.4 (iPr-CH), 23.6 (iPr-Me), 23.1 (iPr-Me), 16.6 ppm (pyr-Me); 19 F-NMR (375 MHz, CDCl 3 ): d = À62.35 ppm (s, 24F,B (Ar F ) 4 ). Elemental analysis (%) calcd for C 101 H 78 BF 24…”