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Optimization of Ring-Opening Metathesis Polymerization (ROMP) under Physiologically Relevant Conditions.

ABSTRACT: Ring opening metathesis polymerization (ROMP) is widely considered an excellent living polymerization technique that proceeds rapidly under ambient conditions and is highly functional group tolerant when performed in organic solvents. However, achieving the same level of success in aqueous media has proved to be challenging, often requiring an organic co-solvent or a very low pH to obtain fast initiation and high monomer conversion. The ability to efficiently conduct ROMP under neutral pH aqueous conditions would mark an important step towards utilizing aqueous ROMP with acid-sensitive functional groups or within a biological setting. Herein we describe our efforts to optimize ROMP in an aqueous environment under neutral pH conditions. Specifically, we found that the presence of excess chloride in solution as well as relatively small changes in pH near physiological conditions have a profound effect on molecular weight control, polymerization rate and overall monomer conversion. Additionally, we have applied our optimized conditions to polymerize a broad scope of water-soluble monomers and used this methodology to produce nanostructures via ring opening metathesis polymerization induced self-assembly (ROMPISA) under neutral pH aqueous conditions.

SUBMITTER: Church DC

PROVIDER: S-EPMC8009303 | biostudies-literature |

REPOSITORIES: biostudies-literature

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"Click"-capture, ring-opening metathesis polymerization (ROMP), release: facile triazolation utilizing ROMP-derived oligomeric phosphates.

Project description:Soluble, high-load ring-opening metathesis polymerization (ROMP)-derived oligomeric triazole phosphates (OTP) are reported for application as efficient triazolating reagents of nucleophilic species. Utilizing a "Click"-capture, ROMP, release protocol, the efficient and purification-free, direct triazolation of N-, O-, and S-nucleophilic species was successfully achieved. A variety of OTP derivatives were rapidly synthesized as free-flowing solids on a multigram scale from commercially available materials.

| S-EPMC3098766 | biostudies-other

Scope of the ring-opening metathesis polymerization (ROMP) reaction of 1-substituted cyclobutenes.

Project description:The reactivities of a series of 1-substituted cyclobutene derivatives (carboxylate esters, carboxamides, and carbinol esters) were investigated as substrates for ring-opening metathesis polymerization (ROMP) with [(H(2)IMes)(3-Br-pyridine)(2)(Cl)(2)Ru=CHPh]. Both the secondary amides of 1-cyclobutenecarboxylic acid and the esters of 1-cyclobutene-1-methanol undergo polymerization. The secondary amides provide translationally invariant polymers (E-olefins). Although the carbinol esters yield stereo- and regiochemically heterogeneous polymers, the 1-cyclobutenecarboxylic acid esters and tertiary amides undergo ring-opening metathesis (ROM) but not ROMP. The regio- and stereochemical outcomes of these ROMP and ROM reactions were analyzed at the B3LYP/6-31G* and LANL2DZ levels of theory. Calculations suggest that the regiochemistry and stereochemistry of the addition to the propagating carbene to form the metallocyclobutane intermediate depend on both charge distribution and steric interactions.

| S-EPMC2921852 | biostudies-literature

Z-Selective and Syndioselective Ring-Opening Metathesis Polymerization (ROMP) Initiated by MonoAryloxidePyrrolide (MAP) Catalysts.

Project description:We report the Z-selective and syndioselective polymerization of 2,3-bis(trifluoromethyl)bicyclo[2.2.1]hepta-2,5-diene (NBDF6) and 3-methyl-3-phenylcyclopropene (MPCP) by monoaryloxide monopyrrolide imido alkylidene (MAP) catalysts of Mo. The mechanism of polymerization with syn-Mo(NAd)(CHCMe(2)Ph)(Pyr)(OHIPT) (1; Ad = 1-adamantyl, OHIPT = O-2,6-(2,4,6-i-Pr(3)C(6)H(2))(2)C(6)H(3)) as the initiator is proposed to consist of addition of monomer to the syn initiator to yield a syn first insertion product and propagation via syn insertion products. In contrast, the mechanism of polymerization with syn-Mo(NAr)(CHCMe(2)Ph)(Pyr)(OTPP) (4; Ar = 2,6-i-Pr(2)C(6)H(3), OTPP = 2,3,5,6-Ph(4)C(6)H) as the initiator at -78 °C consists of addition of monomer to the syn initiator to yield an anti first insertion product and propagation via anti insertion products. Polymerizations of NBDF6 and MPCP at room temperature initiated by 4 led to polymers without a regular structure. We propose that the syndiotacticity of cis polymers is the consequence of the required inversion at the metal center with each insertion of monomer, i.e., stereogenic metal control of the polymer structure. We also propose that the two mechanisms for forming cis,syndiotactic polymers arise as a consequence of the relative steric bulk of the imido and phenoxide ligands.

| S-EPMC3074984 | biostudies-literature

Carbodiimide Ring-Opening Metathesis Polymerization

Project description:Controlled incorporation

| S-EPMC10311665 | biostudies-literature

Selective ring-opening metathesis polymerization (ROMP) of cyclobutenes. Unsymmetrical ladderphane containing polycyclobutene and polynorbornene strands.

Project description:At 0 °C in THF in the presence of Grubbs first generation catalyst, cyclobutene derivatives undergo ROMP readily, whereas norbornene derivatives remain intact. When the substrate contains both cyclobutene and norbornene moieties, the conditions using THF as the solvent at 0 °C offer a useful protocol for the selective ROMP of cyclobutene to give norbornene-appended polycyclobutene. Unsymmetrical ladderphane having polycyclobutene and polynorbornene as two strands is obtained by further ROMP of the norbornene appended polycyclobutene in the presence of Grubbs first generation catalyst in DCM at ambient temperature. Methanolysis of this unsymmetrical ladderphane gives polycyclobutene methyl ester and insoluble polynorbornene-amide-alcohol. The latter is converted into the corresponding soluble acetate. Both polymers are well characterized by spectroscopic means. No norbornene moiety is found to be incorporated into polycyclobutene strand at all. The double bonds in the polycyclobutene strand are mainly in cis configuration (ca 70%), whereas the E/Z ratio for polynorbornene strand is 8:1.

| S-EPMC6334803 | biostudies-literature

Synthesis of Poly(norbornene-methylamine), a Biomimetic of Chitosan, by Ring-Opening Metathesis Polymerization (ROMP).

Project description:ROMP is an effective method for preparing functional polymers due to its having characteristics of "living" polymerization and rapid development of catalysts. In the present work, poly(norbornene-methylamine), a mimic of chitosan, was synthesized via ROMP reaction. The amino-protected product, 5-norbornene-2-(N-methyl)-phthalimide, was prepared by a reaction of 5-norbornene-2-methylamine with phthalic anhydride, which was then subjected to the ROMP reaction in the presence of Hoveyda-Grubbs 2nd catalyst to afford poly(norbornene-(N-methyl)-phthalimide). The target product, poly(norbornene-methylamine), was obtained by deprotection reaction of poly(norbornene-(N-methyl)-phthalimide). The products in each step were characterized by FTIR and ¹H-NMR, and their thermal stabilities were determined by TG analysis. The effects of molar ratio between monomer ([M]/[I]) and catalyst on the average relative molecular weight ( M n ¯ ) and molecular weight distribution of the produced polymer products were determined by gel permeation chromatography (GPC). It was found that the M n ¯ of poly(norbornene-(N-methyl)-phthalimide) was controllable and exhibited a narrow polydispersity index (PDI) (~1.10). The synthesis condition of 5-norbornene-2-(N-methyl)-phthalimide was optimized by determining the yields at different reaction temperatures and reaction times. The highest yield was obtained at a reaction temperature of 130 °C and a reaction time of 20 min. Our work provides a new strategy to synthesize polymers with controllable structures and free -NH₂ groups via ROMP.

| S-EPMC5532665 | biostudies-other

Unsymmetrical difunctionalization of cyclooctadiene under continuous flow conditions: expanding the scope of ring opening metathesis polymerization.

Project description:Functionalized cyclooctenes (FCOEs) are important monomers in ring-opening metathesis polymerization (ROMP). Herein, a new library of disubstituted FCOEs bearing adjacent heteroatoms were synthesized and applied in ROMP. To address the issues associated with the handling of the reactive thienyl chloride intermediate, a two-step continuous flow method has been developed to prepare 5-thio-6-chlorocyclooctene compounds from abundant cyclooctadiene starting materials. These newly synthesized FCOE monomers were subsequently polymerized through ROMP, giving rise to a range of functionalized polymers with high molecular weights. Furthermore, we demonstrated that the thermal properties of these polymers could be fine-tuned by changing the functional groups in the FCOE monomers. We expect that this functionalization-polymerization strategy will enable the preparation of a range of polymeric materials with complex structures.

| S-EPMC5890785 | biostudies-literature

Practical Route for Catalytic Ring-Opening Metathesis Polymerization.

Project description:Norbornene derivatives are typical monomers for ring-opening metathesis polymerization (ROMP) for synthesizing highly functional polymers. However, the lack of catalytic methods, that is, the lack of readily available chain transfer agents (CTAs) for these monomers has been a significant cost limitation when large-scale syntheses are required. Here, we report commercially available styrene and its derivatives as efficient regioselective CTAs for the catalytic synthesis of metathesis polymers requiring up to 1000 times less ruthenium than in classical ROMP experiments. The molecular weight of the synthesized polymers was controlled by the monomer-to-CTA ratio. Low molecular weight ROMP polymers known for their antimicrobial properties were also synthesized on a gram scale in this report. Polymers were characterized by SEC, 1H NMR spectroscopy, and isotopically resolved MALDI-TOF MS. This approach describes a greener, more cost-effective, and eco-friendly methodology for the preparation of metathesis-based materials on the multigram scale.

| S-EPMC9795566 | biostudies-literature

Towards New Robust Zn(II) Complexes for the Ring-Opening Polymerization of Lactide Under Industrially Relevant Conditions.

Project description:The synthesis of bio-based and biodegradable plastics is a hot topic in research due to growing environmental problems caused by omnipresent plastics. As a result, polylactide, which has been known for years, has seen a tremendous increase in industrial production. Nevertheless, the manufacturing process using the toxic catalyst Sn(Oct)2 is very critical. As an alternative, five zinc acetate complexes have been synthesized with Schiff base-like ligands that exhibit high activity in the ring-opening polymerization of non-purified lactide. The systems bear different side arms in the ligand scaffold. The influence of these substituents has been analyzed. For a detailed description of the catalytic activities, the rate constants k app and k p were determined using in-situ Raman spectroscopy at a temperature of 150 °C. The polymers produced have molar masses of up to 71 000 g mol-1 and are therefore suitable for a variety of applications. Toxicity measurements carried out for these complexes proved the nontoxicity of the systems.

| S-EPMC6664153 | biostudies-literature

Resonance promoted ring-opening metathesis polymerization of twisted amides.

Project description:The living ring-opening metathesis polymerization (ROMP) of an unsaturated twisted amide using the third-generation Grubbs initiator is described. Unlike prior examples of ROMP monomers that rely on angular or steric strain for propagation, this system is driven by resonance destabilization of the amide that arises from geometric constraints of the bicyclic framework. Upon ring-opening, the amide can rotate and rehybridize to give a stabilized and planar conjugated system that promotes living propagation. The absence of other strain elements in the twisted amide is supported by the inability of a carbon analogue of the monomer to polymerize and computational studies that find resonance destabilization accounts for 11.3 kcal mol-1 of the overall 12.0 kcal mol-1 ring strain. The twisted amide polymerization is capable of preparing high molecular weight polymers rapidly at room temperature, and post-polymerization modification combined with 2D NMR spectroscopy confirms a regioirregular polymer microstructure.

| S-EPMC6993617 | biostudies-literature

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