What Polymerization Techniques got wrong, from 43 theses

Tried and failed

acid-catalyzed ring-opening metathesis polymerization applied to strained cyclopropenes. Outcome: unstable. Reason: monomer decomposed under reaction conditions yielding no polymer

Exploration of Carbonyl–Olefin Metathesis Reactions: Ring Opening, Ring Closing and Polymerization. Investigation of Cyclopropenimines for Carbon Dioxide Capture and Its Conjugate · Cornell · PhD

Tried and failed

living ring-opening metathesis at high dilution applied to high molecular weight polymer synthesis. Outcome: unstable. Reason: dominant backbiting and cross-metathesis side reactions led to loss of polymerization control

Biomimetic elastomers from ring-opening metathesis polymerization · UT Austin · PhD

Tried and failed

ring-opening polymerization at low monomer-to-initiator ratio applied to asymmetric cyclic diester polymerization. Outcome: worse than baseline. Reason: low monomer loading promoted dominant transesterification side-reactions, reducing regioselectivity and increasing dispersity

POLYESTER SEQUENCE CONTROL VIA REGIO- AND STEREOSELECTIVE RING-OPENING POLYMERIZATIONS · Cornell · PhD

Tried and failed

ring-opening metathesis polymerization using ruthenium catalyst applied to bridged bicyclic ketone monomers. Reason: insufficient ring strain or unfavorable electronics compared to twisted amide analogues prevented polymerization

Synthesis, reactivity and polymerization of bridged bicyclic twisted amides · Georgia Tech · PhD

Tried and failed

ring-opening metathesis polymerization applied to 1,5-cyclooctadiene monomer. Reason: formed viscous fluids rather than handleable solid polymers

Spatially defined crystallinity within multimaterial polymeric networks · UT Austin · PhD

Tried and failed

stereoselective ring-opening metathesis polymerization applied to cis-cyclooctene polymerization. Outcome: too slow. Reason: catalysts exhibited low catalytic activity yielding low monomer conversions even at elevated temperatures

Spatially defined crystallinity within multimaterial polymeric networks · UT Austin · PhD

Tried and failed

sterically hindered branching agent in graft-through polymerization applied to ring-opening metathesis star polymer synthesis. Outcome: worse than baseline. Reason: branching agent reduced monomer reactivity, suppressing propagation and yielding incompletely converted intermediates

The design and application of functional enyne reagents in metathesis polymerization · Georgia Tech · PhD

Tried and failed

driving copolymerization to high conversion applied to random ring-opening copolymer synthesis. Reason: reactivity ratio disparity causes compositional drift and loss of random copolymer architecture at high conversion

RATIONAL DESIGN OF HIGH-PERFORMANCE AMORPHOUS POLYMER ELECTROLYTES · Cornell · PhD

Tried and failed

extending reaction time to increase conversion applied to anionic ring-opening polymerization. Reason: monomer conversion plateaued due to ring-chain equilibrium

RATIONAL DESIGN OF HIGH-PERFORMANCE AMORPHOUS POLYMER ELECTROLYTES · Cornell · PhD

Considered and rejected

Considered and rejected: Rejected direct polymerization of cyclic monomers bearing polar groups due to low polymer yields (e.g., 3-37%).

High Permittivity Siloxanes as Promising Materials for Dielectric Elastomer Transducers: From Synthesis to Application · EPFL · PhD

Tried and failed

nitrogen bubbling deoxygenation applied to atom transfer radical polymerization. Outcome: unstable. Reason: incomplete or variable oxygen removal led to batch-to-batch kinetic inconsistency and low-molecular-weight tailing

Polymer-Ligated Nanocrystals with Tunable Dimensions, Compositions, and Architectures · Georgia Tech · PhD

Tried and failed

reversible deactivation radical polymerization network synthesis applied to crosslinked polymer network mechanical properties. Outcome: worse than baseline. Reason: controlled growth delayed percolation leading to more brittle networks and increased molecular damage under strain

Leveraging living copolymerizations as a tool to tailor the architecture and mechanical properties of polymer networks · UT Austin · PhD

Tried and failed

photoredox ATRP using organic photosensitizers alone applied to controlled radical polymerization of methacrylates. Reason: insufficient photocatalytic activity or energy transfer without quantum dot photocatalysts resulted in negligible monomer conversion

Synthesis, Properties, and Assemblies of Uniform Polymer-ligated Nanocrystals · Georgia Tech · PhD

Tried and failed

low concentration initiator and accelerator free-radical polymerization applied to salt-containing hydrogel synthesis. Reason: insufficient active radicals formed to overcome salt inhibition and induce gelation

Physics and Engineering of Moisture-Capturing Hydrogels for Water and Heat Harvesting · MIT · PhD

Lost to a baseline

Acrylate-NBE monomers showed lower grafting efficiency and slower polymerization kinetics than non-photolabile acrylate systems (such as PEGMA or acrylic acid) due to radical inhibition by nitro groups.

Photo-responsive polymer networks for the design of polymer coatings with light-tunable properties · Politecnico di Torino · PhD

Considered and rejected

Considered and rejected: Rejected controlled radical polymerisations (ATRP, RAFT, NMP) in favour of GTP due to slower kinetics, transition metal toxicity/removal issues (ATRP), and toxic/odorous thiol CTAs (RAFT)

Effects of composition and architecture on the thermo-induced aggregation of thermoresponsive OEGMA-based block terpolymers · Imperial · PhD

Considered and rejected

Considered and rejected: Discarded DDMAT as RAFT agent for copolymerizations due to inability to control MMA methacrylates.

Synthesis of random and block copolymers from terpene-based and acrylate-based monomers · Nottingham

Tried and failed

exponential feed rate of control agent applied to reversible deactivation radical polymerization. Reason: lag in regulator accumulation caused initial unmediated polymerization, yielding bimodal distributions

Investigating the Structure-Property Relationships in Thermoplastic Elastomers and Polymers for Explosion-Resistant Coatings · Cornell · PhD

Tried and failed

radical polymerization of functionalized aromatic monomers applied to monomers lacking a flexible alkyl spacer. Reason: absence of a flexible spacer between the polymerizable group and aromatic core inhibited radical polymerization

Controlling the Properties of Polymer Metal-Organic Frameworks and Cages Through Polymer Ligand Design · MIT · PhD

Tried and failed

anionic and radical polymerization applied to sulfinyl diene monomers. Reason: no polymer product formed under initiator conditions

Functional Polymer Materials: From Iptycenes to Ring-Opening Polymerizations · MIT · PhD

Lost to a baseline

Polymerisations run in toluene solvent had lower conversion and lower molecular weight (Mp 21.2–32.5 kDa) than equivalent bulk polymerisations (Mp 22.9–35.4 kDa).

Polymer from pyrolysis liquid: pyrolymer · Nottingham · Doctorate

Tried and failed

room temperature polymerization without thermal regulation applied to thermoresponsive hydrogel synthesis. Reason: polymerization exotherm heated the reaction mixture above its lower critical solution temperature, causing phase separation and opacity

Sensor-Enabled Accelerated Engineering of Soft Materials · Virginia Tech · Doctorate

Tried and failed

high monomer concentration free radical polymerisation applied to solution polymer synthesis. Reason: a minimum volume of solvent was required for successful polymerisation

Deep venous valve · Imperial · PhD

Tried and failed

solvent-free thermal bulk polymerization without initiator applied to vinyl monomer network synthesis. Reason: produced an inhomogeneous, glassy product instead of a uniform polymer network

Fracture of Highly Entangled Polymer Networks · Harvard · PhD

Considered and rejected

Considered and rejected: Using HA polymer concentrations exceeding 3% was rejected because the resulting high viscosity hindered experimental operations and caused hydrogel non-uniformity and structural defects.

Tough Injectable Hydrogels by Combining Elastic and Energy Dissipation · University College Dublin · PhD

Considered and rejected

Considered and rejected: Rejected full acrylation of lignin bio-oil hydroxyls because multiple polymerizable vinyl sites per oligomer caused uncontrolled crosslinking and thermoset gelation instead of linear thermoplastics.

Lignin valorization for carbon based materials · Iowa State · PhD

Considered and rejected

Considered and rejected: Rejected electrochemically initiated chain-growth polymerization because it causes uncontrolled polymer formation and precipitation away from 3D micro-architected surfaces.

Two-component electrochemical coupling reaction for end-group assisted electrodeposition of ultrathin polymer films · Boston University · Master's

Tried and failed

trans-tissue photopolymerization of synthetic hydrogels applied to in situ hydrogel formation through tissue. Reason: Severe light attenuation through tissue and low reactive group density prevented polymerization

Engineered synthetic hydrogel platform for human intestinal organoids in vitro culture and in vivo therapeutic delivery · Georgia Tech · PhD

Tried and failed

macromolecular photoinitiator steric shielding of encapsulated molecules applied to photocrosslinkable hydrogel photo-switch encapsulation. Outcome: unstable. Reason: cleaved radical fragment lacking the bulky polymer group caused radical degradation of sensitive encapsulated photoswitches

Donor-acceptor stenhouse adducts: a basis for dynamic, light-switchable hydrogels · Imperial · PhD

Considered and rejected

Considered and rejected: Rejected methacrylated alginate cryogel crosslinking via TEMED and APS redox free-radical polymerization for T cell encapsulation due to generation of free radicals that react with and damage encapsulated proteins; adopted tetrazine-norbornene click chemistry.

Modulating T cell Therapies with Biomaterials · Harvard · PhD

Considered and rejected

Considered and rejected: Rejected UV photopolymerization (e.g., of gelatin methacrylate) due to toxic radical photoinitiators preventing germinal center response.

Immune Organoids to Study Antigen Presentation · Cornell · PhD

Lost to a baseline

EMI-composite showed lower final storage modulus than EMI-ionogel due to ceramic aggregates blocking UV penetration during photopolymerization.

Towards Solid-State Hybrid Polymer Electrolytes by Innovative, Rapid, and Solvent-Free Procedures · Politecnico di Torino · PhD

Tried and failed

direct sequential photopolymerisation without an intermediate adhesive applied to hydrophobic-hydrophilic bilayer actuators. Reason: post-curing degraded interfacial radical availability or excessively crosslinked the hydrogel, impairing responsiveness

3D printed stimuli-responsive biomaterials for programmable drug delivery · Imperial · PhD

Considered and rejected

Considered and rejected: Rejected cationic photopolymerization because moisture in watery hydrogel structures inhibits the reaction.

PHOTOCURABLE HYDROGELS FOR TISSUE ENGINERING APPLICATIONS · Politecnico di Torino · PhD

Tried and failed

free radical polymerisation with chemical initiators applied to nanoparticle encapsulation in hydrogels. Outcome: unstable. Reason: slow polymerisation kinetics allowed particles to aggregate before the matrix gelled

Effect Of Probe Characteristics And Hydrogel Structure On Single Nanoparticle Dynamics · Penn · PhD

Tried and failed

continuous monomer feeding in emulsion polymerization applied to thermoresponsive hydrogel nanoparticles. Outcome: worse than baseline. Reason: particle size growth plateaued, yielding insufficient particle dimensions for effective infrared transmittance modulation

Disordered Optics for Multidimensional Information Processing · MIT · PhD

Tried and failed

incorporating functionalized nanoparticles in miniemulsion polymerization applied to waterborne acrylic nanocomposite latex synthesis. Outcome: unstable. Reason: elevated monomer phase viscosity caused massive latex coagulation during polymerization

Incorporating cellulose nanocrystals into waterborne acrylic coatings towards eco-friendly formulations · Georgia Tech · PhD

Tried and failed

solution polymerisation in polar organic solvents applied to crosslinked polyester dimethacrylate nanoparticle synthesis. Reason: failed to yield discrete nanoparticles without aqueous precipitation driving phase separation

Design, synthesis, and analysis of crosslinked polymeric nanoparticles for drug delivery applications · Imperial · PhD

Considered and rejected

Considered and rejected: Rejected direct copolymerization of unprotected hydrophilic monomers in the emulsion core due to formation of microscale polymer networks/aqueous phase polymerization; substituted with TMS-protected monomers (TMS-HEMA).

A biodegradable pH-responsive carrier system for targeted siRNA delivery in inflammatory bowel diseases and cancer · UT Austin · PhD

Considered and rejected

Considered and rejected: Poly(4-vinylpyridine) homopolymer was rejected in favor of poly(4-vinylpyridine)-co-styrene (P4VP-r-PS, 90:10) to prevent emulsion coalescence during solvent evaporation.

Ring-opening Metathesis Polymerization for the Creation of Responsive Colloids and Surfaces · MIT · PhD

Tried and failed

UV-initiated free-radical inverse emulsion polymerization applied to hydrogel nanoparticle synthesis. Outcome: unstable. Reason: produced non-uniform particle sizes, high batch-to-batch variability, and severe particle aggregation

Itaconic acid-based pH-responsive nanoscale hydrogels for the oral delivery of high isoelectric point proteins · UT Austin · PhD

Tried and failed

immersion interfacial polymerization without solvent solubility tuning applied to porous substrate surface coating. Outcome: no signal. Reason: insufficient poor-solvent fraction prevented polymer precipitation onto the substrate

Spatially-Directed Interfacial Polymerization · MIT · PhD

Tried and failed

incorporating long fluorinated chains into interfacial polymerization monomers applied to ultrathin polyamide membrane synthesis. Outcome: worse than baseline. Reason: poor precursor solubility and slow interfacial diffusion prevented defect-free film formation, lowering permeance

Development of ultrathin polyamide membranes incorporating multi-oligomer amines for organic solvent nanofiltration · Imperial · PhD

Tried and failed

interfacial polymerization using branched multifunctional monomers applied to thin-film composite desalination membranes. Outcome: worse than baseline. Reason: membrane defect formation led to poor salt rejection

Structure-Property Relationships in the Design of High Performance Membranes for Water Desalination, Specifically Reverse Osmosis, Using Sulfonated Poly(Arylene Ether Sulfone)s · Virginia Tech · Doctorate

Tried and failed

interfacial polymerization without surface pre-treatment applied to large-pore or acidic membrane supports. Reason: proton interference and excessive pore size prevented defect-free selective layer formation

Nanostructured solvent-stable membranes for solvent permeation and pharmaceutical separation · Imperial · PhD

Tried and failed

direct in-situ interfacial polymerization on porous support applied to nanofiltration membrane fabrication. Outcome: worse than baseline. Reason: large self-assembled macromolecular aggregates blocked support pores smaller than their size

Development of ultrathin polyamide membranes incorporating multi-oligomer amines for organic solvent nanofiltration · Imperial · PhD

Left open

Model and control phase separation kinetics and domain uniformity in interpenetrating polymer networks using controlled radical polymerization methods. Blocker: Requires a polymer synthesis wet lab to perform and validate controlled radical polymerization experiments

Light-based mechanical patterning in soft matter materials · UT Austin · PhD

Left open

Conduct in vivo animal model testing of APGD for functional soft tissue repair such as cartilage, muscle, vasculature, or skin. Blocker: Requires wet lab synthesis of APGD polymer and in vivo animal testing facilities

3D Printed Biodegradable And Shape Memory Polymer Poly(Glycerol Dodecanedioate) (PGD) For Soft Tissue Reconstruction · Georgia Tech · PhD

Left open

Toughen soft, elastic, and functional polyether networks using advanced polymer network design strategies. Blocker: Requires wet lab chemical synthesis and mechanical testing of polyether networks

Leveraging living copolymerizations as a tool to tailor the architecture and mechanical properties of polymer networks · UT Austin · PhD

Left open

Apply non-toxic, heavy-atom-free thionaphthalimide photopolymers to fabricate biocompatible tissue scaffolds. Blocker: Requires a wet chemistry and biomaterials laboratory for photopolymerization and biocompatibility testing

A guide to photocuring catalyst selection · UT Austin · PhD

Left open

Develop branching metathesis polymerization by increasing selectivity between alkyne addition and monomer cycloaddition to synthesize hyperbranched polymers. Blocker: Requires wet lab chemical synthesis, polymerization equipment, and Grubbs ruthenium catalysts

The design and application of functional enyne reagents in metathesis polymerization · Georgia Tech · PhD

Left open

Synthesize and evaluate APGD co-polymers to reduce in vitro cytotoxicity and tune mechanical properties for soft-hard interfaces. Blocker: Requires a wet chemistry and biomaterials lab for polymer synthesis, photocuring, mechanical testing, and in vitro cytotoxicity assays

3D Printed Biodegradable And Shape Memory Polymer Poly(Glycerol Dodecanedioate) (PGD) For Soft Tissue Reconstruction · Georgia Tech · PhD

Left open

Develop synthetic polymer tissue surrogates with controlled viscosity to replicate temporary wound cavity expansion and radial cracking under ballistic impact. Blocker: Requires materials synthesis laboratory and physical ballistic testing apparatus.

Predicting blast injury to the torso · Imperial · PhD

Left open

Perform cytotoxicity testing and biocompatibility assays on thermoresponsive methacrylic terpolymers near body temperature. Blocker: Requires wet lab cell culture facilities and physical synthesis of the terpolymer samples

Self-assembled block copolymers: micelles, polymersomes and gels · Imperial · PhD