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The commercial field of radical polymerized polymers, such as polyvinyl alcohol, is very broad partly because they are easy to polymerize and cheap. One aspect that could improve their commercial range is to enhance their degradation rate. As the environmental aspect of polymers grows bigger an enhancement of biological degradation is a great improvement. This thesis deals with the prospect of polymerizing polyvinyl alcohol with degradable linkages in the main chain. In order to achieve the aim the monomer 2-methylene-1,3-dioxepane is successfully synthesized and characterized. The synthesis is followed by copolymerization of 2-methylene-1,3-dioxepane with vinylacetate at the feed compositions; 30/70, 50/50, 70/30 mol% respectively. The copolymerization was successful and reached over 90% conversion at the reaction time 3-4 hours with the conditions 60°C and 5mol% 2,2-Azobis(2-methylpropionitrile) as initiator. The copolymerization is followed by hydrolysis with potassium hydroxide or Candida Rugosa Lipase. The results show that chain scission occurs when the polymer is hydrolyzed by potassium hydroxide but not by lipase. There is also a tendency toward hydrolysis of the chain with lipase.

Thesis advisor: Jia Niu / This dissertation discusses two main projects focusing on synthesizing degradable vinyl copolymers. The first project describes the development of a general approach to synthesizing degradable vinyl random copolymers through photocontrolled radical ring-opening cascade copolymerization (rROCCP). The rROCCP of a macrocyclic allylic sulfone with acrylates or acrylamides mediated by visible light at ambient temperature achieved near-unity comonomer reactivity ratios over the entire range of feed compositions. Such a powerful approach provides degradable vinyl random copolymers with comparable material properties to their non-degradable counterparts. Experimental and computational evidence also revealed an unusual reversible inhibition of chain propagation by in situ generated sulfur dioxide (SO2), which was successfully overcome by reducing the solubility of SO2 during polymerization. The second project depicts a general method for organocatalyzed photocontrolled radical copolymerization of a macrocyclic allylic sulfone and various types of vinyl monomers, including acrylates, acrylamides, styrene, and methacrylate. Catalyzed by Eosin Y under visible light irradiation, copolymerization of the macrocyclic allylic sulfone and acrylic monomers displayed near unity comonomer reactivity ratios by fitting the copolymer composition to the Beckingham-Sanoya-Lynd integrated model. The macrocyclic allylic sulfone was also successfully copolymerized with styrene or methyl methacrylate to generate degradable polystyrene and poly(methyl methacrylate). These degradable vinyl copolymers exhibited tunable thermal properties correlated with the incorporation of degradable main-chain diester motif. / Thesis (PhD) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Percutaneous transluminal balloon angioplasty followed by drug-eluting stent implantation has been of great benefit in coronary applications, whereas in peripheral applications, success rates remain low. Analysis of healing patterns in successful deployments shows that six months after implantation the artery has reorganized itself to accommodate the increase in caliber and there is no purpose for the stent to remain, potentially provoking inflammation and foreign body reaction. Thus, a fully biodegradable polymeric stent that fulfills the mission and steps away is of great benefit. Biodegradable polymers have a widespread usage in the biomedical field, such as sutures, scaffolds and implants. Degradation refers to bond scission process that breaks polymeric chains down to oligomers and monomers. Extensive degradation leads to erosion, which is the process of mass loss from the polymer bulk. The prevailing mechanism of biodegradation of aliphatic polyesters (the main class of biodegradable polymers used in biomedical applications) is random scission by passive hydrolysis and results in molecular weight reduction and softening. In order to understand the applicability and efficacy of biodegradable polymers, a two pronged approach involving experiments and theory is necessary. A constitutive model involving degradation and its impact on mechanical properties was developed through an extension of a material which response depends on the history of the motion and on a scalar parameter reflecting the local extent of degradation and depreciates the mechanical properties. A rate equation describing the chain scission process confers characteristics of stress relaxation, creep and hysteresis to the material, arising due to the entropy-producing nature of degradation and markedly different from their viscoelastic counterparts. Several initial and boundary value problems such as inflation and extension of cylinders were solved and the impacts of the constitutive model analyzed. In vitro degradation of poly(L-lactic acid) fibers under tensile load was performed and degradation and reduction in mechanical properties was dependent on the mechanical environment. Mechanical testing of degraded fibers allowed the proper choice of constitutive model and its evolution. Analysis of real stent geometries was made possible with the constitutive model integration into finite element setting and stent deformation patterns in response to pressurization changed dramatically as degradation proceeded.

I det här utvecklas en reproducerbar polymerisationsmetod för att uppnå en stabil produktion av poly(ε-caprolakton-co-p-dioxanon) (PCLDX), skala upp filamenttillverkningen för att producera 1.75 mm långa filament och optimera 3D-utskriftsprocessen för att tillverka ställningar/anordningar för mjukvävnadsteknik. PCLDX, med högre nedbrytningshastighet och bättre flexibilitet jämfört med poly(ε-caprolactone) (PCL), syntetiserades på ett reproducerbart sätt genom sampolymerisering. Den syntetiserade PCLDX uppvisade önskvärd sammansättning (85 mol% CL : 15 mol% DX), molmassa (cirka 40 kg∙mol-1), dispersitet (cirka 1.8) och relativt låg smältpunkt (cirka 45 ℃). För att tillverka tredimensionella matriser av PCLDX utformades och optimerades två processer, filamenttillverkning och 3D printning. För filamenttillverkningsprocessen användes låg extruderingstemperatur (65 och 80 ℃) och låg extruderingshastighet (100 cm∙min-1) för att spara energi och minimera nedbrytningen. PCLDX-filament med en jämn diameter på 1.75 mm tillverkades genom att använda en passande partikelstorlek (diameter på 3-4 mm) och en kylmetod (blandning av vatten och torris, 0 ℃). De erhållna filamenten uppvisade lägre Youngs modul (25 % lägre än PCL), PCLDX batch oberoende termiska egenskaper, god ytkvalitet och printbarhet. Den termiska nedbrytningen av PCLDX under processen var försumbar och molmassan var nästintill oförändrad. Processen har skalats upp för att producera stora mängder PCLDX-filament, vars produktivitet nådde upp till 140 g∙h-1. Tredimensionella matriser tillverkades genom att printa önskad design genom manuell matning och låg printhastighet (5 mm/s). En isplatta användes för att kyla ner maskinen under printningen för att undvika bucklingproblem. Det optimerade printprotokollet genererade ingen termisk nedbrytning av polymeren, påverkade inte polymerens molmassa eller dispersitet. De producerade matriserna hade samma termiska egenskaper oavsett polymerbatch och god ytkvalitet. Det optimerade printprotokollet användes också framgångsrikt för att skriva ut komplicerade prototyper, t.ex. menisk och knäprotes för potentiella biomedicinska tillämpningar. / In this project, we develop a reproducible polymerization method to achieve stable production of poly(ε-caprolactone-co-p-dioxanone) (PCLDX), scale-up the filament fabrication to produce 1.75 mm filaments and optimize 3D printing process to manufacture scaffolds/devices for soft tissue engineering. PCLDX, with a higher degradation rate and better pliability compared to poly(ε-caprolactone) (PCL), was successfully synthesized by reproducible copolymerization of ε-caprolactone (CL) and p-dioxanone (DX). The synthesized PCLDX exhibited a polymer composition of 85 mol% CL : 15 mol% DX, molar mass around 40 kg∙mol-1, dispersity around 1.8, and relatively low melting point around 45 ℃. From PCLDX particles to final scaffolds, two processes, including filament fabrication and scaffold manufacturing, were designed and optimized. For the filament fabrication process, low extrusion temperature (65 and 80 ℃) and low extrusion speed (100 cm∙min-1) were applied to save energy and minimize degradation. PCLDX filaments with an even diameter of 1.75 mm were fabricated using suitable particle sizes (diameter of 3-4 mm) and a cooling method (mixture of water and dry ice, 0℃). The obtained filaments exhibited lower young’s modulus (25% lower than PCL), consistent thermal properties, good surface quality, and printability. The thermal degradation of PCLDX during the process was negligible, and the molar mass was kept almost unchanged. The process has been scaled up to produce high amounts of PCLDX filaments, whose productivity rate reached up to 140 g∙h-1. For the scaffold manufacturing process, porous scaffolds were manufactured by feeding manually and printing slowly (5 mm/s). The printability was assessed and validated using produced PCL/PCLDX filaments and commercial PCL filaments. The optimized printing protocol maintained the molar mass and dispersity of the material. The produced scaffolds possessed consistent thermal properties independent on polymer batches and good surface quality. The optimized printing protocol was also successfully applied to print complicated prototypes, such as meniscus and knee prosthesis for potential biomedical applications.