A Bifunctional Monomer Derived from Lactide for Toughening Polylactide

Feng, Jing; Hillmyer, Marc A.

doi:10.1021/ja804357u

Cited by 155 publications

(161 citation statements)

References 33 publications

Supporting

Mentioning

159

Contrasting

Order By: Relevance

“…[21] Hillmyer and coworkers recently reported the synthesis of a norbornene-functional monomer (4, Scheme 2) that is directly derived from lactide in a 3 step procedure. ROP of this monomer, again using organocatalytic methods, results in a poly(ester) with pendant norbornene units (1 per repeat unit).…”

Section: Resultsmentioning

confidence: 99%

“…[17] The resulting polymer was shown to be readily functionalized by the copper-catalyzed Huisgen-1,4-cycloaddition of azide-containing molecules. Reports of the highly efficient reaction between norbornenes and tetrazine-containing molecules [18][19][20] and the recent report of the synthesis and ROP of a norbornene functional cyclic diester monomer that can be directly synthesized from lactide, [21,22] led us to investigate the compatibility of these chemistries. Herein we report the post-polymerization functionalization of norbornene-functional PLAs by the addition of tetrazines as an efficient and mild method to modify the properties of polymers derived from sustainable resources.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Tetrazine‐Norbornene Click Reactions to Functionalize Degradable Polymers Derived from Lactide

Barker

Hall

Hansell

et al. 2011

Macromol. Rapid Commun.

View full text Add to dashboard Cite

Post-polymerization modification of polymers derived from sustainable resources using the click reaction between tetrazines and norbornenes is shown to provide a mild and efficient route for the synthesis of functional degradable polymers. Norbornene chain-end functional poly(lactide) was synthesized using organocatalytic methods and functionalized by the addition of 3,6-di-2-pyridyl-1,2,4,5-tetrazine without degradation of the polymer backbone. The versatility of this reaction was demonstrated by the application of analogues bearing amine and poly(ethylene oxide) groups to realize amine-functional polymers and block copolymers. Poly(spiro[6-methyl-1,4-dioxane-2,5-dione-3,2'-bicyclo[2.2.1]hept[5]ene]) was prepared from lactide. The pendant norbornene group on the backbone of the resultant polymer was modified in a similar manner to produce functional degradable polymers and graft co-polymers.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tetrazine‐Norbornene Click Reactions to Functionalize Degradable Polymers Derived from Lactide

Barker

Hall

Hansell

et al. 2011

Macromol. Rapid Commun.

View full text Add to dashboard Cite

show abstract

“…Among a variety of polymeric nanomedicines, PAHA-based nanoparticles (NPs) have attracted much attention. 34 20,21 and copolymerization with other cyclic esters. 19 Because of their ready availability, structure modulability, and high polymerizability, OCAs are promising monomers for the preparation of PAHAs with tailored architectures and accessible functionalities.…”

Section: Biomedical Applications Of Functional Pahasmentioning

confidence: 99%

Synthesis and Biomedical Applications of Functional Poly(α-hydroxy acids) via Ring-Opening Polymerization of O-Carboxyanhydrides

Yin

Wang

et al. 2015

Acc. Chem. Res.

View full text Add to dashboard Cite

Poly(α-hydroxy acids) (PAHAs) are a class of biodegradable and biocompatible polymers that are widely used in numerous applications. One drawback of these conventional polymers, however, is their lack of side-chain functionalities, which makes it difficult to conjugate active moieties to PAHA or to fine-tune the physical and chemical properties of PAHA-derived materials through side-chain modifications. Thus, extensive efforts have been devoted to the development of methodology that allows facile preparation of PAHAs with controlled molecular weights and a variety of functionalities for widespread utilities. However, it is highly challenging to introduce functional groups into conventional PAHAs derived from ring-opening polymerization (ROP) of lactides and glycolides to yield functional PAHAs with favorable properties, such as tunable hydrophilicity/hydrophobicity, facile postpolymerization modification, and well-defined physicochemical properties. Amino acids are excellent resources for functional polymers because of their low cost, availability, and structural as well as stereochemical diversity. Nevertheless, the synthesis of functional PAHAs using amino acids as building blocks has been rarely reported because of the difficulty of preparing large-scale monomers and poor yields during the synthesis. The synthesis of functionalized PAHAs from O-carboxyanhydrides (OCAs), a class of five-membered cyclic anhydrides derived from amino acids, has proven to be one of the most promising strategies and has thus attracted tremendous interest recently. In this Account, we highlight the recent progress in our group on the synthesis of functional PAHAs via ROP of OCAs and their self-assembly and biomedical applications. New synthetic methodologies that allow the facile preparation of PAHAs with controlled molecular weights and various functionalities through ROP of OCAs are reviewed and evaluated. The in vivo stability, side-chain functionalities, and/or trigger responsiveness of several functional PAHAs are evaluated. Their biomedical applications in drug and gene delivery are also discussed. The ready availability of starting materials from renewable resources and the facile postmodification strategies such as azide-alkyne cycloaddition and the thiol-yne "click" reaction have enabled the production of a multitude of PAHAs with controlled molecular weights, narrow polydispersity, high terminal group fidelities, and structural diversities that are amenable for self-assembly and bioapplications. We anticipate that this new generation of PAHAs and their self-assembled nanosystems as biomaterials will open up exciting new opportunities and have widespread utilities for biological applications.

show abstract

“…32 Block copolymers were synthesized in the ratio of 1:1 and 1:3 parts T1 to CO. The molecular weight was also systematically varied for the 1:3 copolymer to observe the effect of M n on thermal and mechanical properties.…”

Section: Articlementioning

confidence: 99%

Triptycene‐containing polyetherolefins via acyclic diene metathesis polymerization

Sydlik

Delgado

Inomata

et al. 2013

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

Several new triptycene-containing polyetherolefins were synthesized via acyclic diene metathesis (ADMET) polymerization. The well-established mechanism, high selectivity and specificity, mild reaction conditions, and well-defined endgroups make the ADMET polymerization a good choice for studying systematic variations in polymer structure. Two types of triptycene-based monomer with varying connectivities were used in the synthesis of homopolymers, block copolymers, and random copolymers. In this way, the influence of the triptycene architecture and concentration in the polymer backbone on the thermal behavior of the polymers was studied. Inclusion of increasing amounts of triptycene were found to increase the glass transition temperature, from À44 C in polyoctenamer to 59 C in one of the hydrogenated triptycene homopolymers (H-PT2). Varying the amounts and orientations of triptycene was found to increase the stiffness (H-PT1), toughness (PT1 1 -b-PO 1 ) and ductility (PT1 1 -ran-PO 3 ) of the polymer at room temperature.

show abstract

A Bifunctional Monomer Derived from Lactide for Toughening Polylactide

Cited by 155 publications

References 33 publications

Tetrazine‐Norbornene Click Reactions to Functionalize Degradable Polymers Derived from Lactide

Tetrazine‐Norbornene Click Reactions to Functionalize Degradable Polymers Derived from Lactide

Synthesis and Biomedical Applications of Functional Poly(α-hydroxy acids) via Ring-Opening Polymerization of O-Carboxyanhydrides

Triptycene‐containing polyetherolefins via acyclic diene metathesis polymerization

Contact Info

Product

Resources

About