Ep10 Alkenes and pi bonds, block copolymers, dendrimers - UC San Diego - NANO 134 Darren Lipomi
TLDRIn this lecture, the professor discusses the grading of exams and explains anionic and cationic polymerization. The focus is on the impact of electron-donating and withdrawing groups on vinyl monomers and their susceptibility to polymerization. Detailed mechanisms of radicals and charges interacting with alkenes are explored, along with resonance structures and the behavior of polymer chains in various polymerization processes. The lecture concludes with the introduction of block copolymers and dendrimers, highlighting their significance in polymer science.
Takeaways
- π The lecture discusses anionic and cationic polymerization, focusing on how electron-donating and electron-withdrawing groups influence the reactivity of vinyl monomers towards positive or negative charges.
- π It explains the molecular orbitals of alkenes and alkynes, highlighting the sp2 hybridization of carbon atoms and the formation of pi and sigma bonds.
- π The script details the resonance structures of vinyl monomers and how radicals and charges stabilize on more substituted carbon atoms.
- π¬ For cationic polymerization, the presence of electron-rich alkenes and the role of electron-donating substituents like lone pairs or pi electrons are emphasized.
- βοΈ The mechanism of the first step in cationic polymerization is described, including the formation of resonance structures that lead to a positive charge on a more substituted carbon atom.
- π« Anionic polymerization requires electron-poor alkenes with electronegative atoms like oxygen or nitrogen that withdraw electron density from the double bond.
- π The script contrasts the characteristics of anionic and cationic polymerization, noting that anionic polymerization does not terminate by itself and is highly reactive.
- π The concept of block copolymers is introduced, explaining how they can combine the properties of different monomers to achieve a balance of elasticity and toughness.
- π Dendrimers are introduced as three-dimensional nanostructures used for applications like drug delivery, with their monodispersity and tunable size and functionality being key features.
- π οΈ The synthesis of dendrimers is briefly touched upon, mentioning divergent synthesis and the use of protected and deprotected branched molecules to build generations.
- π The lecture concludes with a mention of upcoming topics, including the thermodynamics of polymer solutions and regular solution theory.
Q & A
Why are grades not being returned immediately after the exams?
-Grades are not returned immediately because there is a possibility that some grades may increase by a few points due to a review process or additional considerations.
What are the key differences between anionic and cationic polymerization?
-Anionic and cationic polymerization differ in the type of charge involved and the nature of the substrate. Anionic polymerization involves negatively charged species, while cationic polymerization involves positively charged species. The reactivity of the substrate towards these charges is influenced by electron-donating or electron-withdrawing groups.
What is the significance of electron donating and withdrawing groups in polymerization?
-Electron donating groups increase the reactivity of a substrate towards anionic polymerization by donating electron density to the Ο bond. Conversely, electron withdrawing groups make a substrate more susceptible to cationic polymerization by stabilizing the positive charge on the carbon atom.
What is the role of the Ο bond in alkene and alkyne chemistry?
-The Ο bond in alkenes and alkynes is a carbon-carbon double bond that allows for restricted rotation and provides a cloud of electrons above and below the inter-nuclear axis, which can react with radicals and charges.
How does the sp2 hybridization of carbon atoms in alkenes affect the formation of Ο and Ο bonds?
-In sp2 hybridization, carbon atoms have one unhybridized p orbital that interacts with another to form a Ο bond. The remaining hybridized orbitals form Ο bonds with other atoms, such as hydrogen, creating a trigonal planar geometry.
What is the mechanism of the first step in cationic polymerization?
-In the first step of cationic polymerization, an electron-rich alkene reacts with an acid or a Lewis acid, leading to a resonance structure where the positive charge is stabilized on the more substituted carbon atom, which then reacts with the next monomer.
Why are anionic polymerizations considered 'living' or 'quasi-living'?
-Anionic polymerizations are considered 'living' because they do not terminate on their own. The chain ends remain active indefinitely, allowing for controlled growth and the possibility of chain end functionalization with high yields.
What are the characteristics of anionic polymerization that make it suitable for certain materials?
-Anionic polymerization is suitable for materials that require high reactivity and control over molecular weight and polydispersity. It allows for the synthesis of polymers with low dispersity, active chain ends, and the ability to perform chain end functionalization.
How can block copolymers be synthesized using anionic polymerization?
-Block copolymers can be synthesized using anionic polymerization by first polymerizing one type of monomer and then adding a different monomer to the reaction. The reactive nature of anionic polymerization ensures that the second monomer will polymerize off the first, forming a block copolymer.
What is a dendrimer and how is it synthesized?
-A dendrimer is a three-dimensional, tree-like, nanostructure polymer synthesized from a multifunctional core and branching monomers. It is typically made using a divergent synthesis approach, where generations of branches are added sequentially, with protection and deprotection steps to control the growth.
How do dendrimers find applications in drug delivery?
-Dendrimers are used in drug delivery due to their monodisperse nature, tunable size, and chemical functionality. They can encapsulate drug molecules within their internal cavities and have surface groups that can interact with biological targets, allowing for targeted drug release.
Outlines
π Polymerization Fundamentals and Alkene Reactivity
The paragraph introduces the topic of polymerization, specifically anionic and cationic processes. It discusses the grading of exams and hints at grade adjustments, then delves into the chemistry of polymerization, explaining the influence of electron-donating and electron-withdrawing groups on the reactivity of vinyl monomers. The instructor provides an in-depth look at the molecular orbitals of alkenes and the sp2 hybridization of carbon atoms involved in the formation of pi bonds. The role of resonance in vinyl monomers and the stability of radicals and charges on substituted carbon atoms are also highlighted.
π¬ Mechanism of Cationic Polymerization
This section focuses on the mechanism of cationic polymerization, explaining the need for an electron-rich alkene and the role of substituents in the process. The resonance structures that lead to the formation of a positive charge on the more substituted carbon atom are discussed, along with the initiation of the polymerization by an acid. The paragraph also touches on the concept of formal charge and its calculation, providing insight into the stabilization of the growing polymer chain.
π Anionic Polymerization and Electron Withdrawing Groups
The paragraph explores anionic polymerization, contrasting it with cationic polymerization by emphasizing the need for electron-poor alkenes and electronegative atoms that withdraw electron density. It describes the resonance structures that result in a reactive carbon atom with a formal positive charge, which is essential for the anionic polymerization process. The use of alkyl lithium reagents and the concept of 1-4 conjugate addition are also mentioned, illustrating how the polymer chain grows.
π Characteristics of Anionic Polymerization
This section highlights the unique characteristics of anionic polymerization, including its non-terminating nature and the ability to perform chain end functionalization with high efficiency. The discussion covers the 'living' nature of anionic polymerization, where chains grow simultaneously and can be intentionally terminated by adding substances like water. The paragraph also explains the limitations of anionic polymerization in terms of its incompatibility with electrophilic groups.
π Chain End Functionalization and Block Copolymers
The paragraph discusses the technique of chain end functionalization in anionic polymerization, which allows for the alteration of the polymer chain's end group with high yield. It also introduces the concept of block copolymers, explaining how they can be created using living polymerization methods to achieve a covalent linkage between different polymer chains. The benefits of block copolymers in combining mechanical properties such as elasticity and toughness are also explored.
π© The Significance of Block Copolymers in Material Properties
This section delves into the types of block copolymers, including their formation and the benefits they offer in material science. It explains how block copolymers can be synthesized using anionic polymerization and how they differ from statistical or random copolymers, alternating copolymers, and graft copolymers. The paragraph also touches on the challenges of mixing polymers and the advantages of creating block copolymers to achieve desired material properties.
πΏ Synthetic Polymer Structures Beyond Copolymers
The paragraph introduces the concept of synthetic polymer structures beyond copolymers, such as dendrimers, which are three-dimensional nanostructures. It explains the synthesis of dendrimers through divergent synthesis, starting from a multifunctional core and adding generations of branched molecules. The unique properties of dendrimers, including their monodispersity and potential applications in drug delivery, are highlighted.
π Dendrimers in Drug Delivery and Nanoparticle Therapeutics
This section focuses on the application of dendrimers in drug delivery and the development of nanoparticle therapeutics. It describes the process of synthesizing dendrimers, emphasizing the importance of protection groups in controlling the growth of the dendrimer structure. The paragraph also discusses the potential for dendrimers to carry and release drug molecules, as well as their use in targeting specific biological environments such as tumors.
π Upcoming Discussion on Polymer Solution Thermodynamics
The final paragraph teases the upcoming lecture on the thermodynamics of polymer solutions, with a focus on regular solution theory. It acknowledges the groans from students at the mention of thermodynamics but promises to make the topic as engaging as possible. The paragraph also invites any questions from the audience on the topics covered during the session.
Mindmap
Keywords
π‘Anionic Polymerization
π‘Cationic Polymerization
π‘Electron Donating Groups
π‘Electron Withdrawing Groups
π‘Vinyl Monomers
π‘Living Polymerization
π‘Block Copolymers
π‘Dendrimers
π‘Resonance Structures
π‘Formal Charge
π‘Controlled Radical Polymerization (CRP)
Highlights
Exam grades will be available online with a possibility of an increase in some grades due to a grading review.
Discussion on anionic and cationic polymerization, focusing on substrate suitability and the influence of electron donating and withdrawing groups.
Explanation of the molecular orbitals involved in alkene and alkyne structures, including the sp2 hybridization of carbon atoms.
Clarification on the reactivity of alkenes towards radicals and charges, and the role of resonance structures in vinyl monomers.
Mechanism of cationic polymerization, emphasizing the role of electron-rich alkenes and the resonance stabilization of positive charges.
Introduction to the concept of formal charge in the context of understanding the reactivity of atoms in polymerization reactions.
Examples of materials polymerized by cationic polymerization, such as polyvinyl carbonyl used in holographic materials and polyisobutylene in car tires.
Differences between anionic and cationic polymerization in terms of electron density requirements and the types of alkenes suitable for each.
Characteristics of anionic polymerization, including its non-terminating nature and the ability for chain end functionalization.
The uniqueness of anionic polymerization in achieving living polymerization without the need for recombination or disproportionation.
Strategies for creating copolymers and block copolymers to combine desired properties of different materials, such as elasticity and toughness.
The importance of block copolymers in achieving the best of both worlds in material properties through covalent linkage.
Different types of copolymers, including statistical, alternating, and block copolymers, and their synthesis methods.
Introduction to dendrimers as three-dimensional nanostructures with applications in drug delivery and their synthesis via divergent synthesis.
The monodisperse nature of dendrimers, which allows for uniform size and potential drug targeting capabilities.
Upcoming discussion on the thermodynamics of polymer solutions, starting with regular solution theory.
Transcripts
Browse More Related Video
Ep9 Cationic and Anionic Polymerization - UC San Diego - NANO 134 Darren Lipomi
Polymer | Cationic mechanism | Addition polymerizations | engineering chemistry | Mohan dangi
Ep13 Cloud point and phase diagrams - UC San Diego - NANO 134 Darren Lipomi
Polymers - Basic Introduction
Polymer Chemistry: Crash Course Organic Chemistry #35
Polymer | classification of polymer on the basis of Synthesis | engineering chemistry | Mohan dangi
5.0 / 5 (0 votes)
Thanks for rating: