Living polymerization techniques can be used to achieve a high degree of control over polymer chain architecture. Examples of the type of polymers that can be synthesized include block copolymers, comb-shaped polymers, multiarmed polymers, ladder polymers, and cyclic polymers. This control of structure, in turn, results in polymers with widely diverse physical properties, even though they are made from readily available low-cost monomers.

https://science.sciencemag.org/content/sci/251/4996/887.full.pdf

Living Polymerization Methods

Strategies for compatibilization of polymer blends

Synthesis and aqueous solution properties of near-monodisperse tertiary amine methacrylate homopolymers and diblock copolymers

Anionic polymerization is a powerful tool for the synthesis of a variety of model materials with well-defined molecular characteristics. However specially designed apparatuses and appropriate high vacuum techniques are needed in order to exclude from the reaction environment all reactive contaminants with the anionic centers. This review describes the basic principles of anionic polymerization as well as detailed experimental methods for the purification of the reagents usually used for the synthesis of model polymeric materials. In addition a few examples of the synthesis of polymers with complex architecture are given. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3211–3234, 2000

https://onlinelibrary.wiley.com/doi/pdf/10.1002/1099-0518%2820000915%2938%3A18%3C3211%3A%3AAID-POLA10%3E3.0.CO%3B2-L

Anionic polymerization: High vacuum techniques

1.3. Scope of Review 5161 2. Methacrylate Polymerization 5161 2.1. Lanthanide Complexes 5161 2.1.1. Nonbridged Lanthanocenes 5161 2.1.2. ansa-Lanthanocenes 5164 2.1.3. Half-Lanthanocenes 5166 2.1.4. Non-lanthanocenes 5166 2.2. Group 4 Metallocenes 5170 2.2.1. Nonbridged Catalysts 5170 2.2.2. ansa-C2v-Ligated Catalysts 5173 2.2.3. ansa-C2-Ligated Catalysts 5173 2.2.4. ansa-C1-Ligated Catalysts 5176 2.2.5. ansa-Cs-Ligated Catalysts 5177 2.2.6. Constrained Geometry Catalysts 5178 2.2.7. Half-Metallocene Catalysts 5180 2.2.8. Supported Catalysts 5180 2.3. Other Metallocene Catalysts 5180 2.4. Nonmetallocene Catalysts 5181 2.4.1. Group 1 and 2 Catalysts 5181 2.4.2. Group 13 Catalysts 5183 2.4.3. Group 14 Catalysts 5186 2.4.4. Transition-Metal Catalysts 5187 3. Acrylate Polymerization 5188 3.1. Lanthanocenes 5188 3.2. Group 4 Metallocenes 5189 3.3. Nonmetallocenes 5190 4. Acrylamide and Methacrylamide Polymerization 5191 4.1. Acrylamides 5191 4.2. Methacrylamides 5192 4.3. Asymmetric Polymerization 5193 5. Acrylonitrile and Vinyl Ketone Polymerization 5196 5.1. Acrylonitrile 5196 5.2. Vinyl Ketones 5196 6. Copolymerization 5197 6.1. Polar-Nonpolar Block Copolymers 5197 6.2. Polar-Nonpolar Random Copolymers 5199 6.3. Polar-Polar Copolymers 5204 7. Ion-Pairing Polymerization 5206 8. Summary and Outlook 5208 9. Acknowledgments 5208 10. References 5208

Coordination polymerization of polar vinyl monomers by single-site metal catalysts.

The living anionic polymerization of glycidyl methacrylate (GMA) in THF at low temperature initiated with diphenyl hexyl lithium, 9-anthracenyl methyl lithium, and α-methylstyryl lithium leads to well characterized homo- and block copolymers, with predictable and narrow molecular weight distributions and with all the oxirane groups intact. Broadening of the molecular weight distributions above a certain and very critical supported the idea that the living polymerization at low temperature might proceed in micelle-like structures. Diffusional restriction of the monomer access towards the living centers, due to lesser solvation and increasing compactness of the polymer coils is thought to give rise to broadening of the molecular weight distribution of PGMA homo-and block copolymers.

/pdf/controlled-living-anionic-polymerization-of-glycidyl-1xx747nmwe.pdf

Controlled “living” anionic polymerization of glycidyl methacrylate

The emulsifying activity of a poly(hydrogenated butadiene-b-methyl methacrylate) (HPB-b-PMMA) copolymer is investigated in incompatible blends of a low density polyethylene and poly(styrene-co-acrylonitrile) resins (mainly ABS) prepared in the melt state on a two-roll mill. Optical and scanning electron microscopy observations clearly demonstrate that a moderate amount of copolymer (5 wt %) very significantly decreases the particle size and enhances interfacial adhesion. The block copolymer is also responsible for a strong improvement in both the ductility and Charpy impact resistance of PE/ABS blends.

/pdf/molecular-design-of-multicomponent-polymer-systems-xv-4unaehl2lm.pdf

Molecular design of multicomponent polymer systems. XV. Morphology and mechanical behavior of blends of low density polyethylene with acrylonitrile‐butadiene‐styrene (ABS), emulsified by a poly(hydrogenated butadiene‐b‐methyl methacrylate) copolymer

New developments in block polymerization

Etude de l'effet emulsifiant des 2 copolymeres sur des melanges PS-PVC; amelioration des proprietes mecaniques des melanges riches en PVC apportee particulierement par le copolymere PMMA-PS

https://onlinelibrary.wiley.com/doi/pdf/10.1002/pola.1989.080270828

Molecular design of multicomponent polymer systems. IV: Comparative behavior of poly(styrene-b-ε-caprolactone) and poly(styrene-b-methylmethacrylate) diblock copolymers in blends of polystyrene with polyvinyl chloride

Kinetics and mechanism of anionic polymerization processes can be modified on purpose by ligands specific of the active anionic species. The reactivity enhancement promoted by cation-binding agents is well-documented, whereas complexing the well-known alkyllithium initiators to non reactive alkyl metals or metal alkoxides can affect the kinetics and improve the stereoregulation of the polymerization. Quite interestingly, some inorganic salts, such as lithium chloride, exhibit an important regulating effect in the anionic polymerization of alkyl acrylates. Indeed, side-reactions are now controlled to such an extent that the propagation is a living process and leads to polymers with an unimodal and narrow molecular weight distribution.

Roger Fayt

Papers

Controlled “living” anionic polymerization of glycidyl methacrylate

Molecular design of multicomponent polymer systems. XV. Morphology and mechanical behavior of blends of low density polyethylene with acrylonitrile‐butadiene‐styrene (ABS), emulsified by a poly(hydrogenated butadiene‐b‐methyl methacrylate) copolymer

New developments in block polymerization

Molecular design of multicomponent polymer systems. IV: Comparative behavior of poly(styrene-b-ε-caprolactone) and poly(styrene-b-methylmethacrylate) diblock copolymers in blends of polystyrene with polyvinyl chloride

The Anionic Polymerization of Alkyl Acrylates : A Challenge