New polymer architectures by cationic ring-opening polymerization

Goethals, E.; Dubreuil, M.; Wang, Y.; Witte, I. De; Christova, Darinka; Verbrugghe, Sam; Yanul, N. A.; Tanghe, Leen M.; Mynarczuk, G.; Prez, Filip Du

doi:10.1002/1521-3900(200003)153:1<209::aid-masy209>3.0.co;2-1

Cited by 18 publications

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“…[5,6] These living and controlled polymerization techniques allow the synthesis of polymers with controlled molecular weight (distribution) and monomer composition, as well as different architectures such as star-shaped, comb, and graft (co)polymers. These possibilities combined with the numerous different monomers that can be polymerized provide an inexhaustible parameter space that can be explored.…”

Section: Introductionmentioning

confidence: 99%

Poly(2‐oxazoline)s: Alive and Kicking

Hoogenboom

2007

Macro Chemistry & Physics

110

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The development of various living/controlled polymerization techniques has allowed the synthesis of a large variety of well‐defined (co)polymers with varied polymer length, composition, and architecture, for example. Screening this large possible parameter space for a polymer with certain properties can be a very demanding process. Therefore, we aim to rapidly synthesize and systematically screen libraries of copolymers to determine structure‐property relationships that might allow the future design of novel (co)polymers with predictable properties. The cationic ring‐opening polymerization of 2‐oxazolines has been adapted for the synthesis of libraries of well‐defined (co)polymers. In this contribution, the optimization of the polymerization procedure using both high‐throughput experimentation and microwave irradiation is discussed. Subsequently, the microwave‐assisted synthesis of well‐defined libraries of (co)poly(2‐oxazoline)s and the determination of structure‐property relationships for these polymers is described. Moreover, the polymerization of a soy‐based 2‐oxazoline monomer will be illustrated as a ‘green’ approach to replace current oil‐based feedstock by renewable resources.magnified image

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Section: Introductionmentioning

confidence: 99%

Poly(2‐oxazoline)s: Alive and Kicking

Hoogenboom

2007

Macro Chemistry & Physics

110

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“…[8] Our previous report also disproves this idea for swollen segmented polymer networks consisting of PVCL and PTHF. [10,23] It was demonstrated that the T CP of the swollen networks increases with the amount of hydrophobic PTHF in the networks. As mentioned in the introduction part, this unexpected behavior was explained by the fact that the heterogeneous networks consist of rigid PTHF microdomains that decrease the mobility of the PVCL segments and therefore prevent the globular aggregation until higher temperatures.…”

Section: Cloud Point Study Of Pvcl-pthf Graft Copolymersmentioning

confidence: 99%

Thermo‐Responsive and Emulsifying Properties of Poly(N‐vinylcaprolactam) Based Graft Copolymers

Verbrugghe

Bernaerts

Prez

2003

Macro Chemistry & Physics

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Thermo‐responsive graft copolymers have been synthesized based on a poly(N‐vinylcaprolactam) (PVCL) backbone and either hydrophilic poly(ethylene oxide) (PEO) or hydrophobic poly(tetrahydrofuran) (PTHF) side chains. The phase separation behavior of the graft polymers in water was studied by transmittance measurements and compared to that of the corresponding swollen segmented polymer networks and aqueous solutions of both polymers. The influence of the concentration and length of the grafts on the cloud point temperature (TCP) has been demonstrated. PVCL‐g‐PTHF copolymers have been synthesized by using the macromonomer technique, i.e. the radical copolymerization of VCL with a PTHF macromonomer. A special feature of these amphiphilic graft copolymers is their ability to stabilize aqueous emulsions below the TCP and to suddenly break them above the TCP. PVCL‐g‐PEO copolymers were prepared by a grafting onto method. First, succinimide groups were introduced in the backbone, to which amino terminated PEO chains were grafted in the second step. This leads to di‐hydrophilic copolymers that become amphiphilic after heating their aqueous solutions above the TCP.

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“…Although not extensively studied, various architectures such as star and comb polymers have also been synthesized [Bielawski et al, 2000;Goethals et al, 2000].…”

Section: -12c Block Copolymersmentioning

confidence: 99%

Ring‐Opening Polymerization

Odian

2004

Principles of Polymerization

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A wide variety of cyclic monomers have been successfully polymerized by the ring-opening process [Frisch and Reegan, 1969; Ivin and Saegusa, 1984;Saegusa and Goethals, 1977]. This includes cyclic amines, sulfides, olefins, cyclotriphosphazenes, and N-carboxy-a-amino acid anhydrides, in addition to those classes of monomers mentioned above. The ease of polymerization of a cyclic monomer depends on both thermodynamic and kinetic factors as previously discussed in Sec. 2-5.The single most important factor that determines whether a cyclic monomer can be converted to linear polymer is the thermodynamic factor, that is, the relative stabilities of the cyclic monomer and linear polymer structure [Allcock, 1970;Sawada, 1976]. Table 7-1 shows the semiempirical enthalpy, entropy, and free-energy changes for the conversion of cycloalkanes to the corresponding linear polymer (polymethylene in all cases) [Dainton and Ivin, 1958;Finke et al. 1956]. The lc (denoting liquid-crystalline) subscripts of ÁH, ÁS, and ÁG indicate that the values are those for the polymerization of liquid monomer to crystalline polymer.Polymerization is favored thermodynamically for all except the 6-membered ring. Ringopening polymerization of 6-membered rings is generally not observed. The order of thermodynamic feasibility is 3,4 > 8 > 5,7 which follows from the previous discussion (Sec. 2-5c) on bond angle strain in 3-and 4-membered rings, eclipsed conformational strain in the 5-membered ring, and transannular strain in 7-and 8-membered rings. One notes that RING-OPENING POLYMERIZATION RING-OPENING POLYMERIZATION

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New polymer architectures by cationic ring-opening polymerization

Cited by 18 publications

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Poly(2‐oxazoline)s: Alive and Kicking

Poly(2‐oxazoline)s: Alive and Kicking

Thermo‐Responsive and Emulsifying Properties of Poly(N‐vinylcaprolactam) Based Graft Copolymers

Ring‐Opening Polymerization

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