Branched and functionalized polybutadienes by a facile two-step synthesis

Frederik Wurm; Francisco J. López-Villanueva; Holger Frey

doi:10.1002/macp.200700574

Branched and functionalized polybutadienes by a facile two-step synthesis

Frederik Wurm, Francisco J. López-Villanueva, Holger Frey^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

29 Citations (Scopus)

Abstract

Anionic polymerization was used to prepare silane-endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9000 to 34000 g · mol^-1 These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB ₂ + A type "pseudocopolymerization" method. All branched polymers were analyzed by SEC, SEC-MALLS, SEC-viscosimetry. ¹H NMR spectroscopy, and DSC concerning their branching ratio. The branching parameters for the branched polymers exhibited similar characteristics as for hyperbranched polymers obtained from conventional AB₂ monomers. Detailed kinetic studies showed that the polymerization occurred very rapidly in comparison to the hydrosilylation polymerization of classical AB₂ type carbosilane monomers.

Original language	English
Pages (from-to)	675-684
Number of pages	10
Journal	Macromolecular chemistry and physics
Volume	209
Issue number	7
DOIs	https://doi.org/10.1002/macp.200700574
Publication status	Published - 4 Apr 2008
Externally published	Yes

Keywords

Anionic polymerization
Dendritic materials
Hydrosilylation
Hyperbranched polymers
Macromonomers
Polybutadiene
Polyisoprene

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title = "Branched and functionalized polybutadienes by a facile two-step synthesis",

abstract = "Anionic polymerization was used to prepare silane-endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9000 to 34000 g · mol-1 These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB 2 + A type {"}pseudocopolymerization{"} method. All branched polymers were analyzed by SEC, SEC-MALLS, SEC-viscosimetry. 1H NMR spectroscopy, and DSC concerning their branching ratio. The branching parameters for the branched polymers exhibited similar characteristics as for hyperbranched polymers obtained from conventional AB2 monomers. Detailed kinetic studies showed that the polymerization occurred very rapidly in comparison to the hydrosilylation polymerization of classical AB2 type carbosilane monomers.",

keywords = "Anionic polymerization, Dendritic materials, Hydrosilylation, Hyperbranched polymers, Macromonomers, Polybutadiene, Polyisoprene",

author = "Frederik Wurm and L{\'o}pez-Villanueva, {Francisco J.} and Holger Frey",

year = "2008",

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doi = "10.1002/macp.200700574",

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T1 - Branched and functionalized polybutadienes by a facile two-step synthesis

AU - Wurm, Frederik

AU - López-Villanueva, Francisco J.

AU - Frey, Holger

PY - 2008/4/4

Y1 - 2008/4/4

N2 - Anionic polymerization was used to prepare silane-endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9000 to 34000 g · mol-1 These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB 2 + A type "pseudocopolymerization" method. All branched polymers were analyzed by SEC, SEC-MALLS, SEC-viscosimetry. 1H NMR spectroscopy, and DSC concerning their branching ratio. The branching parameters for the branched polymers exhibited similar characteristics as for hyperbranched polymers obtained from conventional AB2 monomers. Detailed kinetic studies showed that the polymerization occurred very rapidly in comparison to the hydrosilylation polymerization of classical AB2 type carbosilane monomers.

AB - Anionic polymerization was used to prepare silane-endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9000 to 34000 g · mol-1 These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB 2 + A type "pseudocopolymerization" method. All branched polymers were analyzed by SEC, SEC-MALLS, SEC-viscosimetry. 1H NMR spectroscopy, and DSC concerning their branching ratio. The branching parameters for the branched polymers exhibited similar characteristics as for hyperbranched polymers obtained from conventional AB2 monomers. Detailed kinetic studies showed that the polymerization occurred very rapidly in comparison to the hydrosilylation polymerization of classical AB2 type carbosilane monomers.

KW - Anionic polymerization

KW - Dendritic materials

KW - Hydrosilylation

KW - Hyperbranched polymers

KW - Macromonomers

KW - Polybutadiene

KW - Polyisoprene

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DO - 10.1002/macp.200700574

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VL - 209

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EP - 684

JO - Macromolecular chemistry and physics

JF - Macromolecular chemistry and physics

SN - 1022-1352

IS - 7

ER -

Branched and functionalized polybutadienes by a facile two-step synthesis

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Keywords

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