Linear Low-Density Polyethylene Containing Precisely Placed Hexyl Branches

Sworen, John C.; Wagener, Kenneth B.

doi:10.1021/ma070317k

Cited by 50 publications

(56 citation statements)

References 81 publications

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“…[4][5][6][7][8][9] Research in this area has shown that imparting these materials with such structural regularity results in a behavior unique to this class of polymers. [1,4,5,7,10] A recent area of effort in our laboratory has been the synthesis of polyethylene (PE) with precise placement of hydrophilic branches. Although these polymers resemble traditional amphiphilic graft copolymers, there are a number of notable differences.…”

Section: Introductionmentioning

confidence: 99%

Probing the Effects of Hydrophilic Branch Size, Distribution, and Connectivity in Amphiphilic Polyethylene

Berda

Wagener

2008

Macro Chemistry & Physics

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Acyclic diene metathesis (ADMET) polymerization/hydrogenation methodology was used to synthesize a family of amphiphilic polyethylenes (PEs) with precisely placed poly(ethylene glycol) branches. Four structural parameters are varied in this report: size of the hydrophilic pendant group, manner in which the pendant group is connected to the backbone, distance between the pendant moieties along the backbone, and saturation of the polyolefin backbone. Varying the branch size with other parameters held constant results in negligible effects on thermal behavior. However, when either the distribution of branches or manner of connection of the branches is altered, changes in the thermal behavior become clear. These slight structural changes allow tunability of the structural morphology from fully amorphous to semicrystalline materials melting over a range of temperatures above 60 °C.magnified image

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Section: Introductionmentioning

confidence: 99%

Probing the Effects of Hydrophilic Branch Size, Distribution, and Connectivity in Amphiphilic Polyethylene

Berda

Wagener

2008

Macro Chemistry & Physics

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“…The preparation of branched PE is a major area of research and is used as a method to tune the final properties of PE polymers . Here, we demonstrate that using different alkyl thiols is a simple and convenient route to prepare branched PEs.…”

Section: Methodsmentioning

confidence: 88%

“…A range of techniques have been developed to prepare functional PE polymers . The Wagner group has developed a number of strategies using acyclic diene metathesis (ADMET) polymerizations . Recently, Hillmyer and coworkers developed a two‐step synthesis using ring‐opening metathesis polymerization (ROMP) of acetoxy functional cyclooctene to produce stereo regular functional polyolefins.…”

Section: Methodsmentioning

confidence: 99%

“…Recently, Hillmyer and coworkers developed a two‐step synthesis using ring‐opening metathesis polymerization (ROMP) of acetoxy functional cyclooctene to produce stereo regular functional polyolefins. A range of functional groups have been incorporated into PE's structure including: phosphonic ester and phosphonic acid, carboxylic acid, amino, alcholol, methylimidazolium bromide . Most of the strategies developed require functionalization of monomers.…”

Section: Methodsmentioning

confidence: 99%

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Facile and versatile platform for the preparation of functional polyethylenes via thiol‐ene chemistry

Xiao

Bennett

Connal

2015

J. Polym. Sci. Part A: Polym. Chem.

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Polyethylene (PE) is the most used commodity polymer today. The reason PE has found widespread use in a range applications is due to the unique and tuneable properties available by tuning the molecular weight, the degree of branching, and choice of comonomers made by Ziegler-Natta or metallocene chemistry.1 The common industrial techniques used to make PEs have limited versatility to prepare functional PEs with, especially with polar comonomers. However, the range of applications could be increased further with the ability to prepare functional polyolefins.A range of techniques have been developed to prepare functional PE polymers. 3 The Wagner group has developed a number of strategies using acyclic diene metathesis (ADMET) polymerizations. [4][5][6][7][8] Recently, Hillmyer and coworkers 9 developed a two-step synthesis using ring-opening metathesis polymerization (ROMP) of acetoxy functional cyclooctene to produce stereo regular functional polyolefins. A range of functional groups have been incorporated into PE's structure including: phosphonic ester and phosphonic acid, 10 carboxylic acid, 11 amino, 12 alcholol, 13 methylimidazolium bromide. 6Most of the strategies developed require functionalization of monomers. Herein, we describe a versatile platform synthesis whereby the one polymer platform can be functionalized with a number of polar or nonpolar groups.Here, we have taken inspiration from work that has utilized norbornene 14 and internal double bonds produced from ROMP polymers [15][16][17] and poly(butadienes) 18 as functional handles using thiol-ene chemistry; this is a new strategy in the development of a range of functional polyolefins. Our simple and versatile approach to develop functional polyethylenes is based on the preparation of polycyclooctene (P oct ) by ROMP of cyclooctene with Grubbs second generation catalyst. Subsequent functionalization reactions of the internal alkene bond can be achieved with a range of thiol functional molecules, via photoactivated thiol-ene click chemistry to prepare a range of functional PEs,19,20 providing a unique and versatile technique to functionalize PEs.ROMP polymerizations of cyclooctene were performed for 1 h in dichloromethane at 30 C, resulting in a library of polymers with M n ranging from 7 to 165 kDa and typical dispersity index of about 1.6, see Supporting Information Table S1 for details. These versatile platform polymers were used to demonstrate facile functionalization strategies using thiol-ene photochemistry, with a wide range of thiols (Scheme 1). The thiol-ene photoinitiated reactions were performed in appropriate solvents with an excess amount of thiol-containing small molecules (2-5 equivalents per double bond). 2,2-Dimethoxy-2-phenylacetophenone (DMPA) was used as a photoinitiator and irradiated with UV (365 nm) light for 6 h.

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“…Although biodegradability is sometimes a desired property due to accumulating plastic waste and some special applications require degradability (e.g., agriculture or medicine), it is not always desired. [13] Attempts to synthesize a number of linear low density polymers via ADMET polymerization was also reported by Wagener, [14,15] but the monomers used were not renewable.…”

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confidence: 99%

Renewable Polyethylene Mimics Derived from Castor Oil

Türünç

Espinosa

Meier

2011

Macromol. Rapid Commun.

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An increasing number of reports on the syntheses of carbohydrate- and plant oil-based polymers has been published in ongoing efforts to produce plastic materials from renewable resources. Although many of these polymers are biodegradable and this is a desirable property for certain applications, in some cases non-degradable polymers are needed for long-term use purposes. Polyolefins are one of the most important classes of materials that have already taken their places in our daily life. On the other hand, their production relies on fossil resources. Therefore, within this contribution, we discuss synthetic routes toward a number of polyethylene mimics derived from fatty acids via thiol-ene and ADMET polymerization reactions in order to establish more sustainable routes toward this important class of polymers. Two different diene monomers were thus prepared from castor oil derived platform chemicals, their polymerization via the two mentioned routes was optimized and compared to each other, and their thermal properties were investigated.

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Linear Low-Density Polyethylene Containing Precisely Placed Hexyl Branches

Cited by 50 publications

References 81 publications

Probing the Effects of Hydrophilic Branch Size, Distribution, and Connectivity in Amphiphilic Polyethylene

Probing the Effects of Hydrophilic Branch Size, Distribution, and Connectivity in Amphiphilic Polyethylene

Facile and versatile platform for the preparation of functional polyethylenes via thiol‐ene chemistry

Renewable Polyethylene Mimics Derived from Castor Oil

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