Synthesis and Characterization of Surface-Functionalized 1,2-Polybutadiene Bearing Hydroxyl or Carboxylic Acid Groups

Carey, Deborah H.; Ferguson, Gregory S.

doi:10.1021/ma00103a005

Cited by 25 publications

(34 citation statements)

References 12 publications

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“…We note that it was possible to quickly restructure the surface to a starting contact angle of $1058 if the sample was heated in water and allowed to slowly air cool versus quenching in 25 8C water. This result is consistent with the findings of Carey et al [13] and Holmes-Farley et al [11] for surface restructuring of oxidized polybutadiene and oxidized polyethylene, respectively.…”

Section: Tailored Wettability Switching Kinetics and Reconstruction Rsupporting

confidence: 92%

“…[12] By varying substrate elasticity and composition of oxidized butadienes to create a system with a controlled rate of surface reconstruction, Ferguson and coworkers argued that surface reconstruction was dictated by shifts in enthalpic and entropic driving forces on the surface free energy. [13][14][15] Surface reconstruction is also associated with surface segregation of polymers and their reorientation at the surface. These two modes often act in accord and contribute simultaHere, the formation of responsive polymeric materials with tunable response time is reported.…”

Section: Introductionmentioning

confidence: 99%

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Formation and Properties of Responsive Siloxane‐Based Polymeric Surfaces with Tunable Surface Reconstruction Kinetics

Crowe-Willoughby

Genzer

2009

Adv Funct Materials

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Here, the formation of responsive polymeric materials with tunable response time is reported. These structures are fabricated by chemically modifying poly(vinylmethyl siloxane) (PVMS) networks with alkanethiols bearing a hydrophilic end‐group (COOH or OH). The response time is facilitated by the liquid nature of the PVMS backbone and increases with increase in length of the methylene spacer (CH2)n in the alkanethiol pendent group. While for n = 2 and 6, the surface reconstructs almost instantaneously, specimens with n = 11 resist reconstruction because of strong van der Waals forces, leading to the formation of semi‐crystalline regions. It is demonstrated that the responsive nature of PVMSS(CH2)11OH can be fine‐tuned by varying the temperature; it possesses a faster response at temperatures above the melting point of the S(CH2)11OH moiety.

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Section: Tailored Wettability Switching Kinetics and Reconstruction Rsupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Formation and Properties of Responsive Siloxane‐Based Polymeric Surfaces with Tunable Surface Reconstruction Kinetics

Crowe-Willoughby

Genzer

2009

Adv Funct Materials

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“…In all the investigated systems, experimental data confirmed both the previous reactivity trend of the PB constitutive units and the anti-Markovnikov selectivity of the reaction. The same behaviours were also observed by Carey and coworkers, [43,44] as discussed in two works on the functionalisation of long-chain syndiotactic 1,2-PB with TGA or thioacetic acid.…”

Section: Introductionsupporting

confidence: 82%

Thiol‐Ene Radical Addition of L‐Cysteine Derivatives to Low Molecular Weight Polybutadiene

Lotti

Coiai

Ciardelli

et al. 2009

Macro Chemistry & Physics

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The functionalisation of a low molecular weight, liquid 1,2‐polybutadiene (PBL) was performed by the addition of either N‐acetyl‐L‐cysteine or its methyl ester through the thiol‐ene radical reaction. The functionalisation runs were carried out in 1,4‐dioxane solution and in the presence of a free radical initiator (2,2′‐azobisisobutyrronitrile, AIBN). The initial feed ratio polymer/cysteine derivative/initiator was varied, in order to highlight the occurrence of side reactions and to understand their possible influence on the process. The 1H NMR determination of the functionalisation degree brought out high addition degrees of thiols, regardless of the initial thiol/double bonds ratio. This caused a drastic change in the macroscopic properties of the PBL with improved solubility in hydrophilic solvents (for instance in alkaline aqueous solutions) and impressive increase of the glass transition temperature. The propagation of chiral properties from the functionalising agents to the modified polymers was evaluated by polarimetry and circular dichroism in solution.magnified image

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“…[55] PVMS Modification with a Thiol-ene Reaction-Transitioning from Crystalline-like to Liquid-like Modification of a vinyl substituent via a thiol-ene reaction had been successfully carried out by both Ferguson's and Chojnowski's groups. [46,56] Implementing a similar addition route [51], we modified PVMS substrates with 3-mercaptopropionic acid and 11-dodecanethiol. The addition to the vinyl bond was confirmed via the elimination of the C=C peaks at 960, 1407 and 1587 cm" 1 in ATR-FTIR spectroscopy.…”

Section: Rapid Formation Of Hydrophilic Surfacesmentioning

confidence: 99%

“…Evaluating poly(vinylmethylsiloxane) (PVMS) was a logical choice; an intermediate was available for synthesizing PVMS of varying molecular weights and the vinyl moiety provides a convenient route for preparing a wide variety of functionalized silicone elastomers using simple chemical methods. [45,46] Besides the physical surface treatments such as ultraviolet oxidation, radiation, plasma or corona exposure, direct covalent attachment of the desired functionality through addition reactions such as hydrosilation, hydrosulfidation, hydrophosphination, epoxidation, and alkyl halide addition reactions allows for a myriad of possibilities. [47][48][49][50] The remainder of this chapter describes our work on modifying PVMS and its resultant properties.…”

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confidence: 99%

Manipulating Siloxane Surfaces: Obtaining the Desired Surface Function via Engineering Design

Crowe

Efimenko

Genzer³

2007

ACS Symposium Series

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We present a synopsis of recent accomplishment in our group in the area of surface-functionalized silicone elastomer networks.Specifically, we show that by combining mechanical manipulation of poly(dimethylsiloxane) (PDMS) networks with activation via ultraviolet/ozone (UVO) treatment and subsequent chemical modification of the preactivated surfaces, one can generate so-called mechanically assembled monolayers (MAMs). This technology can be successfully applied to create a variety of surfaces, including dense polymer brushes, long-lived superhydrophobic surfaces, molecular gradients comprising tunable length scales and twodimensional chemical gradients. In addition, the UVO modification of mechanically strained PDMS sheets provides a convenient route for creating "buckled" elastomeric sheets. These surfaces have a multitude of applications; ranging from anti-fouling surfaces to directed particle assembly. Finally we demonstrate control of surface wettability and responsiveness using poly(vinylmethylsiloxane) (PVMS) networks. We have shown that PVMS surfaces can be chemically tailored by reacting with thiols. The degree of response (including response rate) of such surfaces to hydrophobic-hydrophilic interactions can be adjusted by varying the chemical and structural properties of the side-group modifiers. 222

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Synthesis and Characterization of Surface-Functionalized 1,2-Polybutadiene Bearing Hydroxyl or Carboxylic Acid Groups

Cited by 25 publications

References 12 publications

Formation and Properties of Responsive Siloxane‐Based Polymeric Surfaces with Tunable Surface Reconstruction Kinetics

Formation and Properties of Responsive Siloxane‐Based Polymeric Surfaces with Tunable Surface Reconstruction Kinetics

Thiol‐Ene Radical Addition of L‐Cysteine Derivatives to Low Molecular Weight Polybutadiene

Manipulating Siloxane Surfaces: Obtaining the Desired Surface Function via Engineering Design

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