Surface functionalization of cross-linked poly(dicyclopentadiene)

Martina, Alberto Della; Garamszegi, László Zsolt; Hilborn, Jöns

doi:10.1016/j.reactfunctpolym.2003.07.003

Cited by 15 publications

(20 citation statements)

References 12 publications

(12 reference statements)

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“…Like aerogels, polyHIPEs are also highly porous featuring a fully interconnected porous structure, and therefore DLO phenomena with homogeneous oxidation throughout the sample thickness can also be expected. In our case, accelerated oxidation at 80 °C was applied which resulted in fully oxidized DCPD polyHIPE membranes after 24 h. Upon that time, samples underwent a color change from white to brown/yellow which coincided with the formation of oxidation products such as carbonyl and hydroxyl groups, verified by IR‐ATR (Figure S6) as well as bridging peroxides . Upon elemental analysis (EA), unoxidized DCPD polyHIPE membranes were found to contain 3.1% of oxygen (empirical sum formula C 7 H 9 O 0.2 ), while fully oxidized membranes contain 30.4% of O (empirical sum formula C 5 H 6 O 2 , Table S2).…”

Section: Resultsmentioning

confidence: 73%

“…In our case, accelerated oxidation at 80 8C was applied which resulted in fully oxidized DCPD polyHIPE membranes after 24 h. Upon that time, samples underwent a color change from white to brown/yellow which coincided with the formation of oxidation products such as carbonyl and hydroxyl groups, verified by IR-ATR ( Figure S6) as well as bridging peroxides. [53] Upon elemental analysis (EA), unoxidized DCPD polyHIPE membranes were found to contain 3.1% of oxygen (empirical sum formula C 7 H 9 O 0.2 ), while fully oxidized membranes contain 30.4% of O (empirical sum formula C 5 H 6 O 2 , Table S2). During the oxidation process, additional crosslinking via two pathways takes place within the pDCPD network leading to an increase of the crosslink density: i) covalent crosslinking, the reaction of radicals at the carbon-carbon double bonds, [50] and ii) non-covalent crosslinking through hydro-gen bonding between hydroxyl, carbonyl and hydroperoxy groups that is most likely responsible for the brittleness of the oxidized DCPD polyHIPEs as discussed in our previous work.…”

Section: Preparation and Characterization Of Membranesmentioning

confidence: 99%

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Macroporous Polyolefin Membranes from Dicyclopentadiene High Internal Phase Emulsions: Preparation and Morphology Tuning

Kovačič

Preishuber-Pflügl

Slugovc

2014

Macromol. Mater. Eng.

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The curing of 200 mm thick, surfactant-stabilized water-in-dicyclopentadiene high internal phase emulsion films by ring opening metathesis polymerization yielded 140-200 mm thick, open-cellular macroporous membranes with 81.5 AE 2% porosity. Depending on the support on which high internal phase emulsion (HIPEs) were cast, different polyHIPE membrane surface morphologies ranging from almost closed (on steel) to fully open (on glass) were obtained. At the same time, the interior morphology of the membranes was identical, featuring cavity and window diameters of 7 AE 5 and 1.4 AE 0.6 mm, respectively. The membranes were tough and ductile, as revealed by a Young's modulus of 125 AE 8 MPa and an ultimate strength at break, which occurred at 20 AE 2% elongation and 3.1 MPa. The swelling behavior of the membranes was tested in several solvents and finally the swollen membranes were functionalized by bromination, yielding still ductile membranes of 80.6 AE 1% porosity and bromide loading of 5 mmol g À1 .

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Section: Resultsmentioning

confidence: 73%

Section: Preparation and Characterization Of Membranesmentioning

confidence: 99%

Macroporous Polyolefin Membranes from Dicyclopentadiene High Internal Phase Emulsions: Preparation and Morphology Tuning

Kovačič

Preishuber-Pflügl

Slugovc

2014

Macromol. Mater. Eng.

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“…Thus, there are different possible functionalization routes, as recently demonstrated 23, 24. Also, an initiator was grafted to their surface and atom transfer radical polymerization was performed to obtain a thick grafted layer of poly(methyl methacrylate) 25…”

Section: Introductionmentioning

confidence: 99%

Macroporous poly(dicyclopentadiene) beads

Martina

Graf

Hilborn

2005

J of Applied Polymer Sci

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Macroporous poly(dicyclopentadiene) beads have been produced via chemically induced phase separation in suspension polymerization. Phase separation is promoted by the enthalpic and entropic changes induced by the polymerization of dicyclopentadiene. By using poly(1,2-butylene glycol) monobutyl ether (M n 500 g/mol), which is not soluble in the suspending medium, as the porogen, the stabilized droplets of the monomer/porogen mixture can be considered microreactors in which both polymerization and phase separation occur, resulting in solid, biphasic microspheres. The porogen is then extracted with methanol and the particles are finally dried. The resulting macroporous crosslinked poly(dicyclopentadiene) beads are analyzed by scanning electron microscopy, mercury intrusion porosimetry, and nitrogen adsorption and are compared with similar bulk samples. Materials containing isolated pores as well as microstructures built with agglomerated particles have been produced. The porous microspheres showed micrometric average pores' access diameters and specific surface areas ranging from 1.3 to 3.1 m 2 /g.

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“…Recently, polydicyclopentadiene (PDCPD) emerged as a new material with applications in surface science and chromatography. 167,[387][388][389][390][391][392][393][394][395] PDCPD has found many applications because of its toughness and, more recently, the presence of a high density of olefins. Because of its toughness and resistance to fracture, this material is used to make the covers on snowmobile sleds and as a protective material for hoods on semitrucks.…”

Section: Introductionmentioning

confidence: 99%

“…388,[391][392][393][394] PDCPD is also being explored for uses as the solid phase in chromatography because of its ease of synthesis in a variety of containers, its highly cross-linked structure, and the presence of olefins that can be functionalized to introduce additional selectively to separations. 167,387,388 We wished to study the surface chemistry of this polymer because its properties and low price may lend it to a variety of applications where other polymers are currently used. Others studied the functionalization of PDCPD by growing new polymers from the surface, but no one has reported the assembly of monolayers on its surface.…”

Section: Introductionmentioning

confidence: 99%

Functionalization and patterning of monolayers on silicon(111) and polydicyclopentadiene

Perring¹

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The formation of a functional surface combines the properties of a substrate and monolayer to produce a new hybrid that can combine aspects of each. Monolayers can be made on many surfaces, and well defined functionalized monolayers were assembled on silicon(111) and polydicyclopentadiene (PDCPD). Acid terminated monolayers were assembled on silicon(111) and their functionalization chemistry explored. It was shown that using trifluoroacetic anhydride to generate an intermediate reactive anhydride, the surface could be functionalized with amines. It was further shown that using soft lithography these functionalized surfaces could be patterned. Mixed monolayers of methyl and olefin terminated surfaces on silicon(111) were used to develop a new soft lithographic technique with polydimethylsiloxane (PDMS). PDMS can be controllably etched using fluoride species. The surface is first activated by the attachment of the Grubbs' 1 st generation catalyst. A PDMS microfluidic device is then placed on the surface. By using a cross metathesis reaction, the exposed channel can be pacified. The next step, a fluoride etchant is used to remove PDMS, exposing an unreacted surface. Polymer brushes were then grown by ring opening metathesis polymerization (ROMP) in this region. Functionalization of the emerging polymer PDCPD was conducted through two different routes. ROMP formed PDCPD has double bonds that can be functionalized. In the first process, the double bonds were reacted with bromine. This is a rapid reaction and proceeds to a significant depth in the material. Bromines can then be displaced with amines in a substitution reaction. This was demonstrated with a fluorinated amine that when examined by XPS were shown to be present only at the surface, further more we were able to pattern this surface too. Secondly, a process using epoxides was developed. The epoxidation reaction could not be quantified, but formation in the second step of an Results and Discussion .

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Surface functionalization of cross-linked poly(dicyclopentadiene)

Cited by 15 publications

References 12 publications

Macroporous Polyolefin Membranes from Dicyclopentadiene High Internal Phase Emulsions: Preparation and Morphology Tuning

Macroporous Polyolefin Membranes from Dicyclopentadiene High Internal Phase Emulsions: Preparation and Morphology Tuning

Macroporous poly(dicyclopentadiene) beads

Functionalization and patterning of monolayers on silicon(111) and polydicyclopentadiene

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