Selective Surface Modification of Poly(propylene) with OH and COOH Groups Using Liquid‐Plasma Systems

Joshi, Ranjit; Schulze, R.‐D.; Meyer‐Plath, Asmus; Friedrich, Jörg

doi:10.1002/ppap.200700175

Cited by 54 publications

(41 citation statements)

References 38 publications

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“…[4] The process parameters for generation within underwater capillary discharge, relevance of surface functionalization to the distance of the polymer surface from the plasma source, and a close insight to the concept of selectivity of the process, were studied in depth and discussed elaborately in our earlier communication on the similar topic line. [1] Extension to the same study, herewith presented and discussed, are the effects of addition of hydrogen peroxide on the selectivity of functionalization, and its relevance to underwater plasma process. Selectivity being an output of gas-phase chemical derivatization using Trifluroacetic anhydride, the generated hydroxyl groups on the PP surface using this process under discussion is elaborated in detail.…”

Section: Introductionmentioning

confidence: 92%

Selective Surface Modification of Polypropylene using Underwater Plasma Technique or Underwater Capillary Discharge

Joshi¹,

Schulze²,

Meyer‐Plath³

et al. 2009

Plasma Processes & Polymers

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Among new types of plasma processes, the underwater plasma is one of the most attractive methods for functionalization of polymer surfaces. The interesting features of plasma solution system are that the material surfaces to be modified remain in contact with the plasma‐moderated solution. The role of plasma‐moderated liquids, allows the reach of the reactive species through solution onto the geometrically hindered sites. The UV radiation produced in plasma formation helps in generating additional excited, ionized, and dissociated molecules and species in the reaction solution. An interesting feature of the technique is its flexibility to use a wide variety of additives as or in solution system. This allows us to create a selective or monotype functionalization of material surfaces. Such system was studied for the selective hydroxyl functionalization of polypropylene surface. The oxidation of polymer surfaces and the introduction of O‐containing functional groups by underwater plasma was found to exceed concentrations typically achieved in oxygen low‐pressure gas discharge plasmas up‐to two‐folds (maximal 56 O/100 C). The fraction of OH groups among all O‐containing moieties amounts from 25 to 40% in comparison to that in the gas plasma of about 10% OH groups. Addition of hydrogen peroxide into this same system increases the fraction of CO bonds up to 75% (27‐OH/100 O). A study was focused to optimize the role of hydrogen peroxide on the efficiency of oxidation and selectivity with chemical derivatization with respect to the formation of mono‐sort hydroxyl functionalities, calculated using a chemical derivatization technique.

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Section: Introductionmentioning

confidence: 92%

Selective Surface Modification of Polypropylene using Underwater Plasma Technique or Underwater Capillary Discharge

Joshi¹,

Schulze²,

Meyer‐Plath³

et al. 2009

Plasma Processes & Polymers

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“…For this purpose, many polymerization techniques [1][2][3][4] have been explored and exhibited the different advantages, in which radiation [5], ultrasonic [6] and plasma [7] syntheses have attracted many researchers. More recent Joshi et al [8] reported an effective selective surface modification by using liquid-plasma system. In addition, for improving the scratch resistance of PMMA the hardcoating techniques have also been studied [9][10][11][12].…”

Section: Introductionmentioning

confidence: 98%

Synthesis and Characterization of Polymethylmethacrylate by Using Glow Discharge Electrolysis Plasma

Wang

Gao

et al. 2009

Plasma Chem Plasma Process

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An approach for polymerization to produce polymethylmethacrylate (PMMA) was developed, in which the reaction was initiated by the glow discharge electrolysis (GDE) rather than chemical initiators. The highest number-average molecular weight (M n ) and the lowest polydispersity index (PDI) of the resulting polymer were 1.12 9 10 6 g/mol and 1.21, respectively. The following parameters such as the applied voltage, discharge time, the content of methylmethacrylate (MMA), the amount of a suspension stabilizer (polyvinyl alcohol), polymerization temperature and time were examined in detail, which could affect the conversion, molecular weight and polydispersity index. The M n and PDI of polymer can be monitored by changing the discharge parameters and polymerization conditions. PMMA was characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FT-IR), cold field emission scanning electron microscopy (FESEM), nuclear magnetic resonance (NMR) and thermogravimetric analysis (TGA). Results indicate that using the GDE technique to initiate the polymerization reaction is successful, because the product obtained has the same properties with one obtained by chemical method, for example, in chemical structure, tacticity and thermal stability. Moreover, the polymer particles for the former are smaller than the latter. The kinetic observation was that the polymerization of MMA initiated by the GDE plasma obeys the first order of reaction with an obvious induction period.

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“…[1][2][3][4]. A densely functionalized polyolefin surface with preferably monotype functional groups is needed to graft molecules chemically for producing special surface properties as necessary for biochips, sensors, anti-fouling layers, etc.…”

Section: Introductionmentioning

confidence: 99%

“…The exposure of the aliphatic polymer to the UWP that is enriched with OH species (· OH, HO − ) offers greater possibilities to introduce OH groups onto the polymer surface in much higher concentration and with higher (OH) selectivity [1,3] than the treatment in an oxygen gas plasma [12]. Thus, the polymer surface also acts as an OH radical scavenger [7,13,14].…”

Section: Introductionmentioning

confidence: 99%

Role of Hydrogen Peroxide in Selective OH Group Functionalization of Polypropylene Surfaces using Underwater Capillary Discharge

Joshi

Friedrich

Wagner

2011

Journal of Adhesion Science and Technology

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Plasma chemical methods are well suited for introducing functional groups to the surfaces of chemically inert polymers such as polyolefins. However, a broad variety of functional groups are often formed. Unfortunately, for further chemical processing such as grafting of molecules for advanced applications a highly dense monotype functionalized polyolefin surface is needed. Therefore, the main task was to develop a selective surface functionalization process, which formed preferably only a single type of functional groups at the surface in high concentration. Amongst the novel plasma methods, the underwater plasma process (UWP) is one of most attractive options to solve the problem of monotype functionalization. Such plasma is an efficient source of ions, electrons, UV-radiation, high-frequency shock waves, radicals such as hydroxyl radical, and reactive neutral molecules such as hydrogen peroxide.In contrast to established gas phase glow discharge processes, the water phase limits the particle and radiation energies and thus the energy input into the polymer. By virtue of the liquid water environment, which moderates highly energetic plasma species, extensive oxidation, degradation, cross-linking and radical formation on the polymer are more limited as compared to gas plasma exposure. The variety of plasma produced species in the water phase is also much smaller because of the limited reaction possibilities of the plasma with water. The possibility to admix a broad variety of chemical additives makes underwater plasma even more attractive.Hydrogen peroxide and the catalyst (Fe-ZSM5) should influence and increase the equilibrium concentration of OH radicals in the underwater plasma process. It was found that these radicals played a very important role in OH functionalization of polyolefin surfaces. Hydrogen peroxide was identified to be the most prominent precursor for OH group formation in the UWP. The catalyst would affect the steady state of OH radical formation and its reaction with the substrate surface and thus accelerates the functionalization process.

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Selective Surface Modification of Poly(propylene) with OH and COOH Groups Using Liquid‐Plasma Systems

Cited by 54 publications

References 38 publications

Selective Surface Modification of Polypropylene using Underwater Plasma Technique or Underwater Capillary Discharge

Selective Surface Modification of Polypropylene using Underwater Plasma Technique or Underwater Capillary Discharge

Synthesis and Characterization of Polymethylmethacrylate by Using Glow Discharge Electrolysis Plasma

Role of Hydrogen Peroxide in Selective OH Group Functionalization of Polypropylene Surfaces using Underwater Capillary Discharge

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