Palladium Catalyzed Vinyl Addition Poly(norbornenes): Formic Acid as a Chain Transfer Agent. Mechanism and Polymer Optical Properties

Kandanarachchi, Pramod; Chang, Chun Yen; Smith, Steven D.; Bradley, Patrick; Rhodes, Larry F.; Lattimer, Robert P.; Benedikt, George M.

doi:10.2494/photopolymer.26.431

Cited by 7 publications

(11 citation statements)

References 26 publications

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“…Polymerization experiments at different concentrations of formic acid were carried out for the 80/20 isomeric mixture. With increasing formic acid concentration the molecular weight of the polymer decreases accordingly as expected based on our previous report [4]. The optical density of these polymers is relatively high and do not change much over the molecular weight range examined.…”

Section: Polymerization Studiessupporting

confidence: 61%

“…Formic acid has been shown to act as an intermolecular chain transfer agent producing poly(norbornene) with hydrogen end groups [4]. As such, the polymers are quite transparent to 193 nm radiation.…”

Section: R H R Nmentioning

confidence: 94%

“…Previously, we reported that depending on the catalyst used, the molecular weight of poly(norbornene) can be dictated by an unusual intramolecular β, γ-carbon-carbon bond cleavage that occurs prior to the molecular weight limiting β-hydrogen elimination chain transfer step [4,10]. As a result of this reaction a polymer end group containing an exo-methylene cyclohexene functionality is formed.…”

Section: Discussionmentioning

confidence: 99%

“…However, H 2 and silanes are not ideal since H 2 is highly flammable and residual silane byproducts can deleteriously affect the etch properties of the photopolymer composition. This led us to develop formic acid as an alternative CTA [4]. Formic acid does not suffer from these limitations and produces poly(norbornene) that is highly transparent at 193 nm.…”

Section: Introductionmentioning

confidence: 99%

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The Effect of endo/exo-Norbornene Isomer Ratio on Poly(norbornene) Optical Density at 193 nm

Chang

Bell

Shick

et al. 2014

J. Photopol. Sci. Technol.

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The polymerization of exo- [(norbornenemethoxy)methyl]-1,1,1,3,3,3-hexafluoro-2-propanol (2) using a palladium catalyst gave a significantly higher M w polymer than the endo isomer or the 80/20 mixture of endo/exo-2. To achieve similar M w higher concentrations of formic acid chain transfer agent was needed for the exo isomer than for the 80/20 mixture. As a result, the optical density at 193 nm of the exo isomer polymer is substantially lower since less olefinic polymer end groups were formed. A subtle interplay between chain transfer mechanisms and propagation rates explains the results obtained. Isomer content in poly(2) does not affect the dissolution rate in TMAH.

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Section: Polymerization Studiessupporting

confidence: 61%

Section: R H R Nmentioning

confidence: 94%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Effect of endo/exo-Norbornene Isomer Ratio on Poly(norbornene) Optical Density at 193 nm

Chang

Bell

Shick

et al. 2014

J. Photopol. Sci. Technol.

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“…The addition of formic acid also produces the termination of the polynorbornene chain and occurs via formation of Pd-H species and reductive elimination of H-polynorbornenyl polymer chains. 144 Rhodes and co-workers proposed a mechanism for the termination pathway in the vinylic addition polymerization of an ester-functionalized norbornene with the catalyst [Pd(NCMe)4](BF4)2 in absence of any chain transfer additive. 145 The VA-polymerization of 2-acetoxymethyl-5-norbornene with [[Pd(NCMe)4](BF4)2 as catalyst (ratio monomer/Pd = 1000:1) proceeded with low yield (34 %) and gave polymers with low molecular weight (Mn = 1130 Da).…”

Section: The Mechanism For the Vinylic Addition Polymerization Of Norbornene: A Puzzling Termination Stepmentioning

confidence: 99%

Polymerization of norbornene and alkenyl-norbornenes catalyzed by palladium-benzyl or nickel-aryl complexes: Effects in polymer structure and application as catalyst support

Ortega¹

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Index 1.4.7. Reaction of complex 6e with R-(+)-limonene 1.4.8. Generation in situ of complex [PdH(PPh3)3](BF4) (10) 1.4.9. X-ray structure determinations Chapter 2 2. Homo-and Co-polymerization of Norbornene and Alkenyl Norbornenes Employing -Pentafluorophenylmethyl Benzylic Complexes of Palladium(II) 2.1. Introduction to the polymerization of norbornene and their derivatives 2.1.1. Radical polymerization of norbornene 2.1.2. Cationic polymerization of norbornene and alkenyl-norbornenes 2.1.3. ROMP (Ring Opening Metathesis Polymerization) of norbornene and alkenylnorbornenes 2.1.4. Vinylic addition polymerization of norbornene and their derivatives 2.1.5. Aim of the work in this chapter 2.2. Results and Discussion 2.2.1. Activity of benzylic complexes of palladium(II) in the homopolymerization of norbornene 2.2.2. Activity of complex 4e in the homopolymerization of substituted norbornenes 2.2.3. Activity of complex 4e in the copolymerization of substituted norbornenes with norbornene 2.2.4. New catalytic system with high activity in the polymerization of alkenylnorbornenes 2.2.5. Mechanistic information for the vinylic addition polymerization of norbornene and 5-vinyl-2-norbornene with the catalyst 4e and the system 1/PCy3/NaBAr4 f 2.2.6. Functionalization post-polymerization of VA-Co-PNB-VNB (15) and VA-Co-PNB-BNB (16) 2.3. Conclusions 2.4. Experimental Section 2.4.1. Materials and general considerations Index 2.4.2. Homopolymerization and oligomerization experiments 2.4.3. Copolymerization Experiments 2.4.4. Homopolymerization experiments of VNB and ENB with the precatalyst mixture 1/AgBF4 or NaBAr4 f /phosphine 2.4.5. Functionalization post-polymerization of VA-Co-PNB-VNB (15) and VA-Co-PNB-BNB (16) Chapter 3 3. Study of the Vinylic Addition Polymerization of Norbornene: A New Propagation Pathway by -Carbon Elimination Index 3.4. Experimental Section 3.4.1. Materials and General Considerations. 3.4.2. Polymerization experiments 3.4.3. Formation in situ of complexes 33, 34 and 37 3.4.4. Synthesis of nickel(II) complexes 3.4.5. Synthesis of dimers of norbornene 3.4.6. Data for X-Ray structure determinations Chapter 4 4. Synthesis of Supported Trispyrazolylborate Copper(I) Complexes on VA-PNBs 4.1. Introduction 4.1.1. Copper supported catalysis: An approach to green chemistry 4.1.2. Trispyrazolylborates (Tp x ) as convenient ligands to support Cu(I) complexes 4.1.3. Aim of the work in this chapter. 4.2. Results and Discussion 4.2.1. Synthesis of the Tp-functionalized VA-polynorbornenes 4.2.2. Synthesis of the CuTp x VA-polynorbornenes 4.2.3. Application of the Tp x -functionalized VA-polynorbornenes in some selected catalytic reactions 4.3. Conclusions 4.4. Experimental Section 4.4.1. Materials and General considerations 4.4.2. Synthesis of polymer VA-Co-PNB-VNB (15) 4.4.3. Synthesis of polymer VA-Co-PNB-NB(CH2)2(B(pz Me2 )3Li) (41) 4.4.4. Synthesis of polymer VA-Co-PNB-(CH2)2(B(pz Me2 )3Cu(NCMe)) (41-Cu) 4.4.5. Synthesis of polymer VA-Co-PNB-NB(CH2)2B(pz Me2 )3Cu(CO) 4.4.6. Catalytic reactions employing the VA...

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Polymers of norbornenyl‐4‐phenol: Dissolution rate characteristics, positive tone photo‐patterning, and polymer properties

Evans

Brick

Bell

et al. 2017

J of Applied Polymer Sci

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Vinyl addition norbornene polymers with phenol pendent groups are obtained by methanolysis of the 4-acetoxyphenyl norbornene polymer. Thin films of this polymer blended with additives such as norbornene polymers with hexafluoroalcohol pendent groups and diazonaphthoquinone compounds result in linear dissolution in tetramethylammonium hydroxide developer. Good resolution, positive tone patterns are obtained from image-wise exposure of thin films of blends of the diazonaphthoquinone additives with both phenol pendent norbornene homopolymer and with norbornene copolymers with both phenol and hexafluoroalcohol pendent groups. Properties such as transparency, dielectric constant, chemical, and thermal resistance were determined for cured copolymer compositions containing an epoxy crosslinker.

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Palladium Catalyzed Vinyl Addition Poly(norbornenes): Formic Acid as a Chain Transfer Agent. Mechanism and Polymer Optical Properties

Cited by 7 publications

References 26 publications

The Effect of endo/exo-Norbornene Isomer Ratio on Poly(norbornene) Optical Density at 193 nm

The Effect of endo/exo-Norbornene Isomer Ratio on Poly(norbornene) Optical Density at 193 nm

Polymerization of norbornene and alkenyl-norbornenes catalyzed by palladium-benzyl or nickel-aryl complexes: Effects in polymer structure and application as catalyst support

Polymers of norbornenyl‐4‐phenol: Dissolution rate characteristics, positive tone photo‐patterning, and polymer properties

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