Ring opening polymerization of 3-semifluoro- and 3-bromomethyloxetanes to poly(2,2-substituted-1,3-propylene oxide) telechelics for soft blocks in polyurethanes

Makal, Umit; Uilk, Janelle; Kurt, Pinar; Cooke, Robert S.; Wynne, Kenneth J.

doi:10.1016/j.polymer.2005.01.069

Cited by 32 publications

(57 citation statements)

References 46 publications

(45 reference statements)

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“…Base‐U and 3F‐U have soft block T g 's close to the precursor diols. Previously, a T g of −37 °C was found for IPDI/BD(40)‐P(3F‐3400) 63. This led to an estimated 84% soft block in the pure soft block domain (Fox equation).…”

Section: Resultsmentioning

confidence: 98%

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A Polyurethane Surface Modifier: Contrasting Amphiphilic and Contraphilic Surfaces Driven by Block and Random Soft Blocks Having Trifluoroethoxymethyl and PEG Side Chains

Zhang

Fujiwara

Taşkent

et al. 2012

Macro Chemistry & Physics

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A conventional MDI-BD-PTMO polyurethane was modified using 2 wt.% polyurethanes (U) having copolyoxetane soft blocks with hydrophobic 3F, CF3CH2OCH2- and hydrophilic MEn, CH3O(CH2CH2O)nCH2-, n = 3, 7) side chains. In contrast to neat 3F-co-MEn-U, 2 wt.% 3F-co-MEn-U compositions have physically stable morphologies and wetting behavior. Surface composition (XPS) and amphiphilic or contraphilic wetting are controlled by the 3F-co-MEn polyoxetane soft block architecture and MEn side chain length. Importantly, θrec can be tuned for 2 wt.% 3F-co-MEn-U compositions independent of swelling, which is controlled by the bulk polyurethane. AFM imaging led to a new morphological model whereby fluorous/PEG-hard block nano-aggregates combine to form near surface features culminating in micron scale texturing.

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Section: Resultsmentioning

confidence: 98%

“…Polyurethanes were synthesized by modification of the two step, soft block first method described previously 63. As shown in Scheme , MDI and BD were used for the hard segment with P[3F‐ co ‐MEn] copolyoxetanes as the soft segment.…”

Section: Methodsmentioning

confidence: 99%

A Polyurethane Surface Modifier: Contrasting Amphiphilic and Contraphilic Surfaces Driven by Block and Random Soft Blocks Having Trifluoroethoxymethyl and PEG Side Chains

Zhang

Fujiwara

Taşkent

et al. 2012

Macro Chemistry & Physics

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“…1 Telechelics. BBOx was copolymerized with either 3FOx or ME2Ox monomers via cationic ring-opening polymerization 24 1,4-Butanediol (0.45 g, 5 mmol) and BF 3 ‚OEt 2 (1.42, 10mmol) were added to 20 mL anhydrous CH 2 Cl 2 and kept at ambient temperature for 45 min under a slow nitrogen purge, then cooled to -5°C. Through an additional funnel, 3FOx (16.56 g, 90 mmol) and BBOx (2.37 g, 10 mmol) dissolved in 20 mL of CH 2 Cl 2 were added dropwise to the solution over a 3 h period.…”

Section: Methodsmentioning

confidence: 99%

“…23,24 To our knowledge, the compositions reported herein are the first polyurethanes with cationic side chains on the soft block. The highly efficient antimicrobial behavior of the P[AB]-polyurethane surface modifiers was previously communicated.…”

Section: Introductionmentioning

confidence: 95%

Co-Polyoxetanes with Alkylammonium and Fluorous or PEG-Like Side Chains: Soft Blocks for Surface Modifying Polyurethanes

Kurt

Wynne

2007

Macromolecules

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The goal of this work was to prepare polyurethanes having P[AB] co-polyoxetane soft blocks, where A is a surface active (fluorous) or PEG-like side chain and B represents a desired function (alkylammonium). To this end, poly(2,2-substituted-1,3-propylene oxide) ran-co-telechelics with bromobutoxymethyl (-CH 2 O(CH 2 ) 4 -Br) and either trifluoroethoxymethyl (3FOx, -CH 2 OCH 2 CF 3 )) or PEG-like (2-(2-methoxyethoxy)ethoxy)methyl (ME2Ox, (-CH 2 (OCH 2 CH 2 ) 2 OCH 3 )) side chains were prepared via cationic ring-opening polymerization. Characterization utilized 1 H NMR spectroscopy, temperature modulated differential scanning calorimetry (MDSC) and thermogravimetric analysis (TGA). Molecular weights (M n ) by 1 H NMR end group analysis were ∼6 kDa while bromobutoxymethyl co-telechelic T g s were -68 and -48°C for ME2Ox and 3FOx, respectively. Bromobutoxymethyl groups were completely substituted with N,N-dimethylalkyl amines to obtain oxetane B repeats with six carbon (C6) and twelve carbon (C12) alkylammonium side chains. P[AB] T g s remained low after amine substitution. Co-telechelics were incorporated into polyurethanes (PUs) having 4,4′-(methylene bis (p-cyclohexyl isocyanate) (H 12 MDI) and butanediol (BD) as the hard block (30 wt %). Characterization by 1 H NMR, GPC, MDSC, and TGA is described. From DSC data, using the Fox equation, the weight fraction of pure soft block in the soft block domain (w 1 ) was very high (0.96-0.99) for polyurethanes with fluorous soft blocks, while soft blocks with PEG-like side chains were phase mixed (w 1 ) 0.73-0.75). To our knowledge, this is the first time that a polycationic telechelic has been incorporated in a polyurethane. TGA in nitrogen confirmed stoichiometry and showed that both alkylammonium co-telechelics and polyurethanes had good thermal stability.

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“…With the development of PU coatings, more and more attention has been paid to synthesize PU with new‐type monomers,15–18 such as various polyethers, polyesters, and diisocyanates. However, few investigations were reported on asymmetrical polyethers with different hydroxyls.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of linear asymmetrical poly(propylene oxide) diol

Yang

Zhu

et al. 2010

J of Applied Polymer Sci

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Linear asymmetrical poly(propylene oxide) was synthesized through four-step reactions: selective benzylation, alcohol exchange reaction, propylene oxide anionic polymerization, debenzylation. One terminal of the asymmetrical polymer chains is alcohol hydroxyl and the other is phenol hydroxyl. It was characterized with infrared (IR) and 1 H Nuclear Magnetic Resonance ( 1 H-NMR). Peaks at 1.11, 3.38, and 3.53 ppm were attributed to side groups (AOCH 2 CH(CH 3 )A), backbone units (AOCH 2 CH (CH 3 )A) and (AOCH 2 CH(CH 3 )A) of poly(propylene oxide), respectively. Molecular weight and molecular weight distribution were measured with 1 H-NMR and laser light scattering (LLS), which showed that the linear asymmetrical poly(propylene oxide) was mono-disperse (PDI ¼ 1.02-1.07). Then, its carbamate reaction with phenyl isocyanate was studied; the reaction rate constants for phenol hydroxyl and alcohol hydroxyl of poly(propylene oxide) were k 1 ¼ 0.209 mol L À1 min À1 and k 2 ¼ 0.051 mol L À1 min À1 . There was a great reactivity difference for two types of hydroxyls in asymmetrical poly(propylene oxide), contrasting to the single carbamate reaction rate constant of symmetrical poly(propylene oxide) (k 3 ¼ 0.049 mol L À1 min À1 ).

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Ring opening polymerization of 3-semifluoro- and 3-bromomethyloxetanes to poly(2,2-substituted-1,3-propylene oxide) telechelics for soft blocks in polyurethanes

Cited by 32 publications

References 46 publications

A Polyurethane Surface Modifier: Contrasting Amphiphilic and Contraphilic Surfaces Driven by Block and Random Soft Blocks Having Trifluoroethoxymethyl and PEG Side Chains

A Polyurethane Surface Modifier: Contrasting Amphiphilic and Contraphilic Surfaces Driven by Block and Random Soft Blocks Having Trifluoroethoxymethyl and PEG Side Chains

Co-Polyoxetanes with Alkylammonium and Fluorous or PEG-Like Side Chains: Soft Blocks for Surface Modifying Polyurethanes

Synthesis and characterization of linear asymmetrical poly(propylene oxide) diol

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