Synthesis of PTHF-Grafted PMMA Based on the Reaction of Methyl Esters with Quaternary Ammonium Salts

Tong, Jiang‐Dong; Prez, Filip Du; Goethals, Eric J.

doi:10.1021/ma001149y

Cited by 4 publications

(4 citation statements)

References 27 publications

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“…Alkyne-functionalized PTHF, the other "click" component, was prepared by terminating living PTHF chains with propargyl alcohol (Scheme 2), based on earlier developed synthetic routes for other end-functionalized PTHF systems. 47 As can be seen from Table 2, the molecular weights determined by GPC and 1 H NMR measurements were in good agreement with the theoretical ones, except for the higher molecular weight polymer. The observed difference may be attributed to the limits of the accuracy of estimation by 1 H NMR.…”

Section: Resultssupporting

confidence: 80%

Polytetrahydrofuran/Clay Nanocomposites by In Situ Polymerization and “Click” Chemistry Processes

et al. 2008

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Polytetrahydrofuran (PTHF)/clay nanocomposites were prepared by two routes: in situ cationic ring opening polymerization (CROP) and a method involving "click" chemistry. In the first method, PTHF chains were grown from the surface of the organo-modified montmorillonite clay by CROP of tetrahydrofuran (THF) through the hydroxyl functions of the clay by using trifluoromethanesulfonic anhydride, in the presence of 2,6di-tert-butylpyridine as proton trap and dichloromethane as solvent. The polymerizations were affected by the clay content ratios. The living characteristics of the polymerization were demonstrated by the semilogarithmic first order kinetic plot. In the second method, CROP of THF has been performed independently to produce alkynefunctionalized PTHF and the obtained polymers were subsequently anchored to azide-modified clay layers by a "click" reaction. The exfoliated polymer/clay nanocomposites obtained by both methods were characterized and compared by X-ray diffraction spectroscopy, thermogravimetric analysis, and transmission electron microscopy. Compared to the virgin polymer, the nanocomposites exhibited improved thermal stabilities regardless of the preparation method. However, the nanocomposites prepared by the "click" chemistry approach appeared to be thermally more stable than those prepared by in situ polymerization. Moreover, the "click" chemistry method also provided better exfoliation.

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Section: Resultssupporting

confidence: 80%

Polytetrahydrofuran/Clay Nanocomposites by In Situ Polymerization and “Click” Chemistry Processes

et al. 2008

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“…In a separate step, polymers that have been end-functionalized are prepared. These end-functionalized polymers are subsequently reacted covalently with the functional groups distributed along the original polymer backbone. ,− This approach allows the chains that eventually serve as branches to be characterized extensively before incorporation into the backbone and is often called the “grafting onto” approach.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Comblike Poly(butyl methacrylate) Using Reversible Addition−Fragmentation Chain Transfer and an Activated Ester

et al. 2004

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Comblike polymers of poly(n-butyl methacrylate) were prepared using an activated estertype comonomer (N-acryloxysuccinimide, NAS) to generate branch points. The conventional solution freeradical copolymerization kinetics of n-butyl methacrylate (BMA) and NAS were first investigated by following individual monomer consumption rates by 1 H NMR spectrometry and reactivity ratios of BMA and NAS determined using the terminal model. The reactivity ratios so obtained are both close to 0.2; the joint confidence interval is also determined. Reversible addition-fragmentation chain transfer (RAFT) was then used to grow polymers with controlled backbone and branch chain length. Because both reactivity ratios have similar values, this implies that the copolymer will have a random distribution of NAS and hence of branch points. RAFT-mediated polymerization was first used to synthesize linear poly(BMAco-NAS) chains. Primary hydroxy-functionalized RAFT agents were then immobilized on this linear poly-(BMA-co-NAS) through nucleophilic substitution on the activated ester units of the NAS. From these immobilized RAFT agents, branches were grown upon addition of a further aliquot of monomer (BMA) and initiator (AIBN). The amount of NAS in the starting BMA/NAS composition was varied without adversely affecting the uniformity of the NAS distribution along the resulting linear poly(BMA-co-NAS) backbone. This results in branched polymers whose molecular weight, branching density, and degree of polymerization of branches are all relatively narrow and controlled.

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“…Tong et al have demonstrated that a carboxylate anion can act as a nucleophile in an exchange reaction with onium ions at 140 °C, 11 and alkyl group displacements from quaternary ammonium halides by amine nucleophiles have been well documented. 12 We have similarly observed the ability of amines to participate in alkyl exchange with BPMN-derived compounds.…”

Section: Resultsmentioning

confidence: 99%

Amine Substitution Reactions of Brominated Poly(isobutylene-co-isoprene): New Chemical Modification and Cure Chemistry

et al. 2002

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Nucleophilic substitution reactions of brominated poly(isobutylene-co-isoprene) (BIIR) with amines are characterized through studies of a model compound, brominated 2,2,4,8,8-pentamethyl-4nonene (BPMN), and analysis of BIIR cure rheology. Nucleophilic amines do not accelerate HBr elimination from the allylic bromide within BIIR but readily engage in N-alkylation reactions with this functional group. N-Alkylation and accompanying proton-transfer reactions are shown to be reversible, and the distribution of allylic bromide, ammonium bromide salts, and their corresponding amines is dictated by equilibrium thermodynamics. N,N-Dimethyloctylamine and N-methyloctadecylamine undergo a single N-alkylation reaction with BPMN, while octylamine forms bis-N-alkylation products that can be used to generate stable cross-linked BIIR networks.

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Synthesis of PTHF-Grafted PMMA Based on the Reaction of Methyl Esters with Quaternary Ammonium Salts

Cited by 4 publications

References 27 publications

Polytetrahydrofuran/Clay Nanocomposites by In Situ Polymerization and “Click” Chemistry Processes

Polytetrahydrofuran/Clay Nanocomposites by In Situ Polymerization and “Click” Chemistry Processes

Synthesis of Comblike Poly(butyl methacrylate) Using Reversible Addition−Fragmentation Chain Transfer and an Activated Ester

Amine Substitution Reactions of Brominated Poly(isobutylene-co-isoprene): New Chemical Modification and Cure Chemistry

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