Chemical Reactions of Model Polyenes and Macromolecular Polyenes

Pinazzi, Christian; Lévesque, Guy; Reyx, Danièle; Brosse, Jean‐Claude; Pleurdeau, A.

doi:10.1021/ba-1969-0091.ch027

Cited by 6 publications

(5 citation statements)

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“…Specifically, the methyl protons of the acetyl group near 2.0 ppm were integrated relative to the protons of the polymer chain to determine the degree of hydroxylation of the functionalized product. 1 H NMR analysis of the acetylated products was consistent with the functionalized products having one to three hydroxyl functional groups per chain or 0.4-1.1 hydroxyl groups per 100 backbone carbons. 58 From IR analysis, we also know that carbonyl groups are present in groups P2-P5 as well.…”

Section: Resultsmentioning

confidence: 56%

“…The chemical modification of polymers is a valuable method for the preparation of new materials with tailored properties and useful functionality. A widespread example is the postpolymerization modification of polydienes, utilizing reactions such as hydrogenation, epoxidation, chlorosilation, hydroboration, and carbene addition. − These reactions apply established transformations of carbon−carbon double bonds to add functionality within and along a polymer backbone. In the case of polyolefins (macromolecular alkanes), postpolymerization modification is challenging due to the absence of any suitably reactive functional groups.…”

Section: Introductionmentioning

confidence: 99%

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Selective and Mild Oxyfunctionalization of Model Polyolefins

Boaen

Hillmyer

2003

Macromolecules

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The direct oxyfunctionalization of a model polyolefin, polyethylene-alt-propylene (PEP), was achieved utilizing a straightforward, mild process. In the presence of a manganese complex, manganese meso-tetra-2,6-dichlorophenylporphyrin acetate (Mn(TDCPP)OAc), imidazole, a phase transfer agent, and potassium peroxymonosulfate (Oxone), PEP was functionalized under ambient conditions without chain degradation. The primary oxidation products contained tertiary alcohols and ketones based on IR, 1 H NMR, 13 C NMR, and DEPT 13 C NMR spectroscopy of the oxyfunctionalized products. The oxyfunctionalization of squalane, a small molecule, structural analogue of PEP, was also demonstrated. Spectroscopic analyses of the main products from the squalane oxidation were nearly identical with the functional groups identified in the PEP oxidation products. The degree of functionalization was modulated by changing the relative concentration of the oxidant, Oxone. The degree of functionalization and the thermal properties are reported for these new polymeric materials.

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Section: Resultsmentioning

confidence: 56%

Section: Introductionmentioning

confidence: 99%

Selective and Mild Oxyfunctionalization of Model Polyolefins

Boaen

Hillmyer

2003

Macromolecules

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“…Using this method, various authors7–15 have introduced reactive double bonds as end‐groups in telechelic hydroxy polybutadiene (HTPBd). The oldest surveys were carried out by Pinazzi et al,7 who reported the chemical change of HTPBd by phosgene and methacryloyl chloride.…”

Section: Introductionmentioning

confidence: 99%

“…The oldest surveys were carried out by Pinazzi et al,7 who reported the chemical change of HTPBd by phosgene and methacryloyl chloride. In 1984, Kimura et al8 used such reactive oligomer‐type materials after dilution in an acrylate to study UV‐curing optical fibers and compared them to acrylate silicone resins. In another investigation, the same authors9 compared the dynamic mechanical properties of the same diacrylate polybutadiene oligomers in formulation with a series of reactive diluents, corresponding polyether and epoxy acrylate resins.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and thermal properties of bismaleate and bisfumarate telechelic oligomers from hydroxytelechelic polybutadienes

Boutevin

Robin

Boutevin

et al. 2003

J. Appl. Polym. Sci.

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ABSTRACT:The preparation of original telechelic bismaleate and bisfumarate polybutadienes and their thermal properties are presented. These functional oligomers were synthesized by the esterification of a hemiester of maleic anhydride and methanol or an ethyl hemiester fumarate with hydroxytelechelic polybutadiene (HTPBd) in 94 and 63% yields, respectively. The thermal and thermomechanical properties of the materials obtained from the radical copolymerization of these telechelic bismaleate and bisfumarate polybutadienes with hexane-1,6-dimethacrylate (HDDMA) were investigated and compared to those of a classic polyurethane (PU) resin prepared from HTPBd and hexamethylene diisocyanate. Calorimetry identified only one glass transition temperature of Ϫ75°C assigned to the polybutadienic backbone for all three resins, while a second transition at 48°C attributed to the methacrylate network and was noted by thermomechanical analysis. Both bismaleate and bisfumarate oligomers led to materials having a slightly better thermal stability than that of the PU resin. Thermomechanical analyses indicated that the elastic moduli of the materials achieved from bismaleate and bisfumarate oligomers are higher than that of the PU resin, whatever the temperature.

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“…Chemical transformation of functional groups in polymers has often been used as a method to prepare polymers with specific properties (1). Polymer-analogous reactions with polydienes have been described (2,3) and recently we reported on the chemical modification of polyisoprenes (43). By addition of chlorosulfonyl isocyanate (CSI) to C% bonds, modified polyisoprenes were obtained with N-chlorosulfonyl p-lactam and 0, y-unsaturated N-chlorosulfonyl carbonamide groups.…”

Section: Introductionmentioning

confidence: 99%

Modified polymers from CIS‐1,4‐polyisoprene

Does

Duijl

Sederel

et al. 1980

J. Polym. Sci. B Polym. Lett. Ed.

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Chemical transformation of functional groups in polymers has often been used as a method to prepare polymers with specific properties (1). Polymer-analogous reactions with polydienes have been described (2,3) and recently we reported on the chemical modification of polyisoprenes (43). By addition of chlorosulfonyl isocyanate (CSI) to C% bonds, modified polyisoprenes were obtained with N-chlorosulfonyl p-lactam and 0, y-unsaturated N-chlorosulfonyl carbonamide groups. A second-step modification by reaction with NaOH resulted in the formation of water-soluble polyelectrolytes with anticoagulant activity (5-7).are presented which give information about the chemical structure of the modified polymers.This article deals with the modification of cis-l,4-polyisoprene and results ExperimentalSolutions of cis-l,4-polyisoprene (Cariflex IR 307, cis content more than 96%) in toluene (0.2M) were added to stirred solutions of CSI in the same solvent. Reactions were carried out at 0 or 20°C in a nitrogen atmosphere. After 1 hr the solid cis-l,4-polyisoprene-CSI adducts were isolated and washed with diethylether. Polyelectrolytes were synthesized from these adducts by heating with 2M NaOH for 1 hr. Subsequently they were precipitated by pouring the alkaline solutions in ethanol.More experimental details have been published elsewhere (43). Results and DiscussionThe reaction of cis-l,4-polyisoprene with CSI (Scheme I) leads to the formation of a modified polymer with predominantly structure a, whereas structure b is also formed (43). It was found that with a 50% molar excess of CSI, addition takes place to an extent of 65% at 20°C (Table I , exp. 1). The degree of addition decreases by lowering the temperature, as can be seen from the results of exp. 2. The effect of a prolonged reaction time (6 hr) is supposed to be of minor importance, because an increase of the reaction time (exp. 3) does not lead to an increase of the degree of addition (cf. also the results of exps. 5 and 6). The effect of an increase of the CSI:cis-l,4-polyisoprene molar ratio, on the other hand, is apparent, as can be seen from the results of exps. 3 and 4.

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Chemical Reactions of Model Polyenes and Macromolecular Polyenes

Cited by 6 publications

References 0 publications

Selective and Mild Oxyfunctionalization of Model Polyolefins

Selective and Mild Oxyfunctionalization of Model Polyolefins

Synthesis and thermal properties of bismaleate and bisfumarate telechelic oligomers from hydroxytelechelic polybutadienes

Modified polymers from CIS‐1,4‐polyisoprene

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