<i>cis</i>‐polychloroprene

Aufdermarsh, Carl A.; Pariser, Rudolph

doi:10.1002/pol.1964.100021103

Cited by 13 publications

(7 citation statements)

References 10 publications

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“…The relative intensity of olefinic proton signals at 6.7−5.8 ppm was 95:5, indicating that 95% and 5% of the cis and trans 1,4 structures, respectively, were included in the polymer. A similar tendency was observed in the free-radical polymerization of 1,3-dienes containing bulky substituents on the 2 position of the butadienyl skeleton such as 2-tributylstannyl-1,3-butadiene and 2-triisopropoxysilyl-1,3-butadiene . In either case, the steric hindrance might have controlled the microstructure as pointed out in a literature…”

Section: Resultssupporting

confidence: 76%

Polymerization of 1,3-Dienes with Functional Groups. 1. Free-Radical Polymerization of 2-Triethoxymethyl-1,3-butadiene

1999

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Free-radical polymerization behavior of 2-triethoxymethyl-1,3-butadiene, a potential precursor for poly[2-(ethoxycarbonyl)-1,3-butadiene], whose carboxyl group was masked as an ortho ester, was investigated. When polymerization was carried out in bulk at 60°C for 50 h with using 1 mol % of 2,2′-azobisisobutyronitrile as an initiator, viscous polymer was obtained in 36% yield without forming gel. The resulting polymer containing an ortho ester function was soluble in common organic solvents, including methanol. It can readily be converted to carboxylic ethyl ester by adding small amount of dilute hydrochloric acid. The microstructure of the resulting polymer with ethyl ester group was predominantly a 1,4-E, cis-1,4 structure about the main chain. IntroductionThere have been many reports on the free-radical polymerization of vinyl monomers. 1 Although this polymerization mechanism is applicable to a variety of monomers; however, polymerization of 1,3-butadiene derivatives containing functional groups is still quite limited. This was presumably due to the fact that functional groups directly attached to the polymerizable 1,3-butadienyl skeleton often affect the stability and the polymerizability of the dienes. As a matter of fact, nonfunctional alkyl-, phenyl-, and halogen-substituted butadienes were reported to give high polymers by freeradical polymerization. 2 On the other hand, some functional groups, especially those substituted at the 2 position of the butadienyl frame, decrease the stability of the monomer. To our knowledge, 1,3-butadiene derivatives having a carboxyl group and its ester at the 2 position have not been isolated whereas its isomer, ethyl 2,4-pentadienoate, was synthesized and polymerized under ordinary reaction condition. 3 2-Cyano-1,3-butadiene is reported to dimerize upon heating under polymerization conditions. 4 These reactions are presumably due to the high tendency of the reactants to form Diels-Alder dimers, which is caused by the electronwithdrawing character of the functional group. One of the methods to overcome this difficulty would be the transformation of such functional groups to the other group, which is inert during the polymerization. We chose here an ortho ester function, the trialkoxymethyl group, as a suitable masking group of carboxyl group. This protecting group is known to be stable under basic and neutral conditions whereas it can readily be hydrolyzed to carboxylic ester under mild acidic condition. 5 There have been a few examples where the ortho ester was applied for polymer syntheses. Padis and Hall have reported the free-radical polymerization of methacrylates containing bicyclic ortho ester group. 6 Ishizone et al. used the same protecting group for the anionic polymerization of styrene derivatives containing three hydroxyl groups in each of the monomer units. 7 The bicyclic ortho esters are reported to be more stable than acyclic ortho esters such as the triethoxymethyl group. 5 Because polydienes are potentially to be cross-linked under acidic conditions, the pr...

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Section: Resultssupporting

confidence: 76%

Polymerization of 1,3-Dienes with Functional Groups. 1. Free-Radical Polymerization of 2-Triethoxymethyl-1,3-butadiene

1999

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“…231 It should be noted that there is one report of cis-polychloroprene but it was synthesised via post-polymerisation modification and not thoroughly characterised. 237 1,4-Polybutadiene (PB) is the unsubstituted analogue to PI and the absence of the methyl group yields a softer polymer and lower T g affording a material with a wider operating temperature range than polyisoprene. PB (from 1,3-butadiene) was first synthesised in a stereo-controlled manner using Zeigler-Natta type catalysts (transition metal and lanthanide complexes) and metal based catalysts continue to remain useful today.…”

Section: Main-chain Stereochemistry: Cis/trans Stereoisomerism Polydimentioning

confidence: 99%

Stereochemical enhancement of polymer properties

et al. 2019

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The importance of stereochemistry to the function of molecules is generally well understood. However, to date, control over stereochemistry and its potential to influence properties of the resulting polymers are, as yet, not fully realised. This review focuses on the state-of-the-art with respect to how stereochemistry in polymers has been used to influence and control their physical and mechanical properties as well as begin to control their function. A brief overview of the synthetic methodology by which to access these materials is included, with the main focus directed towards stereochemical control over properties such as mechanical, biodegradation and conductivity. Additionally, the advances being made towards enantioseparation, enantioselective catalyst supports and stereo-directed transitions are discussed. Finally, we also consider the opportunities that the rich stereochemistry of sustainably-sourced monomers could offer in this field. Where possible, parallels and general design principles are drawn together to identify opportunities and limitations that these approaches may present in their effects on materials properties, performance and function.

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“…79 Organotin-containing polymers, 23, have been made from 2-tributyltin-1,3-butadiene. 92 The polymerization is slow, but using a bulk process and azo-bis-isobutyronitrile at 60ºC, a clear colorless liquid product is formed after about 24 days.…”

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confidence: 99%

Organotin Polymers

Carraher

2005

Macromolecules Containing Metal and Metal‐Like Elements

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cis‐polychloroprene

Cited by 13 publications

References 10 publications

Polymerization of 1,3-Dienes with Functional Groups. 1. Free-Radical Polymerization of 2-Triethoxymethyl-1,3-butadiene

Polymerization of 1,3-Dienes with Functional Groups. 1. Free-Radical Polymerization of 2-Triethoxymethyl-1,3-butadiene

Stereochemical enhancement of polymer properties

Organotin Polymers

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