Classification of polar additives with respect to their influence on the microstructure in anionic polymerization of butadiene with butyllithium by transition energy measurements

Hesterwerth, Dieter; Beckelmann, Dirk; Bandermann, Friedhelm

doi:10.1002/(sici)1097-4628(19990822)73:8<1521::aid-app21>3.3.co;2-z

Cited by 4 publications

(3 citation statements)

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“…Here, the mass fraction of 1,4-structures increases. The results obtained are in good agreement with published data [14]. It is interesting to note that the dependence of the microstructure of the copolymer on the molar ratio of monomer to NBL is linear in nature.…”

Section: The Influence Of the Concentration Of An Initiating System Csupporting

confidence: 91%

The Influence of the Concentration of an ‘n-butyllithium–amine-containing Modifier’ Initiating System on the Copolymerisation of 1,3-butadiene and Styrene

Vagizov

Khusainova

Akhmetov

et al. 2017

International Polymer Science and Technology

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The influence of the concentration of an initiating system consisting of n-butyllithium and an amine-containing modifier on the copolymerisation of 1,3-butadiene and styrene in a hexane solvent was studied. The molecular characteristics and the microstructure of specimens of the obtained solution-polymerised styrene butadiene rubber (s-SBR) were determined by gel permeation chromatography on a Breeze liquid chromatograph (Waters) and by IR spectroscopy on a Spectrum GX 100 spectrometer (PerkinElmer) in accordance with ISO 21561/2. It was shown that a reduction in the amount of the initiating system is accompanied with a reduction in the copolymerisation rate and in the monomer conversion, and also with an increase in the average molecular weights of the copolymer. It was established that a reduction in the initiating system concentration in the reaction medium leads to a reduction in the content of 1,2-units in the rubber. A comparative analysis of data for rubber compounds based on the synthesised s-SBR and data for rubber compounds based on standard rubber indicates that their mechanical properties are at the same level. However, the tg δ at 60°C (determined on an RPA 2000 instrument) for rubber compounds based on a trial specimen has a lower value, which will make it possible to produce tyre rubbers providing a lower tyre rolling resistance.

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Section: The Influence Of the Concentration Of An Initiating System Csupporting

confidence: 91%

The Influence of the Concentration of an ‘n-butyllithium–amine-containing Modifier’ Initiating System on the Copolymerisation of 1,3-butadiene and Styrene

Vagizov

Khusainova

Akhmetov

et al. 2017

International Polymer Science and Technology

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“…In the case of the use of AMD, which contains the functional groups -NH, -OBa, and -ONa in its structure, the synthesised copolymer is characterised by a high content of 1,2-units in the butadiene part of up to 66.3%, but with increase in temperature to 70°C there is a reduction in 'vinyl' structures in the rubber to 42.8%. The results obtained are in good agreement with literature data [10].…”

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confidence: 92%

The Influence of Temperature on the Copolymerisation of 1,3-butadiene and Styrene using a Modified Lithium-containing Initiating System

Vagizov

Khusainova

Akhmetov

et al. 2017

International Polymer Science and Technology

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The relationships governing 1,3-butadiene copolymerisation in a hexane solvent in the temperature range 30-70°C were studied. The copolymerisation process was initiated by n-butyllithium. A mixture of alkali metal and alkaline earth metal amine-containing alcoholates (AMD) was used as the modifier. The microstructure and macrostructure of the obtained p-SBR specimens were investigated. In p-SBR specimens obtained in the presence of AMD in the investigated temperature range, the distribution of styrene units in block was not found. The introduction of AMD leads to the disappearance of the induction period and to an increase in the copolymerisation rate, i.e. the reactivity of the system increases, and a reduction in temperature accelerates this process. It was shown that, with increase in the process temperature, there is a reduction in the average molecular weights of the copolymer. In the presence of AMD, lowering of the copolymerisation temperature leads to 'enrichment' of the butadiene part in 1,2-units (up to 66.3%).

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“…For instance, polar modifiers and retarders have been investigated for the polybutadiene system [ 35 ] and for polyisoprene. [ 36–41 ] In brief, previous studies revealed an increase of the 1,2 addition instead of the 1,4 diene addition mode with increasing content of polar modifier. [ 42 ] The microstructures and the content of possible 1,2‐, 3,4‐ and 1,4‐ polymyrcene units ( Figure ) were determined by 1 H NMR spectroscopy.…”

Section: Methodsmentioning

confidence: 99%

Temperature Variation Enables the Design of Biobased Block Copolymers via One‐Step Anionic Copolymerization

Bareuther

Plank

Kuttich

et al. 2020

Macromol. Rapid Commun.

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A one‐pot approach for the preparation of diblock copolymers consisting of polystyrene and polymyrcene blocks is described via a temperature‐induced block copolymer (BCP) formation strategy. A monomer mixture of styrene and myrcene is employed. The unreactive nature of myrcene in a polar solvent (tetrahydrofuran) at −78 °C enables the sole formation of active polystyrene macroinitiators, while an increase of the temperature (−38 °C to room temperature) leads to poly(styrene‐block‐myrcene) formation due to polymerization of myrcene. Well‐defined BCPs featuring molar masses in the range of 44–117.2 kg mol−1 with dispersities, Ð, of 1.09–1.21, and polymyrcene volume fractions of 30–64% are accessible. Matrix assisted laser desorption ionization‐time of flight mass spectrometry measurements reveal the temperature‐controlled polymyrcene block formation, while both transmission electron microscopy and small‐angle X‐ray scattering measurements prove the presence of clearly microphase‐separated, long range‐ordered domains in the block copolymers. The temperature‐controlled one‐pot anionic block copolymerization approach may be general for other terpene‐diene monomers.

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Classification of polar additives with respect to their influence on the microstructure in anionic polymerization of butadiene with butyllithium by transition energy measurements

Cited by 4 publications

References 0 publications

The Influence of the Concentration of an ‘n-butyllithium–amine-containing Modifier’ Initiating System on the Copolymerisation of 1,3-butadiene and Styrene

The Influence of the Concentration of an ‘n-butyllithium–amine-containing Modifier’ Initiating System on the Copolymerisation of 1,3-butadiene and Styrene

The Influence of Temperature on the Copolymerisation of 1,3-butadiene and Styrene using a Modified Lithium-containing Initiating System

Temperature Variation Enables the Design of Biobased Block Copolymers via One‐Step Anionic Copolymerization

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