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SYNTHESIS OF STYRENE-BUTADIENE STATISTIC COPOLYMERS CONTAINING MAGNESIUM INITIATOR

https://doi.org/10.20914/2310-1202-2015-1-159-163

Abstract

The article discusses the use of organomagnesium initiators in the synthesis of styrene-butadiene random copolymer (SBR) obtained solution polymerization and their influence on the properties of rubber. Selected organic magnesium dialkyl initiator is combined with a modifier, which is a mixed alkoxide of an alkali and alkaline earth metals, which allows to control the micr ostructure of the diene polymer and its molecular weight characteristics. Alcohol derivatives selected high-boiling alcohols tetra (hydroxypropyl) ethylenediamine (lapromol 294) and tetrahydrofurfuryl alcohol (TGFS). Selection of high-boiling alcohols due to the fact that the destruction of alkoxide with aqueous polymer degassing they do not fall into the return solvent and almost fall into the exact water. The metal components of alkoxides are lithium, sodium, potassium, magnesium and calcium. The resulting solutions are stable when stored modifier t hroughout the year even at -40 °C. The scheme of obtaining the new catalyst systems based organomagnesium and alcoxide of alkali and alkaline earth metals, which yields as functionalized SBR with a statistical and a distribution block of butadiene and styrene was developed. The process of copolymerization with styrene to butadiene organomagnesium initiators as using an organolithium compound (n-butyllithium) was carried out, and without it. Found that the addition of n-butyllithium in the reaction mixture leads to a sharp increase in the rate of reaction. The results of studies of the effect of composition of the initiator system on the structure of diene polymers. It was revealed that a mixed initiator system affords a high conversion of monomers (to 90 % in 1 hour) 1,2-polybutadiene content increased to 60 %. The process of polymerization of only a mixture of organomagnesium initiators and alcoxide of alkali and alkaline earth metals are not actively proceeds, conversion of the monomers reaches to 90 % in 4 hours, the microstructure of the polybutadiene corresponds low vinyl polymers (28 % 1,2 units) in the presence invention. The providing the necessary initiation systems for preparing random polymers. The results of research showed that the magnesium alkyls in combination with alkali metal alcoholates as pathogens copolymerization of dienes and vinylaromatic compounds may be used.

About the Authors

A. V. Firsova
Voronezh state university of engineering technology
Russian Federation
Graduate, Department of chemistry and chemical technology organic compounds and polymer processing


O. V. Karmanova
Voronezh state university of engineering technology
Russian Federation
Professor, Department of chemistry and chemical technology organic compounds and polymer processing


V. S. Glukhovskoi
Voronezh branch NIISK
Russian Federation
Professor


V. V. Sitnikova
Voronezh branch NIISK
Russian Federation
Senior researcher


References

1. Tkachev A.V, Sedykh V.A. Recent techniques of anionic polymerization of monomers. Vestnik VGUIT. [Bulletin of VSUET], 2013, no. 3, pp. 143-156. (In Russ.).

2. Firsova A.V, Karmanova O.V., Glukhovskoi V.S., Zemskii D.N. Study of the effect of mixed alkoxides oxypropylated aromatic secondary amines on the structure of diene polymers. Vestnik VGUIT. [Bulletin of VSUET], 2014, no. 4, pp. 147 150. (In Russ.).

3. Glukhovskoi V.S., Litvin Yu.A., Sitnikova V.V.et al. Modifiers of n-butyllitthium for synthesis of polybutadiene and styrene-butadiene rubbers. Kauchuk i rezina. [Rubber & Rubber], 2013, no. 4, pp. 10. (In Russ.).

4. Halasa A.F., Austin L.E., Weakland S.A. Catalyst system for the synthesis of rubbery polymers. Patent US, no 5629256 A, 1997.


Review

For citations:


Firsova A.V., Karmanova O.V., Glukhovskoi V.S., Sitnikova V.V. SYNTHESIS OF STYRENE-BUTADIENE STATISTIC COPOLYMERS CONTAINING MAGNESIUM INITIATOR. Proceedings of the Voronezh State University of Engineering Technologies. 2015;(1):159-163. (In Russ.) https://doi.org/10.20914/2310-1202-2015-1-159-163

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ISSN 2226-910X (Print)
ISSN 2310-1202 (Online)