Ethylene‐butadiene copolymers, 1. Preparation with modified vanadium catalysts
Abstract
The copolymerization of ethylene with 1,3‐butadiene to give crystalline, homopolymer‐free, high molecular weight, substantially linear copolymer is described. Butadiene polimerizes almost exclusively in a trans‐1,4 structure, ranging in content from zero to 50 mole‐%. At relatively low content of butadiene monomeric units (≤30 mole‐%) X‐ray crystallinity is of polyethylene type with a slight variation of the structural parameters. At higher levels of butadiene monomeric units, crystallinity of trans‐1,4‐polybutadiene is also observed. The products with little unsaturation (1–5 mole‐%) melt at about 132°C and are able to crosslink with sulfur‐based recipes. A 13 C NMR study shows a block‐type structure, but the copolymer appears homogeneous in composition. The product of the reactivity ratios was evaluated. The catalyst system consists of vanadium tris(acetylacetonate), diethylaluminium chloride, and an acidic compound or its precursor. The nature and the amount of the acidic modifier regulate the polymerization rate as well as the molecular weight, composition, and long branching of the copolymer, so that a strict control of the catalyst system is required. The behaviour of the catalyst is tentatively explained by the polarity of the active carbon‐vanadium bond, which depends on substituents and complexing agents.
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- Authors
- Bruzzone, M., Carbonaro, A., & Corno, C.
- Affiliations
- Snam (Italy) (IT)
- Corresponding author
- Carbonaro, Antonio
- Venue
- Die Makromolekulare Chemie
- Publisher
- Wiley
- Published
- 1978-09
- Volume
- 179
- Issue
- 9
- Pages
- 2173-2185
- ISSN
- 0025-116X (ISSN-L)
- OpenAlex
- W1508096128
- Cited by
- 29
- References
- 12
- Citations by year
- 2025: 1 · 2024: 2 · 2021: 3 · 2020: 1 · 2019: 1 · 2018: 2 · 2017: 3
- FWCI
- 2.35
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Die Makromolekulare Chemie (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- vanadium catalysts, ethylene polymerization, 1,3-butadiene, trans-1,4-polybutadiene, block copolymer structure, crystallinity, reactivity ratios, diethylaluminium chloride, crosslinking, molecular weight control
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