Synthesis of Novel-dl-α-Tocopherol-Based and Sterically-Hindered-Phenol-Based Monomers and Their Utilization in Copolymerizations over Metallocene/MAO Catalyst Systems: A Strategy To Remove Concerns about Additive Compatibility and Migration

Markku Auer, Ronan Nicolas, Ari Rosling, Carl-Eric Wilen (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

15 Citations (Scopus)

Abstract

In this paper we present an initial study on various synthetic routes to novel polymerizable dl-α-tocopherol derivatives and to a styrenic sterically hindered phenol which was stimulated by our desire to conduct copolymerization with these monomers with α-olefins over different metallocene/methylalumoxane (MAO) catalyst systems. The syntheses of 6-hydroxyl-2,5,7,8-tetramethyl-2-(but-3-enyl)chroman (1) and 5,7,8-trimethyl-3-(hex-5-enyl)benzofuran-6-ol (2) were achieved by cyclocondensation of trimethylhydroquinone (TMHQ) with 3-methylhept-1,6-dien-3-ol and 2,7-octadienol, respectively. However, the latter tocopherol compound (2) could only be obtained in low yields, and all our attempts to isolate the product from its ring-opened isomers failed. This can be attributed to the fact that the reaction between TMHQ and 2,7-octadienol gave rise to a highly complex reaction mixture. Compound 3, 6-hydroxyl-2,2,8,9-tetramethyl-6-allylchroman, was prepared from the corresponding allylchromanoxy ether via Claisen rearrangement. In addition facile synthetic pathways to 4-methylene(3,5-di-tert-butyl-4-phenoxy)styrene (4) and its trimethylsilylated derivative 5, i.e., 4-methylene(3,5-di-tert-butyl-4-trimethylsiloxyphenyl)styrene, were successfully developed. The chromanol 1 was copolymerized with ethylene over a rac-[dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichloride/MAO catalyst system, and monomers 4 and 5 were copolymerized with styrene over an (η5-indenyl)trichlorotitanium (IndTiCl3)/MAO catalyst system. The copolymers contained from 2.3 to 6.8 wt % functional units and exhibit enhanced thermooxidative stabilities in comparison to the corresponding homopolymers as determined by TGA and DSC analysis.
Original languageEnglish
Pages (from-to)8346-8352
Number of pages7
JournalMacromolecules
Volume36
Issue number22
DOIs
Publication statusPublished - 2003
MoE publication typeA1 Journal article-refereed

Fingerprint

Styrene
Tocopherols
Phenol
Copolymerization
Phenols
Monomers
Hydroxyl Radical
Catalysts
Chromans
Derivatives
Alkenes
Homopolymerization
Zirconium
Isomers
Ether
Olefins
Ethers
Ethylene
Copolymers
metallocene

Keywords

  • tocopherol
  • vitamin E
  • antioxidants
  • polyolefins
  • additives
  • food additives
  • food packaging

Cite this

@article{96be8a8b9de041a1b1f0f7280aa630e0,
title = "Synthesis of Novel-dl-α-Tocopherol-Based and Sterically-Hindered-Phenol-Based Monomers and Their Utilization in Copolymerizations over Metallocene/MAO Catalyst Systems: A Strategy To Remove Concerns about Additive Compatibility and Migration",
abstract = "In this paper we present an initial study on various synthetic routes to novel polymerizable dl-α-tocopherol derivatives and to a styrenic sterically hindered phenol which was stimulated by our desire to conduct copolymerization with these monomers with α-olefins over different metallocene/methylalumoxane (MAO) catalyst systems. The syntheses of 6-hydroxyl-2,5,7,8-tetramethyl-2-(but-3-enyl)chroman (1) and 5,7,8-trimethyl-3-(hex-5-enyl)benzofuran-6-ol (2) were achieved by cyclocondensation of trimethylhydroquinone (TMHQ) with 3-methylhept-1,6-dien-3-ol and 2,7-octadienol, respectively. However, the latter tocopherol compound (2) could only be obtained in low yields, and all our attempts to isolate the product from its ring-opened isomers failed. This can be attributed to the fact that the reaction between TMHQ and 2,7-octadienol gave rise to a highly complex reaction mixture. Compound 3, 6-hydroxyl-2,2,8,9-tetramethyl-6-allylchroman, was prepared from the corresponding allylchromanoxy ether via Claisen rearrangement. In addition facile synthetic pathways to 4-methylene(3,5-di-tert-butyl-4-phenoxy)styrene (4) and its trimethylsilylated derivative 5, i.e., 4-methylene(3,5-di-tert-butyl-4-trimethylsiloxyphenyl)styrene, were successfully developed. The chromanol 1 was copolymerized with ethylene over a rac-[dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichloride/MAO catalyst system, and monomers 4 and 5 were copolymerized with styrene over an (η5-indenyl)trichlorotitanium (IndTiCl3)/MAO catalyst system. The copolymers contained from 2.3 to 6.8 wt {\%} functional units and exhibit enhanced thermooxidative stabilities in comparison to the corresponding homopolymers as determined by TGA and DSC analysis.",
keywords = "tocopherol, vitamin E, antioxidants, polyolefins, additives, food additives, food packaging",
author = "Markku Auer and Ronan Nicolas and Ari Rosling and Carl-Eric Wilen",
year = "2003",
doi = "10.1021/ma0205008",
language = "English",
volume = "36",
pages = "8346--8352",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society ACS",
number = "22",

}

Synthesis of Novel-dl-α-Tocopherol-Based and Sterically-Hindered-Phenol-Based Monomers and Their Utilization in Copolymerizations over Metallocene/MAO Catalyst Systems : A Strategy To Remove Concerns about Additive Compatibility and Migration. / Auer, Markku; Nicolas, Ronan; Rosling, Ari; Wilen, Carl-Eric (Corresponding Author).

In: Macromolecules, Vol. 36, No. 22, 2003, p. 8346-8352.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Synthesis of Novel-dl-α-Tocopherol-Based and Sterically-Hindered-Phenol-Based Monomers and Their Utilization in Copolymerizations over Metallocene/MAO Catalyst Systems

T2 - A Strategy To Remove Concerns about Additive Compatibility and Migration

AU - Auer, Markku

AU - Nicolas, Ronan

AU - Rosling, Ari

AU - Wilen, Carl-Eric

PY - 2003

Y1 - 2003

N2 - In this paper we present an initial study on various synthetic routes to novel polymerizable dl-α-tocopherol derivatives and to a styrenic sterically hindered phenol which was stimulated by our desire to conduct copolymerization with these monomers with α-olefins over different metallocene/methylalumoxane (MAO) catalyst systems. The syntheses of 6-hydroxyl-2,5,7,8-tetramethyl-2-(but-3-enyl)chroman (1) and 5,7,8-trimethyl-3-(hex-5-enyl)benzofuran-6-ol (2) were achieved by cyclocondensation of trimethylhydroquinone (TMHQ) with 3-methylhept-1,6-dien-3-ol and 2,7-octadienol, respectively. However, the latter tocopherol compound (2) could only be obtained in low yields, and all our attempts to isolate the product from its ring-opened isomers failed. This can be attributed to the fact that the reaction between TMHQ and 2,7-octadienol gave rise to a highly complex reaction mixture. Compound 3, 6-hydroxyl-2,2,8,9-tetramethyl-6-allylchroman, was prepared from the corresponding allylchromanoxy ether via Claisen rearrangement. In addition facile synthetic pathways to 4-methylene(3,5-di-tert-butyl-4-phenoxy)styrene (4) and its trimethylsilylated derivative 5, i.e., 4-methylene(3,5-di-tert-butyl-4-trimethylsiloxyphenyl)styrene, were successfully developed. The chromanol 1 was copolymerized with ethylene over a rac-[dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichloride/MAO catalyst system, and monomers 4 and 5 were copolymerized with styrene over an (η5-indenyl)trichlorotitanium (IndTiCl3)/MAO catalyst system. The copolymers contained from 2.3 to 6.8 wt % functional units and exhibit enhanced thermooxidative stabilities in comparison to the corresponding homopolymers as determined by TGA and DSC analysis.

AB - In this paper we present an initial study on various synthetic routes to novel polymerizable dl-α-tocopherol derivatives and to a styrenic sterically hindered phenol which was stimulated by our desire to conduct copolymerization with these monomers with α-olefins over different metallocene/methylalumoxane (MAO) catalyst systems. The syntheses of 6-hydroxyl-2,5,7,8-tetramethyl-2-(but-3-enyl)chroman (1) and 5,7,8-trimethyl-3-(hex-5-enyl)benzofuran-6-ol (2) were achieved by cyclocondensation of trimethylhydroquinone (TMHQ) with 3-methylhept-1,6-dien-3-ol and 2,7-octadienol, respectively. However, the latter tocopherol compound (2) could only be obtained in low yields, and all our attempts to isolate the product from its ring-opened isomers failed. This can be attributed to the fact that the reaction between TMHQ and 2,7-octadienol gave rise to a highly complex reaction mixture. Compound 3, 6-hydroxyl-2,2,8,9-tetramethyl-6-allylchroman, was prepared from the corresponding allylchromanoxy ether via Claisen rearrangement. In addition facile synthetic pathways to 4-methylene(3,5-di-tert-butyl-4-phenoxy)styrene (4) and its trimethylsilylated derivative 5, i.e., 4-methylene(3,5-di-tert-butyl-4-trimethylsiloxyphenyl)styrene, were successfully developed. The chromanol 1 was copolymerized with ethylene over a rac-[dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichloride/MAO catalyst system, and monomers 4 and 5 were copolymerized with styrene over an (η5-indenyl)trichlorotitanium (IndTiCl3)/MAO catalyst system. The copolymers contained from 2.3 to 6.8 wt % functional units and exhibit enhanced thermooxidative stabilities in comparison to the corresponding homopolymers as determined by TGA and DSC analysis.

KW - tocopherol

KW - vitamin E

KW - antioxidants

KW - polyolefins

KW - additives

KW - food additives

KW - food packaging

U2 - 10.1021/ma0205008

DO - 10.1021/ma0205008

M3 - Article

VL - 36

SP - 8346

EP - 8352

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 22

ER -