Polymerization with TMA‐protected polar vinyl comonomers. I. Catalyzed by group 4 metal complexes with η5‐type ligands

Marques, Maria Margarida; Correia, Sandra G.; Ascenso, José R.; Ribeiro, Alejandro F. G.; Gomes, Pedro T.; Dias, Alberto R.; Foster, Patrick; Rausch, Marvin D.; Chien, James C. W.

doi:10.1002/(sici)1099-0518(19990715)37:14<2457::aid-pola20>3.3.co;2-p

Cited by 3 publications

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“…Recently, we reported a scheme9a,b to copolymerize remotely substituted polar monomers α,ω‐alkenol and α,ω‐alkenoic acid by first passivating or blocking the polar functional groups with TMA and then copolymerizing the protected polar monomer with ethylene. Non‐rigid, constrained geometry and ansa EMC together with MAO were able to catalyze the process 9. However, 1/MAO was much more efficient by comparison 9.…”

Section: Resultsmentioning

confidence: 99%

“…Non‐rigid, constrained geometry and ansa EMC together with MAO were able to catalyze the process 9. However, 1/MAO was much more efficient by comparison 9. Polar monomers of up to 10 mol% were incorporated in the case of remotely substituted polar monomers.…”

Section: Resultsmentioning

confidence: 99%

“…Typically, TMA in one or two times the monomer concentration was used to block the B group followed by adding the cocatalyst MAO in an Al MAO : Ni ratio of 2000 to activate 1 for the polymerization 17a,b. This approach was also found to be effective for the proximately substituted functional monomers 9c–e. In this case, lower percentages, around 0.5% of comonomer incorporation, were obtained.…”

Section: Resultsmentioning

confidence: 99%

“…In this paper, which is Part VI of our systematic investigation of transition metal catalysis of polar substituted monomers,9 we report first the observation that DEAC is a more efficient cocatalyst than MAO for [bis( N , N ′‐dimesitylimino)acenaphthene]dibromonickel, (MesBIAN)NiBr 2 (Fig 1, 1 )8a, 10, 11 in the polymerization of both E and P except if very high ratios of Al/Ni (around 4000) are used in the case of MAO. With a small amount of DBM, DEAC is also a good cocatalyst for the polymerization of proximately substituted polar monomers instead of using large quantities of MAO and TMA.…”

Section: Introductionmentioning

confidence: 84%

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Polymerization of olefins and polar monomers catalyzed by bis(imino)Ni(II)/dibutylmagnesium/alkylaluminium halide systems

Chien

Fernandes

Correia

et al. 2002

Polymer International

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[Bis(N,N′‐dimesitylimino)acenaphthene]dibromonickel (1) when activated with diethylaluminium chloride (DEAC) is a very active catalyst for ethylene homopolymerization. The activity (AE) of 1/100 DEAC is twenty times greater than that of 1/100 MAO and of the same order of magnitude as 1/2000 MAO. In the case of homopolymerization of propylene the highest activity (AP) was obtained at a ratio of 25/15 for AlDEAC/Ni. Trialkylaluminium compounds were also found to act as cocatalysts for 1. The PE synthesized with four different cocatalysts was found by 13C NMR to have dissimilar branching distributions. 1/DEAC shows no activity for the polymerization of proximately substituted polar monomers. The introduction of dibutylmagnesium, (DBM) activates the 1/DEAC system to copolymerize ethylene and a number of proximately substituted polar monomers. Compared with the 1/MAO/monomer.AlR3 catalyst system the former is three times more active for copolymerization of 5‐hexene‐1‐ol or 10‐undecen‐1‐oic acid with ethylene. The activity of copolymerization is 1/24, 1/5 and 1/2 as active as homopolymerization, respectively, in the case of methyl vinyl ketone, vinyl acetate and ϵ‐caprolactam. In the case of tetrahydrofuran/ethylene, the 1/MAO catalyst produced copolymers using AlR3 pretreated THF whereas the 1/DEAC/DBM catalyst produces homopolyethylene only. No polymerization occurred with an acrylonitrile/ethylene mixture in the presence of 1/DBM/DEAC catalyst. © 2002 Society of Chemical Industry

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 84%

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Polymerization of olefins and polar monomers catalyzed by bis(imino)Ni(II)/dibutylmagnesium/alkylaluminium halide systems

Chien

Fernandes

Correia

et al. 2002

Polymer International

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“…The copolymerization of ethylene with alkylaluminum-protected polar comonomer has been studied extensively for the synthesis of functionalized polyethylene bearing alcohol [7][8][9][10][11][12][13][14][15][16][17][18], ester [8,9,19,20], ether [10,21], and acid functionalities [8,9,11,17]. However, the copolymerization activity of almost all of these catalytic systems dropped significantly compared to the homopolymerization of ethylene.…”

Section: Introductionmentioning

confidence: 94%

Reactivity Comparison of ω-Alkenols and Higher 1-Alkenes in Copolymerization with Propylene Using An Isospecific Zirconocene-MMAO Catalyst

Nyangoye

Chen

et al. 2015

Polymers

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Abstract:Copolymerizations of propylene with ω-alkenols (aluminum-protected 5-hexene-1-ol (AH) and 10-undecene-1-ol (AU)) and non-polar analogues (1-hexene and 1-dodecene) were conducted with a rac-[Me 2 Si(2-Me-4-Ph-Ind) 2 ]ZrCl 2 activated by modified methylaluminoxane. The catalytic system showed high activity for each copolymerization, of which value was independent on the comonomer used and decreased with the increase of the comonomer concentration. The comonomer content of the copolymers obtained also decreased with the increase of the comonomer concentration in each copolymer. The evaluation of the monomer reactivity ratios indicates a preference for the propylene insertion regardless of the last inserted monomer unit in growing polymer chain in all the copolymerizations. The relative reactivity of ω-alkenols was however significantly lower than that of non-polar analogues. These results suggested that the aluminum protection of polar monomer do not affect the activity of copolymerization but significantly decrease the comonomer reactivity.

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Synthesis of Sequence-Specific Polymers with Amide Side Chains via Regio-/Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted cis-Cyclooctene

2016

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Highly regio-/stereoregular (trans-head-to-tail) polymers with amide side chains on every eighth backbone carbon were successfully synthesized by ring-opening metathesis polymerization (ROMP) of 3-substituted cis-cyclooctene (3RCOE) using Grubbs second-generation catalyst (G2). Regioregular linear ethylene–acrylamide copolymers were also prepared via hydrogenation of the obtained poly(3RCOE)s. The thermal properties and solubility of the obtained polymers were strongly influenced by the presence of amide hydrogen in the side chains, the presence of unsaturated bonds in the carbon backbone, and the side chain density. The presence of amide hydrogen in the side chains resulted in the formation of crystalline polymers and the lack of solubility of these polymers in common organic solvents. In contrast, the absence of amide hydrogen in the side chains led to the formation of amorphous polymers exhibiting good solubility in common organic solvents, and decreasing values of T g were observed for amorphous polymers as a result of the saturation of double bonds in the backbone via hydrogenation.

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Polymerization with TMA‐protected polar vinyl comonomers. I. Catalyzed by group 4 metal complexes with η5‐type ligands

Cited by 3 publications

References 0 publications

Polymerization of olefins and polar monomers catalyzed by bis(imino)Ni(II)/dibutylmagnesium/alkylaluminium halide systems

Polymerization of olefins and polar monomers catalyzed by bis(imino)Ni(II)/dibutylmagnesium/alkylaluminium halide systems

Reactivity Comparison of ω-Alkenols and Higher 1-Alkenes in Copolymerization with Propylene Using An Isospecific Zirconocene-MMAO Catalyst

Synthesis of Sequence-Specific Polymers with Amide Side Chains via Regio-/Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted cis-Cyclooctene

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