Aminoendgruppenhaltige polymere durch anionische polymerisation von vinylverbindungen mit 3-Dimethylaminopropyllithium als initiator

Abstract

Herrn Prof. Dr. I I. ,Mark rnit herzlichen Gluckwunschen zum 80. Geburtstag gcwidmct IEingangsdatum: 22. Oktober 1974) ZUSAM M ENFASSU NG : cl-Methylstyrol (inTHF) sowieStyrol bzw. Butadien (in Benzol) wurden rnit 3-Dimethylaminopropyllithium ( I ) als Initiator homopolymerisicrt : dabci uurden aufgrund dcs Einflusses der tcrtilren Aminogruppe bei dcr Polymerisation in apolarem Medium, verglichen rnit der lnitiierung durch Butyllithium, Vcrlnderungcn dcr Mikrostruktur dcr Polymeren bcobachtet. Dic Molekulargewichte der Polymeren sind hoher. als sich nach dcm cingesetzten Monomerilnitiator-Verhaltnis berechnctc.Der Aminoendgruppengehalt der Polymeren wurdc elcmcntaranalytisch sowie NMKspektroskopisch quantitativ bestimmt; dic tcrtilren Aminoendgruppcn konnten rnit Methyljodid quantitativ zum quartlren Salz umgesetzt werdcn. mit Hromidcn dagcgcn nur teilweise. SUMMARY:z-Mcthylstyrene (in THF), styrene and butadicne (in benzene) were homopolymcrizcd with 3-dimethylaminopropyl lithium (1) as initiator; in the apolar medium. as a conscquencc of the tertiary amino group of thc initiator. thc microstructure of the polymer was different to that obtained with butyllithium. The molecular weights of the polymers were higher than calculated from the initial monomer,'initiator ratio.By mcans of clemcntal analysis as well as by NMK-spectroscopy, the end group content of thc polymcrs was quantitatively deterniincd: the tertiary amino end groups could be reacted quantitativcly with methyl iodide to the quaternary snlt. but only partially nith bromides. * I C. 11. Eisenbach, Teil dcr Dissertation, UniversitSt Mainz, 1974.

Über makrozwitterionen, 10. Versuche zur darstellung von makrozwitterionen aus α,ω‐bifunktionellem poly(α‐methylstyrol)

“…Als Initiator wurde DMAP-Li") verwendet, das hinsichtlich der Reaktivitat etwa rnit Butyllithium (1) vergleichbar ist 16) und die im anionischen System stabile tert. Aminogruppe tragt.…”

End-Functionalized Block Copolymers of Styrene and Isoprene: Synthesis and Association Behavior in Dilute Solution

“…They were assigned to methyl protons attached to the positively charged nitrogen of the zwitterion group and methylene protons of the carbon attached to sulfur, respectively. [42][43][44] Unfortunately, the low intensity of the peaks and the noisy base line do not permit quantitative interpretation. Additionally, no characteristic peaks of the sultone could be detected.…”

Association of Amino-Terminated Polystyrenes. 2. Dynamic Light Scattering of Associating Linear Chains

“…The solid lines represent the theoretical predictions due to Akcasu and Benmouna 36 for polymers in good solvents (k D°) 8X 3 + 6X 2 ) and the semiempirical approach by Cotts and Selser 35 (k D°) 4.8X 3 -2). Recently, Douglas 40,41 et al obtained k D°) 4X 3 -7/4 based on an approximation that treats the polymer as a droplet with a fluidity similar to that of the surrounding solvent. The scatter of the data, resulting all from linear polystyrenes or poly(R-methylstyrenes) in the good solvent toluene, brings into question the suitability of the parameter X as a proper variable to describe the k D parameter.…”

“…26,[35][36][37][38][39][40][41] Usually, these calculations express the k D parameter in terms of the parameter X, which is defined as with Figure 4 shows the same data as in Figure 2 but now plotted against the parameter X. The solid lines represent the theoretical predictions due to Akcasu and Benmouna 36 for polymers in good solvents (k D°) 8X 3 + 6X 2 ) and the semiempirical approach by Cotts and Selser 35 (k D°) 4.8X 3 -2). Recently, Douglas 40,41 et al obtained k D°) 4X 3 -7/4 based on an approximation that treats the polymer as a droplet with a fluidity similar to that of the surrounding solvent.…”

“…In these functionalized polymers, the end groups are tertiary amino groups. From the work of Eisenbach et al − and Broze et al., it is well known how to introduce tertiary amino end groups by anionic polymerization. This can be done either by a termination or by an initiation reaction.…”