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Title: Living polymerization of butadiene at both chain ends via a bimetallic nickel initiator. Preparation of hydroxytelechelic poly(butadiene) and symmetric poly(isocyanide-b-butadiene-b-isocyanide) elastomeric triblock copolymers

Abstract

A bifunctional nickel initiator, bis([mu]-trifluoroacetato) ([eta][sup 3]:[eta][sup 3]-2,2[prime]-biallyl)dinickel(II), IV, was synthesized to promote the living polymerization of butadiene to high cis-1,4-content polymer with both chain ends active. Other potential initiators, [1,4-phenylenebis(([eta][sup 3]-1-allyl)nickel trifluoroacetate)][sub n], II, and [1,4-cyclohexanediylbis(([eta][sup 3]-1-allyl)-nickel trifluoroacetate)][sub n], III, were found to be completely ineffective due to intermolecular carboxylate bridges which gave the complexes polymeric structures. The intramolecular bridges in IV and its molecularity were confirmed by X-ray crystallography. IV cocrystallizes in space group P[bar 1] with 0.5 equiv of 2.3-bis((trifluoroacetoxy)methyl)-1,3-butadiene in the unit cell with constants of a = 9.5600(8) [angstrom], b = 9.6554(9) [angstrom], c = 11.7615(10) [angstrom]; [alpha] = 73.711(7)[degree], [beta] = 73.537(7)[degree], [gamma]= 71.938(7)[degree]; V = 967.50(15) [angstrom][sup 3]; and Z = 2. Refinement of the model, which contained a disordered C[sub 6]H[sub 8] unit, led to convergence with R[sub F] = 5.8%, R[sub WF] = 6.9%, and GOF = 2.21 for 276 variables refined against those 2852 data with [vert bar]F[sub o][vert bar]> 3.0[sigma]/([vert bar]F[sub o][vert bar]). The living polybutadiene samples were successfully used to prepare triblock copolymers of the structure poly(1-phenylethyl isocyanide-b-butadiene-b-1-phenylethyl isocyanide). 24 refs., 5 figs., 1 tab.

Authors:
;  [1];  [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Irvine, CA (United States)
Publication Date:
OSTI Identifier:
7019664
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (United States)
Additional Journal Information:
Journal Volume: 116:6; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BUTADIENE; POLYMERIZATION; COPOLYMERS; CALORIMETRY; CHEMICAL ANALYSIS; GEL PERMEATION CHROMATOGRAPHY; NUCLEAR MAGNETIC RESONANCE; TRANSMISSION ELECTRON MICROSCOPY; NICKEL COMPLEXES; CRYSTALLOGRAPHY; SYNTHESIS; X-RAY DIFFRACTION; ORGANOMETALLIC COMPOUNDS; ORGANIC FLUORINE COMPOUNDS; CHEMICAL REACTIONS; CHROMATOGRAPHY; COHERENT SCATTERING; COMPLEXES; DIENES; DIFFRACTION; ELECTRON MICROSCOPY; HYDROCARBONS; MAGNETIC RESONANCE; MICROSCOPY; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; ORGANIC POLYMERS; POLYENES; POLYMERS; RESONANCE; SCATTERING; SEPARATION PROCESSES; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 400100 - Analytical & Separations Chemistry; 400102 - Chemical & Spectral Procedures

Citation Formats

Deming, T J, Novak, B M, and Ziller, J W. Living polymerization of butadiene at both chain ends via a bimetallic nickel initiator. Preparation of hydroxytelechelic poly(butadiene) and symmetric poly(isocyanide-b-butadiene-b-isocyanide) elastomeric triblock copolymers. United States: N. p., 1994. Web. doi:10.1021/ja00085a016.
Deming, T J, Novak, B M, & Ziller, J W. Living polymerization of butadiene at both chain ends via a bimetallic nickel initiator. Preparation of hydroxytelechelic poly(butadiene) and symmetric poly(isocyanide-b-butadiene-b-isocyanide) elastomeric triblock copolymers. United States. doi:10.1021/ja00085a016.
Deming, T J, Novak, B M, and Ziller, J W. Wed . "Living polymerization of butadiene at both chain ends via a bimetallic nickel initiator. Preparation of hydroxytelechelic poly(butadiene) and symmetric poly(isocyanide-b-butadiene-b-isocyanide) elastomeric triblock copolymers". United States. doi:10.1021/ja00085a016.
@article{osti_7019664,
title = {Living polymerization of butadiene at both chain ends via a bimetallic nickel initiator. Preparation of hydroxytelechelic poly(butadiene) and symmetric poly(isocyanide-b-butadiene-b-isocyanide) elastomeric triblock copolymers},
author = {Deming, T J and Novak, B M and Ziller, J W},
abstractNote = {A bifunctional nickel initiator, bis([mu]-trifluoroacetato) ([eta][sup 3]:[eta][sup 3]-2,2[prime]-biallyl)dinickel(II), IV, was synthesized to promote the living polymerization of butadiene to high cis-1,4-content polymer with both chain ends active. Other potential initiators, [1,4-phenylenebis(([eta][sup 3]-1-allyl)nickel trifluoroacetate)][sub n], II, and [1,4-cyclohexanediylbis(([eta][sup 3]-1-allyl)-nickel trifluoroacetate)][sub n], III, were found to be completely ineffective due to intermolecular carboxylate bridges which gave the complexes polymeric structures. The intramolecular bridges in IV and its molecularity were confirmed by X-ray crystallography. IV cocrystallizes in space group P[bar 1] with 0.5 equiv of 2.3-bis((trifluoroacetoxy)methyl)-1,3-butadiene in the unit cell with constants of a = 9.5600(8) [angstrom], b = 9.6554(9) [angstrom], c = 11.7615(10) [angstrom]; [alpha] = 73.711(7)[degree], [beta] = 73.537(7)[degree], [gamma]= 71.938(7)[degree]; V = 967.50(15) [angstrom][sup 3]; and Z = 2. Refinement of the model, which contained a disordered C[sub 6]H[sub 8] unit, led to convergence with R[sub F] = 5.8%, R[sub WF] = 6.9%, and GOF = 2.21 for 276 variables refined against those 2852 data with [vert bar]F[sub o][vert bar]> 3.0[sigma]/([vert bar]F[sub o][vert bar]). The living polybutadiene samples were successfully used to prepare triblock copolymers of the structure poly(1-phenylethyl isocyanide-b-butadiene-b-1-phenylethyl isocyanide). 24 refs., 5 figs., 1 tab.},
doi = {10.1021/ja00085a016},
journal = {Journal of the American Chemical Society; (United States)},
issn = {0002-7863},
number = ,
volume = 116:6,
place = {United States},
year = {1994},
month = {3}
}