Reactivity Ratios of Comonomers from a Single MALDI-ToF-MS Measurement at One Feed Composition

被引：19

作者：

Huijser, Saskia ^{[1
]}

Mooiweer, Gerben D. ^{[2
]}

van der Hofstad, Remco ^{[2
]}

Staal, Bastiaan B. P. ^{[3
]}

Feenstra, Jon ^{[1
]}

van Herk, Alex M. ^{[1
]}

Koning, Cor E. ^{[1
]}

Duchateau, Rob ^{[1
]}

机构：

[1] Eindhoven Univ Technol, Dept Chem Engn & Chem, Lab Polymer Chem, NL-5600 MB Eindhoven, Netherlands

[2] Eindhoven Univ Technol, Dept Math & Comp Sci, NL-5600 MB Eindhoven, Netherlands

[3] BASF AG, D-67056 Ludwigshafen, Germany

来源：

MACROMOLECULES | 2012年 / 45卷 / 11期

关键词：

FREE-RADICAL COPOLYMERIZATION; RING-OPENING POLYMERIZATION; N-BUTYL METHACRYLATE; METHYL-METHACRYLATE; EPSILON-CAPROLACTONE; MULTICOMPONENT POLYMERIZATION; NMR-SPECTROSCOPY; GRAPHIC METHOD; L-LACTIDE; STYRENE;

D O I：

10.1021/ma300400d

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The reactivity ratios in a copolymerization are needed to predict the microstructure (random, gradient, block or alternating) of the produced copolymer. This microstructure reflects on the physical properties of the polymeric material. Conventional ways to determine these reactivity ratios demand in most cases tedious laboratory work and several experiments at different monomer feed compositions. Here, a novel method is described to derive these ratios from a single MALDI-ToF-MS spectrum obtained at one feed composition by employing either a Monte Carlo approach to numerically simulate a first order Markov chain or the analytical form of the first order Markov chain. A single MALDI-ToF-MS spectrum proved to give very good estimates of the reactivity ratios of comonomers from copolymer's synthesized by free radical polymerization, ring-opening polymerization of lactones and lactides, or ring-opening copolymerization of anhydrides plus epoxides.

引用

页码：4500 / 4510

页数：11

共 59 条

[1] SYNTHESIS AND CHARACTERIZATION OF POLY(1,5-DIOXEPAN-2-ONE-CO-L-LACTIC ACID) AND POLY(1,5-DIOXEPAN-2-ONE CO-D,L-LACTIC ACID) [J].

ALBERTSSON, AC ;

LOFGREN, A .

JOURNAL OF MACROMOLECULAR SCIENCE-PURE AND APPLIED CHEMISTRY, 1995, A32 (01) :41-59

[2] SYNTHESIS OF COPOLYMERS OF 1,3-DIOXAN-2-ONE AND OXEPAN-2-ONE USING COORDINATION CATALYSTS [J].

ALBERTSSON, AC ;

EKLUND, M .

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 1994, 32 (02) :265-279

[3] DEGRADABLE HIGH-MOLECULAR-WEIGHT RANDOM COPOLYMERS, BASED ON EPSILON-CAPROLACTONE AND 1,5-DIOXEPAN-2-ONE, WITH NON-CRYSTALLIZABLE UNITS INSERTED IN THE CRYSTALLINE-STRUCTURE [J].

ALBERTSSON, AC ;

GRUVEGARD, M .

POLYMER, 1995, 36 (05) :1009-1016

[4]

[Anonymous], 1989, POLYM HDB

[5] DIFFUSION-CONTROLLED TERMINATION IN FREE RADICAL COPOLYMERIZATION [J].

ATHERTON, JN ;

NORTH, AM .

TRANSACTIONS OF THE FARADAY SOCIETY, 1962, 58 (478) :2049-&

[6] A METHOD FOR DETERMINING REACTIVITY RATIOS WHEN COPOLYMERIZATIONS ARE INFLUENCED BY THE PENULTIMATE GROUP EFFECTS OF BOTH MONOMERS [J].

BARSON, CA ;

FENN, DR .

EUROPEAN POLYMER JOURNAL, 1989, 25 (7-8) :719-720

[7]

BERO M, 1993, MAKROMOL CHEM, V194, P907

[8] REACTIVITIES OF ACRYLATES AND METHACRYLATES [J].

BEVINGTON, JC ;

HARRIS, DO .

JOURNAL OF POLYMER SCIENCE PART B-POLYMER LETTERS, 1967, 5 (9PB) :799-+

[9] REACTIVITY RATIOS AND MICROSTRUCTURE DETERMINATION OF VINYL-ACETATE ALKYL ACRYLATE COPOLYMERS BY NMR-SPECTROSCOPY [J].

BRAR, AS ;

CHARAN, S .

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 1995, 33 (01) :109-116

[10] SEQUENCE DETERMINATION IN METHYL-METHACRYLATE NORMAL-BUTYL METHACRYLATE COPOLYMERS BY C-13 NMR-SPECTROSCOPY [J].

BRAR, AS ;

KAPUR, GS .

POLYMER JOURNAL, 1988, 20 (09) :811-817

← 1 2 3 4 5 6 →