Search results for "Chain transfer"

Carbanionic Polymerization: Kinetics and Thermodynamics

1989

For a kinetic analysis, the process of anionic polymerization has to be divided into at least three main reactions common to all types of polymerization (equations 1–3). I* denotes initiator, M monomer, Pi* and Pi′ an active or inactive polymer chain of degree of polymerization i, respectively, and X a terminating agent.

Solid-state polymerization of oxetanes. II. Investigation of the growth of the polymer phase as related to the mechanism of polymerization

1973

The radiation-induced solid-state polymerization of 3,3-bischloromethyloxetane (BCMO) was investigated by direct observation of the development of the morphology of the growing polymer phase in single crystals of the monomer. Electron microscopy shows that the polymerization gives rise to amorphous polymer in the first step. The polymer forms irregular platelets which aggregate into larger units without reflecting the crystalline order of the monomer. Subsequent to polymerization, the amorphous polymer crystallizes to the β-modification of poly-BCMO. If the partially polymerized crystals are extracted by solvents of the monomer, crystallization of the polymer is enhanced, and morphological …

What Limits the Molecular Weight and Controlled Synthesis of Poly(3-alkyltellurophene)s?

2016

Polytellurophenes are an emerging class of conjugated polymers; however, their controlled polymerization leading to high molecular weight materials has been a major challenge. Here we present a systematic investigation of the synthesis of poly(3-alkyltellurophene)s using the catalyst transfer polycondensation methodology. Learning that previous syntheses were limited by both polymerization reaction kinetics and polymer solubility, we design new tellurophene monomers to overcome these limitations. Controlled polymerization behavior up to Mn = 25 kDa, chain extension, block copolymerization, external initiation, and well-defined end groups are demonstrated for poly(3-alkyltellurophene)s with …

Branched and Functionalized Polybutadienes by a Facile Two-Step Synthesis

2008

Anionic polymerization was used to prepare silane-endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9 000 to 34000 g .mol- 1 . These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB 2 + A type "pseudocopolymerization" method. All branched polymers were analyzed by SEC, SEC-MALLS, SEC-viscosimetry…

Kinetic Analysis of “Living” Polymerization Processes Exhibiting Slow Equilibria. 5. Effect of Monomer Transfer in Cationic Polymerization and Simila…

1996

This work deals with the kinetics of polymerization processes with chain transfer to monomer and reversible formation of dormant species. Such a mechanism is typical for cationic polymerization in the presence of Lewis acids as co-initiators. The expressions of number- and weight-average degrees of polymerization and polydispersity index are derived rigorously for a mechanism with free ions as the active species, but it is also applied to other mechanisms, e.g., ion pairs as active species. Plots of polydispersity index versus monomer conversion can be easily computed on a PC computer even though the expressions for the weight-average degree of polymerization and the concentration of residu…

The calculation of the number-average degree of polymerization starting from intrinsic viscosity and overall rate

1962

The relation between the intrinsic viscosity [η] and the number-average degree of polymerization Pn is a function of the molecular weight distribution of the polymer. In a polymer in which the termination of polymer radicals occurs partly by combination of two growing chains, this molecular weight distribution depends on number and extent of additional reactions such as chain transfer; i.e., it is variable. Therefore Pn of such polymers cannot be obtained from intrinsic viscosity measurements by means of an equation of the type [η] = KPna. A new method is proposed which allows the evaluation of Pn in these cases, without necessity of osmotic (or related) measurements or fractionation. The v…

Some kinetic effects in the polymerization of 1,3,5-trioxane

1960

Primary radical termination and chain transfer in vinyl polymerization

1974

Cyclodextrins in polymer synthesis: free radical polymerization of cyclodextrin host-guest complexes of methyl methacrylate or styrene from homogenou…

2000

The polymerization of methylated β-cyclodextrin (m-β-CD) 1 : 1 host-guest compounds of methyl methacrylate (MMA) (1) or styrene (2) is described. The polymerization of complexes 1 a and 2 a was carried out in water with potassium peroxodisulfate (K2S2O8)/sodium hydrogensulfite (NaHSO3) as radical redox initiator at 60°C. Unthreading of m-β-CD during the polymerization led to water-insoluble poly(methyl methacrylate) (PMMA) (3) and polystyrene (4). By comparison, analogously prepared polymers from uncomplexed monomers 1 and 2 in ethanol as organic solvent with 2,2′-azoisobutyronitrile (AIBN) as radical initiator showed significantly lower molecular weights and were obtained in lower yields i…

Macromonomers on the basis of 2-phenyl-2-oxazoline

1988

By initiation of the ring-opening polymerization of 2-phenyl-2-oxazoline (1) with p-iodomethylstyrene a macromonomer with a styrene end-group (2) is obtained. The degree of polymerization was varied between 10 and 16. The radical copolymerization of 2 with styrene is described. 1 forms with methyl triflate a very stable oxazolinium salt which is a good initiator for the bulk polymerization of 1 at temperatures of 50–70°C. It was conclusively proved that under these conditions the polymerization proceeds by a living mechanism. By termination with N, N-dimethylaminopropylmeth-acrylamide a macromonomer (5) was obtained. 5 can be radically homopolymerized. This comb-like polymer 6 has the typic…