Oligomers Relatederms: Oligomersarelow molecularweightpolymerscomprisinga smallnumber of Carbon Chitosan repeatunits whosephysicabropertiesaresignificantlydependenton the Copolymer Dimer, Ester length of the chain. Monomer, Polymer Silica Polymerization From: Referencélodule in MaterialsSciencaand MaterialsEngineering 2016 Oligomerization Viewfull index Multi-Step/Step-Wise Polymerization of Well-Defined Oligomers G.Haerner, R. Padmanabhan, in Reference Module in Materials Science and Materials Engineering, 2016 Abstract (Oligomers are low molecular weight polymers comprising a small number of repeat units whose physical properties are ‘Significantly dependent on the length of the chain. Oligomers are essentially intermediates of the polymerization reaction that find wide, direct applications in material soience. Oligomers can be grouped into addition oligomers and ‘condensation oligomers, based on the structure of the repeating unit. Step growth polymerization occurs one step at a time through a series of simple organic reactions, such as carbonyl addition-elimination reactions used for the Preparation of polyesters and polyamides, or addition to multiple bonds, used for the preparation of polyurethanes and polyakylene sulfides. Depolymerization of high polymers and chemical modification of oligomeric species are additional routes for the synthesis of oligomers. This article describes the basics of oligomer synthesis and reoent developments in the synthesis of oligomers and their potential applications, SYNTHETIC POLYMERS | 'Thin-Layer (Planar) Chromatographyx LS. Litvinova, in Reference Modul (Chemistry, Molecular Sciences and Chemical Engineering, 2013 Oligomers Oligomers are built from the same monomer units as polymers, but their chain is much shorter (MM < 10 kDa). Polymers in dilute solutions are characterized by the following types of interactions: solvent-solvent, solvent—polymer ‘segment, polymer segment-segment, solvent-surface, and polymer segment-surfave, whereas for oligomer segment segment interaction and local entropy effects are small, Oligomers without end groups are readily separated into ‘oligomer homologues on polar adsorbents by adsorption chromatography. It is aso easy to separate aoonrding to MM. oligomers with end groups for which the energies of interaction with adsorbent for the oentral (é2) and end (é,) units ere ‘Similar. If the energy of interaction with silica gel is much lower for the antral chain unit than for the end groups (&<€), separation according to the types of functionality will take plane. Therefore, to separate according to MM it is necessary to use silica gel modified either chemically for example, RP.) or dyriamically (for example, the separation of PEO oligomers in a pyridine-water mixture, 0.1:10).Iwo-component mooie phases are known to separate some oligomers aocoraing to MIM on silica ge: HS, poly (propylene glycol), PEO and its various derivatives, oligoacrylates, etc. Ifthe MM of one of the members of the homologous series on the chrometogram is known, corresponding standards are not neoessary to calculate MMD. For oligomers used in the production of synthetic polymers, the distribution aocording to the types of functionality (FTD) is very important. It characterizes the reletive content of macromolecules with different functionalities in the oligomer. ‘The functionality type of chemical compounds is determined by the number and nature of functional group. For macromolecular compounds the concept ‘functionality’ just as the concept ‘molecular mass weight’ has a statistical ‘Significance. In order to characterize distribution width according to functionality types the values of number-average ()and weight-average( functionality are used: where n= p/MM, is the number of moles of macromolecules / with molecular mass IMM, functionality f, and weight p, Oligomers are separated according to the number and nature of functional groups by adsorption chromatography under the critical conditions or under conditions close to critical. An example ofthis seperation is shown in Figurese4. A scanning densitometer or a videodensitometer can be used for quantitative FTD determination SYNTHETIC POLYMERS | Thin-Layer (Planar) Chromatography L'S.Litvinova, in Encyclopedia of Seperation Science, 2000 Oligomers Oligomers are built from the same monomer units as polymers, but their chain is much shorter (MW<10 kDa).Polymers- in dilute solutions are characterized by the following types of interactions: solvent-solvent, solvent-polymer segment, polymer segment-segment, solvent-surface, and polymer segment-surface, whereas for oligomer segment-segment interaction and loca entropy effects are small. Oligomers without end groups are readily separated into oligomer homologues on polar adsorbents by adsorption chromatography. It is also easy to separate avcording to MW, oligomers with end groups for which the energies of interaction with adsorbent for the central (€,) and end (€,) units are similar. If the energy of interaction with silica gel is much lower for the central chain unit than for the end groups (€.<€.), ‘separation according to the types of functionality will take place. Therefore, to separate according to MW it is necessary to use silica gel modified either chemically (for example, RP,s) or dynamically (for example, the separation of PEO oligomers in a pyridine-water mixture, 0.1:10). ‘Two-component mobile phases are known to separate some oligomers according to MW on silica gel: PS, Pi, poly (propylene glycol), PEO and its various derivatives, oligoacrylates, etc. If the MW of one of the members of the homologous series on the chromatogram is known, corresponding standards are not necessary to calculate MWD. For oligomers used in the production of synthetic polymers, the distribution according to the types of functionality (FTD) is veryimportant. It characterizes the relative content of macromolecules with different functionalities in the oligomer ‘The functionality type of chemical compounds is determined by the number and nature of functional group. For macromolecular compounds the concept ‘functionality’ just as the concept ‘molecular weight’ has a statistical ‘Significance. In order to characterize distribution width according to functionality types the values of number-average (F) ‘and weight-average (F,) functionality are used: where n=p/MMi (is the number of moles of macromolecules i with molecular weight MWY, functionality f, and weight p. Oligomers are seperated according to the number and nature of functional groups by adsorption chromatography underthe critical conditions or under conditions close to critical. An example of this separation is shown in Figure 4. A ‘scanning densitometer or a videodensitometer can be used for quantitative FTD determination. Modelling degradation of biodegradable polymers X. Han, X. Zhang, in Science and Principles of Biodegradable and Bioresorbable Medical Polymers, 2017 15.3.4.2 Computer modelling for polyesters — oligomer diffusion ‘Short oligomer diffusion and oligomer production from polymer chain scission both contribute to short oligomer chain ‘concentration change. The short oligomer chain concentration change rate can be expressed by: (15.21 where Cy is the short oligomer mole concentration per unit volume, Dis the diffusion ooefficient. As short oligomer diffusion proceeds, micro pores will be generated in the device. These pores are oocupied with water molecules immediately. The diffusion coefficient of short oligomers in these pores (Opa) is much higher than that in bulk polymers (Oyoymar). More precisely, Dis the effective diffusion coefficient which changes with time. It is related with Ops, Dpayma and the volume fraction of pores (Vjae) using the following equation (Weng et al, 2008) (1522) The production rate of oligomers can be obtained from the differential version of Eq. (15.19), which is: (1523) Substituting Eq. (15.21) into Eq. (15.20) we have: (15.24) Eqs (15.18)and (15.22)are reaction diffusion equations for biodegradation of polyesters. This type of equation was first proposed by Gillespie (1976) and Grizzi et al, (1995), and then modified by Pan and Han (Han et a., 2010).In Eq. (19.12), Gooou Can be expressed in terms of Rand Cy (15.25, here Caco is the initial number of polymer chains. The value Gaooy isinoreased due to chain scissions. At the meantime, it was decreased because some of the short oligomers diffuse. Step Polymerization Fietro Maravigna, Giorgio Montaud, in Comprehensive Polymer Science and Supplements, 1989 5.4.6 Sulfides Qydic oligomers with sulfide (or disulfide)bridges have been reported in the literature, originating from both step- {growth polymerization reactions and thermal or catalyzed depolymerizations 22222106115 Aliphatic sulfides (Table 8; compounds 291-328) have been extensively investigated 2°1%-1"" A series of aliphatic polysulfides has been obtained from the polycondensation of dibromoalkanes with dithiols, and GPC and MShave been, Used to detect and identify the cyclic oligomers formed in the polymerization reactions "2°" The GPC trace given in Figure 10 shows that the soluble fraction extracted from the crude sample of poly(thiotrimethylene)contains a series of low molecular weight compounds. The identification of these compounds wes achieved by fractional distillation of the oligomers in the MS? Only cydic oligomers with an even number of repeat units were detected (Table 9), and alinear dependence of elution volume on log /M could be established for these compounds (Figure 11). The fact that only an even number of repeating units are contained in the cydic oligomers (Table 9; compounds 304-320) suggests that these cydic oligomers are formed through an end-biting process of the type shown in equation (3) Oligomers containing up to 14 Units were separated by GPC, and the higher molecular weight products are most likely also macrocyeles *