Elemental analysis, copolymers

The copolymer composition equation relates the r s to either the ratio [Eq. (7.15)] or the mole fraction [Eq. (7.18)] of the monomers in the feedstock and repeat units in the copolymer. To use this equation to evaluate rj and V2, the composition of a copolymer resulting from a feedstock of known composition must be measured. The composition of the feedstock itself must be known also, but we assume this poses no problems. The copolymer specimen must be obtained by proper sampling procedures, and purified of extraneous materials. Remember that monomers, initiators, and possibly solvents are involved in these reactions also, even though we have been focusing attention on the copolymer alone. The proportions of the two kinds of repeat unit in the copolymer is then determined by either chemical or physical methods. Elemental analysis has been the chemical method most widely used, although analysis for functional groups is also employed. 

The polymers initiated by BP amines were found to contain about one amino end group per molecular chain. It is reasonable to consider that the combination of BP and such polymers will initiate further polymerization of vinyl monomers. We investigated the photopolymerization of MMA with BP-PMMA bearing an anilino end group as the initiation system and found an increase of the molecular weight from GPC and viscometrical measurement [91]. This system can also initiate the photopolymerization of AN to form a block copolymer, which was characterized by GPC, elemental analysis, and IR spectra. The mechanism proposed is as follows ... 

The methyl ester gives rise to a fairly sharp singlet at 3.59 ppm, and the ester carbonyl exhibits an infrared band at 1730 cm"1. The MM content of the copolymer is easily ascertained by integration of the 1H NMR spectrum and may be corroborated by elemental analysis. 

Copolymerization of isopropenylferrocene with styrene was accomplished in two ways. In one method (polymer 16 of Table III) styrene and isopropenylferrocene were mixed together in CH2CI2 at 20°C at a mole ratio of 23/77 of isopropenylferrocene to styrene, and polymerization was initiated with BF3 0Et2. From the 250-MHz NMR spectrum of the product, 27% styrene and 73% isopropenylferrocene units were found to be present in the copolymer, which had an Mu of 2900. This ratio was also confirmed by elemental analysis. 

Isopropenylferrocene does not homopolymerize under free radical conditions using AIBN as an initiator, but it does copolymerize with styrene.Preliminary results indicate that the IDM monomer also copolymerizes with styrene using AIBN. In benzene solvent at 50°C in 24 h, a 10.6% yield of copolymer (IR vc=0 2020, 1945 cm , vN=0 1675 cm-- -, V q 1601 cm-- -, v 3020 cm-- -) resulted having an M f 5700 and containing 6.8% of IDM as determined by elemental analysis. The initial monomer mixture contained 17% of IDM. 

Recently, Kroeze et al. prepared polymeric iniferter 34 including poly(BD) segments in the main chain [152]. They successfully synthesized poly(BD)-block-poly(SAN), which was characterized by gel permeation chromatography, elemental analysis, thermogravimetric analysis, NMR, dynamic mechanical thermal analysis, and transmission electron microscopy. By varying the polymerization time and iniferter concentration, the composition and the sequence length were controlled. The analysis confirmed the chain microphase separation in the multiblock copolymers. 

The molecular weight () of the poly(dimethyl siloxane), PDMSX, was determined by both proton NMR and non-aqueous potentiometric titration (5). Proton NMR was used routinely to determine immediately after synthesis and prior to use in any copolymerization. Experimental confirmation of percent silicon in the copolymers was determined by elemental analysis (Galbraith Laboratories). 

Thioetherification of PECH is feasibly performed in DA-solvents as already described in the patent (20J. For example, the highest substitution was obtained by the reaction of P(ECH-EO)(1 1 copolymer of epichloro-hydrin and ethylene oxide) and equimolar thiophenoxide in HMPA at 100°C for 10 h as DS 83% for sodium and 93% for potassium salts. The DS in our nucleophilic substitution was estimated by the elemental analysis as well as the titration of liberated chloride ion with mercuric nitrate (21). In the latter method, reacted medium was pretreated with hydrogen peroxide when the reductive nucleophiles which can react with mercuric ion were used. As described before for PVC, thiolation was also achieved conveniently with iso-thiuronium salt followed by alkaline hydrolysis without the direct use of ill-smelling thiolate. The thiolated PECH obtained are rubbery solids, soluble in toluene, methylene chloride, ethyl methyl ketone and DMF and insoluble in water, acetone, dioxane and methanol. 

Copolymer Amoimt of DTIBP. Mol% Reaction Amount of Time. His. Styrene Added. mL Wint Mvll Elemental Analysis C H... 

R values were calculated from elemental analysis for carbon, hydrogen, and chlorine. It can be seen again that temperature has a very marked effect on composition. Even at 100°, however, about 16 mol% sulfur dioxide is present. There was also produced a small quantity (1 to 10% of the amount of copolymer) of the cyclic addition product, 3-chloro-2,5-dihydrothiophene-l,1-dioxide, m.p. 99-100°. 

This mechanism could be demonstrated via nitrogen elemental analysis of polymers and copolymers treated with amine acid salts and thermally cured (Table II and Experimental). In a control experiment, ammonium acetate was added In excess to a vinyl acetate/ethylene emulsion copolymer without amlnoplast crosslinker to confirm that essentially all of the ammonia volatilized from the unfunctlonallzed polymer during cure (much poorer volatilization was observed If NH4CI was used In place of NH4OAC). 

The copolymers obtained for the P(DMA)-itat-(HPA) (Scheme 9) library revealed relatively low PDI values below 1.3 and increasing Mn,opc values with increasing HPA content, as listed in Tables. It should be noted that a poly(methyl methacrylate) (PMMA) calibration was used for the calculation of the Mn pc values and this causes an overestimation for HPA containing polymers. The copolymer compositions were calculated from the H NMR spectra however, this method was not suitable for reliable conversion determination since the DMA-C//3 groups overlap in the NMR spectra not only with the HPA-O// group but also with broad backbone signals, which obstruct any reliable integration. Therefore, elemental analysis was used as an alternative method for the calculation of the molecular composition of the copolymers. 

Qualitative and quantitative elemental analysis of polymers can be carried out by the conventional methods used for low-molecular-weight compounds. So a detailed description is not needed here. Elemental analysis or determination of functional groups is especially valuable for copolymers or chemically modified polymers. For homopolymers where the elemental analysis should agree with that of the monomer, deviations from the theoretical values are an indication of side reactions during polymerization. However, they can also sometimes be caused by inclusion or adsorption of solvent or precipitant, or, in commercial polymers, to the presence of added stabilizers. The preparation of the sample for... 

Quantitative analysis of copolymers is relatively simple if one of the comonomers contains a readily determinable element or functional group. However, C,H elemental analyses are only of value when the difference between the carbon or hydrogen content of the two comonomers is sufficiently large. If the composition cannot be determined by elemental analysis or chemical means, the problem can be solved usually either by spectroscopic methods, for example, by UV measurements (e.g., styrene copolymers), by IR measurements (e.g., olefin copolymers), and by NMR measurements, or by gas chromatographic methods combined with mass spectroscopy after thermal or chemical decomposition of the samples. 

Average copolymer compositions of SAN samples were determined by elemental analysis, yielding weight percent acrylonitrile in the polymer. Compositions of S/MA and S/MA/MM were determined by sequential hydrolysis and pyridine titration to obtain maleic anhydride content and by infrared analysis for methyl methacrylate content. 

Table II compares compositional analysis results by Reman spectroscopy with elemental analysis (C,H,N) for various mixtures of P(M-CN) copolymers the agreement between the two methods is quite good and the results are consistent with published (, 3, 13.) reactivity ratios for this system. Because of the limited range of composition of the available samples of this copolymer, reactivity ratios were not calculated.

In the pmr data for the terpolymer, overlap between the CH3 absorption of the oxime ester and the backbone absorption is greater than in the copolymer pointed out in Figure k. Thus, while the agreement between the Raman and pmr data for the terpolymer is not very good, (lT-32 difference), it is completely within the experimental error of the pmr data. This large error and the fact that pmr can only distinguish two of the components of the terpolymer demonstrate that it is unsuited for compositional analysis of this system. Based on the agreement with published reactivity ratios and with the elemental analysis of the P(M-CN) copolymer, it is assumed that the Raman data are more accurate. 

Feed Ratio Mole J Wtl Raman (Wt ) ) Copolymer Ratio Elemental Analysis (Wt %)... 

Materials. GMC and PCLS were synthesized by free radical solution polymerization initiated by benzoyl peroxide as described previously (5,6). Nearly mono and polydisperse polystyrenes were obtained from Pressure Chemical Co. and the National Bureau of Standards respectively. Molecular weight and polydispersity were determined by gel permeation chromatography (GPC) using a Water Model 244 GPC, equipped with a set (102-106 A) of —Styragel columns using THF as the elution solvent. The molecular parameters of the above three polymers are listed in Table I. The copolymer, poly(GMA-co-3-CLS), contained 53.5 mole % 3-CLS and 46.5 mole % GMA, as determined by chlorine elemental analysis. The structure of the copolymer is shown in Figure 1. 

The compositions of copolymers of methacrylates or aldehydes were determined by 1H NMR spectroscopy or elemental analysis. 

After polymerization the polymer sheet is detached from the glass plates and cut into disks using a punch. Disks are washed in methanol for several days and then in 50/50 (v/v) methanol/water overnight to remove unreacted components and the sol fraction. Disks are then dried, first at room temperature for 24 h and then at 50 °C under vacuum for another 24 h. It has been confirmed that further drying steps leads to no measurable change in polymer weight. Elemental analysis of the copolymers reveals that the resulting polymer networks have the same comonomer content as the feed. 

Elemental analysis for this amide derivative, case b, indicates that side reactions occur. Elemental analysis shows that C (39.06%), H (3.66%), Cl (11.37%), F (24.45%) and N (6.12%) comprise 84.66% of the mass of the polymer. It is assumed that oxygen comprises the remaining 15.34% of the mass of the polymer. Assuming the derivative is an idealized copolymer, a degree of functionalization of 84% is calculated based on the %N reported in the elemental analysis. However, a degree of functionalization of 50% is calculated based on the %H reported in the elemental analysis. Thus, competing carbonylation and/or elimination clearly skew the results. In any case, the polymer is clearly functionalized to a significant extent. 

Ionomers have been synthesized from reaction of tin II and tin IV metal halides and organostannane halides through reaction with an ethylene-acrylic acid copolymer. Mass spectral, infrared spectral, and elemental analysis results are consistent with the formation of tin-containing ionomers. The products all exhibit "ionomer-like" properties and soften below 150 C, many softening below 50 C. 

The terpolymerization of CPT-SO2 and acrylonitrile is shown in Table II. It was necessary to accelerate the polymerization by adding azobisisobutyronitrile (AIBN) as initiator. The nature of the propagating species may not be different with a different initiator. Polymerization ceased at a low conversion at 40 °C in toluene. The terpolymer composition calculated from elemental analysis of C, H, N, and S showed an equimolar ratio of CPT and S02. The terpolymers are white powders, soluble in DMF, can be cast into transparent film different from the CPT-SO2 copolymer, and showed melting temperature without decompo-... 

Procedures. A standard recipe for the latex preparation is shown below (St + M2) 20 g, (water + buffer) 160 g, and initiator 5 mmole/1. The weight fraction of M2 in monomer charge (f) was varied from 0.01 to 0.50. Polymerizations were carried out at 55°C or 70°C and pH 2.5 or 9.0 under nitrogen. Samples were withdrawn from the reaction mixture at various time intervals and the polymer was precipitated in an excess of acetone. The conversion and polymer composition were determined by gravimetric means and by elemental analysis, respectively. The M2 fraction in instantaneously-formed copolymer ( Fi ) was calculated from eq. 1 ... 

Biphenyl-phosphole copolymer 65 is isolated as an air-stable and soluble powder exhibiting a rather high molecular weight (Mw = 16 000 Mn = 6200) according to gel permeation chromatographic (GPC) analysis. Although multinuclear magnetic resonance spectroscopy and elemental analysis support the proposed structure, the presence of a small number of diene defects is very likely. Polymer 65... 

In this paper, the surface grafting of rayon fabrics with nitrogen and phosphorus containing polymers in cold plasma is studied. The analytical data (IR spectroscopy, TGA, electron microscopy, elemental analysis, etc.) indicate the formation of grafted copolymers. The grafted rayon fabrics present improved flame-retardant properties, the best behavior was proved by those grafted with polyurea of phosphinic acid. 

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