A 13C-n.m.r. study of radiation-induced racemization in isotactic polypropylene

Unexpectedly large changes in the stereochemistry of isotactic polypropylene have been observed by ¹³C-n.m.r. following γ-irradiation at 25°C up to 250 kGy. The observed G-value of 64 for the loss of isotactic triads is much higher than previously reported G-values for scission, crosslinking or hydrogen formation in irradiated polypropylene. A mechanism of initial chain scission, racemization and subsequent recombination is indicated. The pattern of pentad sequences is inconsistent with the occurrence of isolated random racemization events; this suggests that the energy released on recombination promotes a second racemization within a range of 1–3 monomer units.     

Structural characterization of 1,2-polybutadiene by 13C-n.m.r. spectroscopy: 2. Sequence distribution of 1,2-unit in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were determined in relation to the sequence distribution of 1,2- and 1,4-units on the basis of the ¹³C-n.m.r. signal assignment of the methyl carbons. The observed triad distributions of 1,2- and 1,4-units and configurational distributions of the 1,2-unit are in good agreement with the calculated distributions from transition probabilities. The number average sequence lengths of the 1,2-unit and the 1,2-unit in the racemic addition are 5.7 to 8.0 and 4.1 to 5.4, respectively. From the extrapolation of the plot of the number average sequence length against the crystallinity of the starting 1,2-polybutadienes, the minimum sequence length for crystallization is estimated to be 3.7 for the 1,2-unit in the racemic addition.     

Characterization of polyurethane elastomers by 13C n.m.r. spectroscopy

A ¹³C n.m.r. study of a series of polyurethanes and selected model compounds is reported. Comparison of the observed chemical shifts with values predicted by the Grant and Paul additive theory shows reasonable agreement. The latter approach, therefore, is a useful method for the assignment of carbon resonances in these systems. The positions of carbonyl peaks are more difficult to predict, but model compound studies allow their unambiguous assignment. These peak positions are very useful for qualitative and quantitative measurements. Nuclear Overhauser Enhancement (NOE) factors have been measured for typical copolymers, and it is possible to obtain quantitative estimates of the compositions of unknown polymers and prepolymers.     

Characterisation of some melamine-formaldehyde condensates and some cured resins by 1H, 13C and 15N n.m.r. spectroscopy

Some oligomeric species (condensates) in a melamine-formaldehyde adduct mixture have been isolated by preparative high performance liquid chromatography (h.p.l.c.) and partly identified by high field ¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectroscopy. The oligomers are shown most likely to be largely dimers, trimers and tetramers and to contain both methylene and methylene ether linkages. Some cured melamine-formaldehyde resins are shown by solid-state cross-polarisation magic angle sample spinning (c.p./m.a.s.) ¹³C and ¹⁵N n.m.r. to contain linear and branched methylene and methylene ether linkages but few free methylol groups. The relative proportions of the various linkages in both the oligomers and the cured resins appear to be controlled mainly by the melamine: formaldehyde ratio.     

Molecular motion in α-methylstyrene and styrene-alkane copolymers studied by 13C n.m.r. spectroscopy

The temperature dependence of the ¹³C n.m.r. relaxation times are reported for a series of copolymers formed between methyl styrene or styrene and various α, ω-alkyl dihalides. The polymers studied contained alkyl blocks with n (the number of CH₂ units) varying from 0–10. The relaxation data indicates that the motion of both the styrene and the alkyl blocks change with the value of n. A comparison of the ¹³C relaxation data with that obtained from ultrasonic relaxation measurements supports the hypothesis that in the higher members of each series the alkane chain moves essentially independently of the ‘styrene’ moiety. The variation in the activation energy of the relaxation of the styrene moiety reflects in part a decoupling of the neighbouring phenyl group motion, as a consequence of the introduction of the alkane block.     

Structural characterization of 1,2-polybutadiene by 13C n.m.r. spectroscopy: 1. Signal assignment in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were investigated in relation to the sequence distribution of 1,2- and 1,4-units. The signals at 10.20–10.94 ppm were assigned to the methyl carbons in the isolated 1,2-unit, the 1,2-1,2 dyad sequence flanked by 1,4-unit, and the 1,2-1,2-1,2 triad sequence, in order of increasing magnetic field. The splittings due to the configurational sequences were observed in the signals, reflecting the dyad and triad sequences of the 1,2-unit, which were assigned by considering the relative intensity of the signals and also the chemical shifts of model polymers.     

Quantitative 13C n.m.r. characterization of aqueous formaldehyde resins: 1. Phenol-formaldehyde resins

Phenol-formaldehyde (PF) resins which had experienced a variety of reaction conditions and/or ageing conditions were quantitatively characterized by ¹³C n.m.r. Under the specific conditions of this study, the phenol para position was favoured for reaction over the ortho position on a per site basis, particularly for condensation reactions. Increasing the reaction temperature from 23°C (14 days reaction) to 80°C (3 h reaction) did not alter the type of resin structure. Ageing PF resins resulted in extensive condensation and a drastic reduction in para-substituted methylol and hemiformal groups. This apparently contributes to a sharp reduction in the reactivity of these resins for reactions requiring methylol substituents on the ring.     

Oil-shale analysis by CP/MAS-13C n.m.r. spectroscopy

Solid-state ¹³C n.m.r. (CP/MAS-¹³C n.m.r.) spectroscopy provides a direct method for estimating potential oil yields of oil shale formations. Relative aliphatic resonance areas correlate linearly with oil yield and provide a method for oil yield estimation that obviates the need to determine weight per cent organic carbon for each specimen. This direct measurement is performed using an internal area standard, the carbonyl resonance of N-(2-¹³C-propanonyl)-N,N,N-trimethylammonium chloride, to monitor spectrometer sensitivity. Oil shale samples obtained as a function of depth at a site in the Mahogany Zone of the Green River Formation show a near-constant aliphatic carbon fraction, f_al ≡ (1?f_a), and a twofold, nonlinear variation in oil yield over the vertical dimension of the sampling. Aliphatic carbon resonance band shape changes among these samples are interpreted qualitatively as reflecting a two component mixture composed of the condensed alicyclic structures which link together to form the kerogen matrix and an n.m.r.-distinct but not necessarily chemically distinct contribution from normal-long chain hydrocarbon residues.     

Determination of Gasoline Octane Numbers by 1H- and 13C-NMR spectroscopy

An equation describing the relationship between the research octane number (RON) and the ¹H-and ¹³C-NMR is proposed. This equation relates the RON to the aliphatic, olefinic and aromatic hydrogen and carbon, respectively. To check this relationship 60 samples were investigated with RON values between 65 and 96. The fitting procedure yielded good agreement between the RON measured with the ASTM method and the RON calculated from both the ¹H-and the ¹³C-NMR.     

Investigation of pyridine extracts and residues of coals by solid-state 13C n.m.r. spectroscopy

The ¹³C n.m.r. technique of cross polarization with magic angle spinning was applied to seven coals in their original states and the components obtained after pyridine extraction. It was observed that for the higher rank coals, short and straight alkyl groups are preferentially transferred to the extracts, while long-chain alkyl groups, branched alkyl groups or alicyclic structures are concentrated in the residues. Aliphatic ether or ester moieties were also observed to be concentrated in the residues. For all coals the computer-generated composite extract-residue spectra differed appreciably from the spectra of the original coals, indicating that some structures may be lost or that some structural conversion may occur during the extraction procedure. It was concluded that caution should be used in trying to determine detailed organic structural information of a coal from data obtained on its pyridine extract.     

Distribution of aliphatic and aromatic carbons in H-Coal liquids by quantitative 13C FT-n.m.r. spectroscopy

Three H-Coal liquids, ASO, ASB, and VSO, have been characterized by quantitative FT-n.m.r. spectroscopy. FT-parameters were chosen to allow determination of aromatic:aliphatic carbon ratios to within 1% and 2% error of the theoretical and the absolute number of aromatic and aliphatic carbons in a simulated coal liquid, respectively. The aromaticity, f_a, the C_ar:C_al ratio and, the absolute number of both the aromatic and the aliphatic carbons on a per mol basis, have been derived for each H-Coal liquid using c.m.r. in combination with other physical data. By analysis of the chemical shifts of the c.m.r. spectra, the carbon distributions in the H-Coal liquids have been estimated and compared in terms of six structural types. The molecular parameters thus derived are reasonable correlated with the average molecular structures proposed as working hypothesis for the molecular characterization of the three H-Coal liquids.     

Quantitative determination of the monoclinic crystalline phase content in polyethylene by 13C n.m.r.

Solid-state ¹³C n.m.r. spectroscopy involving the techniques of cross-polarization (CP), magic angle spinning (MAS), and high power proton decoupling, has been used to determine quantitatively the ratio of monoclinic to orthorhombic crystalline phases in compression moalded ultra-high molecular weight polyethylene (UHMWPE) sheet which had been stretched uniaxially. Criteria for expecting quantitative relative intensities in ¹³C CP-MAS spectra are discussed. Attenuation of the non-crystalline (NC) signals relative to crystalline signals was observed. Experiments were therefore carried out to ascertain whether measurable relative intensity distortions exist between the monoclinic crystalline phase (MCP) and the orthorhombic crystalline phase (OCP) resonances due to possible differences in proton ‘spin diffusion’ between the NC and the two crystalline phases during cross-polarization. No relative intensity distortions were detected. This result, coupled with experiments in which spin diffusion was monitored at times longer than those used for cross-polarization, suggests that the average distance from the protons in a given crystalline phase to the nearest protons in the NC regions is the same for the MCP and the OCP. Finally, non-spinning ¹³C spectra of the deformed polyethylene were recorded to determine the orientation of the chains in the crystalline and NC regions. The Hermans orientation function, F_c, was determined independently for the crystalline (combined OCP and MCP) and NC regions, and found to be 0.66 + 0.06 and 0.23 + 0.04 respectively. The occurrence of orientation in the NC regions may be evidence for internal stresses, which, it is suggested, also stabilize the metastable MCP in the stretched sample.     

Study of structural parameters on some petroleum aromatic fractions by 1H n.m.r./i.r. and 13C, 1H n.m.r. spectroscopy

¹H n.m.r. and i.r. spectroscopy were used to derive molecular parameters of petroleum fractions. Relative amounts are estimated of methylene and methyl groups in substituted alkyl side chains bonded to the aromatic ring system. The resolution of equation combinations leads to estimation of $\text{H}{}_{\mathrm{s}}\text{C}{}_{\mathrm{s}}\text{(=x)}$, which is an important parameter for structural analysis. Several petroleum fractions were characterized in terms of hypothetical average molecular structures using ¹H n.m.r./i.r. procedures, ¹³C coupled proton n.m.r. and Brown—Ladner methods. It is proposed that the ¹H n.m.r./i.r. method gives more precise average molecular parameters than the Brown-Ladner method with the most precise analytical procedure, up to date, being ¹³C coupled proton n.m.r. analysis. The Brown-Ladner method is especially suitable for structural analysis of low aromaticity molecular structures with long straight-chain alkyl substituents.     

Characterization of coals and coal oxidation by magic-angle 13C n.m.r. spectroscopy

Magic-angle ¹³C n.m.r. spectra have been obtained for a series of vitrinite concentrates. Proper modification of the cross-polarization pulse sequence allows separation of protonated and nonprotonated carbon resonances. This technique is used to determine the relative fraction of nonprotonated aromatic carbons for each of the vitrinites, a parameter observed to decrease with increasing rank. Another parameter, related to the aromatic hydrogen content, is also calculated from these data and the results correlate with those from Fourier transform i.r. spectroscopy. The methods used for analysis of the vitrinite concentrates were then applied to the low-temperature oxidation of coal. The fractional aromaticity as determined by n.m.r. increases with longer oxidation times, indicating preferential attack on aliphatic structures. Here the FT-i.r. results are in quantitative agreement with those from n.m.r. Finally, the advantages of using various pulse sequences to extend the range of magic-angle n.m.r. and of combining FT-i.r. and n.m.r. results are discussed in the context of their potential for coal science.     

Structural investigation of coal-tar pitches and coal extracts by 13C n.m.r. spectroscopy

The structural composition of hard and brown coal tar pitches and coal extracts is analysed by ¹³C n.m.r. spectroscopy on the basis of the chemical-shift data for selected model compounds. For hard-coal-tar pitch, the high aromaticity is confirmed, the predominance of alternant hydrocarbon building blocks established, and the minute aliphatic resonances assigned to definite types of methyl groups and methylene linkages. In brown-coal-tar pitch, long straight-chain alkanes are identified as the major constituents. For three coal extracts obtained by different technical processes, the similar ¹³C spectral patterns demonstrate their analogous composition. The most striking feature in these spectra is an aliphatic resonance at 30 ppm which is assigned to a structural principle of the dihydrophenanthrene type, in accordance with a modified Given model for the structure of coal.     

Quantitative aspects of solid state 13C n.m.r. of coals and related materials

The quantitative aspects of cross-polarization (CP), which is used in conjunction with dipolar decoupling and magic-angle rotation to obtain high resolution ¹³C n.m.r. spectra of coals, have been studied using a bituminous coal (82 wt% C, dmmf basis) and asphaltenes from an extract of the same coal. The condition for obtaining reliable quantitative data, that rotating frame ¹H relaxation times (T_1p′ these govern the extent of CP) are much longer than the time required to polarize the carbons present (≈1 ms), was met for the asphaltenes. In contrast, about half the protons in the coal have T_1p5 of ≈ ? 1 ms, these times being too short to allow CP of all the carbons. Although the aromaticities obtained for this coal were fairly constant (≈0.75) using (CP) contact times > 0.5 ms, the total peak intensity decreased markedly as the contact time was increased and was much less than that for the asphaltenes. These results indicate that not all the carbons in bituminous coals are observed by CP and, as a consequence, aromaticities reported in the literature for some bituminous coals appear to be low.     

Structural characterization of non-reductively ethylated coal by 13C and 1H n.m.r.

A major portion of some coals can be solubilized by non-reductive ethylation. A part of the solubilized portion of a bituminous highly caking coal was studied by ¹H and ¹³C nuclear magnetic resonance techniques. It was demonstrated that important structural information can be obtained by this method for the original insoluble material in coal. It was found that, in the investigated coal, about 40% of the aromatic carbon atoms are protonated and that 6–10% of total carbon atoms existed in original coal as active sites that were amenable to ethylation.