Quantitative evaluation of H-donating abilities of C(sp3)-H bonds of nitrogen-containing heterocycles in hydrogen atom transfer reaction.

Nitrogen-containing heterocycles are an important class of antioxidants, and their reactivity and selectivity in hydrogen atom reactions have attracted significant interest from chemists. In this work, the kinetics of hydrogen atom transfer reactions from C(sp3)-H bonds of 28 nitrogen-containing heterocycles, oxygen-containing heterocycles, alicyclic amines and cycloalkanes, which were denoted as XH, to the CumO˙ radical, were investigated. The characteristic physical parameter of the substrate, i.e., the thermo-kinetic parameter ΔG≠o(XH), was determined using the kinetic equation [ΔG≠XH/Y = ΔG≠o(XH) + ΔG≠o(Y)] to quantitatively evaluate the H-donating ability of XH. The effects of the substrate structure, substituent attached to the nitrogen atom, and ring size on the H-donating ability were discussed carefully. By comparing the H-donating abilities of cycloalkanes, alicyclic amines and nitrogen/oxygen-containing heterocycles, the influence of the introduction of N, O, or carbonyl groups in the carbon ring on the H-donating ability of C(sp3)-H bond was determined. The electronic, steric and stereo-electronic effects of the groups were also discussed. Herein, we not only quantitatively determined the H-donating ability of the substrate, but also provided ideas for the synthesis of new antioxidants.

Preparation of Rubber Accelerator Tetrabenzylthiuramdisulfide and Its Spectral Analysis.

In the study, rubber accelerator tetrabenzylthiuramdisulfide (TBzDT) was synthesized with two-step method with hydrogen peroxide as oxidant firstly. TBzDT was detected and characterized with XRD, FT-IR, TG-DTA. Its micro-structure was revealed. Chemical bond types into TBzDT molecule were revealed with FT-IR. TBzDT phase composition and structure were given by crystallographic data from XRD detecting such as cell parameters, crystal face index. The phase composition and qualitative identification of TBzDT structure were completed. Two kinds of information were detected with TG-DTA as to quality change and thermal effect. TBzDT phase transition and decomposition temperature were 142.5, 200.9 ℃ respectively. The decomposition temperature of TBzDT was relevtively high. It could provided reference with research on rubber vulcanizing properties by TBzDT on rubber vulcanizing machine. A little SC2 contained into TBzDT was revealed by FTIR, TG-DTA from different sides.

[Study on the Preparation of N-Tert-Butylbenzothiazole-2-Sulphenamide and Its Spectral Analysis].

In the study, N-tert-butylbenzothiazole-2-sulphenamide (TBBS) was synthesized with one-step method with hydrogen peroxide as the oxidant. TBBS was detected and characterized with FTIR，UV-Vis，XRD and TG-DSC. Its micro-structure and intrinsic regularity were revealed. Chemical bond types into TBBS molecule were revealed with FTIR. The final product was determined TBBS. Three absorption peaks were detected by UV-Vis at 228.3，281.5，298.3 nm respectively, due to n→σ*，π→π*，n→π* electronic transitions. It could provide experimental basis with enterprise to test TBBS product quality and speculate its structure. The phase composition and structure of TBBS were revealed by crystallographic data from XRD detecting such as cell parameters, crystal face index. The phase composition and qualitative identification of TBBS structure were completed. Two kinds of information were detected by TG-DSC as quality change and thermal effect. The DSC curve of TBBS was very complex. There were a small absorption peak of 53.3 ℃ as a small amount of tert-butylamine containing in TBBS was oxidized. Three exothermic peaks of 117.4，269.2，373.7 ℃, due to transition peak and decomposition phase of TBBS respectively. The decomposition temperature of TBBS was very high. It could provide reference for research on rubber vulcanizing properties by TBBS on rubber vulcanizing machine. This study could provide the basis experimental data on the enterprises to designate the working standard tracing detection of TBBS industrialized production. The performance index of TBBS was judged. The project of TBBS industry standard could be declared by the enterprises, written a draft standard.

[Preparation of Rubber Accelerator Tetraisobutylthiuram Monosulfide and Its Spectral Analysis].

In the study, rubber accelerator tetraisobutylthiuram monosulfide (TiBTM) was synthesized by two-step method with hydrogen peroxide as oxidant firstly. TiBTM was detected and characterized by FTIR, XRD, TG-DSC. Its micro-structure and intrinsic regularity were revealed. Chemical bond types into TiBTM molecule were revealed by FTIR. TiBTM phase composition and structure were given by crystallographic data from XRD detecting such as cell parameters, crystal face index. The phase composition and qualitative identification of TiBTM structure were completed. Two kinds of information were detected by TG-DSC as quality change and thermal effect. TiBTM phase transition and decomposition temperature were 75.1 and 287.0 ℃ respectively. Uhe decomposition temperature of TiBTM was very high, samples possessing with high purity, without other impurities. It could provided reference with research on rubber vulcanizing and multiple functional properties by TiBTM on rubber vulcanizing machine. This study can provide the basis experimental data on the enterprises to designate the working standard tracing detection of TiBTM industrialized production. The best technological conditions and parameters could be provided for the enterprises to adopt cleaner production process of TiBTM. Performance index of TiBTM was judged. The project of TiBTM industry standard can be declared by the enterprises, written a draft standard.

[Preparation of Zinc O,O,O',O'-Tetrabutyl Bis(Phosphorodithioate) and Its Spectral Analysis].

In the study, zinc O,O,O',O'-tetrabutyl bis(phosphorodithioate) (ZBPD) was synthesized with two-step method firstly. ZBPD was detected and characterized with UV-vis, FT-IR andTG-DSC. Its micro-structure and intrinsic regularity were revealed. Two absorption peaks were detected with UV-Vis at 212.0 and 227.0 nm respectively caused by n→σ*, π→π* electron transition. The intensity of peaks was changed with the regularity with different ZBPD concentration. It could provide the basic data with the enterprise of ZBPD product quality inspection. Chemical bond types into ZBPD molecule were revealed by FT-IR. Two kinds of information were detected by TG-DSC as quality change and thermal effect. The DSC curve of ZBPD was very complex. There were a wide absorption peak of 84.3 ℃, four exothermic peaks of 245.0, 344.3, 476.1, 344.3 ℃, due to the molecular structure of ZBPD and small amounts of impurities. The decomposition temperature of ZBPD was very high. It could provided reference with research on rubber vulcanizing properties by ZBPD on rubber vulcanizing machine. This study could provide the basis experimental data on the enterprises to designate the working standard tracing detection of ZBPD industrialized production. Performance index of ZBPD was judged. The project of ZBPD industry standard could be declared by the enterprises, written a draft standard.

[Preparation of Rubber Accelerator 3-Methylthiazolidine-2-Thione and Its Spectral Analysis].

In the study, rubber accelerator 3-methylthiazolidine-2-thione (MTT) was synthesized by one-step method firstly. MTT was detected and characterized by XRD, FTIR, TG-DSC. The micro-structure and intrinsic regularity were revealed. Chemical bond types into MTT molecule were revealed by FTIR. MTT phase composition and structure were given by crystallographic data from XRD detecting such as cell parameters, crystal face index. The phase composition and qualitative identification of MTT structure were completed. Two kinds of information were detected by TG-DSC as quality change and thermal effect. MTT phase transition and decomposition temperature were 76.3 and 306.9 ℃ respectively. The decomposition temperature of MTT was very high. It could provided reference with research on rubber vulcanizing properties by MTT on rubber vulcanizing machine. This study can provide the basis experimental data on the enterprises to designate the working standard tracing detection of MTT industrialized production. Performance index of MTT was judged.

[Preparation of Rubber Accelerator 3-Methylthiazolidine-2-Thione and Its Spectral Analysis].

In the study, rubber accelerator 3-methylthiazolidine-2-thione (MTT) was synthesized by one-step method firstly. MTT was detected and characterized by XRD, FTIR, TG-DSC. The micro-structure and intrinsic regularity were revealed. Chemical bond types into MTT molecule were revealed by FTIR. MTT phase composition and structure were given by crystallographic data from XRD detecting such as cell parameters, crystal face index. The phase composition and qualitative identification of MTT structure were completed. Two kinds of information were detected by TG-DSC as quality change and thermal effect. MTT phase transition and decomposition temperature were 76.3 and 306.9 ℃ respectively. The decomposition temperature of MTT was very high. It could provided reference with research on rubber vulcanizing properties by MTT on rubber vulcanizing machine. This study can provide the basis experimental data on the enterprises to designate the working standard tracing detection of MTT industrialized production. Performance index of MTT was judged.

[Study on the Preparation of Zinc Dibenzyl Dithiocarbamate and Its Spectral Analysis].

In the study, Zinc dibenzyl dithiocarbamate (ZBDC) was synthesized with one-step method. ZBDC was detected and characterized with FTIR，UV-Vis，XRD，TG-DSC. Its micro-structure and intrinsic regularity were revealed. Chemical bond types into ZBDC molecule were revealed with FTIR. The final product was determined as ZBDC. Two absorption peaks were detected with UV-Vis at 209.8，266.1 nm respectively, due to n→σ*, π→π* electronic transitions. It could provide experimental basis for enterprise to test ZBDC product quality and speculate its structure. ZBDC phase composition and structure were revealed through crystallographic data from XRD detecting such as cell parameters, crystal face index. The phase composition and qualitative identification of ZBDC structure were completed. Two kinds of information were detected with TG-DSC as quality change and thermal effect. There were three absorption peaks of 194.5，361.1，433.5 ℃, due to transition peak and decomposition phase of ZBDC respectively. The decomposition temperature of ZBDC was very high. It could provided reference for research on rubber vulcanizing properties with ZBDC on rubber vulcanizing machine.

[Preparation of TBSI with NS-Acetic Anhydride Method and Its Spectral Analysis].

In the study, N-t-butyl-2-benzothiazole sulfenimide (TBSI) was prepared by NS-acetic anhydride method with acetic anhydride as solvent. It was detected with FTIR, XRD, UV-Vis, TG-DTA. Micro-structure and essence disciplinarian of them were disclosed. Chemical bond types into TBSI molecule were revealed with FTIR. TBSI phase composition and structure were revealed with crystallographic data from XRD detecting such as cell parameters and crystal face index. The phase composition and qualitative identification of TBSI structure were completed. The absorption peaks were detected by UV-vis at 228.3, 281.3 and 298.3 nm, respectively caused by n→σ*, π→π*, n→π* electron transition. It could provide basic data with the enterprise of ZBPD product quality inspection. Two kinds of information were detected with TG-DTA as quality change and thermal effect. There were three absorption peaks of 46.5, 188.9, 368. 5 ℃ due to a few residual solvent volatilization in the sample, phase transition peak and decomposition peak. The decomposition temperature of TBSI was very high. It could provided reference with research on rubber vulcanizing properties with TBSI on rubber vulcanizing machine. This study could provide basis experimental data on the enterprises to designate the working standard tracing detection of TBSI industrialized production. Performance index of TBSI was judged. The project of TBSI industry standard could be declared by the enterprises, written a draft standard.

[Preparation of Zinc Dibenzyl Dithiocarbamate and Its Spectral Analysis].

In the study, zinc methyl mercaptobenzimidazole (MMBZ) was synthesized by one-step method. MMBZ was detecued and characterized by FTIR, UV-Vis, XRD, TG-DSC. Its micro-structure and intrinsic regularity were revealed. Chemical bond types into MMBZ molecule were revealed by FTIR. The final product was determined MMBZ. There absorption peaks were detected by UV-Vis at 219.6，245.5，302.2 nm respectively, due to n→σ(*)，π→π(*)，π→π(*) electronic transitions, led by S­C, benzene and five element heterocyclic in MMBZ molecule. It could provide experimental basis with enterprise to test MMBZ product quality and speculate its structure. It was shown that MMB was a ligand of MMBZ, and its basic structure of MMB was retained still by XRD spectra. The structure of MMBZ molecule was amorphous. Two kinds of information were detected with TG-DSC as quality change and thermal effect. There were five absorption peaks of 67.5, 155.3, 253.7, 324.8, 391.3 ℃, due to impurity solvent decomposition peak, phase transition peak and decomposition of MMBZ respectively. The scheme of one step preparation of composite environment-friendly rubber antioxidant MMBZ was feasible. The structure of MMBZ could be speculated by results of its detecting. It could provide the basis of experimental data on association MMBZ performance, exploring its anti-aging mechanism and extending the scope of MMBZ application.

[Preparation of Rubber Accelerator Zinc Diethyldithiocarbamate and Its Spectral Analysis].

In the study, rubber accelerator Zinc diethyldithiocarbamate (EZ) was synthesized firstly. Complex EZ of single crystal was cultivated by solvent evaporation method. EZ was detected and characterized by XRD single crystal diffraction, FTIR and TG-DSC. The micro-structure and intrinsic regularity were revealed. Its highly efficient performance of rubber vulcanization promotion was decided due to its orientation structure? and high order. The result of TG-DSC showed that complex EZ was possessed with a little CS2. The chemical bond types in EZ were revealed by FTIR, the same as single crystal? diffraction testing by different way. The decomposition temperature of EZ was very high. It could provided reference with research on rubber vulcanizing properties by EZ on rubber vulcanizing machine. This study can help the enterprises to designate the working standard tracing detection of EZ industrialized production. Performance index of EZ was judged. The project of EZ industry standard can be declared by the enterprises, written a draft standard on the basis experimental data.

[Preparation of Rubber Accelerator Tetramethyl Thiuram Monosulfide and Its Spectral Analysis].

In the study, rubber accelerator tetramethyl thiuram monosulfide (TMTM) was synthesized firstly. Single crystal TMTM was cultivated by solvent evaporation method. TMTM was detected and characterized by XRD single crystal diffraction, FTIR, TG-DSC. The micro-structure and intrinsic regularity were revealed. The TMTM microstructure was revealed by XRD single crystal diffraction from the diffraction data, part of bond length and bond angle. Its highly efficient performance of rubber vulcanization promotion was decided due to its orientation structure and high order. Properties of TMTM was disclosed by TG-DSC analysis from the heat effect. The results of TG-DSC and FTIR showed that single crystal TMTM possessed with little CS2. The chemical bond types in TMTM were revealed by FTIR the same as single crystal diffraction testing by different way. The decomposition temperature of TMTM was very high. It could provided reference with research on rubber vulcanizing properties by TMTM on rubber vulcanizing machine. This study can help the enterprises to designate the working standard tracing detection of TMTM industrialized production. Performance index of TMTM was judged. The project of TMTM industry standard can be declared by the enterprises, written a draft standard. It can provide the basis experimental data on completing the revision of the national ministry of industry and information technology standard system project plan.

[Preparation of δ-Valerolactone and Its Spectral Analysis].

In the study, CuO/ZnO/Al2O3 was prepared by sol-gel method. Its catalytic activity was evaluated by gas-phase catalytic dehydrogenation of 1, 5-Pentanediol to δ-valerolactone as a probe reaction. CuO/ZnO/Al2O3 and long period reactive CuO/ZnO/Al2O3 were detected by XRD. Micro-structure and essence disciplinarian of CuO/ZnO/Al2O3 were disclosed. Metal ions had a cooperative effects during the catalytic dehydrogenation of 1, 5-pentanediol to δ-valerolactone. After CuO/ZnO/Al2O3 deactivation, crystal particle size was increased clearly. It were found that characteristic diffraction peaks were caused by the catalyst temperature raising in methanol catalytic synthesis of ZnO. 1, 5-Pentanediol and δ-valerolactone were detected by FTIR. Their internal chemical bond and molecular structure were disclosed. The purity of δ-valerolactone product was very high. δ-Valerolactone and its polymer were detected by DSC. δ-Valerolactone possessed with poor stability. Polymerization reaction was easily happened by itself. So it was worth focusing on how to improve the stability of the δ-valerolactone monomer. This study could provide basic data and experimental basis for gas-phase catalytic dehydrogenation of 1, 5-Pentanediol to δ-valerolactone in pilot and industrial scale up research.

[Preparation of premonitory Li(x)MoS2 and its spectral analysis].

Under the effect of ultrasonic waves, premonitory Li(x)MoS2 was prepared by n-butyl lithium intercalating in the MoS2 layers, using the single-molecular-layer exfoliated-restacked technology. The value of x was in the range from 0.93 to 0.96 determined by atomic absorption spectrometry. Micro-structure and essential regularity of Li(x)MoS2 were disclosed, for example octahedral configuration of Li(x)MoS2 was metastable. It could provide experimental data for synthesizing new hydrogenation catalysts for interaction of MoS2 with high activity and selectivity. This work will lay the foundation for the research on hydrogenation catalysts and the production of high value-added MoS2.

[Purification of sulfolene and its UV-Vis and FTIR spectral analysis].

Purification of raw sulfolene was investigated by adsorption method using activated carbon and exchange resin, and the sulfolene was detected by UV-Vis, FTIR and XRD. FTIR spectra of sulfolene and sulfolane were especially analyzed. The results showed that it was the best way to purify industrial grade sulfolene by activated carbon connected exchange resin. The sulfolane with high quality was synthesized by purified sulfolene through catalytic hydrogenation with catalyst. The conversion efficiency was more than 99.8%. It could provide experimental data for the technical reform of industry equipment.

[Preparation of Mo-Fe catalysts by sol-gel method and its XRD, FTIR spectral analysis].

The effect of catalyst atomic ratio on the performance of selective oxidation of p-xylene as a probe reaction over Mo-Fe catalysts prepared by sol-gel method was investigated. The catalyst evaluation results show that the optimum catalyst atomic ratio is n(Mo) : n(Fe) : n(Co) = 2.4 : 1 : 0.02 with a high catalytic activity. The composition of the catalyst is Fe2 (MoO4)3 and a little MoO3 having a cooperative effects during the oxidation of p-xylene, which was detected by XRD and FTIR. This study could provide experimental data for the technical reform of industry equipment.

[XRD and FTIR spectra characteristics of nacreous layer in perna viridis].

The XRD and FTIR of aragonites in nacreous and prismatic layer of perna viridis were systematically measured, and the frequency variations of v1, v2 and v4 band of aragonites were especially analyzed. The results showed that both of them were aragonite and the frequency of v2 band differed in them, but the frequencies of other two bands were not altered and had the same values with cavernous aragonite. In the same specie of shell, the frequency of v2 band in nacreous layers was greater than that in prismatic layers, and there was a frequency shift of v2 band between them. For the first time, the phase transformation of biogenic aragonite was detected. After nacreous aragonite was heated at 300 degrees C, the frequency shift of v2 band was found. So it is concluded that the biogenic aragonite is related to the thermal effects in crystallizing process, meanwhile it stores excess energy. All of these can provide experiential basis for studying biomineralization theory.