16492-16-3Relevant academic research and scientific papers
Flame-retardant additive, preparation method therefor and application of flame-retardant additive
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Paragraph 0063-0068, (2020/01/03)
The invention discloses a flame-retardant additive, a preparation method therefor and an application of the flame-retardant additive. In view of that phosphorus-containing flame retardants in the prior art have many performance disadvantages and the problem of high manufacturing and service costs, the invention provides a novel phosphorus-containing flame retardant. The flame retardant is used asa flame-retardant additive in an electrolyte of a non-aqueous electrolytte secondary battery. The invention simultaneously provides the preparation method for the flame retardant. The phosphorus-containing flame retardant prepared by the method not only can effectively improve safety of batteries, but also has a specific positive-negative pole membrane forming function, and thus, comprehensive properties such as high-/low-temperature, cycling and storage properties of the secondary battery can be remarkably improved. The preparation method for the flame retardant, provided by the invention, has the advantages that the raw material cost is low, the preparation process is simple in step, the operation is safe, the product purity is high, and the environmental pollution is light.
SILICON-PHOSPHORUS ANALOGIES. NUCLEOPHILIC CATALYSIS IN THE ALCOHOLYSIS OF CHLOROPHOSPHORUS DERIVATIVES
Corriu, Robert J. P.,Lanneau, Gerard F.,Leclercq, Dominique
, p. 1959 - 1974 (2007/10/02)
The mechanism of the alcoholysis of chlorophosphonates and chlorophosphates in presence of nucleophilic catalysts like hexamethylphosphotriamide, pyridine and N-methylimidazole is discussed on the basis of kinetic and stereochemical results.We have proposed a mechanism for the reaction, which is governed by entropy, involving reaction of the alcohol with a pentacoordinated intermediate.This accounts for the differences in the stereochemical outcome and the rate equation which can be derived for the reaction with a variety of substrates in addition to the absence of common ion + solvent effects observed.
NUCLEOPHILIC SUBSTITUTIONS AT SILICON AND PHOSPHORUS. A COMPARISON OF CONTROLLING FACTORS
Corriu, R.J.P.
, p. 1 - 12 (2007/10/02)
The stereochemical behavior of functional organosilanes is explained considering electronic factors.The reactivity depends on the stereochemistry.Retention and /or inversion are controlled by a frontier orbital process.The same conclusions can be extended to the mechanism of nucleophilic substitution of halogenophosphorus compounds.The kinetic data show that the electronic interaction between the incoming nucleophile and the leaving group is very deep when they are both in the apical position of a tbp intermediate.By contrast, the influence of the nucleophile is minimized when the approach of the nucleophile affords a 90 deg angle, i. e. overall retention at phosphorus.The hydrolysis of silicates should be certainly more connected to the process of hydrolysis of phosphates through a mechanism involving pseudorotation of the pentacoordinated intermediates.
INVESTIGATIONS OF THE NUCLEOPHILIC DISPLACEMENT AT THE TETRAHEDRAL PHOSPHORUS - KINETIC EFFECTS OF THE NUCLEOPHILE FOR A GIVEN STEREOCHEMISTRY.
Corriu, Robert J. P.,Lanneau, Gerard F.,Leclercq, Dominique
, p. 5591 - 5600 (2007/10/02)
A kinetic study of alcoholysis and aminolysis of 2-chloro-2-oxo-1,3,2-dioxaphospholane, 1, shows a rate levelling effect of the nucleophile, where the stereochemistry is retention at phosphorus.On the other hand, the substitutions with inversion of the 2-chloro-2-oxo-1,3,2-dioxaphosphorinane 2, or the diethylchlorophosphate, 3, show a marked influence of the nucleophile upon the reactivity.Furthermore, the large rate increase which has been observed for the hydrolysis of the five-membered ring phosphorus esters compared to phosphates (an oxygen always displaces an oxygen) is not reproduced when the leaving group is different of the nucleophile.We suggest that the mechanistic implications, established in the case of phosphate esters hydrolysis cannot be directly extended to the general case of SN2(P).The mechanism of nucleophilic substitution of P(4) species is better interpreted in terms of HOMO-LUMO interactions between the nucleophile and the substrate, a process now well established in silicon chemistry.
Organophosphorus Antioxidants. IV. Chemical Induced Polarization of 31P Nuclei in the Reaction of Cyclic Phosphites with Hydroperoxides
Koenig, T.,Grossmann, G.,Schwetlick, K.,Rueger, C.
, p. 763 - 771 (2007/10/02)
31P-n.m.r.CIDPN is observed in the reactions of cyclic o-phenylene and ethylene phosphites with hydroperoxides.Polarized phosphorus nuclei appear especially in the phosphonate and phosphate regions.Application of Kaptein's rule shows that these products are cage or escape products of secondary or tertiary radical pairs.Solvent molecules are involved in the formation of the tertiary radical pairs.The concentration of the products formed from polarized 31P nuclei is very low.
A NEW EFFICIENT AND VERSATILE SYNTHESIS OF ALKYL PHOSPHORYLCHOLINES
Magolda, R. L.,Johnson, P. R.
, p. 1167 - 1170 (2007/10/02)
A short and general synthetic method is described for the preparation of new phosphorylcholines.
Organophosphorus Antioxidants. III. Kinetics and Mechanism of the Decomposition of Cumyl Hydroperoxide by Cyclic Phosphites
Rueger, C.,Koenig, T.,Schwetlick, K.
, p. 622 - 632 (2007/10/02)
The reaction mechanism of cyclic esters of phosphorous acids I to VIII with cumyl hydroperoxide has been studied kinetically by means of 31P n.m.r. spectroscopy, high performance liquid chromatography and iodometric titration.The five-membered cyclic phosphites (I and II) react with cumyl hydroperoxide to give the corresponding phosphates (AI and AII) and cumyl alcohol.With more hydroperoxide or water they form the open chain phosphate esters (BI and BII) which decompose cumyl hydroperoxide catalytically giving phenol and acetone.Higher membered cyclic phosphites (III to VIII) react with cumyl hydroperoxide to give the corresponding phosphates and alcohol only.The mode of reaction depends on the hydrolysis behaviour of the cyclic phosphates (AI to AVIII).Only fivemembered cyclic phosphites which give easily hydrolyzable phosphates are able to decompose cumyl hydroperoxide catalytically.The nature of the exocyclic group in the phosphites has no influence on this behaviour.The kinetic parameters of the separate reaction steps are given.The ionic mechanism of hydroperoxide decomposition is accompanied by a homolytic one.
SILICON-PHOSPHORUS ANALOGIES. RATE CONTROLLING FACTORS IN SN2(P) REACTIONS. INFLUENCE OF THE NUCLEOPHILE FOR A GIVEN STEREOCHEMISTRY.
Corriu, Robert J.P.,Lanneau, Gerard F.,Leclercq, Dominique
, p. 4323 - 4326 (2007/10/02)
SN2(P) reactions of chlorophosphates, which take place with inversion of configuration, are higly dependent upon the nature of the nucleophile.On the contrary, exocyclic substitutions of five-membered ring chlorophosphates with retention show a marked kinetic levelling effect.
EXOCYCLIC SUBSTITUTION OF FIVE-MEMBERED RING CHLOROPHOSPHATES A REEXAMINATION OF THE RULE FOR NUCLEOPHILIC SUBSTITUTION AT PHOSPHORUS
Corriu, R. J. P.,Lanneau, G. F.,Leclercq, D.
, p. 197 - 200 (2007/10/02)
Opposite to the SN2(P) reactions taking place with inversion, which are highly dependent upon the nature of the nucleophile, exocyclic substitutions of five-membered ring chlorophosphates with retention show a marked kinetic levelling effect, emphasing silicon-type argumentations.
