/LABORATORY ANIMALS: Acute Exposure/ No deaths occured following inhalation exposure of mice for 4 hr to "saturated" vapors; however, mucosal irritation, loss of coordination and decreased mobility were noted. Recovery occured in 24 hours.
The absorption and metabolism of (hexyl-2-14C)di-(2-ethylhexyl)terephthalate (DEHT) mixed with corn oil and administered by gavage at 100 mg/kg of body weight in 10 male Sprague Dawley rats (2 animals fasted for 4 hrs after dosing, remaining animals were allowed access to food immediately following dosing). Test material was rapidly hydrolyzed to 2-ethylhexanol (2-EH), mono-(2-ethylhexyl) terephthalate (MEHT) and unlabeled terephthalic acid (TPA). Radioactivity was excreted in the feces (95.6 +/- 12.2% of the dose) as DEHT (36.6%), MEHT (2.5%), and polar metabolites. Radioactivity was excreted in the urine (31.9% +/- 10.9%) as metabolic products of MEHT and 2-EH, and was expired as 14CO2 (3.6 +/- 0.9%). All tissues examined contained 14C with the highest concentrations in the liver and fat. Excretion of 95 and 99% of the total urinary and fecal radioactivity occurred by 24 and 48 hrs, respectively. Major metabolites in the urine included TPA (51% of the dose), oxidized metabolites of 2-EH and MEHT, and glucuronic and sulfuric acid conjugates.
In a reproduction study to evaluate differences between different strains of rats, male and female Wistar and CD strain rats were orally exposed to bis(2-ethylhexyl) terephthalate in the diet at concentrations of 0, 0.03, 0.125, 0.5, 2.0 or 5.0% for 90 days. The number of rats/group and the days during which mating took place were not reported. The surviving rats were sacrificed on day 90 of exposure. There were significant differences between treated and control animals in the following: decreased weight gain (highest 3 dose groups, both strains), dose-dependent lethal effects on newborn and young rats (2 and 5% groups, both strains), decreased day 1 newborn body weight and day 21 newborn survival and increased incidence of parental renal and bladder calculi at day 51 (high-dose group, both strains), increased incidence of chronic inflammatory lesions of the urinary bladder and urethra (high-dose group, more frequent in females of both strains), and strain difference with respect to urinary terephthalic acid concentrations at sacrifice (dose level not reported). There were no significant differences between treated and control animals in the following: reproduction or fertility parameters, and microscopic examination of kidney or ureter.
The mutagenicity of urine from Sprague-Dawley rats dosed daily by gavage for 15 days with 2,000 mg/kg of bis(2-ethylhexyl) terephthalate was evaluated in Salmonella tester strains TA 98, TA100, TA1535, TA1537 and TA1538 (Modified Ames Test), both in the presence and absence of Aroclor-induced rat liver S9 metabolic activation and beta-glucuronidase/aryl sulfatase. Cultures were dosed with up to 2 ml of urine using direct plating procedures. The urine of rats treated with di-(2-ethylhexyl) terephthalate did not cause a positive response under any of the test conditions.
The mutagenic effect of bis(2-ethylhexyl) terephthalate was evaluated in Salmonella typhimurium strains TA 1535, TA 1537, TA 1538, TA 98 and TA 100 with and without metabolic activation provided by rat liver S9 fraction. The test article was administered at levels from 0.001 to 10.0 mg/plate and was not found to be mutagenic in the presence or absence of activation. In a preliminary range finding study, bis(2-ethylhexyl) terephthalate levels up to 10 mg/plate were non-toxic to cells.
Rats readily excreted (14)C EHT given in a single dose at 100 mg/kg. 57.9%, 28.6%, and 3.6% of the (14)C was recovered in the feces, urine an expired air, respectively, within 144 hr after admin. Only 2.1% remained in the carcass.
The hydrolysis of di(2-ethylhexyl) terephthalate and di(2-ethylhexyl) phthalate were studied using rat gut homogenate fractions in vitro. Both isomers were hydrolysed by the intestinal fraction; however di(2-ethylhexyl) phthalate was hydrolysed to 2-ethylhexanol and mono(2-ethylhexyl) phthalate in about equal proportions whereas di(2-ethylhexyl) terephthalate was hydrolysed to 2-ethylhexanol and terephthalic acid. The half-lives for disappearance of the diesters were determined to be 12.6 min for di(2-ethylhexyl) phthalate and 53.3 min for di(2-ethylhexyl) terephthalate. 2. The absorption and metabolism of di(2-ethylhexyl) terephthalate were studied by administering (hexyl-(14)C)di(2-ethylhexyl) terephthalate (in corn oil) by oral gavage at a dose level of 100 mg/kg to 10 adult male Sprague Dawley rats. Urine feces and expired air were collected for 144 hr and analysed for the presence of radioactivity and feces and urine were analysed for unlabelled metabolites. 3. Radioactivity was eliminated in feces (56.5 +/- 12.1% of dose) primarily as unchanged di(2-ethylhexyl) terephthalate, small amounts of mono(2-ethylhexyl) phthalate and polar metabolites; excreted in urine (31.9 +/- 10.9% of dose) principally as mono(2-ethylhexyl) phthalate and metabolic products of 2-ethylhexanol; and expired as (14)C02 (3.6 +/-0.9% of dose). Less than 2% of the administered radioactivity was found in the carcass. Small amounts of (14)C were found in the tissues with the highest amounts found in liver and fat. 4. Metabolites identified in urine included terephthalic acid (equivalent to 51% of dose), oxidized metabolites of 2-ethylhexanol and mono(2-ethylhexyl) phthalate, and glucuronic and sulfuric acid conjugates (equivalent to about 10% of dose). 5. These findings indicate that di(2-ethylhexyl) terephthalate was hydrolysed more extensively than di(2-ethylhexyl) phthalate and consequently the urinary metabolite profiles for these two isomeric plasticizers were very different. The hydrolysis and metabolism of di(2-ethylhexyl) terephthalate were found to be similar to those of di(2-ethylhexyl) adipate in that hydrolysis of both ester bonds occurs.
[EN] PROCESS FOR PREPARING CARBOXYLIC ACID ESTERS IN THE PRESENCE OF A TITANIUM-CONTAINING CATALYST<br/>[FR] PROCÉDÉ DE PRÉPARATION D'ESTERS D'ACIDES CARBOXYLIQUES EN PRÉSENCE D'UN CATALYSEUR CONTENANT DU TITANE
申请人：SIBUR HOLDING PUBLIC JOINT STOCK CO
公开号：WO2016043616A1
公开（公告）日：2016-03-24
The present invention relates to a process for preparing carboxylic acid esters, comprising esterification of a carboxylic acid with an alcohol in the presence of a titanium-containing catalyst selected from compounds of a general formula, Tin(OR)x(OR')xOy, wherein n is an integer from 1 to 4; у is an integer from 0 to 6; x can be the same or different and is an integer from 2 to 8; R is a linear or branched C1-C18alkyl, C3-C18cycloalkyl, R' is aryl optionally comprising an electron-donor substituent; or a mixture thereof, with the proviso that if n is 1, then x is 2 and у is 0; and if n>1, then the compounds comprise at least two alkoxy groups and two aryloxy groups. The present invention also relates to a process for preparing carboxylic acid esters, wherein a compound of general formula (I) or (II), wherein q represents an integer of 1 to 4; Y is independently R or R'; or a mixture thereof, with the proviso that the compounds comprise at least two alkoxy groups and two aryloxy groups, is used as a catalyst. The claimed process allows to reduce the amount of a used catalyst and the time of the process duration, while increasing the conversion rate of initial reagents and the yield of a target product.
[EN] HEMI-AMINAL ETHERS AND THIOETHERS OF N-ALKENYL CYCLIC COMPOUNDS<br/>[FR] ÉTHERS ET THIOÉTHERS HÉMIAMINAUX DE COMPOSÉS CYCLIQUES N-ALCÉNYLIQUES
申请人：ISP INVESTMENTS INC
公开号：WO2014116560A1
公开（公告）日：2014-07-31
Described herein are hemi-aminal ethers and thioethers of N-alkenyl cyclic compounds that may be produced through a reaction comprising: (A) at least one first reactant represented by a structure (I), wherein X is a functionalized or unfunctionalized C1-C5 alkylene group optionally having one or more heteroatoms, and each R1, R2, and R3 is independently selected from the group consisting of hydrogen and functionalized and unfunctionalized alkyl groups optionally having one or more heteroatoms, and (B) at least one second reactant having at least one hydroxyl moiety or thiol moiety. The hemi-aminal ethers and thioethers of N-alkenyl cyclic compounds may comprise a polymerizable moiety, in which case they may be left as-is or used to create homopolymers or non-homopolymers, or they may not comprise a polymerizable moiety. A wide variety of formulations may be created using the hemi-aminal ethers and thioethers of N-alkenyl cyclic compounds, including personal care, oilfield, and construction formulations.
Production of Copolyester Monomers from Plant‐Based Acrylate and Acetaldehyde
作者：Lin Yuan、Yancheng Hu、Zhitong Zhao、Guangyi Li、Aiqin Wang、Yu Cong、Feng Wang、Tao Zhang、Ning Li
DOI：10.1002/anie.202113471
日期：2022.1.21
alternative route is developed to prepare PCTA monomer with plant-based acrylate and acetaldehyde as the feedstocks. The features include catalytic MBH reaction, one-step dehydration/Diels–Alder reaction over H2SO4/SiO2 catalyst, and Pd/C-catalyzed dehydrogenation. In addition, commonly used plasticizer di(2-ethylhexyl) benzenedicarboxylate and monomer UNOXOL™ diol can also be manufactured.
开发了一种替代路线，以植物基丙烯酸酯和乙醛为原料制备 PCTA 单体。其特征包括催化MBH反应、H 2 SO 4 /SiO 2催化剂上的一步脱水/Diels-Alder反应和Pd/C催化脱氢。此外，还可生产常用的增塑剂二（2-乙基己基）苯二甲酸酯和单体UNOXOL™二醇。
[EN] HYDROSILYLATION REACTION CURABLE COMPOSITIONS AND METHODS FOR THEIR PREPARATION AND USE<br/>[FR] COMPOSITIONS DURCISSABLES PAR UNE RÉACTION D'HYDROSILYLATION ET LEURS PROCÉDÉS DE PRÉPARATION ET D'UTILISATION
申请人：DOW CORNING
公开号：WO2013000788A1
公开（公告）日：2013-01-03
A composition contains (A) a hydrosilylation reaction catalyst and (B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. The composition is capable of reacting via hydrosilylation reaction to form a reaction product, such as a silane, a gum, a gel, a rubber, or a resin. Ingredient (A) contains a platinum-ligand complex that can be prepared by reacting a platinum precursor and a ligand.
Hydrosilylation Reaction Catalysts and Curable Compositions and Methods for Their Preparation and Use
申请人：Dow Corning Corporation
公开号：US20140296468A1
公开（公告）日：2014-10-02
A composition contains (A) a hydrosilylation reaction catalyst and (B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. The composition is capable of reacting via hydrosilylation reaction to form a reaction product, such as a silane, a gum, a gel, a rubber, or a resin. Ingredient (A) contains an iron-organosilicon ligand complex that can be prepared by reacting an iron carbonyl compound and an organosilicon ligand.
