WO1997003954A1 - Compositions contenant des tetraesters de pentaerythritol et leur procede de preparation - Google Patents

Compositions contenant des tetraesters de pentaerythritol et leur procede de preparation Download PDF

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Publication number
WO1997003954A1
WO1997003954A1 PCT/US1996/011460 US9611460W WO9703954A1 WO 1997003954 A1 WO1997003954 A1 WO 1997003954A1 US 9611460 W US9611460 W US 9611460W WO 9703954 A1 WO9703954 A1 WO 9703954A1
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WO
WIPO (PCT)
Prior art keywords
pentaerythritol
alkylthiopropionate
process according
tetraester
alkyl
Prior art date
Application number
PCT/US1996/011460
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English (en)
Inventor
Daniel Chisholm
Richard Peveler
Garrett Mineo
Mark Klein
Michael Denoux
Original Assignee
Witco Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Witco Corporation filed Critical Witco Corporation
Priority to EP96923726A priority Critical patent/EP0782566A4/fr
Priority to JP9506724A priority patent/JPH10512283A/ja
Publication of WO1997003954A1 publication Critical patent/WO1997003954A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups

Definitions

  • the present invention relates to novel compositions containing tetraesters of pentaerythritol, and to processes by which such compositions can be produced. More specifically, the present invention relates to the production of tetra (3-alkylpropionate) esters of pentaerythritol by a novel process which affords a number of process advantages, which process also produces a novel composition from which its major component, the tetraester, can readily be recovered and purified.
  • Alkyl esters derived from alkylthioalkanoic acids and the like are, in general, known to be useful as stabilizers of organic materials such as polymer resins and the like which are otherwise subject to thermal and oxidative deterioration during processing, extrusion or molding, as well as during use.
  • Esters having this general utility have in the past been prepared by various procedures. Dexter, et al . U.S. Patent No. 3,758,549, for example, basically teaches transesterification procedures for the preparation of these types of products. By such procedures, it is often difficult to obtain a product that has a tetraester content at or above 90% by weight, particularly when the transesterification is carried out on an industrial scale.
  • Stabilizers for enhancing the resistance of polyolefins to deterioration can also be prepared by reacting an alpha-olefin with a multi-functional ester of a mercaptocarboxylic acid.
  • Stabilizers of this type and the process for their preparation are disclosed in Kauder, et al . U.S. Patent No. 4,080,364.
  • Experience with this type of addition reaction indicates the product thus formed has a tetraester content which typically does not meet or exceed 90% by weight.
  • U.S. Patent No. 4,349,468 teaches the preparation of a pentaerythritol tetrakis (3-laurylthiopropionate) stabilizer for polyolefins which is produced by a process including heating an alpha-olefin such a 1-dodecene with a beta- mercaptopropionic acid or ester in the presence of an azonitrile or peroxide catalyst, followed by esterifying the resultant alkylthiopropionic acid with pentaerythritol.
  • the present invention is directed to a process for producing a pentaerythritol tetrakis 3- alkylthiopropionate tetraester wherein each alkyl portion contains 4 to 20 carbon atoms, comprising reacting pentaerythritol and lower alkyl (preferably methyl) 3-alkylthiopropionate in the presence of an organotin catalyst for said reaction under elevated temperature conditions at which said tetraester forms.
  • the pentaerythritol is reacted with one or more lower alkyl 3-alkylthiopropionate esters, wherein the lower alkyl portion contains 1 to 4 carbon atoms and is unbranched, and the alkyl portion contains 4 to 20 carbon atoms.
  • the present invention is also directed to compositions of matter comprising at least about 90 wt.%, and more advantageously at least about 95 wt.%, of one or more tetrakis 3-alkylthiopropionate tetraesters of pentaerythritol wherein each alkyl portion contains 4 to 20 carbon atoms, together with one or more tris (3-alkylthiopropionate) esters of pentaerythritol and with lower (C x to C 4 ) alkyl 3- alkylthiopropionate, i.e. methyl, ethyl, n-propyl or n-butyl 3-alkylthiopropionate, in each of which the alkyl portion contains 4 to 20 carbon atoms.
  • the tetraesters produced in accordance with the present invention are useful as stabilizers of, for instance, polymeric resins against thermal degradation and oxidative deterioration during processing, extrusion or molding, as well as during use of such polymeric materials.
  • the present invention uses lower alkyl 3- alkylthiopropionate, wherein "lower alkyl” denotes an alkyl chain, preferably not branched, which when substituted with -OH is a relatively volatile alkanol.
  • Preferred lower alkyl groups are methyl, ethyl, n- propyl and n-butyl .
  • the most preferred lower alkyl group is methyl.
  • the 3-alkylthiopropionate used in the process of the present invention can have been formed by any of a number of techniques, the preferred one of which is described hereinbelow.
  • the 3-alkylthiopropionate can be made by a direct addition reaction procedure which is carried out in order to minimize the recovery of anything other than the desired 3-alkylthiopropionate.
  • the length of the carbon chain of the alkyl group within the 3-alkylthiopropionate is selected by the carbon chain length of the mercaptan which is charged into the reaction vessel .
  • the selected mercaptan undergoes an addition reaction with methyl acrylate to form the 3-alkylthiopropionate.
  • the mercaptan has the formula RSH, wherein R has a carbon chain length of between 4 and about 20 carbon atoms.
  • exemplary reactants in this regard include n-butylmercaptan, n- octylmercaptan, n-decylmercaptan, n-dodecylmercaptan and the like.
  • Generally equimolar charges of this mercaptan and the ester addition reactant are incorporated into the reaction vessel, although either component may be present at a concentration slightly in excess of the equimolar level.
  • the other addition reactant which may be characterized as the acrylate reactant, can be charged to the reaction vessel as the corresponding lower alkyl acrylate, wherein "lower alkyl" is as defined above.
  • the preferred reactant in this regard is methyl acrylate.
  • the addition reaction is run under strongly basic conditions. Any strong base can be utilized as the catalyst, provided an aqueous solution thereof will impart a pH of at least about 11.
  • the strength of the base can be generally defined as one wherein a 1% aqueous solution thereof has a pH of at least about 13.
  • strong bases in this regard include aqueous potassium hydroxide, and aqueous sodium hydroxide.
  • reaction composition incorporate an adequate concentration of this strong base.
  • the amount is to be adequate to act as a catalyst for the addition reaction.
  • the reaction composition should typically include at least about 1 to 2 mole percent of strong base per mole of acrylate charged into the reaction vessel.
  • the 3-alkylthiopropionate is isolated from the reaction composition by proceeding first with acidification of the reaction mixture, typically with a suitable aqueous mineral acid.
  • Aqueous and organic layers thereby defined are then separated. If necessary, depending upon the carbon chain length of the mercaptan reactant, the layers are maintained at a temperature high enough to keep the alkylthiopropionate molten.
  • the collected organic phase is preferably vacuum stripped in order to remove (and optionally, recover) unreacted components and thereby provide the 3-alkylthiopropionate addition reaction product.
  • the lower alkyl, and preferably methyl, 3- alkylthiopropionate, however produced or obtained, is reacted with pentaerythritol to produce the desired tetraester.
  • this reaction proceeds, at satisfactory rate and yield, when the 3- alkylthiopropionate and the pentaerythritol are reacted in the presence of an organotin catalyst for the reaction, under elevated temperature conditions. It is preferred to employ an amount of the ester representing a stoichiometric excess with respect to the amount of pentaerythritol present.
  • the amount of organotin catalyst can range up to about 5.0 wt.% based on the amount of pentaerythritol present, although higher amounts of catalyst can be used to advantage as well.
  • Preferred catalysts include organotin compounds, in particular monoalkyltin hydroxide, monoalkyltin chloride, monoalkyltin chlorohydroxide, and/or mixtures thereof, wherein the alkyl group contains 1 to 8 carbon atoms . Mixtures of any of the foregoing may also be used to advantage.
  • Particularly preferred catalysts include monobutyltin chloride and monobutyltin hydroxide, and a more preferred catalyst comprises a 50:50 (by weight) mixture of monobutyltin hydroxide and monobutyltin chloride, the total combined amount of catalyst comprising about 1.5 to 2.0 wt.% based on the amount of pentaerythritol present.
  • At least one organotin chloride compound, and more preferably at least one alkyltin chloride, compound is present in the catalyst component.
  • Other useful catalysts include di (C 1 to C 8 ) alkyl tin bis- (C 8 to C 12 ) carboxylate such as dimethyl tin bis-neodecanoate, as well as mono (C- ⁇ to C 8 ) alkyl tin tris (3-alkylthiopropionate) and di (C x to C 8 ) alkyl tin bis (3-alkylthiopropionate) .
  • Preferred examples of the latter include dimethyl tin bis-3- laurylthiopropionate and methyl tin tris-3- laurylthiopropionate.
  • the reaction of the lower alkyl, e.g. methyl, 3-alkylthiopropionate, pentaerythritol, and catalyst should be carried out solvent-free. If desired, a small but effective amount of solvent may be employed, but it would have to be inert to the reactants, have a very high boiling point, and be relatively easily removed from the mixture formed by the reaction.
  • the reaction is carried out at temperatures effective to enable formation of the desired tetraester. Effective reaction temperatures are typically in the range of 150°C to 250°C, and more typically in the range of about 175°C to 225°C. As those experienced in this field will recognize, it may be desirable to adjust the temperature during the course of the reaction, for instance by raising the temperature. The time required for satisfactory conversion in the reaction can typically range from 2 to 20 hours.
  • reaction temperature conditions are able to achieve formation of the desired tetraester product, particularly in significant yields at acceptable rates, has been confirmed and is all the more unexpected in view of the teachings in the prior art, such as U.S. Patent No. 5,057,622, suggesting that production of the desired tetraester by transesterification would not be successful.
  • the process of the present invention accomplished formation of the desired tetraester at yields above about 70% even before isolation of the desired product.
  • the tetraester can be recovered from the reaction mixture by subsequent recovery and purification steps using procedures which are well known in this field. For instance, the catalyst should be filtered off and the product purified by one or more recrystallization steps.
  • the solvent refining medium is one or more organic solvents which are particularly well suited for the specific alkylthiopropionic tetraester being prepared.
  • a preferred solvent is 2-propanol (isopropanol) .
  • Other exemplary solvents include other low molecular weight alcohols and low molecular weight esters, including materials such as methanol, ethanol, ethyl acetate, isopropyl acetate, and the like. It has been found that a suitable solvent or blend will improve work-up purification procedures, when desired, in a manner that minimizes the expense thereof.
  • a blend of methanol and isopropanol is generally preferred for the work-up purification of the liquid tetraester of 3-octylmercaptopropionic acid with pentaerythritol. It has been found that this solvent blend is non-miscible with this tetraester and performs well as an extracting solvent for any triester impurity and unreacted octylmercaptopropionic acid.
  • a typical two-component solvent blend would be at a ratio of between about 9 to 1 and about 1 to 9.
  • a product which contains 90 wt.% or more, preferably 95 wt.% or more, of the desired tetra (3-alkylthiopropionate) ester of pentaerythritol .
  • the composition of matter will also contain minor amounts of the triester, that is, a tri (3-alkylthiopropionate) ester of pentaerythritol, as well as a minor amount of unreacted lower alkyl, e.g. methyl, 3- alkylthiopropionate ester.
  • the amounts of the triester byproduct and of the unreacted ester can comprise up to about 0.1 wt.% or even up to about 1 wt.%, although of course lesser or higher amounts may be present depending on the degree of completion of the reaction.
  • Esters of the type discussed herein are typically suitable for use as stabilizers for polymers.
  • the tetraesters with pentaerythritol have been found to be especially useful as stabilizers for a class of proprietary polymers and polymer blends having a terephthalate ester component and a rubbery tyP e °f component.
  • Articles extruded from these types of proprietary polymers have superior impact resistance properties and can be suitable for use as automobile bumpers and the like.
  • the 3- dodecylthiopropionate tetraester of pentaerythritol has been observed to be generally equal in performance to similar ester stabilizers manufactured on a commercial scale by a process believed to be more complicated than the procedure of the present invention.
  • esters made from dodecylmercaptan are solid at room temperature and less likely to exhibit a noticeable odor when in use as a stabilizer.
  • Esters made from octylmercaptan are basically liquid at room temperature, are less waxy than esters having a greater molecular weight, and can be more compatible, particularly with polymer resins that tend to be liquid at room temperature.
  • Esters prepared from decylmercaptan typically have properties the- reinbetween, and they can exhibit good compatibility without excessive volatility.
  • LM lauryl mercaptan
  • MA methyl acrylate
  • the IPA was then stripped from the two mother liquors by heating under vacuum to 95°C.
  • the two mother liquors were combined and analyzed.
  • the yield based on 2nd crystals and mother liquor crystals was 84.4%.
  • the yield based on pentaerythritol was 96.6% (including rework crystals and known losses) .
  • EXAMPLE 2 The transesterification reaction to produce pentaerythritol tetrakis (3-laurylthiopropionate) was 1 carried out with varying amounts of two different catalysts to assess desirable catalyst amounts. The reactions were run for 6 hours at 205°C with mild vacuum being applied for the last two hours. The mole
  • the catalyst concentration is 0 preferably at least 1000 ppm (based on the total reaction mass) and more preferably at least 1500 ppm.
  • the process of the present invention affords a number of advantages which distinguish it further from past practices.
  • the reaction to form the 5 tetraester can be run solvent-free, thus avoiding the expense, the additional materials handling burden, and the solvent removal burden that are imposed by the use of solvents. Indeed, even the water requirements are minimal, so contamination of product by water is 0 likewise minimized. Removal of recrystallization solvent is easier..
  • the tetraester has a lower acid
  • mother liquors (process streams) employed in the process can be recycled with minimal requirements for purification and without requiring further reactions of the byproducts present.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'esters tétra(3-alkylthiopropionate) de pentaérythritol, dans lesquels chaque partie alkyle contient de 4 à 20 atomes de carbone, et qui consiste à mettre en réaction le pentaérythritol et un ou plusieurs esters 3-alkylthiopropionate d'alkyle inférieur, par exemple méthyle, en présence d'un catalyseur d'organo-étain à température élevée. Elle concerne également une composition contenant ledit tétraester en tant que constituant principal et comprenant également le triester et le 3-alkylthiopropionate d'alkyle inférieur correspondants.
PCT/US1996/011460 1995-07-18 1996-07-09 Compositions contenant des tetraesters de pentaerythritol et leur procede de preparation WO1997003954A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96923726A EP0782566A4 (fr) 1995-07-18 1996-07-09 Compositions contenant des tetraesters de pentaerythritol et leur procede de preparation
JP9506724A JPH10512283A (ja) 1995-07-18 1996-07-09 ペンタエリスリトールテトラエステルを含む組成物およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US50388795A 1995-07-18 1995-07-18
US08/503,887 1995-07-18

Publications (1)

Publication Number Publication Date
WO1997003954A1 true WO1997003954A1 (fr) 1997-02-06

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PCT/US1996/011460 WO1997003954A1 (fr) 1995-07-18 1996-07-09 Compositions contenant des tetraesters de pentaerythritol et leur procede de preparation

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EP (1) EP0782566A4 (fr)
JP (1) JPH10512283A (fr)
CA (1) CA2198618A1 (fr)
WO (1) WO1997003954A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6370073B2 (en) 1998-10-01 2002-04-09 Monlithic System Technology, Inc. Single-port multi-bank memory system having read and write buffers and method of operating same
US7022776B2 (en) 2001-11-07 2006-04-04 General Electric Conductive polyphenylene ether-polyamide composition, method of manufacture thereof, and article derived therefrom
CN102153497A (zh) * 2011-02-22 2011-08-17 利安隆（天津）化工有限公司 季戊四醇四（3-正十二烷基硫代丙酸酯）结晶残液回收季戊四醇四（3-正十二烷基硫代丙酸酯）方法
JP2016199629A (ja) * 2015-04-07 2016-12-01 新中村化学工業株式会社 保存安定性に優れるエポキシ基含有（メタ）アクリレート化合物の製造方法
CN108558719A (zh) * 2018-05-21 2018-09-21 烟台新秀化学科技股份有限公司 一种季戊四醇酯的制备方法
CN112300039A (zh) * 2020-11-12 2021-02-02 江苏极易新材料有限公司 一种抗氧化剂412s季戊四醇四(3-月桂基硫代丙酸酯)的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4349468A (en) * 1977-12-23 1982-09-14 Adeka Argus Chemical Co., Ltd. Stabilizer for polyolefin resin
US5055606A (en) * 1989-08-16 1991-10-08 Witco Corporation Alkylthiopropionic pentaerythritol esters and solvent refining thereof
US5093517A (en) * 1987-03-09 1992-03-03 The Goodyear Tire & Rubber Company Method for the esterification of thiopropionates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4349468A (en) * 1977-12-23 1982-09-14 Adeka Argus Chemical Co., Ltd. Stabilizer for polyolefin resin
US5093517A (en) * 1987-03-09 1992-03-03 The Goodyear Tire & Rubber Company Method for the esterification of thiopropionates
US5055606A (en) * 1989-08-16 1991-10-08 Witco Corporation Alkylthiopropionic pentaerythritol esters and solvent refining thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0782566A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6370073B2 (en) 1998-10-01 2002-04-09 Monlithic System Technology, Inc. Single-port multi-bank memory system having read and write buffers and method of operating same
US7022776B2 (en) 2001-11-07 2006-04-04 General Electric Conductive polyphenylene ether-polyamide composition, method of manufacture thereof, and article derived therefrom
CN102153497A (zh) * 2011-02-22 2011-08-17 利安隆（天津）化工有限公司 季戊四醇四（3-正十二烷基硫代丙酸酯）结晶残液回收季戊四醇四（3-正十二烷基硫代丙酸酯）方法
JP2016199629A (ja) * 2015-04-07 2016-12-01 新中村化学工業株式会社 保存安定性に優れるエポキシ基含有（メタ）アクリレート化合物の製造方法
CN108558719A (zh) * 2018-05-21 2018-09-21 烟台新秀化学科技股份有限公司 一种季戊四醇酯的制备方法
CN112300039A (zh) * 2020-11-12 2021-02-02 江苏极易新材料有限公司 一种抗氧化剂412s季戊四醇四(3-月桂基硫代丙酸酯)的制备方法
CN112300039B (zh) * 2020-11-12 2021-07-20 江苏极易新材料有限公司 一种抗氧化剂412s季戊四醇四(3-月桂基硫代丙酸酯)的制备方法

Also Published As

Publication number Publication date
JPH10512283A (ja) 1998-11-24
EP0782566A1 (fr) 1997-07-09
CA2198618A1 (fr) 1997-02-06
EP0782566A4 (fr) 2000-04-26

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