WO2004018356A1 - Procede de production de soufre polymere - Google Patents

Procede de production de soufre polymere Download PDF

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Publication number
WO2004018356A1
WO2004018356A1 PCT/EP2003/009212 EP0309212W WO2004018356A1 WO 2004018356 A1 WO2004018356 A1 WO 2004018356A1 EP 0309212 W EP0309212 W EP 0309212W WO 2004018356 A1 WO2004018356 A1 WO 2004018356A1
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WIPO (PCT)
Prior art keywords
sulphur
process according
polymeric
combination
elements
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Ceased
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PCT/EP2003/009212
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English (en)
Inventor
Franco Cataldo
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Individual
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Individual
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Priority to AU2003264074A priority Critical patent/AU2003264074A1/en
Publication of WO2004018356A1 publication Critical patent/WO2004018356A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/12—Insoluble sulfur (mu-sulfur)

Definitions

  • the patent covers a new and original process for the production of polymeric sulphur.
  • the process involves a crosslinking reaction of molten sulfur with opportune crosslinking agents added with the twofold scope of increasing the yields and to stabilize the polymeric allotrope of sulphur which is formed at high temperature.
  • the new process involves the adoption of a new safer solvent for the purification of the polymeric sulphur and the elimination of the dangerous and toxic CS 2 .
  • the polymeric sulphur is a fundamental raw material for the rubber industry.
  • polymeric sulphur is known to the experts of the art also as "insoluble sulphur" because, just for its macromolecular chemical structure, is completely insoluble in any organic solvent, including carbon disulfide which is the best solvent for common sulphur (cyclooctasulphur).
  • the polymeric sulphur can be distinguished from common sulphur or rhombic sulphur just for its high molecular weight and chemical structure, being in fact made by long chains of sulphur atoms arranged according to defined supramolecular structures (see for more details: F. Cataldo, Die Angewandte Makromolekulare Chemie vol. 249, p.l 37-149, 1997).
  • the molecular weight of polymeric sulphur is of the order of 10 6 Dalton, as determined by ESR measurements.
  • common sulphur is a molecular solid whose molecules are made by 8 sulphur atoms arranged in eight-member rings, each of which has a molecular weight of 256 Dalton.
  • the common sulphur is called also cyclooctasulphur.
  • the molecules of cyclooctasulphur in the solid state form rhombic crystals or, under special conditions, monoclinic crystals.
  • the cyclooctasulphur crystals are soluble in the common organic solvents thanks to the low molecular weight of the molecules composing these crystals.
  • the polymeric sulphur represents a technological alternative to the common sulphur and it is employed as replacement of the latter under well defined circumstances, for instance when sulphur blooming phenomena represent a major problem in the manufacture of rubber compounds (see more details on this aspect on: F. Cataldo, 1997, cit.).
  • the present patent we desire to cover a process involving sulphur melting at temperature comprised between 150° and 444°C in presence of one ore more sulphur additives acting as crosslinking agents followed by a rapid cooling or quenching of the molten sulphur in an opportune medium, preferably cold water, cold hydrogen peroxide, a chilled organic solvent or even a cryogenic medium such as liquid air or liquid nitrogen.
  • an opportune medium preferably cold water, cold hydrogen peroxide, a chilled organic solvent or even a cryogenic medium such as liquid air or liquid nitrogen.
  • the present patent covers a process for the purification of the polymeric sulphur produced, by an extraction step made with diiodomethane (CH 2 I 2 ) in place of the currently used CS 2 .
  • the sulphur brought at high temperatures and, to be precise, at temperatures above 170°C consists of an equilibrium of at least two species: cyclooctasulphur and chain-sulphur having variable length and hence molecular weight (cfr. F.A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, Wiley- Intersciences, p.406-409, 1962). If the melt is quenched, it gives a mixture of polymeric sulphur and cyclooctasulphur in the approximate proportion of 25% and 75% respectively.
  • the cyclooctasulphur present in the mixture can be removed through an extraction process using for instance CS 2 as solvent.
  • the insoluble sulphur prepared in this way is in a metastable form and in few hours or days it is fully reverted to cyclooctasulphur.
  • the process involving the passage from polymeric sulphur to cyclooctasulphur is known as "reversion". Therefore, the simple sulphur melting process in the form just described above is not suitable for any industrial application both for the very low stability of the polymeric sulphur produced with such a process and for the low yields in polymeric sulphur offered by the mentioned process: just about 25%.
  • heating of sulphur together with opportune sulphur crosslinking agents such as the elements of the 5 th group of the Periodic Table: P, As, Sb, Bi in their elemental state or under the form of derivatives like for instance their sulfides, selenides, tellurides or halides, causes both a neat increase in the yields of insoluble sulphur but also a neat improvement in the reversion resistance of the produced sulphur.
  • crosslinking agent in its preferred form of actuation of the present invention, the preference as crosslinking agent has been given to elemental phosphorous in its red modification in any stoichiometric ratio with sulphur but preferably in S/P ratio between 40 and ⁇ . Elemental phosphorus can be replaced by its derivatives under the form of all class of phosphorus sulphides, phosphorus selenides and phosphorus tellurides in general, with preference for tetraphosphorus decasulphide (P 4 S ⁇ o) or tetraphosphorus trisulphide (P 4 S ) as crosslinking agents and yield enhancers in the production of insoluble sulphur.
  • P 4 S ⁇ o tetraphosphorus decasulphide
  • P 4 S tetraphosphorus trisulphide
  • the object of the present invention is a process which involves the melting of sulphur in presence of an adequate crosslinking agent or crosslinking agents mix, as detailed above, at temperatures comprised between 150°C and 444°C, for times ranging from 1 hour to several hours.
  • the melt In order to ensure an high yield in polymeric sulphur, the melt must be rapidly cooled in an opportune quenching medium consisting of cold water, cold hydrogen peroxide, a chilled organic solvent, preferably diiodomethane, or even a cryogenic medium like liquid air or liquid hydrogen.
  • the melt must be poured in a quenching medium in such a way to ensure the maximum exchange of heat in the shortest possible time.
  • the best way to do this is to pour the melt into the quenching medium under the form of thin threads.
  • the purification of the polymeric sulphur formed in the process involves the extraction of the cyclooctasulphur from the product. This may be performed during the quenching step or after a "maturation" period.
  • the present invention requires the use of diiodomethane as extraction and purification solvent rather than carbon disulfide with the advantage of much lower toxicity and no flammability.
  • the invention represents a big step ahead in the process safety, an innovation which is part of the invention itself.
  • the following examples illustrate the invention in its preferred form of actuation. It is obvious that changes and variations can be easily introduced by experts in the art without exiting from the field protected by the present patent.
  • the flask once charged with the components, is heated in an oil bath to the sulphur melting point. Then the mixture is stirred slowly to homogenize the components and heated up to about 190°-220°C. At this point the stirring speed is increased to the maximum value and the system is kept under the described conditions for 1 hour.
  • the temperature is brought at 240°-280°C and at the end of the second hour the mass is poured as a thin thread into a large cup filled with cold water.
  • the sulphur threads solidify into a solid elastic coil.
  • the sulphur is left to crystallize at room temperature for at least one day. Then the sulphur is crushed in a mortar and grinded in an opportune mill to powder form.
  • the yields have been always quantitative in all examples.
  • the powdered sulphur has then been extracted with CH 2 I 2 (methylene iodide or diiodomethane). Through the extraction with CH 2 I it was possible to separate the soluble sulphur (cyclooctasulfur) from the polymeric and insoluble sulphur. After the extraction the polymeric sulphur was rinsed with dichloromethane (CH 2 C1 2 ) and dried in air. The yield in insoluble sulphur has been determined gravimetrically (see Table 1 for a summary of the results). The solvent extraction causes sometimes the agglomeration and clumping of the particles of insoluble sulphur which need to be grinded again after the extraction process.
  • Example 1 refers to the "blank” i.e. the reference level of polymeric sulphur reachable without additives.
  • blade i.e. the reference level of polymeric sulphur reachable without additives.
  • Si46iPI 7 we mean that every 1461 sulphur atoms there is one phosphorus atom and 7 iodine atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé nouveau et original permettant de produire du soufre polymère. Ce procédé consiste à soumettre le soufre en fusion à une réaction de réticulation avec des agents de réticulation opportuns ajoutés afin de répondre au double objectif d'augmenter le rendement et de stabiliser l'allotrope polymère de soufre formé à haute température. Ce nouveau procédé comprend en outre l'utilisation d'un nouveau solvant pour la purification du soufre polymère, présentant une sécurité améliorée, et l'élimination du CS2 dangereux et toxique.
PCT/EP2003/009212 2002-08-22 2003-08-20 Procede de production de soufre polymere Ceased WO2004018356A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003264074A AU2003264074A1 (en) 2002-08-22 2003-08-20 Process for the production of polymeric sulphur

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000434A ITRM20020434A1 (it) 2002-08-22 2002-08-22 Procedimento per la sintesi di zolfo polimerico.
ITRM2002A000434 2002-08-22

Publications (1)

Publication Number Publication Date
WO2004018356A1 true WO2004018356A1 (fr) 2004-03-04

Family

ID=11456459

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/009212 Ceased WO2004018356A1 (fr) 2002-08-22 2003-08-20 Procede de production de soufre polymere

Country Status (3)

Country Link
AU (1) AU2003264074A1 (fr)
IT (1) ITRM20020434A1 (fr)
WO (1) WO2004018356A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100427386C (zh) * 2005-12-22 2008-10-22 南化集团研究院 中品位不溶性硫磺的制备方法及其生产设备
CN102275879A (zh) * 2011-07-26 2011-12-14 山东阳谷华泰化工股份有限公司 一种不溶性硫磺的生产工艺
CN104192811A (zh) * 2014-08-26 2014-12-10 偃师市宝隆化工有限公司 一种硫磺的简易提纯方法
WO2020088047A1 (fr) * 2018-11-02 2020-05-07 山东阳谷华泰化工股份有限公司 Procédé de préparation de soufre insoluble, et stabilisateur anti-réversion utilisé
CN111377411A (zh) * 2018-12-29 2020-07-07 中国石油化工股份有限公司 一种不溶性硫磺生产方法和生产系统

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1120493A (fr) * 1954-03-13 1956-07-06 Ruhrgas Ag Procédé de fabrication de soufre insoluble
GB802964A (en) * 1956-06-08 1958-10-15 Stauffer Chemical Co Improvements in or relating to treatment of sulphur
US2947614A (en) * 1954-03-13 1960-08-02 Ruhrgas Ag Method of making insoluble sulphur
US3689227A (en) * 1971-11-12 1972-09-05 Union Oil Co Method for producing insoluble sulfur
US4238470A (en) * 1979-07-30 1980-12-09 Stauffer Chemical Company Method for oil-treating insoluble sulfur
RO92799B1 (ro) * 1985-09-06 1987-10-31 COMBINATUL CHIMIC TîRNAVENI Procedeu de obtinere a sulfului insolubil

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1120493A (fr) * 1954-03-13 1956-07-06 Ruhrgas Ag Procédé de fabrication de soufre insoluble
US2947614A (en) * 1954-03-13 1960-08-02 Ruhrgas Ag Method of making insoluble sulphur
GB802964A (en) * 1956-06-08 1958-10-15 Stauffer Chemical Co Improvements in or relating to treatment of sulphur
US3689227A (en) * 1971-11-12 1972-09-05 Union Oil Co Method for producing insoluble sulfur
US4238470A (en) * 1979-07-30 1980-12-09 Stauffer Chemical Company Method for oil-treating insoluble sulfur
RO92799B1 (ro) * 1985-09-06 1987-10-31 COMBINATUL CHIMIC TîRNAVENI Procedeu de obtinere a sulfului insolubil

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; DEAK, MIKLOS ET AL: "Manufacture of insoluble sulfur", XP002265880, retrieved from STN Database accession no. 109:57509 CA *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; SEMENISHIN, E. M. ET AL: "Kinetics of combined grinding and separation of polymeric and soluble sulfur", XP002265881, retrieved from STN Database accession no. 97:200183 CA *
KHIMICHESKAYA TEKHNOLOGIYA (KIEV) (1982), (4), 38-9 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100427386C (zh) * 2005-12-22 2008-10-22 南化集团研究院 中品位不溶性硫磺的制备方法及其生产设备
CN102275879A (zh) * 2011-07-26 2011-12-14 山东阳谷华泰化工股份有限公司 一种不溶性硫磺的生产工艺
CN104192811A (zh) * 2014-08-26 2014-12-10 偃师市宝隆化工有限公司 一种硫磺的简易提纯方法
WO2020088047A1 (fr) * 2018-11-02 2020-05-07 山东阳谷华泰化工股份有限公司 Procédé de préparation de soufre insoluble, et stabilisateur anti-réversion utilisé
US11427469B2 (en) 2018-11-02 2022-08-30 Shandong Yanggu Huatai Chemical Co, Ltd. Preparation method for insoluble sulfur and anti-reversion stabilizer used thereby
CN111377411A (zh) * 2018-12-29 2020-07-07 中国石油化工股份有限公司 一种不溶性硫磺生产方法和生产系统
CN111377411B (zh) * 2018-12-29 2021-12-07 中国石油化工股份有限公司 一种不溶性硫磺生产方法和生产系统

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Publication number Publication date
ITRM20020434A0 (it) 2002-08-22
ITRM20020434A1 (it) 2004-02-23
AU2003264074A1 (en) 2004-03-11

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