EP2106395A2 - Addition de h2s sur des terpènes pour produire de nouveaux régulateurs de masse molaire pour des polymérisations radicalaires - Google Patents

Addition de h2s sur des terpènes pour produire de nouveaux régulateurs de masse molaire pour des polymérisations radicalaires

Info

Publication number
EP2106395A2
EP2106395A2 EP07821303A EP07821303A EP2106395A2 EP 2106395 A2 EP2106395 A2 EP 2106395A2 EP 07821303 A EP07821303 A EP 07821303A EP 07821303 A EP07821303 A EP 07821303A EP 2106395 A2 EP2106395 A2 EP 2106395A2
Authority
EP
European Patent Office
Prior art keywords
carried out
thiols
terpenes
unsaturated
addition
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP07821303A
Other languages
German (de)
English (en)
Inventor
Patrick Deck
Oliver Birkert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP07821303A priority Critical patent/EP2106395A2/fr
Publication of EP2106395A2 publication Critical patent/EP2106395A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation

Definitions

  • the present invention relates to a process for the preparation of thiols by addition of hydrogen sulfide to unsaturated terpenes, wherein this reaction is carried out in the presence of at least one ion exchanger as a catalyst.
  • US 4,140,604 discloses a process for the preparation of mercaptans by reacting ethylenically unsaturated organic compounds with hydrogen sulfide in the presence of ultraviolet radiation.
  • suitable ethylenically unsaturated compounds US Pat. No. 4,140,604 discloses straight-chain and branched olefins and cyclic compounds such as, for example, cyclohexene, 1-methylcyclohexene, vinylcyclohexane, styrene, d-limonene, .alpha.-pinene, .beta.-pinene, camphene, p-menthene, .alpha.-terpineol and other terpenes.
  • US 2,076,875 discloses a process for preparing terpene-mercaptans and sulfides by reacting unsaturated terpenes with hydrogen sulfide in the presence of catalysts comprising acids such as sulfuric acid, phosphoric acid, acetic acid and others or their anhydrides, and bases such as potassium hydroxide, calcium hydroxide, monoamylamine, diamylamine, Triamylamine, metallic aluminum and metal sulphides. Furthermore, it is possible to use mixtures of catalysts which, in addition to the aforementioned catalysts, contain activated carbon or silica gel.
  • Flavor and Fragrance Journal, Volume 8, 289-294 (1993) discloses a process for the preparation of fragrances by addition of hydrogen sulfide to monoterpenes in the presence of aluminum trichloride or aluminum tribromide as a catalyst.
  • US 3,408,403 discloses a process for preparing mixtures of sulfides and thiols by reacting compounds selected from the group of pinene, dipentene, terpinene, terpinolene, terpineol, ⁇ -pinene, ⁇ -pinene, etc., with hydrogen sulfide in the presence of a catalyst selected from the group consisting of Alumina, silica-alumina, bauxite, montmorillonite clay and the like.
  • DE 28 37 509 discloses a process for the preparation of 1, 7,7-trimethylol-bicyclo [2.2.1] heptane-2-thiol by reacting ⁇ -pinene with gaseous hydrogen sulfide in the presence of a complex compound of boron trifluoride with diethyl ether of the formula BF 3 * (C 2 H 5 ) 2 O.
  • the processes for the preparation of thiols by addition of hydrogen sulfide to unsaturated organic compounds include the use of acidic or basic organic and inorganic compounds as catalysts. On the one hand, these can be homogeneously dissolved in the reaction solution and, on the other hand, the catalysts can also be present heterogeneously.
  • the prior art does not describe a process which comprises the use of acidic ion exchanger resins as catalysts for the addition of hydrogen sulfide to unsaturated terpenes.
  • Object of the present invention is to provide a process for the preparation of thiols by addition of hydrogen sulfide to unsaturated terpenes, which is characterized by high conversions per amount of catalyst used and problem-free workup of the reaction mixture.
  • This object is achieved by a process for the preparation of thiols by addition of hydrogen sulfide to at least one unsaturated terpene, wherein the reaction is carried out in the presence of at least one organic ion exchanger.
  • the inventive method is characterized by the fact that the use of organic ion exchangers, the work-up of the reaction mixture is greatly simplified.
  • the catalyst may be separated from the reaction mixture by simple steps such as filtration or decantation. Elaborate steps for the separation of a homogeneously dissolved catalyst omitted.
  • acidic organic ion exchangers are characterized by a high density of reactive centers, so that the addition of the hydrogen sulfide to unsaturated terpenes is greatly accelerated even in the presence of small amounts of ion exchanger.
  • the ion exchangers have a relatively low density so that they have many active sites, for example per kilogram.
  • ion exchangers are regenerated in a simple manner, for example by treatment with acids.
  • the acidic ion exchangers used have about the same acid strength as sulfuric acid, so that they catalyze the reaction according to the invention as well as sulfuric acid, but have the advantages of a solid heterogeneous catalyst (see above).
  • the at least one unsaturated terpene and hydrogen sulfide are brought into contact in the presence of at least one organic ion exchange resin.
  • the temperature during the reaction of at least one unsaturated terpene with hydrogen sulphide is generally from 20 to 150 0 C, preferably 70 to 120 0 C.
  • the pressure prevailing in the process according to the invention is generally set to 0.5 to 50 bar, preferably 2 to 45 bar, particularly preferably 7 to 35 bar, for example 10 or 30 bar, very particularly preferably 8 to 12 bar.
  • a well-suited ratio of hydrogen sulfide to unsaturated terpene is generally at least 1, preferably at least 1, 2 and in a particularly preferred form at least 1, 3 and generally at most 20, preferably at most 10 and more preferably at most 6 mol of hydrogen sulfide per moles of terpene. For example, a ratio of 1, 5 is set.
  • the reaction can be carried out continuously or batchwise. In discontinuous operation, the reaction time and in continuous operation, the residence time in the reactor is adjusted so that the desired conversion is achieved.
  • any organic ion exchanger can be used in the process according to the invention.
  • the organic ion exchanger used is an acidic organic ion exchanger.
  • Organic ion exchangers are solids, for example in granular form, with a three-dimensional, water-insoluble, high molecular weight framework, the so-called matrix, to which numerous so-called anchor groups, for example -SO 3 " , phenolic hydroxy groups or -COO " are covalently bound.
  • anchor groups for example -SO 3 "
  • phenolic hydroxy groups or -COO " are covalently bound.
  • counter ions for example Na +, H +, etc.
  • the acidic ion exchangers act by releasing protons as acids.
  • acidic ion exchange resins are, for example, sulfonated polymers, for example sulfonated styrene or styrene-divinylbenzene polymers. It is also possible to use ion exchangers based on styrene-acrylic acid copolymers which are sulfonated. the. Organic ion exchange resins are either suspended in the reaction mixture or arranged in the form of conventional ion exchanger particles as a fixed bed.
  • sulfonated styrene styrene-divinyl benzene polymers
  • styrene-acrylic acid copolymers for example Amberlyst 15 ® used.
  • the catalyst is used in suspended form, for example in batchwise operation, it is generally used in an amount of from 0.1 to 50% by weight, preferably from 1 to 20% by weight, more preferably in an amount of from 3 to 6 wt .-%, for example, 4.5 wt .-%, each based on the terpene used.
  • unsaturated terpenes are reacted with hydrogen sulfide to give the corresponding thiols.
  • unsaturated means that the suitable terpenes have at least one double bond in the molecule.
  • unsaturated mono-, sesqui-, di- and triterpenes can be used which have at least one double bond in the molecule.
  • Monoterpenes are terpenes having 10 carbon atoms, sesquiterpenes have 15 carbon atoms, diterpenes have 20 carbon atoms, and triterpenes have 30 carbon atoms.
  • Suitable unsaturated monoterpenes are, for example, selected from the group consisting of myrcene, (Z) -oximes, (E) -oximes, cosme, linalool, geraniol, nerol,
  • Suitable unsaturated sesquiterpenes are for example selected from the group consisting of (E) - ⁇ -Farnesen, (Z) - ⁇ -Farnesen, (E) - ⁇ -Farnesen, ⁇ -Bisabolen, ⁇ -Bisabolen, ⁇ -Bisabolol, Zingiberen, ⁇ Curcumen, ⁇ -curcumen, lanceol, ⁇ -elements, ⁇ -elements, elemol, ⁇ -humulene, cerumen, ⁇ -cadins, ⁇ -cadins, ⁇ -cadinol, ⁇ -cadinol, T-muurolol, T-cardinol, khusol , ⁇ -seleins, ⁇ -eudesmol, ⁇ -eudesmol,
  • Suitable unsaturated diterpenes are, for example, selected from the group consisting of vitamin A, cembrene A, (-) - sclareol, forskolin, manool, scoparic acid A and mixtures thereof.
  • Suitable unsaturated triterpenes are, for example, selected from the group consisting of unsaturated steroid hormones, steroid alkaloids, D-vitamins, bile acids, squalene, lanosterol, cycloartenol, agnosterol, 24,25-dihydroanosterol, 24,25-dihydro-agosterin, ⁇ -amyrin, ⁇ -amyrin, Ursolic acid, Bauerenol, Glycyrrhetinklare, oleanolic acid and mixtures thereof.
  • An unsaturated terpene is very particularly preferably selected from the group consisting of terpinolene, limonene, ⁇ -pinene, ⁇ -pinene, camphene, p-menthene and mixtures thereof, in particular preferably terpinolene or limonene.
  • the present invention comprises the reaction of terpinolene (1) into the corresponding thiols:
  • the thiols derived from the very particularly preferred terpenes, preferably terpinolene or limonene, are distinguished by particularly pleasant odors, for example the thiols derived from terpinolene smell like grapefruit. Furthermore, the said thiols are not toxic.
  • the terpenes which can be used according to the invention can be prepared by processes known to the person skilled in the art, see, for example, Römpp, Chemielexikon, 9th edition, pages 4508 to 4510, or are commercially available. Another method of obtaining terpenes is biosynthesis followed by isolation by methods known to those skilled in the art.
  • the process according to the invention can optionally be carried out without solvent or in the presence of a solvent. If a solvent is used, then a solvent inert to the reactants is used. Examples of inert solvents are hydrocarbons or hydrocarbon mixtures such as pentane, hexane, cyclohexane, benzene, benzene, toluene or xylene. Preferably, however, the reaction is carried out in the absence of a solvent.
  • reaction of hydrogen sulphide with the at least one unsaturated terpene is carried out continuously in one embodiment.
  • the reaction of hydrogen sulfide with the at least one unsaturated terpene is carried out discontinuously.
  • the reaction may be carried out in any suitable reactor, for example, batch batch stirred tank, continuous flow tube reactor, with suspended or fixed catalyst.
  • the at least one terpene to be reacted is presaturated in a separate reactor under pressure with H 2 S and then pumped into the catalyst-filled reactor.
  • a further preferred embodiment is to introduce the catalyst and the terpene in the reactor, and then to press hydrogen sulfide at the pressure indicated above.
  • the reactor discharge, if necessary, freed from the solvent.
  • the catalyst optionally present in the crude product is separated off by suitable methods known to the person skilled in the art, for example filtration or decantation.
  • the thiol prepared is purified by conventional methods, this can be done for example by fractional crystallization in the cold or by distillation, preferably in vacuo.
  • the thiols of the invention are well suited as molecular weight regulators in the polymerization, preferably the radical polymerization, of monomers.
  • a process for the radical polymerization of vinylic monomers using thiols prepared by the process according to the invention as MoI mass regulators are known.
  • vinylic monomers which are converted in known manner by free radical polymerization to polymers, wherein the thiols according to the invention are used as molecular weight regulators are butadiene, styrene, carboxylated styrene, acrylic acid, acrylonitrile, acrylic esters, vinyl ethers or their mixtures.
  • these monomers are polymerized in the form of an emulsion in a solvent, for example, and preferably water, to form a dispersion of the polymer in water.
  • the thiols according to the invention are particularly suitable as molecular weight regulators in the polymerization of monomers because of their good odor and their non-toxicity. Therefore, the present invention also relates to the use of terpinolene-derived thiols as molecular weight regulator in the polymerization, preferably the radical polymerization, of monomers.
  • Terpinolene is at a temperature of 100 0 C and a pressure of 10 bar with hydrogen sulfide for 8 hours in the presence of Amberlyst 15, an acidic ion exchanger, to a mixture of the mono- or dithiol comprising the corresponding possible isomers implemented.
  • the separation of the desired isomer is carried out by distillative separation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé servant à produire des thiols par addition d'hydrogène sulfuré sur au moins un terpène insaturé, la réaction se faisant en présence d'au moins un échangeur d'ions organique. L'invention concerne également l'utilisation de thiols dérivés de terpinolène comme régulateurs de masse molaire dans la polymérisation de monomères.
EP07821303A 2006-10-17 2007-10-15 Addition de h2s sur des terpènes pour produire de nouveaux régulateurs de masse molaire pour des polymérisations radicalaires Withdrawn EP2106395A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07821303A EP2106395A2 (fr) 2006-10-17 2007-10-15 Addition de h2s sur des terpènes pour produire de nouveaux régulateurs de masse molaire pour des polymérisations radicalaires

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06122461 2006-10-17
EP07821303A EP2106395A2 (fr) 2006-10-17 2007-10-15 Addition de h2s sur des terpènes pour produire de nouveaux régulateurs de masse molaire pour des polymérisations radicalaires
PCT/EP2007/060936 WO2008046801A2 (fr) 2006-10-17 2007-10-15 Addition de h2s sur des terpènes pour produire de nouveaux régulateurs de masse molaire pour des polymérisations radicalaires

Publications (1)

Publication Number Publication Date
EP2106395A2 true EP2106395A2 (fr) 2009-10-07

Family

ID=39027206

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07821303A Withdrawn EP2106395A2 (fr) 2006-10-17 2007-10-15 Addition de h2s sur des terpènes pour produire de nouveaux régulateurs de masse molaire pour des polymérisations radicalaires

Country Status (4)

Country Link
US (1) US20100010267A1 (fr)
EP (1) EP2106395A2 (fr)
CN (1) CN101535245A (fr)
WO (1) WO2008046801A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8461293B2 (en) 2010-08-03 2013-06-11 Chevron Phillips Chemical Company Lp Methods of mercaptanizing olefinic hydrocarbons and compositions produced therefrom
US20140131618A1 (en) 2012-11-15 2014-05-15 Chevron Phillips Chemical Company Lp Methods of Mercaptanizing Unsaturated Compounds and Compositions Produced Therefrom
US9522975B2 (en) 2015-01-29 2016-12-20 Chevron Phillips Chemical Company Lp Mercaptanized vinylnorbornene compositions and methods of making same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2076875A (en) * 1935-04-11 1937-04-13 Hercules Powder Co Ltd Sulphur-containing terpenes and method of producing
US2535557A (en) * 1948-01-27 1950-12-26 Hercules Powder Co Ltd Emulsion polymerization of unsaturated organic compounds
US3408403A (en) * 1964-12-16 1968-10-29 Phillips Petroleum Co Method of producing a mixture of sulfides and mercaptans
US4140604A (en) * 1978-07-03 1979-02-20 Pennwalt Corporation Process for preparing mercaptans
DE2837509A1 (de) * 1978-08-28 1980-04-17 Baltruschajtis 1,7,7-trimethyl-bicyclo- eckige klammer auf 2,2,1 eckige klammer zu -heptan- 2-thiol und verfahren zu dessen herstellung
FR2627182B1 (fr) * 1988-02-17 1991-03-22 Elf Aquitaine Perfectionnement a la synthese de mercaptans secondaires a partir d'olefines lineaires
DE10340252A1 (de) * 2003-08-29 2005-03-24 Basf Ag tert.-Dodecylmercaptan
FR2866024A1 (fr) * 2004-02-06 2005-08-12 Arkema Procede de fabrication de dodecylmercaptans.
JP2007532715A (ja) * 2004-04-08 2007-11-15 ザ・ジョーンズ・ホプキンス・ユニバーシティ プロセス化可能なモレキュラーインプリンティングポリマー

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008046801A2 *

Also Published As

Publication number Publication date
CN101535245A (zh) 2009-09-16
WO2008046801A2 (fr) 2008-04-24
WO2008046801A3 (fr) 2009-05-14
US20100010267A1 (en) 2010-01-14

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