EP2951151A1 - Polysulfide polyols, their production and use in the synthesis of polyurethanes - Google Patents

Polysulfide polyols, their production and use in the synthesis of polyurethanes

Info

Publication number
EP2951151A1
EP2951151A1 EP14701185.2A EP14701185A EP2951151A1 EP 2951151 A1 EP2951151 A1 EP 2951151A1 EP 14701185 A EP14701185 A EP 14701185A EP 2951151 A1 EP2951151 A1 EP 2951151A1
Authority
EP
European Patent Office
Prior art keywords
sulfur
production
polyurethanes
reaction
containing polyols
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Withdrawn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
EP14701185.2A
Other languages
German (de)
English (en)
French (fr)
Inventor
Marco Balbo Block
Kevin Rhudy
Christoph Fleckenstein
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 EP14701185.2A priority Critical patent/EP2951151A1/en
Publication of EP2951151A1 publication Critical patent/EP2951151A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3

Definitions

  • This invention relates to polysulfide polyols, their production and use.
  • PU polyurethane
  • PU polyurethane
  • mineral wool has poor pipe insulation properties.
  • PU-based foams show good insulation properties, but they have problems to guarantee a service life of 10 to 30 years at 190 °C and more, as the urethane bond slowly degrades at such temperatures.
  • Isocyanurate-modified foams show improved thermal stability, but are still not sufficiently stable and possess poor flow properties in the molds.
  • DD 299 187 A5 describes a process for the production of sulfur-containing organo-silicium compounds.
  • EP 0 466 066 A1 discloses a process for production of certain oligosulfides, and US 6,21 1 ,345 B1 describes the synthesis of cyclic sulfur silanes.
  • the object of the present invention therefore is a process for the production of sulfur-containing polyols by reaction of at least one unsaturated alcohol A with elemental sulfur.
  • a mixture of at least two unsaturated alcohols A is used.
  • the term "polyol” refers to an organic compound having at least two alcohol groups per molecule.
  • the term “unsaturated compound” means an organic compound having at least one unsaturated carbon-carbon bond.
  • the sulfur-containing polyol has a viscosity of less than 10 Pa * s at 25 °C, as determined according to DIN (German industry norm) ISO 2555.
  • the elemental sulfur may be used in solid or in liquid form.
  • the inventive process is performed neat, i. e. no solvent is used in addition to the at least one unsaturated alcohol A and the sulfur.
  • at least one solvent it is possible to use at least one solvent.
  • the solvent preferably has a boiling point of at least 120 °C; furthermore, the solvent preferably contains no sulfur.
  • solvents examples include DMF, xylene and me- sitylene. Also high-boiling alcohols and ethers, for example diglyme, may be used.
  • reaction mixture may also be worked up after the end of the reaction by separating off unreacted sulfur. This may be done by mechanical separation, for example by precipitation and filtration.
  • the inventors have shown by 1 H-NMR experiments that the reaction runs almost quantitatively, i. e. more than 99 % of the unsaturated alcohols A, based on the double-bond equivalents, are reacted with sulfur.
  • the inventive process for the production of sulfur-containing polyols by reaction of at least one unsaturated alcohol A with elemental sulfur provides a product mixture, containing, inter alia, monosulfides, disulfides, trisulfides and tetrasulfides.
  • the inventive products do not smell unpleasant.
  • some of the inventive products when, for example, derived from citronellol as unsaturated alcohol A, even smell rather pleasant.
  • inventive products may be used for the production of polyurethanes, in particular rigid foam polyurethanes.
  • a further object of the present invention is a process for the production of polyurethanes, in particular rigid foam polyurethanes, by reaction of at least one inventive sulfur-containing polyol with at least one isocyanate, optionally in the presence of a blowing agent.
  • Further objects of the present invention is also a process for the production of polyurethanes, in particular rigid foam polyurethanes, by reaction of at least one inventive sulfur-containing polyol with at least one unsaturated polyol and with at least one isocyanate, optionally in the presence of a blowing agent, and a process for the production of polyurethanes, in particular rigid foam polyurethanes, by reaction of at least one inventive sulfur-containing polyol with at least one unsaturated polyol and with at least one isocyanate, in the presence of a vulcanization catalyst and optionally in the presence of a blowing agent.
  • Typical vulcanization catalysts also referred to as vulcanization accelerators, are benzothiazols, thiuramdisulfides, dithiocarbamates, guani- dines, thioureas. They are added to the polyol blend in amounts between 0.25 and 5 w% based on the total weight of the polyol blend.
  • Typical vulcanization activators are Zinc salts of fatty acids or blends of Zinc oxide and fatty acids. They are added to the polyol blend in amounts between 0.25 and 5 w% based on the total weight of the polyol blend.
  • an addi tional step of post-curing is performed.
  • Post-curing in the context of this disclosure, refers to a prolonged thermal exposure to ensure a certain amount of reaction between the polysulfide polyol and the unsaturated polyol within the rigid foam. If the post-curing is performed before the application then post-curing is defined as storage of the PU at ambient humidity or dry conditions for 30min to 14 days (preferably 1 -3 days) at 130-220°C (preferably 160-190°C).
  • the PU can also be submitted to more than one post-curing treatment, if desired.
  • the post-curing leads presumably to an additional crosslinking in the PU.
  • the improvement of mechanical properties of the PU vary with varying post-curing conditions.
  • inventive products can be used as high-temperature stable PU rigid foams, in particular for pipe insulation.
  • Sulfur-containing polyols were synthesized as follows.
  • reaction control via 1 H-NMR.
  • the reaction mixture was cooled down to ambient temperature, then 200 mL methylene chloride and 200 mL water were added. The mixture was stirred for 15 min, then 2 spoons of celite were added and the mixture was filtered via suction filtration (glass fritt, (Por. 3)). The filtrate was transferred into a separation funnel, the lower organic phase was separated and all volatiles were removed via a rotary evaporator (60 °C bath temperature, 1 mbar) to afford a viscous dark reddish oil with small crystals. In order to remove non reacted sulfur from the mixture, the oil was dissolved in 150 mL MTBE and filtered over celite. The filtrate was collected and all volatiles were removed (70 °C, 0,1 mbar) to afford the product as a dark reddish oil (59 g).
  • reaction control via 1 H-NMR After 18 hours quantitative conversion of the alcohol was shown (reaction control via 1 H-NMR). The reaction mixture was cooled down to ambient temperature.
  • reaction control via 1 H-NMR After 1 1 hours quantitative conversion of the alcohol was shown (reaction control via 1 H-NMR). The reaction mixture was cooled down to ambient temperature.
  • the oil was dissolved in 450 mL MTBE and filtered over celite (3 spoons). The filter cake was washed with THF (3 x 100 mL). The filtrates were combined and all volatiles were removed (70 °C, 0,1 mbar) to afford the product as a dark brown, viscous oil (61 g).
  • Zinc stearate vulcanization activator
  • Tetramethyl thiuram disulfide vulcanization catalyst/ -accelerator
  • N/mm 2 0,28 0,36 0,30 0,32 growth after tempering N/mm 2 : -0,03 0,04 0,00 0,03 pressure-E-module fresh foam, N/mm 2 9,00 8,00 7,60 7,70

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP14701185.2A 2013-01-29 2014-01-23 Polysulfide polyols, their production and use in the synthesis of polyurethanes Withdrawn EP2951151A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14701185.2A EP2951151A1 (en) 2013-01-29 2014-01-23 Polysulfide polyols, their production and use in the synthesis of polyurethanes

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13153080 2013-01-29
PCT/EP2014/051310 WO2014118073A1 (en) 2013-01-29 2014-01-23 Polysulfide polyols, their production and use in the synthesis of polyurethanes
EP14701185.2A EP2951151A1 (en) 2013-01-29 2014-01-23 Polysulfide polyols, their production and use in the synthesis of polyurethanes

Publications (1)

Publication Number Publication Date
EP2951151A1 true EP2951151A1 (en) 2015-12-09

Family

ID=47628024

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14701185.2A Withdrawn EP2951151A1 (en) 2013-01-29 2014-01-23 Polysulfide polyols, their production and use in the synthesis of polyurethanes

Country Status (8)

Country Link
EP (1) EP2951151A1 (zh)
JP (1) JP2016505072A (zh)
KR (1) KR20150112013A (zh)
CN (1) CN104968645A (zh)
BR (1) BR112015018009A2 (zh)
RU (1) RU2015136630A (zh)
SG (1) SG11201505939YA (zh)
WO (1) WO2014118073A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107936217A (zh) * 2017-11-24 2018-04-20 锦西化工研究院有限公司 一种含硫聚合物多元醇的合成方法
GB201814852D0 (en) 2018-09-12 2018-10-24 Univ Liverpool Sulfur-based Polymers
IT201900011121A1 (it) * 2019-07-08 2021-01-08 Eni Spa Procedimento per la preparazione di copolimeri ad elevato contenuto di zolfo
WO2023214184A1 (en) * 2022-05-06 2023-11-09 The University Of Liverpool Nanoparticles

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1545034A1 (de) * 1963-09-23 1970-04-09 Thiokol Chemical Corp Verfahren zur Herstellung an der Luft haertbarer Isoliermaterialien
US4273882A (en) * 1980-06-02 1981-06-16 Olin Corporation Preparation of thermally stable rigid polyurethane foam
ZA862362B (en) * 1985-04-08 1987-11-25 Mobil Oil Corp Sulfurized olefins
DD299589A7 (de) 1990-07-13 1992-04-30 Nuenchritz Chemie Verfahren zur herstellung von oligo[4-(2-organo-organooxysilylalkyl)-cyclohexan-1,2-diyl]-bis-oligosulfiden
DD299187B5 (de) 1990-07-13 1996-05-15 Huels Silicone Gmbh Verfahren zur Herstellung von schwefelhaltigen Organosiliciumverbindungen
DE4038589A1 (de) * 1990-12-04 1992-06-11 Bayer Ag Kautschukvulkanisate mit guten mechanischen eigenschaften und verbessertem hystereseverhalten
US5338468A (en) * 1992-10-05 1994-08-16 Mobil Oil Corporation Sulfurized olefins
EP0714970A1 (fr) * 1994-11-28 1996-06-05 Institut Français du Pétrole Hydrocarbures éthyléniques sulfurés par le soufre élémentaire en présence d'hydroxydes de métaux alcalins ou alcalino-terreux et en présence de glycols, polyglycols ou de leurs éthers alkyliques et/ou en présence d'eau
US6211345B1 (en) 1999-12-22 2001-04-03 Witco Corporation Synthesis of cyclic sulfur silanes
MX2011013900A (es) * 2009-06-29 2012-04-02 Polymeright Inc Composiciones de polimericas y metodos para producir y usar las mismas.

Non-Patent Citations (1)

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Title
See references of WO2014118073A1 *

Also Published As

Publication number Publication date
SG11201505939YA (en) 2015-09-29
CN104968645A (zh) 2015-10-07
WO2014118073A1 (en) 2014-08-07
RU2015136630A (ru) 2017-03-07
KR20150112013A (ko) 2015-10-06
JP2016505072A (ja) 2016-02-18
BR112015018009A2 (pt) 2017-07-11

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