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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/14—Polysulfides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
  • C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/04—Polysulfides

Definitions

• the invention relates to polyalkylene polysulfides, processes for their preparation, their use, rubber compositions containing them, their use, vulcanizing agents containing the polyalkylene polysulfides, certain molding compositions containing the polyalkylene polysulfides, moldings produced therefrom, processes for producing the moldings and the use of these molding compositions.
• Polysulfide rubbers are mainly used as sealing materials. Solid types can be processed into sealing rings, while liquid types can be used as joint sealing compounds, for example. Polysulfide rubbers are usually prepared, for example as described in DE-A 675 401, by salt elimination reactions from alkali, ammonium or alkaline earth polysulfides and alkylene dichlorides. A disadvantage is the enormous amount of salt in this manufacturing process.
• US Pat. No. 2,206,641 describes a process for the production of methylene polysulfide in which methylene chloride is reacted with Na 2 S in aqueous solution.
• Vulcanizing agents of this type which are obtained by reaction of sulfur with an olefin at 140 ° C. to 160 ° C. in the presence of a basic catalyst, are disclosed in US Pat. Nos. 4,739,036, 4,740,559 and 2,989,513.
• the properties of the products obtained according to the abovementioned documents lie between polymer sulfur and S 8 sulfur and therefore do not represent an improvement over polymer sulfur.
• they contain a high proportion of soluble S 8 sulfur, which leads to poorer efflorescence than with ⁇ - sulfur leads.
• the object of the invention is to find a manufacturing process for polysulfide rubbers in which the otherwise usual salt accumulation is avoided.
• Another object of the invention is to provide vulcanizing agents based on sulfur copolymers with good efflorescence for vulcanizing rubber compounds.
• R and R are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms or COR", wherein
• R is hydrogen or an alkyl group having 1 to 4 carbon atoms, x is a number from 2 to 20 on average and n is a number> 10.
• polyalkylene polysulfides according to the invention contain chains of the general formula I and preferably consist essentially of chains of the general formula I.
• Polyalkylene polysulfides consisting essentially of chains of the general formula I are those which are predominantly, for example at least 90%, preferably exclusively, repeating units of the general Formula Ia
• x ' is an integer whose value can vary from repetition unit to repetition unit and whose mean is x.
• the polyalkylene polysulfides according to the invention also have end groups. Possible end groups include: SH, OH and H.
• R and R are the same or different and denote hydrogen, alkyl groups with 1-4 carbon atoms, such as methyl, ethyl, n-, iso-, sec- and tert-butyl, or COR ", where R" is hydrogen or one of the above-mentioned alkyl groups.
• x is a number from 2 to 20 on average, preferably 2 to 5, particularly preferably about 4, n is a number> 10.
• the distribution of x is preferably narrow, i.e. in a polyalkylene polysulfide in which x is a number of, for example, an average of 4, x "in
• the radicals R and R ' can always be the same or can vary within the chain.
• the polyalkylene polysulfides according to the invention can be prepared by copolymerizing carbonyl compounds with elemental sulfur and hydrogen sulfide in the presence of a basic catalyst.
• the present invention therefore also relates to a process for the preparation of polyalkylene polysulfides by reacting at least one carbonyl compound of the general formula II
• Suitable carbonyl compounds are aldehydes R-CHO, wherein preferably
• R H, CH 3 , C 2 H 5 , n- and iso-C 3 H 7 , n-, iso-, sek- and tert-C 4 H 9 .
• Suitable carbonyl compounds are also ketones R-CO-RM in which R and R can be the same or different and are preferably CH 3- C 2 H 5 , n- and iso-C 3 H 7 .
• Suitable carbonyl compounds are also glyoxals R-CO-CO-R "in which R and R" may be the same or different and are preferably H, CH, C 2 H 5 , n- and iso-C 3 H 7 .
• Particularly preferred carbonyl compounds are formaledehyde, in particular as a formalin solution, and acetaldehyde.
• One or a mixture of several different carbonyl compounds of the general formula II can be reacted. Exactly one carbonyl compound is preferably reacted.
• the value of x can be adjusted by choosing the molar ratio of carbonyl compounds: elemental sulfur.
• the molar ratio mentioned is generally from 1: 1 to 1: 1S, preferably from 1: 2 to 1: 6 and particularly preferably about 1: 3, based on sulfur atoms.
• polyalkylene polysulfides with an x of approximately 4 are formed on average.
• the stoichiometry of the reaction is such that x-1 S atoms come from elemental (S 8 ) sulfur and one S atom from H 2 S.
• the reaction is carried out in the presence of a basic catalyst.
• a basic catalyst are those with a sulfidic sulfur atom, such as alkali, alkaline earth or ammonium sulfides, hydrogen sulfides or polysulfides, Na 2 S, NaHS and (NH 4 ) HS are particularly preferred.
• Ammonia, amines and hydroxyl compounds such as NH 3 , NBu 3 and NaOH can also be used, sulfidic compounds being formed when the latter non-sulfidic bases are used during the reaction with H 2 S.
• the process is preferably carried out in an aqueous medium at a temperature of generally 117 to 160 ° C., preferably 120 to 140 ° C., particularly preferably 122 to 132 ° C.
• the carbonyl compound or an aqueous compound of the carbonyl compound with elemental sulfur and the basic catalyst is placed in an autoclave and heated to the above-mentioned temperatures while melting the sulfur. Then hydrogen sulfide is injected, with an excess pressure of, for example, 3 bar.
• the process can, but need not, be carried out with an excess of hydrogen sulfide, and is preferably carried out in this way.
• Hydrogen sulfide absorption usually stops automatically when the stoichometric amount is reached, i.e. H. one mole of hydrogen sulfide per mole of carbonyl compound.
• the carbonyl compound is used in the form of its aqueous solution, there is generally also an aqueous phase in addition to the organic product phase. This can be done, for example, by decanting or in a phase separator from the organic Phase are separated.
• the aqueous phase can also, if appropriate together with other volatile constituents, be separated off from the organic product phase by distillation.
• the process according to the invention can be carried out batchwise or continuously. It is preferably carried out continuously using a cascade of stirred tanks, the aqueous phase being separated off by distillation or in a phase separator.
• the separation of the aqueous phase can be omitted when using the pure carbonyl compound.
• the product obtained can be purified from unreacted sulfur and by-products such as small rings of carbon-sulfur by extraction with organic, sulfur-dissolving solvents such as CS 2 , CHC1 3 and CH 2 C1 2 .
• the present invention also relates to polyalkylene polysulfides which can be prepared by one of the production processes described above.
• the polyalkylene polysulfides according to the invention have a melt viscosity, extrapolated to the shear rate 0s "1 , of 1-10 4 Pa s, preferably 5-1000 Pa s.
• polyalkylene polysulfides according to the invention depending on whether they are low-molecular or high-molecular masses, whether they are used unvulcanized or vulcanized and whether they contain other reinforcing fillers and raising the softening temperature, can be used in a wide variety of applications.
• the present invention also relates to the use of the polyalkylene polysulfides for the production of vulcanizing agents, sealing materials, coating materials, impression compounds, adhesives, cable insulation and molding compounds for the production of rubber articles and films.
• the polyalkylene polysulfides have different levels of stickiness. They can be converted into dry, free-flowing powders or granules by mixing fillers.
• the polyalkylene polysulfides according to the invention can be vulcanized by adding crosslinking agents such as ZnO, activated MnO, perborates or peroxides or crosslinked by reaction with compounds containing isocyanates, epoxides and double bonds. As a result, they lose their thermoplastic properties.
• Low molecular weight polyalkylene polysulfides can be processed at room temperature and can be applied as a sealing material or corrosion protection to surfaces such as concrete, artificial stone, natural stone and metal surfaces by brushing, knife coating or spraying. If vulcanizing agents are mixed in shortly before processing, the surface-applied layers are cross-linked and therefore dimensionally stable.
• Higher molecular weight polyalkylene polysulfides can be extruded into profiles and strips at temperatures of, for example, 20 to 120 ° C., whereby they can be mixed with reinforcing fillers. Equipped in this way, they can be extruded through sheet-metal dies into foils with thicknesses of, for example, 1 to 20 mm, which can also be used as sealing materials.
• the use of reinforcing fillers is preferably dispensed with.
• the polyalkylene polysulfides according to the invention are resistant to chemicals and oils and do not swell, which makes them particularly suitable for coating reaction apparatus, chemical containers, valves and pipelines.
• Unvulcanized polyalkylene polysulfides according to the invention have a cold flow under mechanical pressure. This effect in combination with the excellent sealing effect against water can be exploited by distributing the enormous pressure of structures such as houses, bridges, chimneys etc. in flat tubs filled with the polyalkylene polysulfides according to the invention on the substrate. The entire area is used because the polyalkylene polysulfides fill each cavity and also perfectly compensate for the thermal expansion.
• the polyalkylene polysulfides according to the invention can be processed into weldable sealing tapes and films of any shape which are suitable for insulating buildings, roads, substructures, tunnel structures, tank trays, sewer structures, swimming pools, landfills, ships and aircraft tanks.
• polyalkylene polysulfides according to the invention can be used alone or in combination with other compounds as molding compositions and adhesives. Cable insulations and impression materials, such as technical impression materials and dental impression materials, can also be produced from them.
• polyalkylene polysulfides according to the invention are also suitable, in particular as non-blooming vulcanizing agents, for the production of rubber articles.
• the polyalkylene polysulfides according to the invention can be mixed with elastomers containing C-C double bonds at 80-120 ° C, deformed at these temperatures, for example by extrusion, pressing or calendering, and the deformed mixture can be crosslinked at temperatures of 140-200 ° C without the addition of other crosslinking agents.
• Solvent- and oil-resistant, highly sulfur-containing elastomers are obtained for a wide range of applications, for example in the form of profiles, hoses, plates or foils.
• the part by weight of the S copolymers according to the invention for the C-C double bond-containing elastomers is generally 95: 5 to 10: 90, preferably 90: 10 to 30: 70.
• elastomers containing CC double bonds can be used: Natural rubber (polyisopiene) or synthetic rubber, such as polybutadiene, polychloroprene, ethylene / tropylene terpolymers, nitrile rubber, styrene-butadiene rubber, synthetic po yisoprene and butyl rubber.
• Natural rubber polyisopiene
• synthetic rubber such as polybutadiene, polychloroprene, ethylene / tropylene terpolymers, nitrile rubber, styrene-butadiene rubber, synthetic po yisoprene and butyl rubber.
• the present invention also relates to molding compositions containing 10-95% by weight, preferably 30-90% by weight, of the polyalkylene polysulfides according to the invention as component A "and 5-90% by weight, preferably
• Elastomers containing 10 to 70% by weight of CC double bonds as component B " the use of these molding compositions for the production of moldings, such as profiles, hoses, plates or foils, a process for the production of these moldings in which the molding compositions by mixing the components A “and B” are produced at 80-120 ° C, deformed at these temperatures and crosslinked at temperatures of 140-200 ° C in the absence of other crosslinking agents, and the molded parts themselves are produced from the molding compositions.
• the present invention also relates to polyalkylene polysulfide rubber compositions containing
• component A 10-95% by weight of a polyalkylene polysulfide according to the invention as component A,
• Sealing material, coating material, molding compound and molding compound for the production of Rubber articles and foils as well as for other purposes mentioned above can be used.
• the polyalkylene polysulfide rubber compositions according to the invention contain 10-95% by weight, preferably 20-70% by weight, of a polyalkylene polysulfide as component A.
• the polyalkylene polysulfide rubber compositions according to the invention contain 0.1-20% by weight, preferably 1-15% by weight, of a crosslinker as component B.
• Suitable crosslinkers are inorganic crosslinkers, such as lead dioxide, manganese dioxide, potassium permangant, chromates, dichromates, alkali perborates, calcium peroxide , Lithium peroxide, zinc peroxide and organic crosslinkers such as hydroperoxides, for example cumene hydroperoxide, dioximes, di- and polyisothiocyanates.
• the polyalkylene sulfide rubber compositions according to the invention contain 0.1-90% by weight, preferably 1-50% by weight, of fillers and / or pigments as component C.
• Suitable fillers are, for example, finely divided silicon dioxide, titanium dioxide, talc, calcium carbonate, kaolin and carbon black.
• Pigments include titanium dioxide, iron oxide and carbon black.
• the polyalkylene polysulfide rubber compositions according to the invention may further contain 0 to 50% by weight of plasticizer as component D.
• Plasticizers are, for example, phthalic acid esters, benzyl butyl phthalate and chlorinated paraffins.
• the polyalkylene polysulfide rubber compositions according to the invention may further contain 0-20% by weight of conventional additives such as adhesion promoters, thixotropic agents, accelerators, retarders and drying agents as component E.
• conventional additives such as adhesion promoters, thixotropic agents, accelerators, retarders and drying agents as component E.
• polyalkylene polysulfide rubber compositions according to the invention can be formulated both as one-component systems and as two-component systems.
• component 1 may contain the polyalkylene polysulfides and fillers according to the invention, if appropriate in addition to plasticizers and other additives, while component 2 may contain the crosslinking agent if appropriate contains additional plasticizer and other additives, components 1 and 2 being mixed immediately before use.
• the present invention also relates to a vulcanizing agent containing 20-90% by weight, preferably 40-55% by weight, of the polyalkylene polysulfides according to the invention as component A " and 10-80% by weight, preferably 35-60% by weight. %, of a flow, reinforcement and / or stiffening agent as component BM
• the tackiness of the polyalkylene polysulfides according to the invention is eliminated by adding the reinforcing and stiffening agents. By adding an eluent, these are converted into a ready-to-use, free-flowing powder. Suitable flow, reinforcement and stiffening agents are silica, chalk, talc, kaolin and wolastonite, silica is preferred.
• the flow, reinforcement and stiffening agents can e.g. with extruders, kneaders, paddle dryers or other suitable machines. It is also possible to assemble the product by applying the flow, reinforcing or stiffening agent to the surface of the product particles and thus preventing them from sticking together.
• the vulcanizing agents according to the invention are used to vulcanize rubber compounds. All rubber mixtures which contain polymers with vulcanizable multiple bonds are suitable as vulcanizable rubber mixtures. Examples are natural rubber (polyisoprene) or synthetic rubber, such as polybutadiene, polychloroprene, ethylene / propylene terpolymers, nitrile rubber, styrene-butadiene rubber, synthetic polyisoprene and butyl rubber.
• the vulcanizing agents according to the invention are preferably used for vulcanizing natural rubber.
• the polyalkylene polysulfides themselves can also be used to vulcanize the rubber mixtures.
• 0.8-20% by weight, preferably 2-6% by weight, of the vulcanizing agents according to the invention are generally incorporated into the rubber mixture to be vulcanized, for example using a kneader.
• the rubber mixture to be vulcanized can furthermore contain customary auxiliaries and additives, such as accelerators, retarders, anti-aging agents, stabilizers, fillers, adhesion promoters, plasticizers and processing aids.
• the vulcanization is generally carried out at temperatures from 140 to 200 ° C., preferably 160 to 180 ° C. Basic compounds contained in the vulcanizing agent can accelerate vulcanization. If necessary, this can be counteracted by adding acceleration decelerations.
• test specimens are produced from the rubber mixture obtained and vulcanized at 150 ° C. The following measured values are determined on the test specimens produced in this way:

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Sealing Material Composition (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2001
  • 2001-02-14 KR KR1020027010580A patent/KR20020075425A/ko not_active Application Discontinuation
  • 2001-02-14 US US10/203,283 patent/US20030060567A1/en not_active Abandoned
  • 2001-02-14 AU AU2001231748A patent/AU2001231748A1/en not_active Abandoned
  • 2001-02-14 CN CN01805093A patent/CN1400983A/zh active Pending
  • 2001-02-14 EP EP01903769A patent/EP1263838A1/de not_active Withdrawn
  • 2001-02-14 JP JP2001560271A patent/JP2003525318A/ja not_active Withdrawn
  • 2001-02-14 WO PCT/EP2001/001631 patent/WO2001060891A1/de not_active Application Discontinuation
  • 2001-02-14 EP EP03025060A patent/EP1400553A3/de not_active Withdrawn
  • 2001-02-15 TW TW090103407A patent/TW588070B/zh active

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