WO2023052127A1 - Mélange pvc - Google Patents

Mélange pvc Download PDF

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Publication number
WO2023052127A1
WO2023052127A1 PCT/EP2022/075517 EP2022075517W WO2023052127A1 WO 2023052127 A1 WO2023052127 A1 WO 2023052127A1 EP 2022075517 W EP2022075517 W EP 2022075517W WO 2023052127 A1 WO2023052127 A1 WO 2023052127A1
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WIPO (PCT)
Prior art keywords
weight
layer
cable
alkoxyvinylsilane
modified
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PCT/EP2022/075517
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German (de)
English (en)
Inventor
Christian Ernst
Felix WALDRAB
Original Assignee
Leoni Kabel Gmbh
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Publication of WO2023052127A1 publication Critical patent/WO2023052127A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate

Definitions

  • the present invention relates to a cable comprising a layer of PVC blend. Furthermore, the invention relates to a method for producing a cable which comprises this layer.
  • Polyvinyl chloride has been used in the manufacture of cables for many years, partly because of its low water absorption and flame-retardant properties. In a large number of applications for these cables - such as in the automotive sector - sufficient flexibility of the material at low temperatures is essential here in order to prevent the cable or the cable sheath from breaking. Since the thermoplastic PVC in its pure form (i.e. without additives, comonomers, soft phases, etc.) is a rigid and brittle material, monomeric plasticizers (monomer plasticizers?) such as phthalic acid esters of long-chain alcohols are used to ensure sufficient low-temperature flexibility at temperatures down to -40 to reach °C. The cold flexibility can be determined, for example, by testing using a cold wrap in accordance with ISO 19642 or by determining the glass transition temperature as a parameter.
  • test specimens are exposed to heated test oil (usually IRM 902 or 903), after which they must still have a defined residual elongation and residual tensile strength relative to the unaged baseline values exhibit. Since the test oil, which is chemically similar, dissolves the plasticizer from the PVC compound but does not have any flexibilizing properties itself, these tests become increasingly difficult or even impossible to pass with increasing duration and/or temperature if a system based solely on monomer plasticizers is to be used.
  • the monomer plasticizers which are only physically bound and therefore capable of migration, limit the possible uses of the PVC compound in polymer composites, e.g. UL cables with a polyamide skin layer or in data cables with a polyolefinic dielectric.
  • the plasticizer migrates into the dielectric and, due to its polar nature, damages the transmission properties.
  • barrier layers must therefore be introduced, which represents an additional process step and is therefore not only disadvantageous from an economic point of view.
  • polymeric plasticizers such as polyesters of adipic acid (e.g. BASF Palamoll®), or the physical mixing in of compatible rubber phases, such as acrylates, acetates (e.g. DuPont Elvaloy® or also Acrylonitrile-butadiene rubbers, eg Omnova Chemigum®)
  • polymeric plasticizers polymer plasticizers 1
  • polyesters of adipic acid e.g. BASF Palamoll®
  • compatible rubber phases such as acrylates, acetates (e.g. DuPont Elvaloy® or also Acrylonitrile-butadiene rubbers, eg Omnova Chemigum®)
  • the migration properties of the plasticizers incorporated into the PVC are improved, ie reduced, but these are bought at the expense of a reduction in flexibility at low temperatures.
  • polymeric plasticizers Due to their structure, polymeric plasticizers have a far less flexibilizing effect on the PVC matrix than monomeric plasticizers. With the same dosage, the glass transition temperature is up to 40°C higher.
  • NBR acrylonitrile butadiene rubber
  • the actual PVC phase is not made more flexible, so monomer plasticizers have to be added.
  • further technical problems arise from the use of only physically integrated soft phases. For example, resistance to media diffusion can be reduced due to internal interfaces, which is shown, for example, in the water storage test according to ISO 6722-1.
  • WO 2019/072594 A1 describes a UV-curable hot-melt adhesive that is largely resistant to plasticizer migration and contains a UV-crosslinkable poly(meth)acrylate formed from methyl acrylate, C4-18 alkyl (meth)acrylate, monomer with acid groups, copolymerized photoinitiator and optionally others Monomers, wherein the hot melt adhesive also contains an aliphatic polyester polymer.
  • US 6,043,318 A describes a process for preparing a polyvinyl chloride/acrylonitrile butadiene rubber blend by a) coating a polyvinyl chloride resin with a stabilizer to form a precoated PVC, b) blending the precoated PVC with one or more acrylonitrile butadiene rubbers to form a pre-stabilized NBR/PVC blend, and c) applying heat and pressure to mix the pre-stabilized NBR/PVC blend into a flowable NBR/PVC blend.
  • Cable having at least one layer, the layer comprising: a) 5-85% by weight, preferably 35-65% by weight polyvinyl chloride, b) 5-70% by weight, preferably 25-50% by weight halogen-free oligomers, Polymers, or combinations thereof, provided that the oligomers and polymers do not fall under the definition of component c), c) 5-50% by weight, preferably 5-10% by weight of a compatibilizer selected from esters with a molecular weight > 800 g/mol, halogenated polyolefins, polyvinyl chloride being excluded, modified acrylates and acetates or combinations thereof, characterized in that at least component a) and component b) are substituted by siloxane bonds -(CH2)2-Si-O-Si-( CH2)2- are crosslinked.
  • a compatibilizer selected from esters with a molecular weight > 800 g/mol, halogenated polyolefins, polyvinyl chloride being excluded, modified acrylates
  • the cables according to the invention comprehensively meet the diverse, previously mentioned requirements placed on cables by a special PVC layer.
  • a PVC modified with alkoxyvinylsilane groups and an oligomeric or polymeric soft phase containing alkoxyvinylsilane groups and having a sufficiently low glass transition temperature a monomer-plasticizer-free PVC system can be built up with the aid of chemical bonding, which with sufficient low-temperature flexibility for automotive applications.
  • the properties of the PVC system can be further improved by using an oligomeric or polymeric compatibilizer and plasticizing agent.
  • the different components of the system are connected in the same way as in the Sioplas® process, which is widespread in the cable industry, by aging in moist heat "sauna process".
  • the Sioplas® process is a modification of a polymer (or a polymer system) in which a crosslinkable material is processed by crosslinking with water and elevated temperatures.
  • alkoxysilane groups such as methoxysilane, ethoxysilane, etc.
  • the hydrolysis of the alkoxysilane groups to form hydroxy groups can be complete, but alkoxy groups can also remain in the material.
  • the successive crosslinking of the material can lead to steric inhibition of the subsequent hydrolysis and/or crosslinking reactions.
  • process parameters such as temperature, relative humidity or sample thickness, which in turn also determine the point in time at which water completely penetrates the material, can determine the course of the reaction.
  • the basic reaction scheme for crosslinking via alkoxyvinylsilane-modified polymer is shown schematically in FIG. While FIG.
  • FIG. 1 shows the condensation of two hydroxy groups (with elimination of H2O) which are formed by hydrolysis of the alkoxy groups, the condensation can also take place between a hydroxy group and an alkoxy group (with elimination of an alcohol). In the following, the condensation between completely hydrolyzed, i.e. between two -Si(OH)s groups is discussed.
  • FIG. 1 shows schematically the reaction of two identical polymer chains. However, the crosslinking reaction can take place not only between identical polymer chains but also between any two or more alkoxyvinylsilane-modified components.
  • siloxane bond (siloxane single bridge) can be formed in the reaction, as shown in FIG - or triple bridging between two -Si(OH)3 groups, can arise as shown schematically below: where is the linkage to the polymer/oligomer and can be RH, -CH3, or -C2H5.
  • crosslinking of two (hydrolyzed) alkoxysilane groups crosslinking of three or four alkoxysilane groups can also take place, one alkoxysilane group being crosslinked to two or three further alkoxysilane groups via siloxane bonds.
  • the method can also be used for other polymers, such as PVC in the present case.
  • the degree of crosslinking of the components depends on a variety of factors, such as reaction conditions (temperature, humidity), molecular weight of the components, type of silane, possible catalysts, sample thickness and shape, and others.
  • a quantitative determination of the degree of crosslinking can be carried out by Fourier transform infrared spectroscopy (FTIR), the degree of crosslinking being determined by the intensity of the bands for silanol (Si-OH), alkoxysilane (Si-OR) and siloxane (Si- O-Si) bonds can be determined.
  • FTIR Fourier transform infrared spectroscopy
  • the expression "crosslinked by siloxane bonds” or "siloxane-crosslinked” as used herein describes a polymer system in which at least one, preferably part or all of the PVC chains with at least one, preferably part or all of the halogen-free oligomers, polymers , or combinations is crosslinked by at least one siloxane bond.
  • thermomechanical behavior of the crosslinked PVC system in addition to dispensing with monomer plasticizers with their above-described disadvantages, this process also unexpectedly results in improved thermomechanical behavior of the crosslinked PVC system, as shown, for example, by the so-called hot-set test in accordance with DIN EN 60811-2-1 or the sufficient Cold flexibility at low temperatures as required for automotive applications.
  • DOTDL dioctyltin dilaurate
  • a cable having at least one layer comprising: a) 5-85% by weight, preferably 35-65% by weight polyvinyl chloride, b) 5-70% by weight, preferably 25-50% by weight halogen-free Oligomers, polymers, or combinations thereof, provided that the oligomers and polymers do not fall under the definition of component c), c) 5-50% by weight, preferably 5-10% by weight of a compatibilizer selected from esters having a molecular weight from
  • halogenated polyolefins polyvinyl chloride being excluded, modified acrylates and acetates or combinations thereof, characterized in that at least component a) and component b) are substituted by siloxane bonds -(CH2)2-Si-O-Si- (CH2)2- are crosslinked.
  • the layer is made by crosslinking a composition
  • the composition comprises: a) 5-85% by weight alkoxyvinylsilane-modified polyvinyl chloride, b) 5-70% by weight alkoxyvinylsilane-modified halogen-free oligomers, polymers , or combinations thereof, provided that the oligomers and polymers do not fall within the definition of component c), c) 5-50% by weight of a non-alkoxyvinylsilane-modified compatibilizer selected from esters having a molecular weight of
  • halogenated polyolefins where polyvinyl chloride excluding modified acrylates and acetates or combinations thereof, where alkoxyvinylsilane modification means that -(CH2)2-Si-(OR)3- groups are present, where R is selected from H, -CH3, and -C2H5.
  • Cable according to embodiment 1 or 2 characterized in that the layer comprises 15-70% by weight, preferably 35-65% by weight, of alkoxyvinylsilane-modified polyvinyl chloride.
  • the layer comprises 5-60% by weight, preferably 10-50% by weight, more preferably 25-50% by weight of component b).
  • the layer comprises 10-35% by weight, preferably 7-14% by weight, more preferably 5-10% by weight of the compatibiliser.
  • component b) is selected from homo- and copolymers of polyethylene, polypropylene, ethylene-propylene-diene rubber or silanes such as carbosilanes and polysiloxanes, and combinations of any two or several of them.
  • the compatibilizer is an adipic acid ester selected from poly(ethylene adipate), polybutylene adipate terephthalate (PBAT), poly(2-methyl-l,3-propylene adipate), poly(l ,4-butylene adipate), poly(1,4-butanediol/neopentyl glycol-altadipic acid), polyisononyl(1,4-butanediol-2,2-dimethyl-1,3-propanediol) adipate and combinations of any two or more of it is.
  • PBAT polybutylene adipate terephthalate
  • PBAT poly(2-methyl-l,3-propylene adipate)
  • poly(l ,4-butylene adipate) poly(1,4-butanediol/neopentyl glycol-altadipic acid)
  • the layer further comprises fillers in an amount of 0.5-60% by weight, which fillers are preferably selected from carbonates, preferably calcium carbonate; silicates, preferably talc or kaolin; inorganic flame retardants, preferably aluminum hydroxide; and combinations thereof.
  • the layer further contains metal soaps present in an amount of up to 10% by weight, preferably 1-4% by weight, the metal soaps being preferably selected from dilaurates and Distearates of zinc, barium, calcium, magnesium, or combinations of any two or more thereof.
  • the layer further contains acid scavengers present in an amount of up to 18% by weight, preferably 1-8% by weight, the acid scavengers being preferably selected from aluminium /magnesium hydrotalcite, aluminium/magnesium/zinc hydrotalcite, calcium hydroxides, zeolite or combination of any two or more thereof.
  • the layer further contains phenolic antioxidants present in an amount of up to 4% by weight, preferably 0.25-2% by weight, the phenolic antioxidant being optionally selected are derived from ethylene bis(oxyethylene) bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate), octadecyl [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2',3-bis[[3-[3,5-di-tert-butyl-4 - hydroxyphenyl]propionyl]]propionohydrazide and dialkyl esters of thiodipropionic acid.
  • the phenolic antioxidant being optionally selected are derived from ethylene bis(oxyethylene) bis(3-(5-tert-butyl-4
  • the layer further comprises lubricants, the lubricants preferably being selected from fatty acids with a chain length of C8-C18, montan waxes and their esters, chlorinated paraffins with a chain length of C10- C30 and polyolefin waxes, and combinations of any two or more thereof.
  • the layer is free from monomeric plasticizers with a molecular weight of 700 g/mol or less, the layer in particular is free from esters of trimellitic, orthophthalic, terephthalic, pyromellitic, adipic, sebacic, phosphoric and citric acid and their anhydrides with alcohols with a chain length of C2-C15.
  • the layer has phase transitions determined by dynamic mechanical analysis in the range from -25°C to -15°C and in the range from 25°C to 35°C, wherein the layer preferably has no further phase transitions in the range from -80°C to 100°C.
  • the layer has any one or more properties of the following: a) a volume resistivity of > 10 9 Ohm-mm according to ISO 6722-1:2011, b) a low temperature -Winding test according to ISO 6722-1:2011 at -40°C without cracks, breaks or other structural impairments, c) a thermal stability of > 140 minutes according to LV112-1 2014-04, d) a hot water resistance of >10 9 ohms- mm after 1000h at 85°C according to ISO 6722-1:2011, e) short-term aging Oat 130°C for 240h according to ISO 6722-1:2011 without cracks, fractures or other structural impairments, f) a hot set test at 150° C for 15 minutes according to DIN EN 60811-2-1 of ⁇ 100%.
  • the layer is a primary insulation of an electrical conductor, and/or the jacket material for jacketing a plurality of cores.
  • a method of making a layer of cable comprising a) mixing i) 5-85% by weight alkoxyvinylsilane-modified polyvinyl chloride, ii) 5-70% by weight alkoxyvinylsilane-modified halogen-free oligomers, halogen-free polymers or combination thereof, provided that the oligomers and polymers do not fall under the definition of component iii), and iii) 5-50% by weight of a non-alkoxyvinylsilane-modified compatibilizer selected from esters, halogenated polyolefins, with the exception of polyvinylchloride, modified acrylates and acetates or combinations thereof with a molecular weight >800 g/mol, where alkoxyvinylsilane means modification that - (Cl-h)?- Si-(OR)s groups are present, where R is selected from H, -CH3, and -C2H5, b) extruding the mixture obtained in point
  • compositions in the manufacture of a cable or as a layer in a cable, wherein the composition is applied as a layer to cable strands or core ropes by sheath extrusion and is subsequently crosslinked by aging in moist heat to form siloxane bonds, the composition comprising: a) alkoxyvinylsilane-modified polyvinyl chloride in an amount of 5-85% by weight, b) alkoxyvinylsilane-modified halogen-free oligomers, halogen-free polymers or combinations thereof, in an amount of 5-70% by weight %, provided that the oligomers and polymers do not fall under the definition of component c), and c) a compatibilizer selected from esters with a molecular weight > 800 g/mol, halogenated polyolefins, with the exception of polyvinyl chloride, modified acrylates and acetates or combinations thereof, in an amount of 5-50% by weight.
  • the cable according to the invention has at least one layer as described above.
  • the cable comprises at least one layer as defined in the claims. In addition to this layer, the cable can also comprise additional layers. Further layers can be conductive layers, insulating layers, sliding layers, separating layers, lacquer layers, textile carrier layers and others.
  • polymer refers to molecules having a high number of repeating units (monomers) linked together.
  • One type of polymer e.g. the "first polymer”
  • second polymer e.g. the "second polymer”
  • copolymer refers to a polymer having more than one type of monomers.
  • oligomer refers to molecules that are made up of several structurally identical or similar units, whereby, in contrast to polymers, a small change in the number of units already causes a significant change in properties. Typically, the molecular weight of oligomers smaller than 10 kDa (10,000 u).
  • weight percent and its variations (e.g., “wt%”, wt%, etc.) refers to the total weight of the composition of the layer that is part of the cable.
  • alkoxyvinylsilane-modified polyvinyl chloride refers to a polymer of vinyl chloride (polyvinyl chloride) modified with alkoxyvinylsilane.
  • Silane-modified polymers can be prepared in two different ways, among others: grafting of vinylsilane monomers onto the polymer, or Copolymerization of these compounds with the monomer (e.g. vinyl chloride).
  • VTMS vinyltrimethoxysilane
  • VTES vinyltriethoxysilane
  • other vinylalkoxysilanes can be used as the modifying monomer.
  • VTMS and VTES are preferably used.
  • These molecules can be attached to the backbone of the polymer (such as PVC) via a free radical mechanism, for example.
  • the silane group can be grafted onto the PVC or the PVC can be modified with the silane group in different ways. In industrial applications, among other things, the grafting in the melt using peroxides as the initiator of the free-radical mechanism has become established.
  • silane-modified polymers can be prepared by copolymerizing vinyl silane together with other monomers (such as vinyl chloride).
  • amino(alkoxy)silanes such as, for example, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane or N-(2-aminoethyl)-3-aminopropyltriethoxysilane can be grafted onto PVC by nucleophilic substitution.
  • alkoxyvinylsilane-modified halogen-free oligomers, polymers or combinations thereof refers to polymers, oligomers and mixtures of both, which - as previously described for PVC - are modified with alkoxyvinylsilane.
  • Preferably used are homo- and copolymers of polyethylene (PE), polypropylene (PP), polybutylene (PB), polyisobutene (PIB), polyhexene (PH), polyoctene (PO), polydecene (PDC) and polyoctadecene (PODC), polystyrene (PS), ethylene-propylene diene rubber (EPDM) and silanes.
  • the amount of alkoxyvinylsilane used for modification can vary depending on the properties that the modified and crosslinked product is to have.
  • the amount may range from 0.5 to 5.0% by weight based on the weight of the polymer or oligomer, preferably in a range of 0.5 to 2.5% by weight, more preferably in a range of 1.0 to 2.0% by weight based on the weight of the polymer or oligomer.
  • compatibilizer refers to one or more additives that can be added to polymers, copolymers and polymer blends to reduce the interfacial tension between different phases. Compatibilizers thus reduce the tendency for chemically different components to segregate, thereby allowing an additionally improved
  • the compatibilizers are preferably organic compounds, in particular plasticizers based on adipic acid esters with a molar mass >800 g/mol, halogenated polyolefins, in particular halogenated PE, modified acrylates and acetates or combinations of any two or more of these.
  • the components of the layer and the layer itself can be characterized, for example, by nuclear magnetic resonance spectroscopy (NMR).
  • NMR nuclear magnetic resonance spectroscopy
  • signals in the spectrum can be assigned to specific atoms or to the same atoms in chemically or sterically different environments. Since NMR spectra are influenced by local interactions, the method allows conclusions to be drawn about the structure of monomeric, oligomeric or polymeric compounds by shifting the signals in the spectrum. Furthermore, statements about the degree of halogenation or crosslinking in the components can be made by quantitative evaluation of the NMR spectra.
  • the work "Identification of different structures formed during crosslinking of polyethylene with vinyl triethoxysilane FTIR Si 29 NMR and XPS sudy" by Fuzail et al.
  • Plasticizers based on adipic acid esters with a molar mass > 800 g/mol can be used as compatibilizers in the cable layer.
  • Esters such as poly(ethylene adipate), polybutylene adipate terephthalate (PBAT), poly(2-methyl-1,3-propylene adipate), poly(1,4-butylene adipate), poly(1,4-butanediol/neopentyl glycol) can be used -alt-adipic acid), and combinations of any two or more thereof.
  • the compatibilizers can also be selected from halogenated olefins such as chlorinated hydrocarbons, brominated hydrocarbons or fluorocarbons, and are preferably elastomeric compounds.
  • halogenated polyethylene halogenated polypropylene, polybutylene, polyisobutene, polyhexene, polyoctene, polydecene and polyoctadecene can be used.
  • Halogenated polyethylene is preferably used.
  • the halogenated polymers or olefins are preferably produced by post-chlorination of polymers or olefins in a separate process step.
  • the compatibilizers can be selected from modified acrylates and modified acetates.
  • Modified acrylates can be used, including methyl acrylate, ethyl acrylate, n-propyl acrylate, butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isobornyl acrylate, cyclododecyl acrylate, chloromethyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2,3, 4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5-tetrahydroxypentyl acrylate, ethyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate
  • Preferred acrylates are ethylene acetate and ethylene acrylate copolymers and modifications thereof.
  • the copolymers can also contain N-butyl, CO blocks and other copolymerizable units, as well as ethylene/n-butyl acrylates and their copolymers with carbon monoxide.
  • Modified acetates include ethylene vinyl acetate copolymer,
  • fillers describes substances that can be added to the layer of the cable. Fillers that can be added include glass fibers, glass beads, mineral fillers, carbon fiber, carbon black, chalk, wood fibers, wood powder, dried apple powder, kaolin , and magnesium dihydroxide (MDH), and carbonates, silicates, flame retardants, Inorganic carbonates, preferably calcium carbonate, inorganic silicates, preferably talc or kaolin, or inorganic flame retardants, preferably aluminum hydroxide or combinations thereof, can preferably be used.
  • MDH magnesium dihydroxide
  • metal soaps as used herein describes salts of fatty acids and salts of rosin and naphthenic acids with metals to the exclusion of the sodium and potassium salts.
  • metallic soaps of laurate, stearate, and combinations thereof are used.
  • zinc, barium, - Calcium or magnesium salts, as well as combinations of any two or more of these are used.
  • acid scavenger describes basic substances that are used to neutralize traces of acids in polymers and polymer-containing materials, which are, for example, from catalyst residues in the material.
  • Hydrotalcite comprising aluminum and magnesium are preferably used as acid scavengers , Hydrotalcite including aluminum, magnesium and zinc, calcium hydroxides, zeolites and combinations of any two or more thereof used.
  • phenolic antioxidants as used herein, describes free-radical scavengers, which means substances that can be added to the layer of the cable in order to protect it from undesirable oxidative aging processes or to delay aging.
  • processes take place whose irreversible effects collectively referred to as "aging phenomena".
  • pigments, fillers, reinforcing materials and various additives are also involved.
  • Physical aging is initially noticeable in the form of embrittlement. It is caused, in particular, by long-term use at temperatures slightly below the melting or glass transition point of the polymers.
  • natural and synthetic polymers react readily with oxygen. The mechanical and optical properties deteriorate in the process the plastic parts made from it.
  • Lubricant describes substances that can be added to the cable or the layer to reduce the mechanical stress between the individual components of the cable.
  • Lubricants are divided into internal and external lubricants. The transitions are fluid - internal lubricants show often a certain external lubricating effect and vice versa. Lubricants with both effects are referred to as “combined”.
  • Internal lubricants reduce the frictional forces occurring between the PVC molecular chains and thus lower the melt viscosity. They are polar and have a high level of compatibility with PVC. Even with high dosages, they provide excellent transparency and do not tend to exude, which optimizes welding, gluing and printing.
  • External lubricants reduce adhesion between PVC and metal surfaces.
  • lubricants selected from fatty acids (in particular lauric acid and stearic acid), montan waxes and their esters, chlorinated paraffins, and oxidized and non-oxidized polyolefin waxes.
  • Montan wax describes a black-brown, hard, brittle, fossil vegetable wax, which is extracted from bituminous types of lignite.
  • Chlorinated paraffins are substance mixtures of polychlorinated, saturated, unbranched hydrocarbons with 10-30 carbon atoms, which correspond to the general molecular formula C x H(2x- y +2)Cl y . They can be produced by the chlorination of n-alkanes, resulting in complex mixtures of different chloroalkanes. The degree of chlorination can vary between 30 and 70% by weight.
  • Polyolefin wax describes a mixture of hydrocarbons having a melting point between about 30°C and 60°C which when molten forms a low viscosity liquid.
  • Preferred waxes are polyethylene wax, polypropylene wax, and mixtures thereof.
  • the layer of the cable may be free of organotin (such as dioctyltin dilaurate), preferably free of organometallic compounds.
  • Organometallic compounds contain a metal atom bonded to a carbon atom.
  • Organometallic compounds may contain Group 1 alkali metals, Group 2 alkaline earth metals, Groups 3-12 transition metals and Groups 13-15 elements, as well as metalloids such as boron and silicon.
  • Organometallic compounds are used, among other things, as catalysts in polymerisation and often remain in the finished polymer after polymerisation. In addition to polymerization per se, organometallic compounds are also used as catalysts in the subsequent crosslinking of polymers.
  • organometallic compounds used are harmful or potentially harmful to health, such as dioctyltin dilaurate or dibutyltin dilaurate. Due to the combination of alkoxyvinylsilane-modified polyvinyl chloride and alkoxyvinylsilane-modified, halogen-free oligomers and polymers as the soft phase, which are crosslinked by condensation reactions, it is not necessary to use organometallic compounds such as dioctyltin dilaurate (DOTDL).
  • DOTDL dioctyltin dilaurate
  • the layer of the cable can be free of monomeric plasticizers such as mono-, di-, and triglycerides of fatty acids.
  • the layer is preferably free of monomeric plasticizers with a molecular weight of 700 g/mol or less.
  • Monomeric softeners such as phthalic acid esters of long-chain alcohols have been criticized because their effect is similar to that of certain hormones.
  • the layer of the cable is free from monomeric plasticizers such as ASE (Cio-C2i) phenyl alkanesulfonate, BAR butyl O-acetylricinoleate,
  • TDBPP Tris(2,3-dibromopropyl)phosphate
  • TDCPP Tris(2,3-dichloropropyl)phosphate
  • Dynamic mechanical analysis is a method for determining the viscoelastic properties, primarily of polymer materials.
  • elastomers are very stiff below the glass transition temperature (Tg) and have a high modulus of elasticity. Above the Tg they are flexible and cushioning.
  • DMA measures viscoelastic properties during a controlled temperature and/or frequency program. During the test, a sinusoidal force (stress o) is applied to the sample (input). This in turn results in a sinusoidal deformation (elongation E; exit).
  • Stress o sinusoidal force
  • E sinusoidal deformation
  • Certain materials, such as polymers exhibit viscoelastic behavior, that is, they exhibit both elastic (corresponding to a spring) and viscous properties (corresponding to an ideal damper). Because of this viscoelastic behavior, the corresponding stress and strain curves are shifted.
  • the presence of a phase transition in polymeric materials can be determined by DMA.
  • phase transitions determined by DMA in the range from -25°C to -15°C (pure soft phase), 45° appear C to 55°C (crosslinking range of both components, as well as 85°C to 95°C (pure PVC phase).
  • the layer of the cable is characterized in that this layer with compatibilizer has a phase transition in the range from -25°C to -15°C and in the range from 25°C to 35°C.
  • the layer particularly preferably has no further phase transitions in the range from -80.degree. C. to 100.degree.
  • the absence of further phase transitions in the material indicates that after crosslinking there is no longer pure PVC and no pure crosslinked area in the material.
  • the "Hot Set" test is a simple means of determining whether the material used in the insulation or jacketing (e.g. of cables) has been sufficiently crosslinked.
  • a crosslinked material is a material that has been modified to allow the bonding between the polymer chains When cross-linking insulation and sheathing materials, it is usually done to improve mechanical and electrical properties.
  • the hot set test for crosslinked materials can be carried out in accordance with DIN EN 60811-2-1, for example.
  • the recognized test methods are intended to be referenced in cable construction and cable material standards.
  • the hot set test is performed on the insulation or jacket material and not on the complete cable.
  • the first step therefore, is to prepare the cable sample by removing the conductors and any braid, armor or tape.
  • samples are either cut as a tubular disc or cut into smooth, dumbbell-shaped pieces.
  • the central 20mm (or 10mm for smaller samples) are marked by two lines.
  • the test method requires handles with attachable weights.
  • the layer of the cable is preferably as defined in the claims, characterized in that the hot-set test at 170°C according to DIN EN 60811-507 has an elongation in the range of 20-30%, preferably 24-29%.
  • the cable as defined in the claims is characterized in that the layer has a volume resistance of > 10 9 Ohm-mm according to ISO 6722-1:2011, a low-temperature winding according to ISO 6722-1:2011 at -40°C without cracks, fractures or other structural impairments, a thermal stability of > 140 minutes according to LV112-1 2014-04, a resistance to hot water of >10 9 ohm-mm after 1000h at 85°C according to ISO 6722-1:2011, short-term aging at 130°C for 240h according to ISO 6722-1:2011 without cracks, fractures or other structural impairments, a hot set test at 150°C for 15 minutes according to DIN EN 60811-2-1 of ⁇ 100%.
  • the present invention also relates to a method for producing a layer of a cable.
  • the process as defined in the claims comprises: a) mixing i) 5-85% by weight alkoxyvinylsilane-modified polyvinyl chloride, ii) 5-70% by weight alkoxyvinylsilane-modified halogen-free oligomers, halogen-free polymers or combination thereof, provided that that the oligomers and polymers do not fall under the definition of component iii), and iii) 5-50% by weight of a non-alkoxyvinylsilane-modified compatibilizer selected from esters, halogenated polyolefins with the exception of polyvinyl chloride, modified acrylates and acetates or combinations thereof with a molar mass of > 800 g/mol, where alkoxyvinylsilane modification means that - (CH2)2-Si-(OR)s groups are present, where R is selected from H, -CH3, and -
  • the mixture in step b) can also be processed by injection molding or other methods known to those skilled in the art.
  • the material can be processed as cable auxiliary equipment (gaskets, strain reliefs and others) by these methods.
  • the crosslinking step c) can in principle take place at any desired temperature and atmospheric humidity which is suitable for enabling the crosslinking reaction.
  • the process is as defined in the claims, characterized in that the crosslinking is carried out by water storage at a temperature of 70°C to 95°C, preferably 80°C to 90°C, for a period of 8 to 48 hours, preferably 12 to 36 hours, more preferably 18 to 30 hours, or for a period of 24 hours at 85°C.
  • the crosslinking step can take place in a water bath.
  • the present invention relates to a layer of a cable obtained by or obtainable by mixing, extruding and crosslinking the components comprising a) alkoxyvinylsilane-modified polyvinyl chloride in an amount of 5-85% by weight, b) alkoxyvinylsilane-modified halogen-free oligomers, halogen-free polymers or Combination thereof provided that the oligomers and polymers do not fall within the definition of component c) in an amount of 5-70% by weight, and c) a compatibilizer selected from esters having a molecular weight of
  • halogenated polyolefins with the exception of polyvinyl chloride, modified acrylates and acetates or combinations thereof, in an amount of 5-50% by weight.
  • the extrusion is done using mixing elements. This results in the distribution of dyes, microbubbles or other components becoming more homogeneous if they are added.
  • the crosslinking is preferably carried out by a process similar to the Sioplas® process or the sauna process. This means that the silanol groups are preferably crosslinked by aging in moist (non-condensed or condensed) heat or in hot water.
  • the layer of the cable preferably comprises a compatibilizer as described above in addition to the alkoxyvinylsilane modified components
  • the present invention is not so limited.
  • the present invention relates to a cable with a layer comprising the alkoxyvinylsilane-modified components as described above, wherein at least these are crosslinked by siloxane bonds.
  • the present invention relates to a cable having at least one layer, the layer comprising: a) 5-85% by weight polyvinyl chloride, b) 5-70% by weight halogen-free oligomers, polymers, or combinations thereof, characterized in that component a) and component b) are crosslinked by siloxane bonds -(CH2)2-Si-O-Si-(CH2)2-.
  • the present invention relates to a cable having at least one layer, wherein the layer is made by crosslinking a composition, wherein the composition comprises: a) 5-85% by weight alkoxyvinylsilane-modified polyvinyl chloride, b) 5-70 % by weight of alkoxyvinylsilane-modified halogen-free oligomers, polymers, or combinations thereof, where alkoxyvinylsilane modification means that -(CH2)2-Si-(OR)3- groups are present, where R is selected from H, -CH3, and -C2H5, characterized in that at least component a) and component b) are crosslinked in the layer by siloxane bonds -(CH2)2-Si-O-Si-(CH2)2-.
  • the alkoxyvinylsilane-modified halogen-free oligomer is selected from homo- and copolymers of polyethylene, polypropylene, polybutylene, polyisobutene, polyhexene, polyoctene, polydecene and polyoctadecene, polystyrene, ethylene-propylene-diene rubber and silanes, and combinations of any two or more of that.
  • the present invention also relates to a method for producing a layer of a cable.
  • the process comprises: a) mixing i) 5-85% by weight alkoxyvinylsilane-modified polyvinyl chloride, ii) 5-70% by weight alkoxyvinylsilane-modified halogen-free oligomers, halogen-free polymers or combination thereof and b) extruding the ones obtained in point a).
  • a cable having at least one layer comprising: a) 5-85% by weight, preferably 35-65% by weight polyvinyl chloride, b) 5-70% by weight, preferably 25-50% by weight halogen-free Oligomers, polymers, or combinations thereof, provided that the oligomers and polymers do not fall under the definition of component c), characterized in that at least component a) and component b) are linked by siloxane bonds -(CH2)2-Si-O -Si-(CH2)2- are crosslinked.
  • the layer is made by crosslinking a composition
  • the composition comprises: a) 5-85% by weight alkoxyvinylsilane-modified polyvinyl chloride, b) 5-70% by weight alkoxyvinylsilane-modified halogen-free oligomers, polymers , or combinations thereof, wherein alkoxyvinylsilane modification means that -(CH2)2-Si-(OR)3- groups are present, where R is selected from H, -CH3, and -C2H5.
  • Cable according to embodiment 1 or 2 characterized in that the layer comprises 15-70% by weight, preferably 35-65% by weight, of alkoxyvinylsilane-modified polyvinyl chloride.
  • the layer comprises 5-60% by weight, preferably 10-50% by weight, more preferably 25-50% by weight of component b).
  • component b) is selected from homo- and copolymers of polyethylene, polypropylene, ethylene-propylene-diene rubber or silanes such as carbosilanes and polysiloxanes, and combinations of any two or several of them.
  • the layer further contains metal soaps present in an amount of up to 10% by weight, preferably 1-4% by weight, the metal soaps being preferably selected from dilaurates and distearates of zinc, barium, calcium, magnesium, or combinations of any two or more thereof.
  • the layer further contains acid scavengers present in an amount of up to 18% by weight, preferably 1-8% by weight, the acid scavengers being preferably selected from aluminium /magnesium hydrotalcite, aluminium/magnesium/zinc hydrotalcite, calcium hydroxides, zeolite or combination of any two or more thereof.
  • the layer further contains phenolic antioxidants present in an amount of up to 4% by weight, preferably 0.25-2% by weight, the phenolic antioxidant being optionally selected are derived from ethylene bis(oxyethylene) bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate), octadecyl [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2',3-bis[[3-[3,5-di-tert-butyl-4 - hydroxyphenyl]propionyl]]propionohydrazide and dialkyl esters of thiodipropionic acid.
  • the phenolic antioxidant being optionally selected are derived from ethylene bis(oxyethylene) bis(3-(5-tert-butyl-4
  • the layer further comprises lubricants, wherein the lubricants are preferably selected from fatty acids with a chain length of C8-C18, montan waxes and their esters, chloroparaffins with a chain length of C10- C30 and polyolefin waxes, and combinations of any two or more thereof.
  • lubricants are preferably selected from fatty acids with a chain length of C8-C18, montan waxes and their esters, chloroparaffins with a chain length of C10- C30 and polyolefin waxes, and combinations of any two or more thereof.
  • the layer is free from monomeric plasticizers with a molecular weight of 700 g/mol or less, the layer in particular being free from esters of trimellitic, orthophthalic, terephthalic, pyromellitic -, Adipic, sebacic, phosphoric and citric acid and their anhydrides with alcohols with a chain length of C2-C15.
  • the layer has phase transitions determined by dynamic mechanical analysis in the range from -25°C to -15°C and in the range from 25°C to 35°C, wherein the layer preferably has no further phase transitions in the range from -80°C to 100°C.
  • the layer has an elongation in the range of 20-30%, preferably 24-29%, determined by a hot-set test at 170° C. according to DIN EN 60811-507.
  • the layer has any one or more properties of the following: a) a volume resistivity of > 10 9 Ohm-mm according to ISO 6722-1:2011, b) a low temperature -Winding test according to ISO 6722-1:2011 at -40°C without cracks, breaks or other structural impairments, c) a thermal stability of > 140 minutes according to LV112-1 2014-04, d) a hot water resistance of >10 9 ohms- mm after 1000h at 85°C according to ISO 6722-1:2011, e) short-term aging Oat 130°C for 240h according to ISO 6722-1:2011 without cracks, fractures or other structural impairments, f) a hot set test at 150° C for 15 minutes according to DIN EN 60811-2-1 of ⁇ 100%.
  • the layer is a primary insulation of an electrical conductor, and/or the jacket material for jacketing a plurality of cores.
  • a method of making a layer of cable comprising a) mixing i) 5-85% by weight of alkoxyvinylsilane-modified polyvinyl chloride, ii) 5-70% by weight of alkoxyvinylsilane-modified halogen-free oligomers, halogen-free polymers or combination thereof, and wherein alkoxyvinylsilane modification means that - (Cl-h)?-Si-(OR)s- groups are present, where R is selected is composed of H, -CH3, and -C2H5, b) extruding the mixture obtained in point a) as a layer of a cable, c) crosslinking the mixture obtained in point b) at a temperature of at least 20°C, preferably >60°C and a relative humidity of at least 50%, preferably >85%, with at least components i) and ii) being crosslinked by siloxane bonds.
  • compositions in the manufacture of a cable or as a layer in a cable, wherein the composition is applied as a layer to cable strands or core ropes by sheath extrusion and is subsequently crosslinked by aging in moist heat to form siloxane bonds, the composition comprising: a) alkoxyvinylsilane-modified polyvinyl chloride in an amount of 5-85% by weight, b) alkoxyvinylsilane-modified halogen-free oligomers, halogen-free polymers or combination thereof in an amount of 5-70% by weight, provided that the oligomers and polymers do not fall within the definition of component c), and
  • the present invention relates to a composition
  • a composition comprising: a) 5-85% by weight alkoxyvinylsilane-modified polyvinyl chloride, b) 5-70% by weight alkoxyvinylsilane-modified halogen-free oligomers, polymers, or combinations thereof, and optionally c) 5-50% by weight of a non-alkoxyvinylsilane-modified compatibilizer, selected from esters with a molar mass of >800 g/mol, halogenated polyolefins, where alkoxyvinylsilane modification means that -(CH2)2-Si-(OR) 3- groups are present, where R is selected from H, -CH3, and -C2H5, characterized in that at least component a) and component b) in the layer are substituted by siloxane bonds -(CH2)2-Si-O-Si -(CH2)2- are crosslinked.
  • Example 1 Experiments on the phase structure of a cable as defined in the claims
  • a cable comprising a layer as defined in the claims can be manufactured as defined in the claims.
  • the layer of the tested cable according to the claims has the following components:
  • phase transitions There is a clear difference in the behavior of the phase transitions, determined by DMA, between a combination of alkoxyvinylsilane-modified PVC with an incompatible or compatible, alkoxyvinylsilane-modified, polymeric soft phase (hereinafter "silane-modified").
  • silane-modified alkoxyvinylsilane-modified PVC with an incompatible or compatible, alkoxyvinylsilane-modified, polymeric soft phase
  • the system with a compatible, silane-modified soft phase shows a reduction in the number of transition regions from four before crosslinking to three after crosslinking.
  • the hot-set test is passed in 2/3 of the cases.
  • a further improvement results from the introduction of the compatibilizer.
  • a common phase transition for the crosslinking area and the PVC phase can be seen here at a comparatively lower temperature (31°C). We passed the hot-set test in all cases.
  • Example 2 Tests on the thermomechanical behavior of a cable as defined in the claims
  • a cable comprising at least one layer as defined in the claims fulfills both the thermomechanical and the electrical requirements.

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Abstract

La présente invention concerne un câble doté d'une couche telle que définie dans les revendications, la couche comprenant du polychlorure de vinyle modifié par alkoxysilane, des oligomères, polymères ou combinaisons de ceux-ci, exempts d'halogène modifiés par alcoxyvinylsilane, tels que définis dans les revendications, ainsi qu'un agent de compatibilisation, au moins les constituants modifiés par alcoxyvinylsilane étant réticulés par l'intermédiaire de liaisons siloxane. L'invention concerne en outre un procédé de fabrication d'un câble présentant une couche telle que définie dans les revendications.
PCT/EP2022/075517 2021-10-01 2022-09-14 Mélange pvc WO2023052127A1 (fr)

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Cited By (1)

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CN116836489A (zh) * 2023-07-08 2023-10-03 东莞宝特电业股份有限公司 一种用于机器人的高弹力pvc线缆

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US6043318A (en) 1996-09-27 2000-03-28 Hardiman; Christopher John Nitrile rubber/polyvinyl chloride blends
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WO2019072594A1 (fr) 2017-10-11 2019-04-18 Basf Se Adhésif thermofusible durcissable aux uv et résistant à la migration des plastifiants pour films graphiques et étiquettes en pvc souple

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WO2019072594A1 (fr) 2017-10-11 2019-04-18 Basf Se Adhésif thermofusible durcissable aux uv et résistant à la migration des plastifiants pour films graphiques et étiquettes en pvc souple

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CN116836489A (zh) * 2023-07-08 2023-10-03 东莞宝特电业股份有限公司 一种用于机器人的高弹力pvc线缆

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