WO2018056916A1 - Halogen free flame reterdant cable insulation composition and a method of producing the same - Google Patents

Halogen free flame reterdant cable insulation composition and a method of producing the same Download PDF

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Publication number
WO2018056916A1
WO2018056916A1 PCT/TR2016/050351 TR2016050351W WO2018056916A1 WO 2018056916 A1 WO2018056916 A1 WO 2018056916A1 TR 2016050351 W TR2016050351 W TR 2016050351W WO 2018056916 A1 WO2018056916 A1 WO 2018056916A1
Authority
WO
WIPO (PCT)
Prior art keywords
phr
covering material
cable
material according
cable covering
Prior art date
Application number
PCT/TR2016/050351
Other languages
French (fr)
Inventor
Ozgur IPEK
Erdem EKER
Bekir GULER
Original Assignee
Kabkom Kimya San. Ve Tic. A. S.
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 Kabkom Kimya San. Ve Tic. A. S. filed Critical Kabkom Kimya San. Ve Tic. A. S.
Priority to EP16798300.6A priority Critical patent/EP3515976A1/en
Priority to PCT/TR2016/050351 priority patent/WO2018056916A1/en
Publication of WO2018056916A1 publication Critical patent/WO2018056916A1/en

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Classifications

    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • 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
    • H01B3/441—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 alkenes
    • 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
    • H01B3/448—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 other vinyl compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds

Definitions

  • Invention relates to a polymer composition suitable for manufacture of an insulation cover of cables having flame reterdant, halogen free material properties and a process for manufacturing such a polymer composition.
  • Wire and cables for power transmission, control or communication comprising a conductive core material and a insulation cover made of non-conductive substrate protecting the core material.
  • Application of insulation cover to the conductive core includes extrusion of a polymeric material over the metalic core.
  • etylene or propylene polymers have been used as insulation due to easy processablity and beneficial electrical properties. Mechanical properties of the cable insulation compound is expected to meet resistance to long term exposure to the temperature and high flame reterdancy.
  • HFFR halogen-free flame reterdant materials
  • halogen has the disadvantages of being difficult to obtain a flame-retardant covering material having less than 0.5% of halogen and less than 1.5 toxicity index. Additionally, such a base resin is having a poor thermal property at high temperature.
  • US6043312 describe thermoplastic compositions without halogen having various fire reterdants based on mixtures of metallic hydroxide and zinc borate.
  • the resin blends are based exclusively on polyvinyl chloride.
  • Zinc borate provides a synergistic effect on flame retardancy when used in combination with metal hydroxide such as magnesium hydroxide on halogenated formulas.
  • Zinc borate improves flame retardancy but also zinc borate acts as support to the carbonated layer of EVA-LLDPE however halogen use is required.
  • Object of the invention is to provide a halogen free composition for cable insulation with a high degree of flame retardacy.
  • invention is a halogen-free flame retardant composition for a cable covering material used to form a covering layer of cable for power transmission, control and communication.
  • the invention comprising: 32-45 PHR base resin including 14-20 PHR linear low density polyethylene (LLDPE), 18-25 PHR ethylene- vinylacetate (EVA); and 44-50 PHR aluminium (III) hydroxide (ATH) as a primary flame- retardant.
  • LLDPE linear low density polyethylene
  • EVA 18-25 PHR ethylene- vinylacetate
  • ATH aluminium (III) hydroxide
  • LLDPE linear low density polyethylene
  • preferred application uses, 18-25 PHR magnesium hydroxide as a secondary flame retardant.
  • the aluminium hydroxide amount is more particularly 44 PHR.
  • Aluminium hydroxide (ATH) and magnesium hydroxide are enhance flame retardancy properties of the composition at a surprising level. Oxides and water as an output of thermal decomposition retard the flame spread over a cable cover for a certain period of time.
  • a functional element selected from the group of 0,5-1 PHR antioxidant, 2-4 PHR silicone, 4-6 PHR coupling agent, 2-3 PHR ethylene-vinylacetate wax.
  • Antioxydant protect the material from heat, light, moisture, storing conditions and other types of negative environmental conditions. Antioxydant is also delay the induction time.
  • a fire growth rate index of the cable covering material is set between 90-100 W/sn. This index value is sufficiently delay any flame spread over a cable cover for building materials such as power transmission, control or communication cables. In a preferred application the fire growth rate index is particularly set to 97,95 W/sn. This value provide best results for a standard power transmission cable used in the buildings.
  • invention is a method comprising the steps of kneading the base resin and the primary flame retardant in a container until a first mixture in paste form is obtained at a predefined temperature, extruding and cutting the the first mixture to a granule form, cooling the granules. Kneading ensure homogenization of the compounds of the composition and forming a paste. Granulated material is ready to be used for an extrusion process to obtain a cable cover according the the subject matter.
  • the predefined temperature is set to 150°C.
  • the first mixture in paste form can be extruded at the extrusion machines and cut by means of the moulds.
  • the granules are cooled at the cyclones.
  • the method further comprising seperation of the granules based on the average size of the granules. A vibration sieve is suitable for use in such a process step. After cooling the material is ready for packaging step.
  • the present invention relates to a halogen-free flame retardant for a cable covering material used to form a covering layer of cable for power transmission, control and communication
  • a halogen-free flame retardant for a cable covering material used to form a covering layer of cable for power transmission, control and communication one example is comprising: 32 PHR base resin including 18 PHR LLDPE (linear low density polyethylene), 14 PHR ethylene-vinylacetate and 44 PHR aluminium hydroxide (aluminum trihyroxide) as a primary flame-retardant, 18 PHR magnesium hyroxide, 0,5 PHR antioxydant, 4 PHR coupling agent, 2 PHR silicone and 2 PHR EVA Wax.
  • PHR base resin including 18 PHR LLDPE (linear low density polyethylene), 14 PHR ethylene-vinylacetate and 44 PHR aluminium hydroxide (aluminum trihyroxide) as a primary flame-retardant, 18 PHR magnesium hyroxide, 0,5 PHR
  • Diameter 5,70 mm, Lenght: 600 mm
  • ATH Al2(OH)3 contains 35wt % water which is released at the temperatures above 220°C. Such an endothermic reaction absorbs 1970 kJ/kg of the hydrated salt.
  • a mixture of aluminium hydroxide with magnesium hydroxide having water release temperature over 340°C provides two level of endothermic reaction of the cable cover in case of a fire start one after another. This effect of two level endothermic reaction of the cable cover against fire provide excellent flame retardancy.

Abstract

Invention is a halogen free flame retardant for a cable covering material used to form a covering layer of cable for power transmission, control and communication comprising base resin including linear low density polyethylene (LLDPE), ethylene-vinylacetate (EVA); and aluminium (III) hydroxide (ATH) as a primary flame-retardant.

Description

HALOGEN FREE FLAME RETERDANT CABLE INSULATION COMPOSITION AND A
METHOD OF PRODUCING THE SAME
SPECIFICATION
Technical Field
Invention relates to a polymer composition suitable for manufacture of an insulation cover of cables having flame reterdant, halogen free material properties and a process for manufacturing such a polymer composition.
Prior Art
Wire and cables for power transmission, control or communication comprising a conductive core material and a insulation cover made of non-conductive substrate protecting the core material. Application of insulation cover to the conductive core includes extrusion of a polymeric material over the metalic core.
Polymeric materials such as etylene or propylene polymers have been used as insulation due to easy processablity and beneficial electrical properties. Mechanical properties of the cable insulation compound is expected to meet resistance to long term exposure to the temperature and high flame reterdancy. Halogen-free flame reterdant materials (HFFR) is used to provide a base resin in a covering material however halogen has the disadvantages of being difficult to obtain a flame-retardant covering material having less than 0.5% of halogen and less than 1.5 toxicity index. Additionally, such a base resin is having a poor thermal property at high temperature.
US6043312 describe thermoplastic compositions without halogen having various fire reterdants based on mixtures of metallic hydroxide and zinc borate. The resin blends are based exclusively on polyvinyl chloride. Zinc borate provides a synergistic effect on flame retardancy when used in combination with metal hydroxide such as magnesium hydroxide on halogenated formulas.
Zinc borate, improves flame retardancy but also zinc borate acts as support to the carbonated layer of EVA-LLDPE however halogen use is required.
l Brief Description of the Invention
Object of the invention is to provide a halogen free composition for cable insulation with a high degree of flame retardacy.
In order to achieve above objective, invention is a halogen-free flame retardant composition for a cable covering material used to form a covering layer of cable for power transmission, control and communication. The invention comprising: 32-45 PHR base resin including 14-20 PHR linear low density polyethylene (LLDPE), 18-25 PHR ethylene- vinylacetate (EVA); and 44-50 PHR aluminium (III) hydroxide (ATH) as a primary flame- retardant. LLDPE (linear low density polyethylene) provide required tensile, breaking, strain resistance while aluminium (III) hydroxide ensure an endothermic reaction to cool down the polymeric surface when the cable covering material is subject to the heat or fire. In one aspect, preferred application uses, 18-25 PHR magnesium hydroxide as a secondary flame retardant. In a preferred application, the aluminium hydroxide amount is more particularly 44 PHR. Aluminium hydroxide (ATH) and magnesium hydroxide are enhance flame retardancy properties of the composition at a surprising level. Oxides and water as an output of thermal decomposition retard the flame spread over a cable cover for a certain period of time.
When the temparature is over 220°C the formula of the primary flame retardant decomposition is 2AI(OH)3→ Al203 +3H20
Subsequently, when the temperature is over 340°C then the formula of the secondary flame retardant decomposition is Mg(OH)2→ MgO + H20
In a preferred application, a functional element selected from the group of 0,5-1 PHR antioxidant, 2-4 PHR silicone, 4-6 PHR coupling agent, 2-3 PHR ethylene-vinylacetate wax. Antioxydant protect the material from heat, light, moisture, storing conditions and other types of negative environmental conditions. Antioxydant is also delay the induction time.
In a preferred application, a fire growth rate index of the cable covering material is set between 90-100 W/sn. This index value is sufficiently delay any flame spread over a cable cover for building materials such as power transmission, control or communication cables. In a preferred application the fire growth rate index is particularly set to 97,95 W/sn. This value provide best results for a standard power transmission cable used in the buildings.
In order to achieve above objective, invention is a method comprising the steps of kneading the base resin and the primary flame retardant in a container until a first mixture in paste form is obtained at a predefined temperature, extruding and cutting the the first mixture to a granule form, cooling the granules. Kneading ensure homogenization of the compounds of the composition and forming a paste. Granulated material is ready to be used for an extrusion process to obtain a cable cover according the the subject matter.
In a preferred application, the predefined temperature is set to 150°C. In this temperature, the first mixture in paste form can be extruded at the extrusion machines and cut by means of the moulds. In a preferred application, the granules are cooled at the cyclones. In a preferred application, the method further comprising seperation of the granules based on the average size of the granules. A vibration sieve is suitable for use in such a process step. After cooling the material is ready for packaging step. Detailed Description of the Invention
The present invention relates to a halogen-free flame retardant for a cable covering material used to form a covering layer of cable for power transmission, control and communication one example is comprising: 32 PHR base resin including 18 PHR LLDPE (linear low density polyethylene), 14 PHR ethylene-vinylacetate and 44 PHR aluminium hydroxide (aluminum trihyroxide) as a primary flame-retardant, 18 PHR magnesium hyroxide, 0,5 PHR antioxydant, 4 PHR coupling agent, 2 PHR silicone and 2 PHR EVA Wax. In a different example is comprising 45 PHR base resin including 25 PHR LLDPE, 50 PHR aluminum hyroxide, 25 PHR magnesium hyroxide, 1 PHR antioxydant, 6 PHR coupling agent, 3 PHR silicone and 3 PHR EVA Wax. Above mentioned examples provide a composition for a cable cover and such a cable cover for power transmission, control and communication cables pass EN 50399 fire reaction to fire test and below results are obtained with the composition. Test Results according to EN 50399:2011
Total Number of Cables: 26
Cable Diameter: 5,70 mm
Flame application time: 1200 s
Fire load: 20,5 kW
Flame spread: 1 ,10 m
Heat release rate (Peak HRRav): 15,29 kW
Total heat release: 6,20 MJ
Fire growth rate index: 97,95 W/sn
No occurrence of flaming droplets
Smoke production rate (Peak SPRav): 0,04 m2/sn
Total smoke production (TSP): 21 ,54 m2
Test Results according EN60332-1-2
Diameter: 5,70 mm, Lenght: 600 mm
Duration of the fire test: 60 sn
Lenght of the burnt part: 1 10 mm
Number of cable: 7
Light transmittance: 90% pH measurement and determination of conductivity
pH = 5,6
Conductivity = 0,9 με/ηΐΓΤΐ Results show suprisingly successful flame retardancy and supression of the smoke of the cables using above compositions. ATH Al2(OH)3, as herein referred aluminium hydroxide, contains 35wt % water which is released at the temperatures above 220°C. Such an endothermic reaction absorbs 1970 kJ/kg of the hydrated salt. A mixture of aluminium hydroxide with magnesium hydroxide having water release temperature over 340°C provides two level of endothermic reaction of the cable cover in case of a fire start one after another. This effect of two level endothermic reaction of the cable cover against fire provide excellent flame retardancy.
2AI(OH)3→ Al203 +3H20
Mg(OH)2→ MgO + H20

Claims

1 - Halogen free flame retardant (HFFR) for a cable covering material used to form a covering layer of cable for power transmission, control and communication comprising:
32-45 PHR base resin including 14-20 PHR linear low density polyethylene
(LLDPE), 18-25 PHR ethylene-vinylacetate (EVA); and 44-50 PHR aluminium (III) hydroxide (ATH) as a primary flame-retardant.
2- A composition for a cable covering material according to claim 1 , further comprising 18- 25 PHR magnesium hydroxide as a secondary flame retardant.
3- A composition for a cable covering material according to one of the preceding claims, wherein the ATH amount is more particularly 44 PHR. 4- A composition for a cable covering material according to one of the preceding claims, further comprising a functional element selected from the group of 0,5-1 PHR antioxidant, 2-4 PHR silicone, 4-6 PHR coupling agent, 2-3 PHR ethylene-vinylacetate wax.
5- A cable made of a cable covering material according to any one of the preceding claims, wherein a fire growth rate index of the cable covering material is set between 90-100 W/sn.
6- A cable made of a cable covering material according to claim 5, wherein the fire growth rate index is particularly set to 97,95 W/sn. 7- A production method for a cable covering material according to claims 1-4, comprising the steps of kneading the base resin and the primary flame retardant in a container until a first mixture in paste form is obtained at a predefined temperature, extruding and cutting the the first mixture to a granule form and cooling the granules. 8- A production method for a cable covering material according to claim 7, wherein the predefined temperature is set to 150°C. 9- A production method for a cable covering material according to any one of the claims 7 to 8, wherein the method further comprising seperation of the granules based on the average size of the granules.
10- A production method for a cable covering material according to any one of the claims 7 to 9, wherein the granules are cooled at the cyclones.
PCT/TR2016/050351 2016-09-26 2016-09-26 Halogen free flame reterdant cable insulation composition and a method of producing the same WO2018056916A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP16798300.6A EP3515976A1 (en) 2016-09-26 2016-09-26 Halogen free flame reterdant cable insulation composition and a method of producing the same
PCT/TR2016/050351 WO2018056916A1 (en) 2016-09-26 2016-09-26 Halogen free flame reterdant cable insulation composition and a method of producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TR2016/050351 WO2018056916A1 (en) 2016-09-26 2016-09-26 Halogen free flame reterdant cable insulation composition and a method of producing the same

Publications (1)

Publication Number Publication Date
WO2018056916A1 true WO2018056916A1 (en) 2018-03-29

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WO (1) WO2018056916A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043312A (en) 1989-06-27 2000-03-28 The Furon Company Low flame and smoke compositions for plenum cables
EP1956609A1 (en) * 2007-02-01 2008-08-13 Borealis Technology Oy Cable with improved flame retardancy
EP2355111A2 (en) * 2010-01-27 2011-08-10 King Abdulaziz City for Science and Technology Cross-linked clean flame retardant wire and cable insulation compositions for enhancing mechanical properties and flame retardancy
US20140030520A1 (en) * 2012-07-25 2014-01-30 Hitachi Metals, Ltd. Halogen-free flame-retardant polymer composition, insulated electric wire, and cable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043312A (en) 1989-06-27 2000-03-28 The Furon Company Low flame and smoke compositions for plenum cables
EP1956609A1 (en) * 2007-02-01 2008-08-13 Borealis Technology Oy Cable with improved flame retardancy
EP2355111A2 (en) * 2010-01-27 2011-08-10 King Abdulaziz City for Science and Technology Cross-linked clean flame retardant wire and cable insulation compositions for enhancing mechanical properties and flame retardancy
US20140030520A1 (en) * 2012-07-25 2014-01-30 Hitachi Metals, Ltd. Halogen-free flame-retardant polymer composition, insulated electric wire, and cable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUBER: "PERFORMANCE FIRE RETARDANT ADDITIVES FOR WIRE AND CABLE", 1 November 2011 (2011-11-01), XP055373605, Retrieved from the Internet <URL:https://www.hubermaterials.com/userfiles/files/PFDocs/Performance%20Fire%20Retardant%20Additives%20for%20Wire%20and%20Cable.pdf> [retrieved on 20170517] *

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