WO2009005249A1 - Composition de polymère ignifuge - Google Patents

Composition de polymère ignifuge Download PDF

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Publication number
WO2009005249A1
WO2009005249A1 PCT/KR2008/003700 KR2008003700W WO2009005249A1 WO 2009005249 A1 WO2009005249 A1 WO 2009005249A1 KR 2008003700 W KR2008003700 W KR 2008003700W WO 2009005249 A1 WO2009005249 A1 WO 2009005249A1
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WO
WIPO (PCT)
Prior art keywords
flame retardant
weight
group
parts
polymer composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2008/003700
Other languages
English (en)
Inventor
Ju-Ha Lee
Gi-Joon Nam
Won-Jung Kim
Jung-Won Park
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LS Cable and Systems Ltd
Original Assignee
LS Cable Ltd
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 LS Cable Ltd filed Critical LS Cable Ltd
Publication of WO2009005249A1 publication Critical patent/WO2009005249A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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 atoms other than carbon or hydrogen
    • C08L23/0853—Ethylene vinyl acetate copolymers
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a flame retardant polymer composition, and in particular, to a flame retardant polymer composition that can easily ensure mechanical characteristics and remarkably improve thermal characteristics, specially flame retardance.
  • a high flame retardant resin composition was prepared by adding magnesium hydroxide or an inorganic filler to a polypropylene resin singularly.
  • Korean Patent Application No. 2000-0040961 added a free -halogen amine flame retardant agent and organized layered clay minerals to a polypropylene resin, thereby ensuring excellent dispersion and improving mechanical characteristics and flame resistance.
  • U.S. Patent Application No. 10/546,176 discloses a flame retardant composition comprising a polyolefin polymer, a metal hydroxide and a nano- silicate, and a coating, a wire or a cable prepared from the flame retardant composition.
  • PCT/GBOO/01652 discloses a polymer composition comprising a polymer and a flame retardant additive combination which comprises a nano-clay and a second filler, and a strong char is formed during combustion.
  • An object of the present invention is to provide a flame retardant polymer composition capable of solving the problem that it is difficult to ensure a sufficient flame retardance when an inorganic flame retardant agent is used singularly with a great amount.
  • a flame retardant polymer composition comprises 50 to 200 parts by weight of an inorganic flame retardant, as a first flame retardant, including at least one selected from the group consisting of aluminium hydroxide; magnesium hydroxide; aluminium hydroxide surface-treated with a polymer selected from the group consisting of vinylsilane, a fatty acid and amino polysiloxane; and magnesium hydroxide surface- treated with a polymer selected from the group consisting of vinylsilane, a fatty acid and amino polysiloxane; 20 to 120 parts by weight of an antimony-based compound, as a second flame retardant, including at least one selected from the group consisting of antimony trioxide, antimony pentoxide, and sodium antimonate; and 1 to 15 parts by weight of a nano-clay, as a flame retardant aid, obtained by organizing and exfoliating at least one selected from the group consisting of montmorillonite, hectorite, saponite and beidellite, based on 100 parts by weight of
  • FKJ. 1 is a photograph of a char formed after burning a flame retardant polymer composition prepared according to an embodiment of the present invention using a cone calorimeter. Best Mode for Carrying Out the Invention
  • a flame retardant polymer composition of the present invention is prepared by an adequate combination of a small amount of a clay, an inorganic flame retardant and an antimony-based compound, and thus can ensure excellent mechanical characteristics and remarkably improve thermal characteristics, specially flame retardance in comparison with a singular use of an inorganic flame retardant.
  • the flame retardant polymer composition of the present invention comprises 50 to 200 parts by weight of an inorganic flame retardant as a first flame retardant, 20 to 120 parts by weight of an antimony -based compound as a second flame retardant, and 1 to 15 parts by weight of a nano-clay as a flame retardant aid, based on 100 parts by weight of a basic resin including 50 to 99 weight% of a polyolefin-based resin and 1 to 50 weight% of a reactive polyolefin-based resin having a polar group.
  • the basic resin is a blend of a polyolefin-based resin and a reactive polyolefin-based resin having a polar group.
  • the polyolefin-based resin is at least one selected from the group consisting of high-density, intermediate-density, low-density or linear low-density polyethylene, polypropylene, ethylene- 1-octene copolymer, ethylene- 1-butene copolymer, alphaolefin block or random copolymer having 3 to 15 carbon atoms, ethylene vinyl acetate copolymer, ethylene ethylacrylate polymer and ethylene methy- lacrylate polymer.
  • the polyolefin-based resin is ethylene vinyl acetate copolymer containing 10 to 40% vinyl acetate.
  • the polyolefin-based resin is included with a content of 50 to 99 weight% based on 100 parts by weight of the basic resin.
  • the content of the polyolefin-based resin is within the above-mentioned range, it is preferable because mechanical characteristics of the composition are improved.
  • the reactive polyolefin-based resin having a polar group may be polyethylene, ethylene vinyl acetate copolymer or ethylene ethylacrylate copolymer that is grafted with a polar group of maleic anhydride or glycidylmetacrylate.
  • the reactive polyolefin-based resin is grafted with the polar group, so that affinity with other resins is improved, and when a flame retardant is added, compatibility is increased, consequently reactivity is increased.
  • the reactive polyolefin-based resin having the polar group is included with a content of 1 to 50 weight% based on 100 parts by weight of the basic resin.
  • the content of the reactive polyolefin-based resin having the polar group is within the above-mentioned range, it is preferable because mutual affinity is increased and mechanical characteristics and processing are improved.
  • the content of the reactive polyolefin-based resin having the polar group is not in the above-mentioned range, mechanical characteristics may be deteriorated.
  • a flame retardant polymer composition may be prepared by using a blend of the polyolefin-based resin and the reactive polyolefin-based resin having the polar group as a basic resin, and adding a flame retardant and a flame retardant aid to the basic resin.
  • the flame retardant may be a mixture of an inorganic flame retardant and an antimony-based compound.
  • the inorganic flame retardant may be an inorganic flame retardant with or without surface treatment. At this time, surface treatment of the inorganic flame retardant may increase affinity with a resin composition to increase relatively mechanical characteristics and flame retardant characteristics of the resin composition.
  • the inorganic flame retardant may be magnesium hydroxide or aluminium hydroxide, and surface-treated by vinyl silane, a fatty acid or aminopolysiloxane.
  • the inorganic flame retardant is included with a content of 50 to 200 parts by weight based on 100 parts by weight of the basic resin.
  • the content of the inorganic flame retardant is less than the above-mentioned minimum, it is not preferable because the required flame retardant characteristics may be satisfied, and in the case that the content of the inorganic flame retardant is more than the above- mentioned maximum, it is not preferable because mechanical characteristics such as elongation and processing may be reduced.
  • the antimony-based compound may be antimony trioxide, antimony pentoxide or sodium antimonate.
  • the antimony-based compound is included with a content of 20 to 120 parts by weight based on 100 parts by weight of the basic resin.
  • the content of the antimony-based compound is less than the above-mentioned minimum, it is not preferable because flame retardant characteristics may be reduced, and in the case that the content of the antimony-based compound is more than the above- mentioned maximum, it is not preferable because dripping phenomenon prevention of the flame retardant characteristics is reduced.
  • the flame retardant aid may be a nano-clay.
  • the nano-clay may be obtained by organizing and exfoliating a layered clay, such as montmorillonite, hectorite, saponite or beidellite.
  • the nano-clay is included with a content of 1 to 15 parts by weight based on 100 parts by weight of the basic resin.
  • the content of the nano-clay is less than the above-mentioned minimum, it is not preferable because effects of the nano-clay are not obtained due to its small content, and in the case that the content of the nano-clay is more than the above-mentioned maximum, it is not preferable because the nano-clay reduces mechanical characteristics such as elongation.
  • the flame retardant polymer composition of the present invention comprising the above-mentioned ingredients may farther comprise an antioxidant, a lubricant and a cr os slinking agent.
  • the antioxidant may be a thioester-based compound, a phenol-based compound, or mixtures thereof and included with a content of 0.5 to 10 parts by weight based on 100 parts by weight of the basic resin.
  • the lubricant and the crosslinking agent may be typical ones used in the art, and each may be included with a content of 0.5 to 10 parts by weight based on 100 parts by weight of the basic resin.
  • the flame retardant polymer composition according to the present invention comprising a blend of a polyolefin-based resin and a polyolefin-based resin having a polar group as a basic resin, an inorganic flame retardant and an antimony-based compound as a flame retardant and a nano-clay as a flame retardant aid has the improved flame retardance than a conventional polymer composition using only a large amount of an inorganic flame retardant due to mutual and complementary effects between ingredients.
  • a sample was manufactured by mixing 100 parts by weight of a basic resin, i.e. a blend of 80 weight% of ethylene vinyl acetate copolymer resin containing 28% vinyl acetate and 20 weight% of ethylene vinyl acetate copolymer grafted with maleic anhydride, an inorganic flame retardant, i.e. 90 parts by weight of magnesium hydroxide without surface treatment, and an antimony-based compound, i.e. 50 parts by weight of antimony hydroxide, a flame retardant aid, i.e.
  • the cone calorimeter test was performed on a test specimen (100 mm x 100 mm size, 3 mm thickness) at 787 0 C with flux of 50 kW/m 2 in aspect of behavior of fire such as magnitude of fire, a growth rate, a smoke release rate and a toxic gas release rate.
  • the measurement items include a rate of heat release (kW/m 2 ), time to ignition, a critical ignition flux, a mass loss rate (g/s), a smoke release rate, effective heat of combustion and a rate of toxic gas release.
  • Each item of the cone calorimeter test has the following meaning.
  • -TTI Time To Ignition
  • both of the examples 1 and 2 used 10 parts by weight of a nano-clay and 90 parts by weight of an inorganic flame retardant, but there was a difference in a content of an antimony -based flame retardant between the example 1 a nd the example 2, that is, the example 1 used 50 parts by weight of an antimony-based flame retardant and the example 2 used 30 parts by weight of an antimony -based flame retardant.
  • the examples 1 and 2 had tensile strength of similar level when compared with the comparative examples 1 to 4, but the example 1 had a relatively lower elongation and the example 2 had a relatively higher elongation.
  • the examples 1 and 2 had a short time to ignition at 1.0 mm thickness, exhibited the extinguishment of flame in a short time and showed little or no drip. According to results of a cone calorimeter test, it was found that the example 1 had a small peak of heat release rate and exhibited stable conditions of char as shown in FKJ. 1.
  • the comparative example 1 did not use an antimony -based flame retardant and a nano-clay.
  • the comparative example 1 used the same amount of a flame retardant as the example 1, but exhibited lower tensile strength than the example
  • the comparative example 1 is good at elongation, but is poor at flame retardance, that is, drip occurred and it was almost burned.
  • the comparative example 2 did not use a nano-clay, and used the same amount of a flame retardant as the comparative example 1.
  • the comparative example 2 exhibited higher tensile strength and elongation than the comparative example 1, but was poor at flame retardance, that is, it was almost burned.
  • the comparative example 3 did not use an antimony-based flame retardant and a nano-clay, and used the same amount of a flame retardant as the comparative example
  • the comparative example 3 exhibited slightly higher tensile strength and slightly lower elongation than the comparative example 2, and was very poor at flame retardance, that is, drip occurred and it was completely burned.
  • the comparative example 4 did not use a nano-clay, and used the same amount of a flame retardant as the comparative example 2.
  • the comparative example 4 exhibited slightly higher tensile strength and similar elongation to the comparative example 2, and was very poor at flame retardance, that is, drip occurred severely and it was completely burned. But, the time to ignition was shorter than that of the comparative example 3.
  • the present invention can easily ensure mechanical characteristics and remarkably improve thermal characteristics, in particular flame retardance through an adequate combination of a small amount of a clay, an inorganic flame retardant and an antimony-based compound.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de polymère ignifuge comprenant 50 à 200 parties en poids d'un ignifuge inorganique, comme premier ignifuge, incluant au moins un élément choisi dans le groupe consistant en hydroxyde d'aluminium traité en surface avec un polymère prédéterminé et hydroxyde de magnésium traité en surface avec un polymère prédéterminé ; 20 à 120 parties en poids d'un composé à base d'antimoine, comme second ignifuge, incluant au moins un élément choisi dans le groupe consistant en trioxyde d'antimoine, pentoxyde d'antimoine et antimonate de sodium ; et 1 à 15 parties en poids d'une nanoargile, comme auxiliaire d'ignifuges, obtenue en organisant et en exfoliant au moins un élément choisi dans le groupe consistant en montmorillonite, hectorite, saponite et beidellite, rapportés à 100 parties en poids d'une résine basique incluant une résine à base de polyoléfine et une résine à base de polyoléfine réactive ayant un groupe polaire.
PCT/KR2008/003700 2007-07-03 2008-06-26 Composition de polymère ignifuge Ceased WO2009005249A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20070066284 2007-07-03
KR10-2007-0066284 2007-07-03

Publications (1)

Publication Number Publication Date
WO2009005249A1 true WO2009005249A1 (fr) 2009-01-08

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807699A (zh) * 2012-07-27 2012-12-05 苏州市兴吴工程塑胶有限公司 一种阻燃聚乙烯塑料的配方
KR101410951B1 (ko) * 2012-05-16 2014-06-30 넥쌍 초저온내성 및 난연성을 모두 갖는 비할로겐계 고분자 수지 조성물
CN114605722A (zh) * 2022-02-28 2022-06-10 深圳市锦昊辉实业发展有限公司 无卤阻燃聚烯烃及其制备方法
WO2025194576A1 (fr) * 2024-03-22 2025-09-25 宝胜科技创新股份有限公司 Matériau de gaine de polyoléfine ignifuge à faible fumée sans halogène thermoplastique à 90°c et procédé de préparation associé

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5462249A (en) * 1977-10-28 1979-05-19 Sumitomo Bakelite Co Ltd Electrically conductive resin composition
KR100387955B1 (ko) * 1996-10-02 2003-06-18 보레알리스 에이/에스 반도전성 중합체 조성물 및 이를 포함하는 케이블 외장
KR20030075503A (ko) * 2002-03-19 2003-09-26 엘지전선 주식회사 절연재료용 고분자 조성물과 이를 이용한 차량용 전선
KR20050112145A (ko) * 2004-05-24 2005-11-29 엘에스전선 주식회사 기계적 물성 및 난연성이 향상된 폴리프로필렌계 수지조성물 및 이를 이용한 전선
KR100581459B1 (ko) * 1997-10-20 2006-05-24 보레알리스 에이/에스 전기 케이블 및 이를 제조하기 위한 방법과 조성물
KR20060091514A (ko) * 2005-02-15 2006-08-21 에스케이케미칼주식회사 난연성 폴리에스테르 엘라스토머 조성물
KR100674748B1 (ko) * 2006-01-18 2007-01-25 엘에스전선 주식회사 수직 난연재 제조용 조성물과 이를 이용한 절연체 및 전선

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5462249A (en) * 1977-10-28 1979-05-19 Sumitomo Bakelite Co Ltd Electrically conductive resin composition
KR100387955B1 (ko) * 1996-10-02 2003-06-18 보레알리스 에이/에스 반도전성 중합체 조성물 및 이를 포함하는 케이블 외장
KR100581459B1 (ko) * 1997-10-20 2006-05-24 보레알리스 에이/에스 전기 케이블 및 이를 제조하기 위한 방법과 조성물
KR20030075503A (ko) * 2002-03-19 2003-09-26 엘지전선 주식회사 절연재료용 고분자 조성물과 이를 이용한 차량용 전선
KR20050112145A (ko) * 2004-05-24 2005-11-29 엘에스전선 주식회사 기계적 물성 및 난연성이 향상된 폴리프로필렌계 수지조성물 및 이를 이용한 전선
KR20060091514A (ko) * 2005-02-15 2006-08-21 에스케이케미칼주식회사 난연성 폴리에스테르 엘라스토머 조성물
KR100674748B1 (ko) * 2006-01-18 2007-01-25 엘에스전선 주식회사 수직 난연재 제조용 조성물과 이를 이용한 절연체 및 전선

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101410951B1 (ko) * 2012-05-16 2014-06-30 넥쌍 초저온내성 및 난연성을 모두 갖는 비할로겐계 고분자 수지 조성물
CN102807699A (zh) * 2012-07-27 2012-12-05 苏州市兴吴工程塑胶有限公司 一种阻燃聚乙烯塑料的配方
CN102807699B (zh) * 2012-07-27 2014-05-14 太仓市天丝利塑化有限公司 一种阻燃聚乙烯塑料的配方
CN114605722A (zh) * 2022-02-28 2022-06-10 深圳市锦昊辉实业发展有限公司 无卤阻燃聚烯烃及其制备方法
WO2025194576A1 (fr) * 2024-03-22 2025-09-25 宝胜科技创新股份有限公司 Matériau de gaine de polyoléfine ignifuge à faible fumée sans halogène thermoplastique à 90°c et procédé de préparation associé

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