TW200938579A - Flame-retardant polyolefin/thermoplastic polyurethane composition - Google Patents

Flame-retardant polyolefin/thermoplastic polyurethane composition Download PDF

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TW200938579A
TW200938579A TW098103854A TW98103854A TW200938579A TW 200938579 A TW200938579 A TW 200938579A TW 098103854 A TW098103854 A TW 098103854A TW 98103854 A TW98103854 A TW 98103854A TW 200938579 A TW200938579 A TW 200938579A
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flame
polyolefin
thermoplastic polyurethane
composition
polyphosphate
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TW098103854A
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Geoffrey D Brown
Robert F Eaton
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Union Carbide Chemicals & Plastics Technology Llc
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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
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • 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
    • H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Description

200938579 六、發明說明： t發明所眉技術領域】 本發明係關於一種用於電線及電纜應用之阻燃調配 物。特別是，本發明係關於一種用於電線用護套、電纜用 5 護套、擠壓板及擠塑型材(extruded profile)之無鹵素阻燃性 聚烯烴/熱塑性聚胺甲酸酯調配物。 C先前技術3 以金屬水合物為基礎的聚烯烴化合物及以膨脹為基礎 〇 的聚烯烴化合物無法同時獲得工業需要的火焰及機械性 10 質。值得注意的是，以40-50重量百分比之負載加入阻燃充 填劑以便獲得好的燃燒測試性能將造成所產生的聚婦烴化 • 合物具有差的機械性質。就其本身而論，想要提供一具有優 良的機械性質之聚烯烴組成物，諸如高伸張率、高彈性(低 模數）、好的抗張強度及改良的變形溫度和優良的燃燒性能。 15 【發明内容】 為此目的，提供本發明之組成物，其包含一聚烯煙、 ® —熱塑性聚胺曱酸酯及一膨脹型多磷酸鹽阻燃劑。特別 是，本發明逹成伸張率>400%及張力強度>1500碎/平方英 寸，然而相同的聚烯烴僅逹成100%的伸張率及<1〇〇〇磅/平 20 方英寸的抗張強度。同樣地，本發明顯示出改良的帶擠壓 陡月b(對僅有TPU的可比較組成物），此指示出可用於擠壓應 用之改良的熔融流變學/製造能力。本發明在製備電線及電 纜護套與其它擠壓物件(諸如，板及型材)上特別有用。 本發明之組成物包含一聚稀烴、一熱塑性聚胺甲酸酯 200938579 及一膨脹型多磷酸鹽阻燃組成物。目前所描述的組成物無 鹵素較佳。 該聚烯烴可為極性、非極性或其混合物。該聚烯烴的 存在量為約5至約90重量百分比。 5 合適的極性聚烯烴包括：⑴乙烯與不飽和酯之共聚物； (ii) 乙烯與不飽和酸(諸如，丙烯酸或甲基丙烯酸)之共聚物； (iii) 乙烯與乙烯基矽烷(例如’乙烯基三甲氧基矽烷及乙烯基 三乙氧基矽烷)之共聚物；及(iv)任何這些共單體之互聚物。 該聚烯烴為一乙烯與不飽和酯的極性共聚物較佳。 10 該共聚物歸因於酯共單體的部分可在範圍約5至約50 重量百分比内（以該共聚物之重量為準），且較佳範圍約15 至約40重量百分比。該乙烯/不飽和酯共聚物的熔化指數範 圍可在每10分鐘約0.5至約50克内。 當該不飽和醋為丙稀酸炫•醋或甲基丙稀酸烧醋時，該 15 燒基可具有1至8個碳原子且具有1至4個碳原子較佳。該丙 烯酸酯及甲基丙浠酸酯的實施例有丙烯酸乙酯、丙稀酸甲 酯、甲基丙烯酸甲酯、丙烯酸三級丁酯、丙烯酸正丁酯、 甲基丙稀酸正丁醋及丙烯酸2-乙基己S旨。 當該不飽和酯為羧酸乙烯酯時，該羧酸酯基團可具有2 20 至8個碳原子且具有2至5個碳原子較佳。該羧酸乙烯酯的實 施例有醋酸乙烯酯、丙酸乙烯酯及丁酸乙烯酯。 合適的非極性聚烯烴包括：⑴乙烯的同聚物；（ii)乙烯 與一或多種α-烯烴及選擇性二烯之共聚物；（iii)含有一氧化 碳、丙稀及丁烯之乙烯共聚物；（iv)丙烯之同聚物；（v)丙烯 200938579 與其它烯烴之共聚物；及(vi)丙烯、乙歸及二稀之三聚物。 熱塑性聚胺甲酸酯聚合物在技藝中已知，且其典型藉 由反應一線性羥基終端的多元醇、一有機二異氰酸鹽及一 鏈增量劑獲得。在本發明中有用的熱塑性聚胺甲酸酯（TPU) 5 包括聚酯TPU及聚醚TPXJ。 值得注意的是，可使用二酸(如己二酸)與二醇（如乙二 醇、丙二醇及丁二醇）來製得該聚酯TPU ;同時可使用聚環 氧乙烧、環氧丙烧及環氧丁烧之多元醇來製得聚_TPU。 Φ 該TPU的存在量為約0.1至95重量百分比。 10 該膨脹型多磷酸鹽阻燃組成物為—下列物質之摻合 物.⑴一膨服型含亂多麟酸鹽及(ii)—蜜胺或蜜胺衍生物共 - 添加劑。該膨脹型含氮多磷酸鹽為多嶙酸链、娘讲多構酸 鹽或其衍生物較佳。該膨脹型含氮多嶙酸鹽為派命多磷酸 鹽更佳。至於膨脹阻燃劑，該含氮多磷酸鹽具有當曝露至 15 火焰時會膨脹及燒焦的特徵。該膨脹型多填酸鹽阻燃組成 物之存在量為約0.1至約70重量百分比。 ® 本發明之組成物可進一步包含其它非函素阻燃劑，諸 如金屬氧化物、金屬氧化物水合物、金屬碳酸鹽、碳酸鹽 加酸或酸產生材料、水泥、尿素及多元醇。 20 該組成物可更包含其它聚合物，諸如非烯烴聚合物、聚 氣乙烯、酯-醚嵌段共聚物、酯/醯胺嵌段共聚物、烯烴嵌段 共聚物及工程塑膠’諸如聚碳酸酯、聚颯及聚醯亞胺。該組 成物亦可進一步包含其它添加劑，諸如無機及過氧化物。 在另一個具體實例中，本發明為一種包含一或多個電 5 200938579 導體或一或多個電導體核心之電纜，其中每個導體或核心 皆由一包含描述於本文的阻燃性聚烯烴/熱塑性聚胺甲酸 酯組成物之阻燃層包圍。 在更另一個具體實例中，本發明為一種包含描述於本 5 文的阻燃性聚烯烴/熱塑性聚胺甲酸酯組成物之擠壓物件。 C實施方式3 實施例 下列非為限制的實施例闡明本發明。 測試 10 (1)屈服強度(磅/平方英寸）； (2) 抗張強度@波峰(磅/平方英寸）； (3) 抗張強度@斷裂(磅/平方英寸）； (4) 伸張率@斷裂(％); (5) 1%正割模數(磅/平方英寸）； 15 (6)2%正割模數(磅/平方英寸）； (7) 5%正割模數(磅/平方英寸）；及 (8) 不燃燒旗標的燃燒性質； (9) 至旗標的時間（秒）； (10) 總時間的燃燒性質（秒）； 20 (11)不完全燃燒； (12) 未燒焦（低於旗標的毫米數）； (13) 未燃燒的液滴； (14) 高熔融流動，其中1無流動（最好），5高流動；及 (15) 整體評分;最好（1)»最差（5)，其中#1無燃燒的 25 液滴；#2燒焦長度；#3a無熔融流動；#3b不燃燒至旗標； #3c至旗標的時間。 200938579 燃燒測試 使用垂直長條測試（垂直U L 9 4燃燒@底部4 5秒）來進行 燃燒測試。所製備的測試樣品為具有埋入的電線及8”長之 75密耳飾板的100密耳長條。 5 例示的组成物 使用下列組分來製備測試樣品： ❹ 10 (1) 佩雷仙（Pellethane)™ 2102-75A己内醋聚醋熱塑性 聚胺甲酸酯’其具有蕭而A硬度77A，比重1.17及可從道化 學公司購得； (2) 佩雷仙™ 2103-80AE聚醚熱塑性聚胺甲酸酯，其具 有蕭而A硬度82A，比重1.13及可從道化學公司購得； 15 ❹ (3) 愛爾維克斯(Elvax)™ 40L-03乙稀/醋酸乙稀酯共聚 物，其具有醋酸乙烯酯含量40百分比及炼化指數3分克/公 尺(在攝氏190度及2· 16公斤下測量），其可從ε·Ι.杜邦狄尼帽 斯及公司購得；及 (4) FP-2100™以膨脹型含氮多磷酸鹽基礎的阻燃劑，其 為一娘°并多填酸鹽與麟酸化合物之摻合物，及可從安芳化 學股份（有限）公司（Amfine Chemical Corporation)或阿戴卡 股份（有限）公司（Adeka Corporation)購得。 20 表1顯示出二個比較例（比較例1及2)及本發明的三個實 施例（實施例3_5)。每個量皆以重量百分比表示。 想要的機械性質包括抗張強度>1500磅/平方英寸及伸 張率>200百分比。對阻燃性能來說，整體火焰評分為2或較 少時可接受。 7 200938579 表1 組分 比較例1 比較例2 實施例3 實施例4 實施例5 佩雷仙™ 2102-75A 60.00 45.00 30.00 15.00 佩雷仙 TM2103-80AE 60.00 愛爾維克斯™40L-03 15.00 30.00 45.00 FP-2100TM阻燃劑 40.00 40.00 40.00 40.00 40.00 充填劑體積(立方公分/克） 0.24 0.24 0.24 0.24 0.24 膨脹體積(立方公分/克） 0.24 0.24 0.24 0.24 0.24 樹脂體積(立方公分/克） 0.51 0.51 0.54 0.56 0.59 樹脂體積分量 0.684 0.684 0.695 0.706 0.716 計算的比重 1.34 1.34 1.30 1.25 1.21 樹脂對多磷酸鹽添加劑 比率 1.50 1.50 1.50 1.50 1.50 物理性質 屈服強度 (磅/平方英寸） 666 974 1073 370 280 抗張強度@波峰 (碎/平方英寸） 3807 1518 2959 1168 456 抗張強度@斷裂 (碎/平方英寸） 3807 1518 2959 1168 456 伸張率@斷裂(％) 515 485 513 518 883 1 %正割模數 (磅/平方英寸） 6228 14204 3697 2321 3159 2%正割模數 (磅/平方英寸） 6093 13119 3875 2459 2236 5%正割模數 (磅/平方英寸） 5350 10921 3583 2478 1798 燃燒結果 不燃燒旗標 2/3 2/3 2/3 2/3 3/3 至旗標的時間(秒） 10 0 1 8 NA 總時間(秒） 11 7,667 7 29 1 不完全燃燒 2/3 2/3 2/3 2/3 3/3 未燒隹 (低於旗標$^米數） 45 50 30 38 57 未燃燒的液滴 2/3 0/3 3/3 3/3 3/3 高熔融流動 3.5 5 2 1.5 3 整體評分 3 4 2 2 2 I：圖式簡單說明3 (無） 【主要元件符號說明】

Claims (1)

  1. 200938579
    10 15
    20 七、申請專利範圍： 1. 一種阻燃性聚烯烴/熱塑性聚胺甲酸酯組成物，其包含： (a) —種聚烯烴； (b) —種熱塑性聚胺曱酸酯；及 (c) 一種膨脹型多磷酸鹽阻燃組成物。 2. 如申請專利範圍第1項之阻燃性聚烯烴/熱塑性聚胺甲 酸醋組成物，其中該組成物無鹵素。 3. 如申請專利範圍第1或2項之阻燃性聚烯烴/熱塑性聚胺 甲酸酯組成物，其中該聚烯烴具極性。 4. 如申請專利範圍第3項之阻燃性聚烯烴/熱塑性聚胺甲 酸酯組成物，其中該極性聚烯烴為乙烯與不飽和酯之共 聚物。 5 ·如申請專利範圍第1或2項之阻燃性聚烯烴/熱塑性聚胺甲 酸酯組成物，其中該膨脹型多磷酸鹽阻燃組成物包含： ⑴一膨脹型含氮多磷酸鹽；及 (ii) 一蜜胺或蜜胺衍生物共添加劑。 6. 如申請專利範圍第5項之阻燃性聚烯烴/熱塑性聚胺曱 酸酯組成物，其中該膨脹型含氮多磷酸鹽選自於由多磷 酸銨及哌畊多磷酸鹽所組成之群。 7. 如申請專利範圍第6項之阻燃性聚烯烴/熱塑性聚胺甲酸 酯組成物，其中該膨脹型含氮多磷酸鹽為哌畊多磷酸鹽。 8. —種電纜，其包含一或多個電導體或一或多個電導體核 心，其中每個導體或核心由一包含如申請專利範圍第1 至7項之任何一項的阻燃性聚烯烴/熱塑性聚胺甲酸酯 9 200938579 四、指定代表圖： (一) 本案指定代表圖為：第（ ）圖。（無) (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：
TW098103854A 2008-02-08 2009-02-06 Flame-retardant polyolefin/thermoplastic polyurethane composition TW200938579A (en)

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CA2714100C (en) 2016-03-29
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MX2010008715A (es) 2010-10-06
US9758672B2 (en) 2017-09-12
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EP2247668B1 (en) 2014-03-26
CA2714100A1 (en) 2009-08-13
KR20100123713A (ko) 2010-11-24
CN101981128A (zh) 2011-02-23
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JP2011511149A (ja) 2011-04-07
BRPI0905902B1 (pt) 2019-01-29

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