TW575624B - Polyolefin compositions - Google Patents

Polyolefin compositions Download PDF

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TW575624B
TW575624B TW87110838A TW87110838A TW575624B TW 575624 B TW575624 B TW 575624B TW 87110838 A TW87110838 A TW 87110838A TW 87110838 A TW87110838 A TW 87110838A TW 575624 B TW575624 B TW 575624B
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weight
density polyethylene
ethylene
accounts
component
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Loic Pierre Rolland
Melanie Beatrice Boisson
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Du Pont
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • 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
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    • 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
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    • 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
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    • C08L23/04—Homopolymers or copolymers of ethene
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • C08L23/0884—Epoxide containing esters
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    • 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
    • C08L23/10—Homopolymers or copolymers of propene
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    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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    • 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
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    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • 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
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Description

經漪部中央標準局負工消費合作沿印繁 5?5624 A7 ___________ ___ B7 $、發明测（！） ' - ~ 复1月領域： 本發明係有關聚烯烴組合物且尤其有關具有良好熱性能 或彈性特性之組合物，及有關由其製得之成型物件。 ^月背景： I氣化乙晞（PVC)組合物已上市多年且慣用於大量用 途。隨著不含氯環境之趨向，某些市場面如建築、汽車及 電線及電纜工業中需要PVC之替代品。已提出交聯之聚締 化合物或氟聚合物與PVC之摻合物，但兩解決之道均過 於昂貴。 W0 93/191 18及W0 89/06256揭示適用於電氣電纜包覆之 不含PVC之組合物。該等組合物含數種類似於所述成分之 成分，但缺乏本發明所述之三聚物。 EP 0703271 A1揭示撓性、不含鹵素之熱塑性聚烯烴組合 物，主要包含乙烯乙酸乙晞酯、乙烯乙酸乙烯酯一氧化碳 及極低密度聚乙烯。雖然該等組合物可用於許多用途，但 發現其在某種高溫應用中會軟化或熔化而無法接受。 發明概述 本發明提供一種聚烯烴組合物，其具良好熱性能或彈性 特性、不含_素且包括下列之摻合物： (1) 含30-90重量。/〇乙烯、10-70重量％丙晞酸正丁酯及 0.5-30重量％丙烯酸或甲基丙烯酸之縮水甘油酯之乙 烯-丙烯酸正丁酯-甲基丙烯酸縮水甘油酯三聚物， (2) 聚烯烴或橡膠，係選自（a)乙晞丙晞二烯亞甲基橡膠 (EPDM)、（b)直鏈低密度聚乙晞、（c)乙烯-丙烯共聚 -4- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公A ) ---------β------IT------φ - (請先閱讀背面之注意事項再填寫本頁) ” 575624 A7 B7 五、發明説明（ 2 經满部中央標準局員工消費合竹社印絜 物，及（d)極低密度聚乙烯，或其掺合物；其各以 0·05-3重量％竣酸或其酸醉接枝，及 (3)聚烯烴，係選自（a)聚丙烯均聚物，（b)極低密度聚乙 烯、（c)直鏈低密度聚乙烯、（(1)低密度聚乙烯、（〇高 金度聚乙缔及（f)乙晞聚丙婦共聚物。 可包含於本發明組合物中之一般添加劑包含溴化填充 ^ 供阻滞火培之銘二水合物或氫氧化鑊、抗氧化劑、二 氧化欽（供UV抗性及對產物提供白色）、加工助劑如硬脂 酸鋅及U V安定劑。 發明詳纟gj明 本發明係有關耐熱性之不含_素之熱塑性聚烯烴摻合 物，其可用於電線及電纜包覆，擠出輪廓、片狀或射出模 製零件；及有關彈性之熱塑性聚烯烴摻合物，其可用於射 出模製零件。該等摻合物通常係藉由使乙晞-丙烯酸正丁 酯甲基丙烯酸縮水甘油酯（EnBAGMA)三聚物，以馬來酸 酐接枝之聚合物或橡膠及聚晞烴組合而得，該等成分均不 含氣。 本發明之聚合物摻合物可形成電線及電纜包覆、 廓、片狀或射出模製零件，其具有許多與含聚氣乙浠(pvc) 之摻合物相當之性質，但比聚丙晞具更佳之耐熱性。 2非另有説明，否則本發明組合物中各成分之重量百分 比範圍係排除可存在之任何添加劑而計算者。 可用於本發明之EnBAGMA三聚物（成分⑴較好含有 90重量％乙晞、：1〇_7()重量％丙埽酸正丁目旨及Q5川重量％ -5 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） (請先閱讀背面之注意事項再填寫本頁)
、1T Φ. I in I > 575624 A7 B7 五、發明説明（3 ) 丙烯酸或甲基丙烯酸之縮水甘油酯，更好爲50-80重量％乙 烯、20-35重量。/〇丙晞酸正丁酯及0·5-10重量％甲基丙烯酸 或丙烯酸之縮水甘油酯。通常，該等EnBAGMA's具有熔融 流動指數（MFI)在1-50克/10分鐘之範圍，較好爲5-20克 /10分鐘，係以ASTMD-1238測定（在2.16公斤及190°C測量） 且爲本技藝悉知者。 成分（1)較好佔本發明組合物之丨_4〇重量％，更好5-25重 量％，又更好10-20重量％。 可用於本發明之接枝聚晞烴或橡膠（成分（2)較好爲以 0.〇5_3重量％馬來酸酐接枝之EPDM。通常，該等EPDM，s具 有溶融流動指數（MFI)在0.05-100克/10分鐘之範圍，較好 小於20克/10分鐘，係以ASTM D-1238測定（在2· 16公斤及 190°C測量）且爲本技藝悉知者。 成分（2)較好佔本發明組合物之5_6〇重量％，更好佔ι〇_4〇 重量％，又更好20-30重量％。 經满部中央標準局员工消費合作社印'繁 (請先閱讀背面之注意事項再填寫本頁) 聚烯te (成分（3))係依據組合物於用途中熱性能或彈性性 質何者較重要而加以選擇，此爲熟悉本技藝者已知者。通 常在熱性能最重要時，較好爲聚丙烯均聚物（pp)，及在彈 性特性最重要時，較好爲極低密度聚乙晞（VLDpE)。對於 用途非極度需要熱性能或彈性特性時，可用直鏈低密度聚 乙晞（LLDPE)、高密度聚乙烯（HDpE)、低密度聚乙晞 (LDPE)及乙缔-丙晞均聚物（E_pp)。 VLDPE及L L D P E之詞包含乙烯與其他從-烯烴如丨_ 丁 締、1 ·己晞及1 -辛晞之共聚物。製造VLDpE、lldpe、 _ -6_ λ紙張尺度適用 1¾家標準（一2—丨〇>< 297公董--—--- 經满部中央標率局員Η消費合作社印f 575624 A7 _________________ B7____ 五、發明説明（4 ) HDPE、LDPE、PP及E-PP之方法爲本技藝悉知者且該等聚 烯烴可以商業級提供。 成分（3)較好佔本發明組合物之20-90重量％，更好40-70 重量％，又更好50-60重量％。 除了其聚合物成分以外，本發明組合物可與作爲相容劑 之馬來酸酐接枝之聚烯烴及/或與一般添加劑如補強及非 補強填充劑、阻燃填充劑如溴化填充劑、氫氧化鑊、鋁三 水合物、抗氧化劑、U V安定劑、潤滑劑（如油醯胺）、抗 結塊劑、抗靜電劑、蠟、填充劑之偶合劑、二氧化鈦、滑 石及聚合物化合領域中已知之加工助劑（如硬脂酸鋅）摻 合。顏料及其他添加劑可佔以聚合物成分加上添加劑之總 組合物之達約7 0重量％ (聚合物成分存在量係與前述界定 之彼此比例有關）；較好顏料及填充劑佔總組合物之約〇至 約70重量％。 本發明摻合物之製備係使用習知粉碎設備例如橡膠研磨 機、班伯德（Brabender)混合機、班布里（Banbury)混合機、 伯斯可（Buss-ko)捏合機、法拉（Farrei)連續混合機或雙螺 旋連續混合機混合聚合成分及視需要之添加劑。混合時間 須充分以獲得均質摻合物並使EnBAGMA之甲基丙烯酸縮 水甘油酯基與接枝聚合物（成分2 )之馬來酸酐充分反應。 令人滿意之混合時間視混合設備種類（剪力強度）而定。一 般，對批次混合機（班伯里）約5分鐘之混合時間即令人滿 意’而對連續混合機（班伯德、伯斯可捏合機、法拉或雙 螺旋）則1.5至2分鐘可令人滿意。若聚合摻合物明顯非均 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------It衣------、玎------ (請先閱讀背面之注意事項再填寫本頁) ， 575624 Α7 Β7 五、發明説明（5 ) 質，則需要進一步混合。 本發明可由下列實例更加了解，其中份數及百分比係以 重量計或每百份橡膠份數（phr)計，及溫度爲攝氏度。 實例1 - 4 説明 MFI=溶融流動指數
EnBAGMA=乙烯-丙烯酸正丁酯-甲基丙晞酸縮水甘油酯 EPDM=乙烯丙烯橡膠 MAH=馬來酸酐 VLDPE=極低密度聚乙晞 LLDPE=直鏈低密度聚乙烯 P P =聚丙烯均聚物 程序 藉由熔融化合下表1所列比例之下列成分製備摻合物。 • 具 MFI (190V2.16 公斤）爲 1 2 之 EnBAGMA (66.75% 乙 烯、28%丙烯酸正丁酯及5.25%甲基丙烯酸縮水甘油酯） • 具 MFI (190°/2.16公斤）爲 2.0 之 ΜΑΗ 接枝之 EPDM (2% ΜΑΗ) • 具 MFI (230V2.16公斤）爲 2 1 之ΡΡ。 經满部中央標準局員Η消費合作社印f (請先閱讀背面之注意事項再填寫本頁) • 具 MFI (190V2.16公斤）爲 250之 ΜΑΗ接枝之 PP (0.55% ΜΑΗ) • 具 MFI (190。/2.16 公斤）爲 40 之 ΜΑΗ 接枝之 LLDPE (0.85% ΜΑΗ)
• 具 MFI (190°/2·16公斤）爲 30之密度 0.870之 VLDPE -8- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 575624 A7 ____ B7 五、發明説明（6 ) ~ 〜 • 溴化阻燃填充劑（SAYTEX 120) • 購自Chemetron之三氧化銻阻燃填充劑（FSp〇 4〇5) • 以IRGANOX 1010購自Ciba之酚類抗氧化劑 • 硬脂酸鋅 在170-190 C以100克批次在雙輕研磨機上溶融化合約5分 鐘。研磨之產物於水力壓力下在170_190°C 5分鐘形成測試 板。隨後進行應力-拉緊（張力強度-張力伸長度）測試 (ASTM D-63 8)、在90及160°C之熱變形（3 0克重掛於厚0.5 毫米、長1 0公分及寬1 0毫米之樣品片）及拉緊時之彈性限 度測試（ASTMD412)。結果示於表1。 衣1Τ------AWI (請先閲讀背面之注意事項再填寫本頁) ， . 經满部中央標準局員,τ消費合竹社印絮 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 575624 A7 ___________ __ 五、發明説明（8 ) 可看出含P P之配方在160°C未顯現變形，因此對熱變形 具有特別良好之抗性，其對汽車主要電線爲主要效益。另 一方面9含VLDPE之配方顯現相當高之彈性限度値，其竟 指具良好彈性性能，其爲射出模製零件所需者。 a ^
(請先閲讀背面之注意事項再填寫本頁} 衣. 訂 #1 經漭部中央標準局员工消費合作社印絮

Claims (1)

  1. 575624
    第087110838號專利申請案 as B8 中文申請專利範圍修正本(91年8月)g· 一種撓性不含齒素之聚合物組合物，包括下列之摻合 物·· 10-70重量％丙烯酸正丁酯及 (1)含30-90重量％乙缔、 0.5-30重量％ (甲基）丙埽酸之縮水甘油酯之乙晞-丙 烯酸正丁酯-甲基丙缔酸縮水甘油酯三聚物， (2) I馬來紅奸接枝之乙埽丙婦二埽亞甲基橡膠（epdm) 或直鏈低密度聚乙缔（LLDPE)，及 (3) 聚丙烯均聚物（PP)或極低密度聚乙婦（Vldpe)， 其中成份（1)佔摻合物之1-40重量％，成份（2)佔摻合物 之5-60重量°/〇 ’及成份（3)佔摻合物之2〇_90重量％。 2·根據申請專利範圍第1項之組合物，其中成份（1)佔接合 物之5-25重量％，成份（2)佔摻合物之1〇-4〇重量％及成 份（3)佔摻合物之40-70重量。/〇。 3· —種成型物件，其係由申請專利範圍第1項之組合物所 形成。 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐）
TW87110838A 1997-07-01 1998-07-04 Polyolefin compositions TW575624B (en)

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