TW201708377A - 用於軟皮之組合物及其用途 - Google Patents

用於軟皮之組合物及其用途 Download PDF

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Publication number
TW201708377A
TW201708377A TW105118022A TW105118022A TW201708377A TW 201708377 A TW201708377 A TW 201708377A TW 105118022 A TW105118022 A TW 105118022A TW 105118022 A TW105118022 A TW 105118022A TW 201708377 A TW201708377 A TW 201708377A
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Taiwan
Prior art keywords
copolymer
composition
weight
hydrogenated
block
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TW105118022A
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English (en)
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TWI593743B (zh
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凱瑟琳Ｊ 萊特
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科騰聚合物美國有限責任公司
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    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/005—Modified block copolymers
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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Abstract

本發明揭示一種組合物，其包含嵌段共聚物、至少一種丁烯均聚物或共聚物及至少一種烯烴均聚物或共聚物，其中該嵌段共聚物具有比重>0.85g/cc之氫化低乙烯基聚丁二烯末端嵌段，及聚烯基芳烴/氫化二烯之受控分佈中間嵌段。儘管該嵌段共聚物具有如三嵌段共聚物之較佳線性結構，其亦可為具有至少2個分支或2個分支以上之支鏈或輻射狀偶合共聚物。該組合物適用於用於製造對用於例如汽車市場之諸如柴油燃料的化學物質具有耐受性之物品的旋轉模製、薄殼模製、注射模製、擠壓或壓縮模製，或熱成型或壓延。該嵌段共聚物之MFR在230℃與2.16kg之重量下為1g/10min至約50g/10min。

Description

用於軟皮之組合物及其用途 相關申請案之交叉參考
本申請案主張2015年6月12日申請之美國臨時申請案第62/174,871號之權益。
關於聯邦政府獎助研究或開發之申明
無。
本發明提供一種嵌段共聚物組合物，該嵌段共聚物組合物可藉由熔融加工方法製造且具有耐受柴油之性質。該組合物可適用於許多應用，諸如用於製造對用於例如汽車市場之柴油燃料具有耐受性之物品的旋轉模製、薄殼模製、注射模製、擠壓或壓縮模製、或熱成型或壓延。
讓與給Kraton Polymers之美國專利公開案第2010/0056721號揭示具有聚乙烯末端嵌段、苯乙烯嵌段聚合物、丁二烯嵌段聚合物、苯乙烯嵌段聚合物及聚乙烯末端嵌段(PE-S-B-S-PE)之五嵌段共聚物。此聚合物適合於旋轉模製。該組合物具有高熔體流動速率(MFR)且該嵌段共聚物對柴油燃料並不具有耐受性。
讓與給Kraton Polymers之歐洲專利第1,474,458號揭示苯乙烯-苯乙烯/丁二烯-苯乙烯(S-S/B-S)受控分佈中間嵌段聚合物。出於定義「受控分佈」之目的，此專利以引用的方式併入本文中。
讓與給Kraton Polymers之美國專利公開案第2012/0070665號中揭示可薄殼模製組合物。其中所揭示之嵌段共聚物較佳為苯乙烯-苯乙烯/乙烯丁二烯-苯乙烯(S-S/EB-S)之三嵌段共聚物，其中中間嵌段組分EB為氫化丁二烯。中間嵌段為以主要影響丁二烯之方式經共聚且接著經氫化之苯乙烯及丁二烯之受控分佈。此嵌段共聚物對柴油燃料並不具有耐受性。
存在對一種嵌段共聚物組合物之需求，該嵌段共聚物組合物為柴油燃料耐受劑，且可藉由諸如用於消費品應用(諸如，但不限於汽車產業)之注射模製、擠壓、旋轉模製或薄殼模製、壓延或熱成型技術之任一熔融加工技術來製造。
本文中所提供之組分組合物為柴油燃料耐受劑。該組合物之主要組分主要為三嵌段共聚物C-A/B-C或(C-A/B)nX，其中C表示受限結晶或半結晶聚烯烴(具有受控分佈中間嵌段A/B之氫化低乙烯基聚丁二烯末端嵌段)，其中A表示聚烯基芳烴且B表示氫化二烯。聚烯基芳烴之中間嵌段組分可為苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、乙烯基萘、對丁基苯乙烯，或此等者中之兩者或兩者以上之混合物。中間嵌段之氫化二烯組分可為氫化丁二烯、氫化異戊二烯或其混合物。該嵌段共聚物可藉由連續聚合或藉由經由陰離子聚合方法分支或偶合來製造，如此項技術中已知。該組合物亦包括丁烯均聚物或共聚物之第二組分。組合物之第三組分為烯烴均聚物或共聚物，該烯烴均聚物或共聚物與三嵌段共聚物之C端嵌段分離。烯烴均聚物或共聚物可為LDPE、LLDPE、HDPE、均聚PP、諸多聚丙烯共聚物(諸如乙烯-丙烯、丙烯-辛烯、丙烯丁烯等)或此等者中之兩者或兩者以上之混合物。該組合物之此等三個組分：三嵌段共聚物、丁烯均聚物或共聚物及烯烴均聚物或共聚物，大體上包含總組合物之 約93重量%至99重量%。其他組分包含其餘之1重量%至7重量%以使得組合物之總重量為100重量%。
該組合物可適用於用於製造對柴油燃料具有耐受性之物品之旋轉模製、薄殼模製、注射模製、擠壓或壓縮模製、或熱成型或壓延。因此，製造物品之方法可包括將嵌段共聚物之組分混合以形成該組合物之均一混合物，將一定量之組合物引入至熔融製程中以形成最終物品或物品之組分。該組合物之均一混合物在經受熔融製程前可呈丸粒或粉末之形式。
廣義而言，本發明提供一種用於藉由旋轉模製或薄殼模製或注射模製或擠壓或壓縮模製或熱成型或壓延來製造物品之組合物，該組合物包含：i)約50重量%至約70重量%之嵌段共聚物；ii)約15重量%至約25重量%之至少一種丁烯均聚物或共聚物；iii)約12重量%至約24重量%之至少一種聚烯烴均聚物或聚烯烴共聚物；及iv)約0.3重量%至約3重量%之至少一種穩定劑；v)其中該嵌段共聚物具有比重大於0.85g/cc之氫化低乙烯基丁二烯末端嵌段，且具有聚烯基芳烴/氫化二烯之受控分佈中間嵌段，且其中該組合物之總重量等於100重量%。
廣義而言，本發明亦關於一種用於製造物品之方法，該方法包含：i)利用組合物旋轉模製或薄殼模製或注射模製或擠壓或壓縮模製或熱成型或壓延物品，該組合物包含：約50重量%至約70重量%之嵌段共聚物；ii)約15重量%至約25重量%之至少一種丁烯均聚物或共聚物；iii)約12重量%至約24重量%之至少一種聚烯烴均聚物或共聚 物；及iv)約0.3重量%至約3重量%之至少一種穩定劑，v)其中該嵌段共聚物具有比重大於0.85g/cc之氫化低乙烯基聚丁二烯末端嵌段，且具有聚烯基芳烴/氫化二烯之受控分佈中間嵌段，且其中該組合物之總重量等於100重量%，且該組合物在該旋轉模製或薄殼模製或注射模製或擠壓或壓縮模製或熱成型或壓延之步驟前，經熔融混合及以丸粒、微丸粒或研磨粉末之形式經擠壓及冷卻。
最後，本文中所提出之共聚物可與並非不利地影響共聚物性質之其他視情況選用之組分複合。可用作額外組分之例示性材料可包括(但不限於)顏料、抗氧化劑、著色劑、界面活性劑、蠟及流動促進劑。亦可將除塵劑以丸粒或粉末之形式添加至均一組合物。該聚合物可適用於廣泛多種應用，包括(例如)經模製及經擠壓之物品。
本發明係關於一種組合物，其包含嵌段共聚物、丁烯均聚物或共聚物及聚烯烴(均聚物或共聚物)。視需要，可將第一穩定劑或第一及第二穩定劑摻入至組合物中。該嵌段共聚物可連續地形成或藉由偶合形成。儘管該嵌段共聚物具有如三嵌段共聚物之較佳連續及經偶合線性結構，但預期其可為具有至少三個分支或三個分支以上之支鏈或輻射狀偶合共聚物。該嵌段共聚物藉由陰離子聚合而形成。
關於製備聚合物之製程，陰離子聚合製程包括藉由鋰引發劑使溶液中之適合單體聚合。用作聚合媒劑之溶劑可為不與成型聚合物之活性陰離子鏈末端反應、易於在市售聚合單元中處理且提供產物聚合物之適當可溶性特性之任何烴。舉例而言，通常缺少可電離氫原子之非極性脂族烴成為特別適合之溶劑。經常使用的為環烷，諸如環戊 烷、環己烷、環庚烷及環辛烷，以上所有者均為相對非極性。可選擇其他適合之溶劑以在一組給定製程條件下有效地執行，其中聚合溫度為所考慮之主要因素中之一者。
鋰引發劑包括(例如)烷基鋰化合物及其他有機鋰化合物，諸如第二丁基鋰、正丁基鋰、第三丁基鋰、戊基鋰及其類似物，包括諸如間二異丙烯基苯之二第二丁基鋰加合物之雙引發劑。其他此類雙引發劑揭示於美國專利第6,492,469號中。在各種聚合引發劑中，第二丁基鋰為較佳的。引發劑可以基於每所需之聚合物鏈一個引發劑分子所計算之量用於聚合混合物(包括單體及溶劑)中。鋰引發劑製程描述於(例如)美國專利第4,039,593號及再版專利第27,145號中，該描述係以引用的方式併入本文中。
製備本文中所描述之嵌段共聚物之聚合條件大體而言通常類似於用於陰離子聚合之彼等條件。聚合較佳在約-30℃至約150℃，更佳約10℃至約100℃且最佳(鑒於產業侷限性)約30℃至約90℃之溫度下進行。聚合在惰性氛圍(較佳氮氣)中進行，且亦可在約0.5巴至約10巴範圍內之壓力下完成。此共聚通常需要少於約12小時，且視溫度、單體組分之濃度及所需聚合物之分子量而定可在約5分鐘至約5小時內完成。
另一重要態樣為控制低乙烯基聚丁二烯末端嵌段中及受控分佈中間嵌段中之共軛二烯之微結構或乙烯基含量。此係因為低乙烯基嵌段具有結晶之傾向，由此賦予溶劑耐受性特性，除其他特性之外，半結晶熱塑性為典型特性。另一方面，在橡膠嵌段中需要較高乙烯基含量，此係因為側乙烯基傾向於破壞結晶度，從而保持此等嵌段之橡膠特徵。術語『乙烯基』已用於描述在1,3-丁二烯經由1,2-加成機制聚合時製得之聚合物產物。所得物為側接於聚合物主鏈之經單取代之烯烴基團乙烯基。就異戊二烯之陰離子聚合而言，經由3,4-加成機制之 異戊二烯之插入得到側接於聚合物主鏈之偕位(geminal)二烷基C=C部分。異戊二烯之3,4-加成聚合對嵌段共聚物之最終性質的影響將類似於丁二烯之1,2-加成的彼等影響。大體而言，當提及共軛二烯單體之使用時，較佳乙烯基含量為如藉由質子NMR分析所測定之約5mol%至80mol%之縮合共軛二烯單元。
乙烯基含量(共軛二烯之加成模式)由聚合溶劑類型、聚合溫度及存在微結構改質劑之選擇有效控制。可使用適用作微結構改質劑之非螯合及螯合極性化合物兩者。
非螯合微結構改質劑之實例為二甲醚、乙醚、乙基甲醚、乙基丙醚、二噁烷、二苄醚、二苯醚、二甲基硫醚、二乙基硫醚、氧化四亞甲基(四氫呋喃)、三丙基胺、三丁基胺、三甲基胺、三乙基胺、吡啶及喹啉及其混合物。
如本文所用之術語「螯合醚」係指如藉由式R(OR')m(OR")o OR例示之具有大於一個氧的醚，其中每一R係單獨地選自1至8個，較佳2至3個碳原子烷基；R'及R"係單獨地選自1至6個，較佳2至3個碳原子亞烷基；且m及o係獨立地選自1至3之整數，較佳1至2之整數。較佳醚之實例包括二乙氧基丙烷、1,2-二氧基乙烷(二側氧基)及1,2-二甲氧基乙烷(乙二醇二甲醚)。其他適合之材料包括CH3 OCH2、CH2 OCH2、CH2 OCH3(C6H14O3-二乙二醇二甲醚)及CH3CH2、OCH2、CH2、OCH2CH2及OCH2CH3。「螯合胺」意謂具有大於一個氮之胺，諸如N,N,N',N'-四甲基伸乙基二胺。
控制極性微結構改質劑的量以便獲得共軛二烯嵌段中所需之乙烯基含量。微結構改質劑與鋰聚合物鏈末端之適合比率揭示於美國專利(再版專利)第27,145號中。極性改質劑可以每莫耳之鋰化合物至少0.1莫耳的量使用，較佳1莫耳至50莫耳，更佳每莫耳之鋰化合物2莫耳至25莫耳之促進劑。替代地，可以基於溶劑及單體之總重量之百萬 分率(按重量計)表達濃度。基於此條件，使用百萬分之十至約1重量百分比，較佳百萬分之一百至百萬分之兩千。然而，此可廣泛地變化，此係因為極少量之一些較佳改質劑為極有效的。在另一極端，尤其在不太有效之改質劑的情況下，該改質劑自身可為溶劑。此等技術係揭示於(例如)美國專利第3,686,366號(Winkler，1972年8月22日)、美國專利第3,700,748號(Winkler，1972年10月24日)及美國專利第5,194,535號(Koppes等人，1993年3月16日)中，該等專利之揭示內容特此以引用之方式併入。
用作聚合媒劑之溶劑可為不與成型聚合物之活性陰離子鏈末端反應、易於在市售聚合單元中處理且提供產物聚合物之適當可溶性特性之任何烴。舉例而言，通常缺少可電離氫之非極性脂族烴成為特別適合之溶劑。經常使用的為環烷，諸如環戊烷、環己烷、環庚烷及環辛烷，以上所有者均為相對非極性。可選擇其他適合之溶劑以在一組給定製程條件下有效地執行，其中溫度為所考慮之主要因素中之一者。
輻射狀(支鏈)聚合物(C-A/B)nX之製備需要被稱作「偶合」之後聚合步驟。在上述選擇性氫化嵌段共聚物之輻射狀式中，「C」為氫化低乙烯基聚丁二烯嵌段，「A」為聚烯基芳烴嵌段聚合物，「B」為氫化二烯嵌段聚合物，「n」為2至約15，較佳約2至約6之整數，且「X」為偶合劑之殘粒或殘基。多種偶合劑可包括(例如)二鹵烷烴、鹵化矽、矽氧烷、多功能環氧化物、二氧化矽化合物、一元醇與羧酸之酯(例如，己二酸二甲酯)及環氧化油。藉由如(例如)美國專利第3,985,830號、第4,391,949號及第4,444,953號，加拿大專利第716,645號中所揭示之聚烯基偶合劑製備星形聚合物。適合之聚烯基偶合劑包括二乙烯基苯，且較佳間二乙烯基苯。較佳為四烷氧基矽烷(諸如四乙氧基矽烷(TEOS)及四甲氧基矽烷)、烷基-三烷氧基矽烷(諸如甲基- 三甲氧基矽烷(MTMS))、脂族二酯(諸如己二酸二甲酯及己二酸二乙酯)及二縮水甘油基芳族環氧化合物(諸如衍生自雙酚A與表氯醇之反應之二縮水甘油醚)。
在嵌段共聚物之合成中偶合效率至關重要，該等共聚物藉由鍵接技術製備。極高之偶合效率為製造諸如本文中所提出之彼等的高強度偶合嵌段共聚物之關鍵。
在一較佳實施例中，嵌段共聚物具有三個相異區域，即C末端嵌段，該等C末端嵌段由A與B之共聚物之受控分佈中間嵌段分離，其中B富集區在中間嵌段之末端上且聚烯基芳烴富集區靠近中間嵌段之中間或中心。在嵌段共聚物中，存在約5重量%至約40重量%之聚烷基芳烴。通常，鄰近於C末端嵌段之區域包含約第一個15重量%至25重量%中間嵌段(及其間之全部點)且包含一或多個B-二烯富集區，其中中間嵌段之其餘部分被視為A-聚烯基芳烴富集區。術語「二烯富集」意謂該區域具有比芳烴富集區可量測更高的二烯與芳烴之比率，且反之亦然。所需的為聚烯基芳烴/共軛氫化二烯受控分佈嵌段共聚物之中間嵌段，其中聚烯基芳烴單元之比例逐漸升高至靠近中間嵌段之中間或中心之最大值(當描述三嵌段結構時)，且隨後逐漸減小直至該聚合物中間嵌段再次為二烯富集區且充分聚合。此結構為獨特的且不同於先前技術中所論述之遞變及/或隨機結構。
所提出之受控分佈嵌段共聚物由Bening等人描述於美國專利第7,169,848號中，該專利以引用的方式併入本文中。Bening之受控分佈嵌段共聚物含有聚烯基芳烴末端嵌段，及聚烯基芳烴與共軛二烯之獨特中間嵌段。出人意料地，(1)用於單體加成之獨特控制及(2)使用乙醚或其他改質劑作為溶劑(其將被稱作「分佈劑」)之組分，此兩者之組合導致兩種單體之某一特性分佈(本文中稱為「受控分佈」聚合，亦即，產生「受控分佈」結構之聚合)，且亦導致聚合物中間嵌段中 存在某一聚烯基芳烴富集區及某些共軛二烯富集區。本文中所用之術語「受控分佈」經定義為指具有以下屬性之分子結構：(1)低乙烯基半結晶聚烯烴「C」末端嵌段，鄰近於低乙烯基半結晶聚烯烴末端嵌段之末端區，該等末端區富集有氫化共軛二烯單元(B單元)(亦即，具有比氫化共軛二烯單元之平均量更大的平均量)；(2)非鄰近於低乙烯基半結晶聚烯烴C末端嵌段之一或多個區，該等區富集有聚烯基芳烴單元(A單元)(亦即，具有比聚烯基芳烴單元之平均量更大的平均量)；及(3)具有相對較低嵌段度之整體結構。出於此處之目的，「富集」經定義為大於平均量，較佳大於平均量5重量%以上。當使用差示掃描熱量測定(「DSC」)(熱)方法或經由機械方法分析時，此相對較低嵌段度可藉由單獨單體之Tg之間存在的僅單一(「Tg」)中間體來展示，或如經由質子核磁共振(「H-NMR」)方法所展示。嵌段度之電位亦可在中間嵌段之聚合期間，在適合於聚苯乙烯基鋰末端基團之偵測之波長範圍內利用UV可見吸收度之量測而推斷。此值急劇且大量增加指示聚苯乙烯基鋰鏈末端大量增加。在此製程中，僅在共軛二烯濃度下降至維持受控分佈聚合之臨界位準以下時將出現此情況。此時任一存在之苯乙烯單體將以嵌段形式加成。術語「苯乙烯嵌段度」(如由熟習此項技術者使用質子NMR所量測)定義為在聚合物鏈上具有兩個S最接近相鄰者之聚合物中之S單元的比例。在按以下步驟使用H-1 NMR量測兩個實驗量之後測定苯乙烯嵌段度。
首先，苯乙烯單元(亦即，在成比例時抵消之任意儀器單元)之總數係藉由將H-1 NMR頻譜中之總苯乙烯芳族信號整合為7.5ppm至6.2ppm且將此數量除以5以在每一苯乙烯芳環上占5個芳族氫來測定。
其次，該嵌段苯乙烯單元係藉由將H-1 NMR頻譜中之芳族信號中之部分整合為6.88ppm與6.80ppm之間的信號最小值至6.2ppm且將此數量除以2以在每一嵌段苯乙烯芳環上占2個鄰位氫來測定。關於彼 等苯乙烯單元之環(其具有兩個苯乙烯最接近相鄰者)上之兩個鄰位氫之此信號的指配報導於F.A.Bovey,High Resolution NMR of Macromolecules(學術出版社，紐約及倫敦，1972年)第6章中。
苯乙烯嵌段度簡言之為嵌段苯乙烯與總苯乙烯單元之百分比：嵌段%=100×(嵌段苯乙烯單元/總苯乙烯單元)。
在處理所得共聚物之強度及Tg中，此受控分佈結構為至關重要的，因為受控分佈結構確保幾乎不存在兩種單體之相分離，亦即，相比於其中單體實際上仍然作為獨立「微相」之嵌段共聚物，具有相異之Tg，實際上卻化學鍵合在一起。此受控分佈結構確保僅存在一個Tg且因此所得共聚物之熱效能為可預測且(實際上)可預測定的。此外，當具有此類受控分佈結構之共聚物隨後在雙嵌段、三嵌段或多嵌段共聚物中用作一個嵌段時，藉助於存在適當構成之受控分佈共聚物區成為可能之相對更高的Tg將趨於改良流動及可加工性。亦可達成某些其他性質之修改。
用於製備本發明之新穎受控分佈共聚物(C-A/B-C或(C-A/B)nX)之起始材料包括初始單體。低乙烯基半結晶「C」末端嵌段可選自比重大於0.85g/cc之低乙烯基可結晶聚二烯之群。較佳地，C嵌段為氫化低乙烯基含量聚丁二烯。「C」嵌段之低乙烯基含量為分別加成至用於丁二烯或異戊二烯之1,2-或3,4-加成模式中之聚合物鏈中之側接碳-碳雙鍵的量。在本發明之上下文中，「低乙烯基」意謂分別用於丁二烯或異戊二烯之1,2-或3,4-加成模式中小於或等於15%，且較佳10%至12%，且更佳8%至9%之碳-碳雙鍵。在任何情況下，乙烯基含量應為足以使C嵌段相與A/B嵌段共聚物分離及結晶之量。以便呈現結晶度之良好特性，而同時促進聚合物之可製造性。「C」嵌段之分子量大於1kg/mol且較佳大於3kg/mol(峰值MW)，但小於20kg/mol。如存在於B嵌段中之「較高乙烯基」意謂大於「低乙烯基」量之量且通常 經由使用微結構改質劑達成。
中間嵌段中之單烯基芳烴可選自苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、鄰甲基苯乙烯、乙烯基甲苯、乙烯基萘及對丁基苯乙烯或其混合物。在此等者中，苯乙烯為最佳的且為可自各種製造商商購的，且相對廉價。中間嵌段之總重量包含5重量%至40重量%之單烯基芳烴，諸如苯乙烯。如先前所陳述，隨後使此等烯基芳烴單體聚合。用於本文中之共軛二烯為1,3-丁二烯，及諸如異戊二烯、戊二烯、2,3-二甲基-1,3-丁二烯及1-苯基-1,3-丁二烯之經取代之丁二烯，或其混合物。在此等者中，1,3-丁二烯為最佳的。如本文中及在技術方案中所使用，「丁二烯」特別指「1,3-丁二烯」。如先前所陳述，隨後使此等共軛二烯單體聚合。在聚合之後，中間嵌段中之共軛二烯經氫化。當丁二烯經氫化後，其被稱作乙烯丁烯。中間嵌段中之氫化共軛二烯構成中間嵌段之總重量之60重量%至95重量%。
可經由先前技術中已知之若干氫化或選擇性氫化製程中之任一者進行氫化。舉例而言，此類氫化已經使用諸如(例如)美國專利第3,595,942號、第3,634,549號、第3,670,054號、第3,700,633號及再版專利第27,145號中揭示之彼等方法的方法實現，該等專利之揭示內容以引用的方式併入本文中。此等方法操作以氫化含有芳族或烯系不飽和基團之聚合物，且此等方法係基於適合之催化劑之操作。此類催化劑或催化劑前驅體較佳包含與適合還原劑(諸如選自元素週期表之I-A族、II-A族及III-B族之金屬(特定言之鋰、鎂或鋁)之鋁烷基或氫化物)組合之VIII族金屬(諸如鎳或鈷)。可在約20℃至約80℃之溫度下在適合溶劑或稀釋劑中完成此製備。其他可用之催化劑包括基於鈦之催化劑系統。
選擇性地氫化嵌段共聚物，且選擇性氫化製程轉化C末端嵌段及A/B受控分佈中間嵌段中之不飽和二烯雙鍵。在選擇性氫化製程期間 不氫化聚單烯基芳烴單元。可經由若干氫化或選擇性氫化製程中之任一者進行選擇性氫化。舉例而言，已使用諸如描述於(例如)美國專利第3,494,942號、第3,634,594號、第3,670,054號、第3,700,633號及再版專利第27,145號中之彼等方法之方法實現此氫化。可在已還原至少約90%之共軛二烯雙鍵，且已還原0%與10%之間之芳烴雙鍵之此類條件下進行氫化。較佳範圍為已還原至少約95%之共軛二烯雙鍵，且更佳已還原約98%之共軛二烯雙鍵。
嵌段共聚物在230℃及2.16kg質量下具有1g/10min至100g/10min，較佳1g/10min至50g/10min且更佳1g/10min至40g/10min之熔體流動速率。根據ASTM D 1238執行熔體流動速率。
在本文中所描述之組合物中，嵌段共聚物構成組合物之約50重量%至約70重量%。按組合物之總重量%計，組合物亦包含15重量%至25重量%之丁烯均聚物或共聚物。按組合物之總重量%計，組合物之第三主要組分包括12重量%至24重量%之至少一種聚烯烴均聚物或共聚物(非嵌段共聚物之部分)。組合物之熔體流動速率在230℃及2.16kg質量下較佳為5g/10min至400g/10min，且較佳5g/10min至300g/10min。根據ASTM D-1238執行熔體流動速率。
丁烯均聚物(「PB均聚物」)或丁烯共聚物(「PB共聚物」)之第二組分可含有少量具有2至20個碳原子之另一α-烯烴或其組合。較佳地，第二組分為均聚物及共聚物之組合(該定義包括三元共聚物)。第二組分可以約15-25重量百分比之量存在，更佳以18至23重量百分比之量存在。就均聚物及共聚物之組合而言，均聚物與共聚物之重量比較佳為約1：1至約10：1，更佳約2：1至約3：1。
在190℃下採用2.16kg重量量測，PB均聚物或共聚物之熔體流動速率(MFR(E)：ASTM D 1238)適當地處於約0.1g/10min至500g/10min之範圍內，較佳約0.5g/10min至250g/10min且更佳約200g/10 min。適合之PB均聚物為來自LyondellBasell之半結晶均聚物，聚丁烯-1級PB0800M。
考慮到丁烯共聚物，待共聚之另一α-烯烴之比率為20莫耳%或20莫耳%以下，較佳地10莫耳%或10莫耳%以下，且尤佳5莫耳%或5莫耳%以下。待共聚之另一α-烯烴之實例包括乙烯、丙烯、己烯、4-甲基戊烯-1、辛烯-1、癸烯-1、十八烯-1等。較佳PB共聚物為以商標Koattro出售，KT AR03級或KT AR05級(由LyondellBasell製造)之塑性體。此共聚物具有約890kg/m3之密度(根據ISO 1183)、約114℃之熔融溫度(藉由DSC量測)及約0.8g/10min之MFR(E)(190℃/2.16kg)。
聚烯烴均聚物或共聚物之第三組分包括(但不限於)聚丙烯、高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、線性低密度聚乙烯、聚乙烯-丙烯共聚物、聚乙烯-辛烯共聚物、聚乙烯-丁烯共聚物及其混合物。
亦可將此項技術中已知之穩定劑摻入至組合物中。穩定劑用於保護製成品在使用期限期間免受(例如)氧化、臭氧及紫外線輻射。此等者亦可用於在高溫處理期間保持穩定以免熱氧化分解。較佳UV抑制劑為UV吸收劑，諸如苯并三唑化合物。調配物中穩定劑之量將大大視產品之所需應用而定。若處理及耐久性之需求適中，則調配物中穩定劑之量將小於1phr。
此外，可將視情況選用之添加劑摻混至本文中所提出之組合物中。本發明中之所需組分(但不為必選)通常為第一抗氧化劑、第二抗氧化劑及碳自由基清除劑。大部分抗氧化劑屬於第一抗氧化劑或第二抗氧化劑之類別且歸因於不同化學結構而具有不同功能。第一抗氧化劑通常為受阻酚或芳基胺。第一抗氧化劑清除烷氧基及過氧基。與苯乙烯類嵌段共聚物相容之諸多第一抗氧化劑可摻入至本發明之組合物中。來自BASF之以商標名Irganox出售之第一抗氧化劑可為適合的， 諸如1010、1076及1330。
第二抗氧化劑亦可與第一抗氧化劑一起使用。第二抗氧化劑通常為亞磷酸酯及硫代增效劑。第二抗氧化劑清除在暴露於熱及氧之聚合物之自氧化循環期間產生之過氧化氫物。以商標名Irgafos®出售之代表高效能有機亞磷酸酯穩定劑之組合物可為適合的且同樣由BASF製造。舉例而言，Irgafos 168®水解穩定亞磷酸酯處理穩定劑及類似者可為適合的。
將碳自由基清除劑視為第三類別之抗氧化劑。此外，可使用(例如)商標名為Sumilizer由Sumitomo Chemical生產之碳自由基清除劑。在下文實例中使用Sumilizer GS。
當最終用途應用並不要求光學透明度時，適合填充劑亦可摻入至此處之組合物中。適合填充劑之實例包括(但不限於)滑石、碳酸鈣、碳黑、飛灰、板岩屑、石灰石、白雲石及矽質填充劑(諸如黏土、雲母及其他層狀矽酸鹽)。可使用不同填充劑之混合物。較佳地，碳酸鈣或滑石可用作填充劑。按嵌段共聚物組合物及填充劑之總重量計，填充劑的量較佳為0重量%至適當地小於8重量%。
在不背離本發明之範疇的情況下，本文中所提出之聚合物摻合物可進一步與其他聚合物、油、填充劑、增強劑、抗氧化劑、阻燃劑、防黏劑、潤滑劑及其他橡膠及塑膠混配成分混配。亦可使用除塵劑以在儲存或運輸期間將聚合物摻合物之丸粒及/或粉末之聚結降至最低。
如本文中所用，柴油燃料耐受性係指在暴露1分鐘之後之細微光澤變化，及亦在暴露1分鐘之後對於擦拭並無紋理變化或色彩遷移。所用拭紙為標準實驗室擦拭紙。
實例1 組合物1至4之製備
利用表1中所述之成分製備組合物1至4。用包含比重大於0.85g/cc之氫化低乙烯基聚丁二烯末端嵌段之嵌段共聚物置換組合物1、2及4之苯乙烯類嵌段共聚物。包括芳族或脂族熱塑性聚胺基甲酸酯作為聚胺基甲酸酯之組合物1及2常常用於要求良好之油、燃料及耐化學性之應用。組合物1及2將經功能上改質之S-S/EB-S摻入至組合物中以改良苯乙烯類嵌段共聚物與熱塑性聚胺基甲酸酯之間的相容性。組合物1及2摻入LDPE或HDPE作為額外成分。所有組合物具有相同量之第一及第二穩定劑。Cabot Plaback為惰性顏料。聚合物A為MD 6951，其為具有35重量%聚苯乙烯含量及在230℃及2.16kg下約48g/10min之熔體流動速率的選擇性氫化之受控分佈苯乙烯類嵌段共聚物。聚合物A具有玻璃態苯乙烯末端嵌段及不具有顯著結晶度之較高乙烯基含量之橡膠嵌段。聚合物B為具有半結晶低乙烯基末端嵌段及不具有顯著結晶度之較高乙烯基含量橡膠嵌段的C-S/EB-C三嵌段。
實例2 組合物之製備及測試
組合物5及6揭示於表2中。對於組合物5，聚合物EDF 9975(C- S/EB-C)為具有低乙烯基半結晶末端嵌段及較高乙烯基橡膠中間嵌段之三嵌段共聚物，且在230℃、2.16kg質量下具有11.5g/10min之熔體流動速率。對於組合物6，聚合物EDF 9938(C-S/EB-C)為具有低乙烯基半結晶末端嵌段及較高乙烯基橡膠中間嵌段之三嵌段共聚物，且在230℃、2.16kg質量下具有17g/10min之熔體流動速率。組合物3、組合物5及組合物6連同組合物1、2及4之若干性質之測試結果一起闡述於表3中。
表3展示肖氏A硬度(Shore A Hardness)(按照ASTM D2240)以及柴 油燃料現場測試及24小時柴油浸沒測試之測試資料。在表3中，皆使用微型D試樣晶粒進一步測試一些組合物之熔體流動速率(根據ASTM D1238)、拉伸強度(根據ASTM D412)及伸長率及模數(根據ASTM D412)。
應注意，組合物3、組合物5及組合物6皆係基於呈現9g/10min至22g/10min之廣泛範圍之MFR的具有C-A/B-C或(C-A/B)nX之分子結構之嵌段共聚物，使其適合於廣泛範圍之熔融加工技術。當經受1分鐘現場測試時，組合物3、組合物5及組合物6皆顯示出對柴油燃料之良好耐受性。組合物3展示對於擦拭僅有輕微光澤度變化且無紋理或色彩遷移。組合物5及組合物6亦藉由無光澤度變化展示類似良好柴油燃料耐受性。組合物3、組合物5及組合物6之柴油燃料耐受性皆明顯地優於組合物1、組合物2及組合物4之柴油燃料耐受性，組合物1、組合物2及組合物4展示對於擦拭具有最低限度之顯著光澤度變化且在一些情況下具有紋理變化及色彩遷移。因為TPU通常用於要求良好的耐化學性之應用的產業中，組合物3、組合物5及組合物6之優異效能顯著地改良。
因此，應顯而易見，本發明已提供一種組合物及一種用於製造充分滿足上述目的、目標及優點之軟TPE物品之方法。儘管本文已提出特定實施例，但明顯地，鑒於前文描述，許多替代方案、修改及變化對於熟習此項技術者將顯而易見。因此，本發明意欲涵蓋屬於所附申請專利範圍之精神及寬廣範疇內的所有該等替代方案、修改及變化。

Claims (19)

  1. 一種用於藉由旋轉模製或薄殼模製或注射模製或擠壓或壓縮模製或熱成型或壓延製造物品之組合物，該組合物包含：約50重量%至約70重量%之嵌段共聚物；約15重量%至約25重量%之至少一種丁烯均聚物或共聚物；及約12重量%至約24重量%之至少一種聚烯烴均聚物或聚烯烴共聚物；其中該嵌段共聚物具有比重大於0.85g/cc之氫化低乙烯基聚丁二烯末端嵌段，且具有聚烯基芳烴/氫化二烯之受控分佈中間嵌段，且其中該組合物之總重量等於100重量%。
  2. 如請求項1之組合物，其中該嵌段共聚物具有C-A/B-C或(C-A/B)nX之結構，其中C為氫化低乙烯基半結晶聚丁二烯嵌段，A/B為單烯基芳烴及具有較高乙烯基含量之丁二烯之受控分佈聚合物中間嵌段，X為偶合劑之殘基且n為2至6。
  3. 如請求項1之組合物，其中該聚烯烴均聚物或聚烯烴共聚物為聚丙烯、高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、線性低密度聚乙烯、聚乙烯共聚物、聚丙烯共聚物、聚丁烯共聚物，或此等者中之兩者或兩者以上之混合物。
  4. 如請求項1之組合物，其中該聚烯基芳烴選自以下之群：苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、乙烯基萘、對丁基苯乙烯或此等者中之兩者或兩者以上之混合物。
  5. 如請求項4之組合物，其中該氫化二烯選自以下之群：氫化丁二烯、氫化異戊二烯或此等者之混合物。
  6. 如請求項4之組合物，其中該嵌段共聚物為C-S/EB-C，其中C為 氫化低乙烯基半結晶聚丁二烯，且S/EB為苯乙烯及氫化丁二烯之受控分佈聚合物中間嵌段。
  7. 如請求項1之組合物，其進一步包括約0.3重量%至約3重量%之至少一種穩定劑。
  8. 如請求項6之組合物，其中該嵌段共聚物在230℃與2.16kg之重量下具有約1g/10min至約50g/10min之熔體流動指數。
  9. 如請求項1之組合物，其中該組合物在230℃及2.16kg下具有5g/10min至400g/10min之熔體流動速率範圍。
  10. 一種用於製造物品之方法，其包含：利用組合物旋轉模製、注射模製、擠壓、壓延、熱成型或薄殼模製物品，該組合物包含：約50重量%至約70重量%之嵌段共聚物；約15重量%至約25重量%之至少一種丁烯均聚物或共聚物；及約12重量%至約24重量%之至少一種聚烯烴均聚物或共聚物；其中該嵌段共聚物具有比重大於0.85g/cc之氫化低乙烯基聚丁二烯末端嵌段，且具有聚烯基芳烴/氫化二烯之受控分佈中間嵌段，且其中該組合物之總重量等於100重量%且該組合物在該旋轉模製或薄殼模製或注射模製或擠壓或壓延之步驟前熔融混合。
  11. 如請求項10之用於製造物品之方法，其中該聚烯烴均聚物或聚烯烴共聚物為聚丙烯、高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、線性低密度聚乙烯、聚乙烯共聚物、聚丙烯共聚物、聚丁烯共聚物，或此等者中之兩者或兩者以上之混合物。
  12. 如請求項10之用於製造物品之方法，其中該聚烯基芳烴選自以下之群：苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、乙烯基萘、對丁基苯乙烯或此等者中之兩者 或兩者以上之混合物。
  13. 如請求項10之用於製造物品之方法，其中該氫化二烯選自以下之群：氫化丁二烯、氫化異戊二烯或此等者之混合物。
  14. 一種用於藉由組合物塗佈織品、發泡體或剛性薄片基板之方法，其包含：藉由擠壓或壓延塗佈織品、發泡體或剛性薄片基板以製造物品，該組合物包含：約50重量%至約70重量%之嵌段共聚物；約15重量%至約25重量%之至少一種丁烯均聚物或共聚物；約12重量%至約24重量%之至少一種聚烯烴均聚物或共聚物；其中該嵌段共聚物具有比重大於0.85g/cc之氫化低乙烯基聚丁二烯末端嵌段，且具有聚烯基芳烴/氫化二烯之受控分佈中間嵌段，且其中該組合物之總重量等於100重量%且該組合物在該塗佈織品、發泡體或剛性薄片基板之步驟前熔融混合。
  15. 如請求項14之用於塗佈織品、發泡體或剛性薄片基板之方法，其中該聚烯烴均聚物或聚烯烴共聚物為聚丙烯、高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、線性低密度聚乙烯、聚乙烯共聚物、聚丙烯共聚物、聚丁烯共聚物，或此等者中之兩者或兩者以上之混合物。
  16. 如請求項15之用於塗佈織品、發泡體或剛性薄片基板之方法，其中該聚烯基芳烴選自以下之群：苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、乙烯基萘、對丁基苯乙烯或此等者中之兩者或兩者以上之混合物。
  17. 如請求項15之用於塗佈織品、發泡體或剛性薄片基板之方法，其中該氫化二烯選自氫化丁二烯、氫化異戊二烯或此等者之混合物。
  18. 一種用於利用組合物藉由注射模製、擠壓、熱成型、旋轉模製或薄殼模製來製造模製品之方法，該組合物包含：約50重量%至約70重量%之嵌段共聚物；約15重量%至約25重量%之至少一種丁烯均聚物或共聚物；約12重量%至約24重量%之至少一種聚烯烴均聚物或共聚物；其中該嵌段共聚物具有比重大於0.85g/cc之氫化低乙烯基聚丁二烯末端嵌段，且具有聚烯基芳烴/氫化二烯之受控分佈中間嵌段，且其中該組合物之總重量等於100重量%且該組合物在該形成模製品之步驟前熔融混合。
  19. 一種包含組合物之物品，其中該組合物包含：(i)按該組合物之總重量計，約50重量%至約70重量%之嵌段共聚物，其中該嵌段共聚物具有兩個末端嵌段及至少一個中間嵌段，其中該等末端嵌段為比重大於0.85g/cc之氫化低乙烯基聚丁二烯末端嵌段，且該中間嵌段為包含聚烯基芳烴及氫化二烯之受控分佈中間嵌段；及(ii)按該組合物之總重量計，約30重量%至約50重量%之至少一種聚烯烴均聚物、丙烯共聚物或丁烯共聚物；其中該組合物之總重量%等於100重量%，且其中該組合物在230℃與2.16kg質量下量測具有約5g/10min至約100g/10min之熔體流動速率。
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EP3307509B1 (en) 2020-08-05
WO2016200783A1 (en) 2016-12-15
US9862819B2 (en) 2018-01-09
CN107848162A (zh) 2018-03-27
KR102546052B1 (ko) 2023-06-20
US20160362544A1 (en) 2016-12-15
JP6837013B2 (ja) 2021-03-03
KR20180014826A (ko) 2018-02-09
EP3307509A4 (en) 2018-10-24
TWI593743B (zh) 2017-08-01
JP2018524431A (ja) 2018-08-30
CN107848162B (zh) 2019-11-15

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