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TWI586743B - 聚合物之摻合物、其所製造之膜或片、由膜或片或管所製造之物品及製備膜或片之方法 - Google Patents

聚合物之摻合物、其所製造之膜或片、由膜或片或管所製造之物品及製備膜或片之方法 Download PDF

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TWI586743B
TWI586743B TW104133365A TW104133365A TWI586743B TW I586743 B TWI586743 B TW I586743B TW 104133365 A TW104133365 A TW 104133365A TW 104133365 A TW104133365 A TW 104133365A TW I586743 B TWI586743 B TW I586743B
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weight
acrylate
meth
group
monomers
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TW104133365A
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TW201619271A (zh
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哈爾恩 高
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羅門哈斯公司
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    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L27/06—Homopolymers or copolymers of vinyl chloride
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    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
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    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
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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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Description

聚合物之摻合物、其所製造之膜或片、由膜或片或管所製造之物品及製備膜或片之方法
本揭示相關於一種聚合物摻合物、由其製備之膜或片或管、由該膜或片製造之物品，以及製備該膜或片之方法。
聚氯乙烯(PVC)為一種多功能材料，其已用於各種市場商品，範圍自建築構造物、藥品與照護用品、商用石墨印刷至汽車之外部或內部裝潢、住宅或商辦建築。為了增進PVC材料之可撓性，一般會加入塑化劑至PVC配方中。然而，使用於可撓性PVC配方中之塑化劑一般為酞酸酯化合物，其通常會隨著時間釋出。
其他可提供機械強度、可撓性、尺寸穩定性與耐候性之添加物，皆可用於本領域中。
本揭示相關於一種聚合物摻合物、由其製 備之膜或片或管、由該膜或片製造之物品，以及製備該膜或片之方法。
在一實施例中，本揭示提供一種聚合物之摻合物，包含：(1)20至90份重之聚氯乙烯樹脂，以該聚合物摻合物之總重量為基準；以及(2)10至80份重之撓性丙烯酸聚合物，以該聚合物摻合物之總重量為基準，其包含：(a)交聯核心，其包含大於95重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組、0.1至5重量%衍生自交聯單體、接枝交聯單體或其組合之單元，以及其中該交聯核心具Tg自-85至-10℃；(b)中間區域，其包含一或多個中間層，其中該中間層之每一者包含88.5至100重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組、0至5重量%衍生自交聯單體、接枝交聯單體或其二或多者組合之單元，任擇地0至2.0重量%衍生自一或多個鏈轉移劑之單元；其中在各中間層間具有組成梯度，以及該組成梯度在較低Tg與較高Tg間轉移，其中該較低Tg為至少-30℃，以及該較高Tg為70℃或更低，以及(c)最外層，其包含98.5至100重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯、苯乙烯單體與其二或多者之組合組成之群組、0至1.5重量%衍生自一或多個鏈轉移劑之單元，並具Tg自40至110℃。
在另一實施例中，本揭示提供一種由此揭示之聚合物摻合物實施例製備之膜、片或管。
在又一實施例中，本揭示提供一種由此揭示之聚合物摻合物任一實施例製備之覆蓋材料。
在又一實施例中，本揭示提供一種製備膜或片或管之方法，包含：選擇聚合物摻合物，其包含：(1)20至90份重之聚氯乙烯樹脂，以該聚合物摻合物之總重量為基準；以及(2)10至80份重之撓性丙烯酸聚合物，以該聚合物摻合物之總重量為基準，其包含：(a)交聯核心，其包含大於95重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組、0.1至5重量%衍生自交聯單體、接枝交聯單體或其組合之單元，以及其中該交聯核心具Tg自-85至-10℃；(b)中間區域，其包含一或多個中間層，其中該中間層之每一者包含88.5至100重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組、0至5重量%衍生自交聯單體、接枝交聯單體或其二或多者組合之單元，任擇地0至2.0重量%衍生自一或多個鏈轉移劑之單元；其中在各中間層間具有組成梯度，以及該組成梯度在較低Tg與較高Tg間轉移，其中該較低Tg為至少-30℃，以及該較高Tg為70℃或更低，以及(c)最外層，其包含98.5至100重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯、苯乙烯單體與其二或多者之組合組成之群組、0至1.5重量%衍生自一或多個鏈轉移劑之單元，並具Tg自40至110℃；以及以選自於壓延(calendaring)、鑄型擠出與射出成形之一或多種製程，將該聚合物摻合物形成 膜或片或管。
【發明內容】
本揭示相關於一種聚合物摻合物、由其製備之膜或片或管、由該膜或片或管製造之物品，以及製備該膜或片之方法。
使用於此，聚氯乙烯樹脂係指含有衍生自氯化乙烯單元之聚合物。
使用於此，術語“(甲基)丙烯酸酯”係指丙烯酸酯或甲基丙烯酸酯。
使用於此，術語“膜或片”係指厚度小於約0.50mm之聚合物薄片。
本揭示提供一種聚合物摻合物、由該膜或片製造之覆蓋材料，以及製備該膜或片之方法，其中該聚合摻合物包含20至90份重之聚氯乙烯樹脂，以該聚合物摻合物之總重量為基準；以及10至80份重之撓性丙烯酸聚合物，以該聚合物摻合物之總重量為基準。20至90份重之聚氯乙烯樹脂之所有單獨數值與次範圍皆包括並揭示於此；例如，聚氯乙烯樹脂之含量範圍可由下限之20、40、60或80份重，至上限之30、50、70、90份重，以該聚合物摻合物之總重量為基準。例如，該聚合摻合物之聚氯乙烯樹脂重量可為20至90份重，或20至60份重，或50至90份重，或40至70份重。10至80份重之撓性丙烯酸聚 合物之所有單獨數值與次範圍皆包括並揭示於此；例如，該聚合物摻合物中之撓性丙烯酸聚合物之含量範圍可由下限之10、30、50、60或70份重，至上限之20、40、60或80份重，以該聚合物摻合物之總重量為基準。例如，該聚合摻合物之撓性丙烯酸聚合物重量可為10至80份重，或10至50份重，或40至80份重，或20至70份重。
示範性聚氯乙烯樹脂包括商品名FORMOLON，其購自Formosa Plastics Corporation,U.S.A.(Livingston,NJ,USA)；或商品名OXYVINYLS，購自Occidental Petroleum Corporation,U.S.A.(Houston,TX,USA)。在某些實施例中，該PVC樹脂可摻合傳統添加物，如熱穩定劑、潤滑劑、塑化劑、填充物、加工輔助劑、衝擊修飾劑、UV與光穩定劑、染料與顏料。
該撓性丙烯酸聚合物包含交聯核心，其包含大於95重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組、0.1至5重量%衍生自交聯單體、接枝交聯單體或其組合之單元，以及其中該交聯核心具Tg自-85至-10℃。大於95重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組，之所有單獨數值與次範圍皆包括並揭示於此。例如，衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組，可大於95重量%，或大於96重量%，或大於97重量%，或大於98重量%，或大於99重量%。示範性烷基(甲基)丙烯酸酯單體包括 C1-C18烷基(甲基)丙烯酸酯單體單元與其組合，包括但不限於，丁基丙烯酸酯、乙基丙烯酸酯、2-乙基己基丙烯酸酯、丙基丙烯酸酯、甲基丙烯酸酯、己基丙烯酸酯、丁基甲基丙烯酸酯、甲基甲基丙烯酸酯、乙基己基甲基丙烯酸酯、硬脂基丙烯酸酯、芐基丙烯酸酯、其摻合物，及其組合。
該撓性丙烯酸聚合物之交聯核心可更包含0.1至5重量%衍生自交聯單體、接枝交聯單體或其組合之單元。0.1至5重量%之所有單獨數值與次範圍皆包括並揭示於此；例如，衍生自交聯單體、接枝交聯單體或其組合之單元含量可為下限0.1、0.5、1、3或4重量%，至上限0.2、0.7、2、4或5重量%。例如，衍生自交聯單體、接枝交聯單體或其組合之單元含量範圍可為0.1至5重量%，或0.1至2.5重量%，或2.4至5重量%，或1至3重量%。可用於交聯核心之示範性但非限制性之交聯單體及/或接枝交聯單體包括丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙烯基苯、二乙二醇二(甲基)丙烯酸酯、二烯丙基馬來酸酯、烯丙基甲基丙烯酸酯、二烯丙基酞酸酯、三烯丙基酞酸酯、三甲醇基丙烷三(甲基)丙烯酸酯、其摻合物，以及其二或多者之組合。在一特定實施例中，該交聯核心包含至少95重量%之丁基丙烯酸酯單元，以及0.1至5.0重量%之丁二醇二丙烯酸酯與烯丙基甲基丙烯酸酯組合之單元。
該撓性丙烯酸聚合物之交聯核心具Tg自-85至-10℃。-85至-10℃之所有單獨數值與次範圍皆包括 並揭示於此；例如，交聯核心之Tg範圍可自下限-85、-65、-45、-25或-15℃，至上限-10、-30、-50、-70或-80℃。例如，交聯核心之Tg範圍可自-10至-85℃，或自-10至-50℃，或自-45至-75℃，或自-25至-75℃。
該撓性丙烯酸聚合物更包含中間區域，其包含一或多個中間層，其中該中間層之每一者包含88.5至100重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組、0至5重量%衍生自交聯單體、接枝交聯單體或其二或多者組合之單元，任擇地0至2.0重量%衍生自一或多個鏈轉移劑之單元；其中在各中間層間具有組成梯度，以及該組成梯度在較低Tg與較高Tg間轉移，其中該較低Tg為至少-30℃，以及該較高Tg為70℃或更低。
該中間層包含88.5至100重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯單體組成之群組。88.5至100重量%之所有單獨數值與次範圍皆包括並揭示於此；例如，中間層中衍生自一或多個烷基(甲基)丙烯酸酯單體之單元含量範圍可自下限之88.5、90、92、94、96、98或99.5重量%，至上限之88.7、91、93、95、97、99或100重量%。中間層中衍生自一或多個烷基(甲基)丙烯酸酯單體之單元含量範圍可為88.5至100重量%，或88.5至95重量%，或94至100重量%，或91至99重量%。可用於中間層之示範性但非限制性之烷基(甲基)丙烯酸酯單體包括丁基丙烯酸酯、乙基己基丙烯酸 酯、乙基丙烯酸酯、甲基甲基丙烯酸酯、環己基(甲基)丙烯酸酯、環戊基甲基丙烯酸酯、四氫呋喃基甲基丙烯酸酯，以及芐基(甲基)丙烯酸酯。在一特定實施例中，本揭示提供於此揭示之任一實施例之聚合物摻合物、由其製造之膜或片或管、由該膜或片製造之物品，以及製備該膜或片或管之方法，除了該中間區域包含一或多層，其含有衍生自丁基丙烯酸酯與甲基甲基丙烯酸酯之單元。在另一實施例中，本揭示提供於此揭示之任一實施例之聚合物摻合物、由其製造之膜或片或管、由該膜或片製造之物品，以及製備該膜或片或管之方法，除了該中間區域包含一或多層，其含有衍生自乙基丙烯酸酯與甲基甲基丙烯酸酯之單元。
該中間層更包含0至5重量%衍生自交聯單體、接枝交聯單體或其二或多者組合之單元。0至5重量%衍生自交聯單體、接枝交聯單體或其二或多者組合之單元之所有單獨數值與次範圍皆包括並揭示於此；例如，衍生自交聯單體、接枝交聯單體或其二或多者組合之單元之含量可為下限0、1、3或4重量%至上限0.5、2、3.5或5重量%。例如，衍生自交聯單體、接枝交聯單體或其二或多者組合之單元之含量可為0至5重量%，或0至2.5重量%，或2.5至5重量%，或1至4重量%。可用於中間層之示範性但非限制性之交聯單體及/或接枝交聯單體包括丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙烯基苯、二乙二醇二(甲基)丙烯酸酯、二烯丙基馬來酸酯、烯丙基甲基丙烯酸酯、二烯丙基酞酸酯、三烯丙基酞酸酯、 三甲醇基丙烷三(甲基)丙烯酸酯、其摻合物，以及其二或多者之組合。
中間層更任擇地包含0至2.0重量%衍生自一或多個鏈轉移劑之單元。0至2.0重量%衍生自一或多個鏈轉移劑之單元之所有單獨數值與次範圍皆包括並揭示於此；例如，衍生自一或多個鏈轉移劑之單元含量範圍可為下限之0、0.5、1或1.5重量%至上限0.25、0.75、1.25、1.5或2重量%。例如，該衍生自一或多個鏈轉移劑之單元含量範圍可為0至2.0重量%，或0至1重量%，或1至2重量%，或0.75至1.75重量%。可用於中間層之示範性但非限制性之鏈轉移劑包括烷基硫醇，如乙基硫醇、正丙基硫醇、正丁基硫醇、異丁基硫醇、第三-戊基硫醇、正己基硫醇、環己基硫醇、正辛基硫醇、正癸基硫醇、正十二基硫醇；含硫醇基之酸，如3-硫醇基丙酸；2-羥基乙基硫醇；醇類，如異丙醇、異丁醇、月桂醇，以及第三-辛醇；以及鹵化化合物，如四氯化碳、四氯乙烯，以及三氯溴乙烷。
該中間層之其他特徵為在各中間層間具有組成梯度，以及該組成梯度在較低Tg與較高Tg間轉移，其中該較低Tg為至少-30℃，以及該較高Tg為70℃或更低。較低Tg與較高Tg之所有單獨數值與次範圍皆包括並揭示於此。例如，該較低Tg可為-30℃，或-20℃，或-10℃。該較高Tg可為70℃，或60℃，或50℃。亦即，在中間區域之組成梯度中之Tg變化(△Tg)可大於0至100℃。大於0至100℃之△Tg之所有單獨數值與次範圍皆包括並 揭示於此；例如，△Tg之下限可大於0、20、40、60、或80℃，至上限10、30、50、70、90或100℃。例如，△Tg可大於0至100℃，或大於0至50℃，或50至100℃，或25至75℃。
該撓性丙烯酸聚合物具最外層，其包含98.5至100重量%衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯、苯乙烯單體與其二或多者之組合組成之群組、0至1.5重量%衍生自一或多個鏈轉移劑之單元，並具Tg自40至110℃。98.5至100重量%衍生自一或多個單體之單元之所有單獨數值與次範圍皆包括並揭示於此。例如，衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯、苯乙烯單體與其二或多者之組合組成之群組，之含量範圍自下限之98.5、99或99.5%，至上限之98.75、99.25、99.75或100重量%。例如，衍生自一或多個單體之單元，該單體選自於由烷基(甲基)丙烯酸酯、苯乙烯單體與其二或多者之組合組成之群組，之含量範圍為98.5至100重量%，或98.5至99.5重量%，或99.5至100重量%，或98.75至99.75重量%。可用於最外層之之示範性、但非限制性之烷基(甲基)丙烯酸酯單體包括丁基丙烯酸酯、乙基己基丙烯酸酯、乙基丙烯酸酯，以及甲基甲基丙烯酸酯。在特定實施例中，最外層包含大於95重量%衍生自乙基丙烯酸酯與甲基甲基丙烯酸酯單體組合之單元。可用於最外層之之示範性、但非限制性之苯乙烯單體包括苯乙烯、α-甲基苯乙烯，以及乙烯基甲苯。
該撓性丙烯酸聚合物之外層更包含0至1.5重量%衍生自一或多個鏈轉移劑之單元。0至1.5重量%衍生自一或多個鏈轉移劑之單元之所有單獨數值與次範圍皆包括並揭示於此。例如，0至1.5重量%衍生自一或多個鏈轉移劑之單元含量範圍可自下限之0、0.5或1重量%，至上限之0.25、0.75、1.25或1.5重量%。例如，外層中衍生自一或多個鏈轉移劑之單元含量範圍可為0至1.5重量%，或0至0.75重量%，0.75至1.5重量%，或0.25至1.25重量%。
該撓性丙烯酸聚合物之外層具Tg自40℃至110℃。40℃至110℃之所有單獨數值與次範圍皆包括並揭示於此；例如，撓性丙烯酸聚合物外層之Tg範圍可自下限之40、60、80或100℃，至上限之50、70、90或110℃。例如，外層之Tg可為40至110℃，或40至77℃，或76至110℃，或60至90℃。
製備具有中間區域之撓性丙烯酸聚合物之方法，已描述於如美國專利申請公開號2013/053544，在此併入本案以作為參考資料。
在一特定實施例中，本揭示依據於此揭示之任一實施例，提供一種聚合物摻合物、由其製備之膜或片或管、由該膜或片製成之物品，以及製備該膜或片或管之方法，除了該撓性丙烯酸聚合物具有一或多種下列特性之外：(a)最外層之Tg為50至97℃；以及(b)交聯核心之Tg為-55至-30℃。
膜或片可由於此揭示之任一聚合物摻合物實施例製備。製造該膜或片或管之方法包括如壓延(calendaring)、鑄型擠出與射出成形。
管可以此揭示之任一聚合物摻合物實施例製備。任何適於製造該管之製造方法皆可使用，包括如擠出與射出成形。
典型之覆蓋材料之厚度可為0.1至1.0mm，其中用於PVC壁板應用，該結構性塑膠之厚度可為約0.8至1.2mm，而用於PVC輪廓應用(profile application)(如PVC窗框、圍欄、裝飾與排水溝)，則其厚度可為約1.2至3.0mm。
範例
下列範例係用於說明本發明，而非限制本發明範疇。
表1提供製備範例所使用之成分組成。
本發明之撓性丙烯酸聚合物範例1：
裝配有攪拌器與濃縮器，以氮氣覆蓋(blanked)之反應器中，注入混合物A。於85℃攪拌中之反應器內加入混合物B、7%混合物C、1.7%混合物D與10.4%混合物E。待放熱反應發生後，反應器到達尖峰溫度，於85℃持續加熱與攪拌5分鐘。剩餘之混合物C與8.7%混合物D逐漸加入反應器中，歷時90分鐘。添加完成後，反應器於85℃維持15分鐘。加入24.3%混合物E至反應器中。混合物F與24.3%混合物D逐漸加入反應器中，歷時90分鐘。添加完成後，反應器於85℃維持15分鐘。加入21.9%混合物E至反應器中。混合物G與21.9%混合物D逐漸加入反應器中，歷時60分鐘。添加完成後，反應器於85℃維持15分鐘。剩餘之混合物E加入反應器中。混合物H與剩餘混合物D逐漸加入反應器中，歷時60分鐘。添加完成後，反應器於85℃維持15分鐘，之後冷卻至室溫。
本發明之撓性丙烯酸聚合物範例1具平均粒徑200nm、固體含量39.3%，以及重量平均分子量42,400。
製備自上述之本發明撓性丙烯酸聚合物範例1之乳化物，係於真空烘箱中冷凍乾燥，所得粉末與PVC母粒(Masterbatch)，以列於表2之比例，於Henschel混合機(得自Henschel Mixers Americas,Houston,Texas)中混合。
PVC母粒(Masterbatch)之製備(PVC MB)：PVC樹脂Formolon 614，購自Formosa Plastics(100phr)、Advastab TM-181(2.0phr)、Advalube F-1005(0.8phr)，以及 Advalube E-2107(0.2phr)得自Dow Chemical Company。各成分係以Henschel混合機(得自Henschel Mixers Americas,Houston,Texas)混合。
PVC母粒(Masterbatch)，在無撓性丙烯酸聚合物存在下，係用於製備比較片範例1。
本發明片範例1與2係以表2所列之比例，摻合PVC MB與本發明撓性丙烯酸聚合物範例1(FA)而製備。PVC MB與FA摻合物係於袋中搖動粉末摻合物之各成分而製備。
本發明片範例之製備。摻合之PVC MB與FA(本發明範例)或PVC MB(比較例)首先使用Collin研磨機(W.H.Collin GmbH Maschienefabrik,Aichach,Germany)於190℃研磨3分鐘。研磨完成後，熔融聚合物於金屬滾輪上刮下，並置於金屬模具中壓製成小片，厚度為1/8英吋。使用CARVER壓製機(Carver Press Inc.,Menomonee Falls,Wisconsin)，操作溫度為190℃，壓製條件為2.268噸持續3分鐘，之後為9.07噸持續2分鐘，以及於9.07噸冷卻(室溫)持續5分鐘。
比較例與本發明片範例之機械特性係示於表2。
測試方法
測試方法包括下列：
張力強度、曲變強度與楊氏模數係依據ASTM D882測得。撓曲模數係依據ASTM D790測得。缺口伊氏衝擊量係依據ASTM D256測得。
丙烯酸聚合物之玻璃轉換溫度，Tg，係於TA儀器Q1000示差掃描熱量儀上測得，使用聚合物小樣本(5-20mg)，密封於小鋁鍋內。小鍋置於DSC裝置中，熱流量反應係以掃描方式記錄，速率為10℃/分鐘，自室溫至180℃。玻璃轉換溫度係由該熱流量曲線上之獨特位移觀察到。
本發明可以其他形式之實施例實施，而不脫離本發明之精神與必要元素，因此，應參照後附之申請專利範圍，而非前述說明書，作為本發明範疇依據。

Claims (10)

  1. 一種聚合物之摻合物，包含：(1)20至90份重之聚氯乙烯樹脂，以該聚合物摻合物之總重量為基準；以及(2)10至80份重之撓性丙烯酸聚合物，以該聚合物摻合物之總重量為基準，係包含：(a)交聯核心，係包含大於95重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基)丙烯酸酯單體組成之群組、0.1至5重量%衍生自交聯單體、接枝交聯單體或其組合之單元，其中該交聯單體及該接枝交聯單體係選自於由丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙烯基苯、二乙二醇二(甲基)丙烯酸酯、二烯丙基馬來酸酯、烯丙基甲基丙烯酸酯、二烯丙基酞酸酯、三烯丙基酞酸酯、三甲醇基丙烷三(甲基)丙烯酸酯、其摻合物，以及其二或多者之組合所組成之群組，以及該交聯核心具Tg自-85至-10℃；(b)中間區域，係包含一或多個中間層，其中該中間層之每一者包含88.5至100重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基)丙烯酸酯單體組成之群組、0至5重量%衍生自交聯單體、接枝交聯單體或其二或多者組合之單元，其中該交聯單體及該接枝交聯單體係選自於由丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯 酸酯、二乙烯基苯、二乙二醇二(甲基)丙烯酸酯、二烯丙基馬來酸酯、烯丙基甲基丙烯酸酯、二烯丙基酞酸酯、三烯丙基酞酸酯、三甲醇基丙烷三(甲基)丙烯酸酯、其摻合物，以及其二或多者之組合所組成之群組，0.5至2.0重量%衍生自一或多個鏈轉移劑之單元；其中在各中間層間具有組成梯度，以及該組成梯度在較低Tg與較高Tg間轉移，其中該較低Tg為至少-30℃，以及該較高Tg為70℃或更低，以及(c)最外層，係包含98.5至100重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基)丙烯酸酯、苯乙烯單體與其二或多者之組合組成之群組、0至1.5重量%衍生自一或多個選自於由烷基硫醇、含硫醇基之酸、醇類，以及鹵化化合物所組成之群組之鏈轉移劑之單元，並具Tg自40至110℃。
  2. 如申請專利範圍第1項所述之聚合物摻合物，其中該撓性丙烯酸聚合物具一或多種下列特性：(a)該最外層具Tg自50至97℃；(b)該交聯核心具Tg自-55至-30℃。
  3. 如申請專利範圍第1或2項所述之聚合物摻合物，其中該中間層之該烷基(甲基)丙烯酸酯單體係選自於由丁基丙烯酸酯、乙基己基丙烯酸酯、乙基丙烯酸酯、甲基甲基丙烯酸酯、環己基(甲基)丙烯酸酯、環戊基甲基丙烯酸酯、四氫呋喃基甲基丙烯酸酯、芐基(甲基) 丙烯酸酯，及其二或多者之組合。
  4. 如申請專利範圍第1或2項所述之聚合物摻合物，其中該交聯核心包含至少95重量%之丁基丙烯酸酯單元，以及0.1至5.0重量%之丁二醇二丙烯酸酯與烯丙基甲基丙烯酸酯之組合之單元。
  5. 如申請專利範圍第1或2項所述之聚合物摻合物，其中該一或多個中間層之每一者係包含衍生自丁基丙烯酸酯與甲基甲基丙烯酸酯之單元。
  6. 如申請專利範圍第1或2項所述之聚合物摻合物，其中該一或多個中間層之每一者係包含衍生自乙基丙烯酸酯與甲基甲基丙烯酸酯之單元。
  7. 如申請專利範圍第1或2項所述之聚合物摻合物，其中該最外層包含大於95重量%衍生自乙基丙烯酸酯與甲基甲基丙烯酸酯單體之組合之單元。
  8. 一種膜，係由如申請專利範圍第1至7項中任一項所述之聚合物摻合物製備。
  9. 一種製備膜之方法，包含：選擇聚合物摻合物，係包含：(1)20至90份重之聚氯乙烯樹脂，以該聚合物摻合物之總重量為基準；以及(2)10至80份重之撓性丙烯酸聚合物，以該聚合物摻合物之總重量為基準，係包含：(a)交聯核心，係包含大於95重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基) 丙烯酸酯單體組成之群組、0.1至5重量%衍生自交聯單體、接枝交聯單體或其組合之單元，其中該交聯單體及該接枝交聯單體係選自於由丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙烯基苯、二乙二醇二(甲基)丙烯酸酯、二烯丙基馬來酸酯、烯丙基甲基丙烯酸酯、二烯丙基酞酸酯、三烯丙基酞酸酯、三甲醇基丙烷三(甲基)丙烯酸酯、其摻合物，以及其二或多者之組合所組成之群組，以及該交聯核心具Tg自-85至-10℃；(b)中間區域，係包含一或多個中間層，其中該中間層之每一者包含88.5至100重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基)丙烯酸酯單體組成之群組、0至5重量%衍生自交聯單體、接枝交聯單體或其二或多者組合之單元，其中該交聯單體及該接枝交聯單體係選自於由丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙烯基苯、二乙二醇二(甲基)丙烯酸酯、二烯丙基馬來酸酯、烯丙基甲基丙烯酸酯、二烯丙基酞酸酯、三烯丙基酞酸酯、三甲醇基丙烷三(甲基)丙烯酸酯、其摻合物，以及其二或多者之組合所組成之群組，0.5至2.0重量%衍生自一或多個鏈轉移劑之單元；其中在各中間層間具有組成梯度，以及該組成梯度在較低Tg與較高Tg間轉移，其中該較低Tg為至少-30℃，以及該較高Tg為70 ℃或更低，以及(c)最外層，係包含98.5至100重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基)丙烯酸酯、苯乙烯單體與其二或多者之組合組成之群組、0至1.5重量%衍生自一或多個選自於由烷基硫醇、含硫醇基之酸、醇類，以及鹵化化合物所組成之群組之鏈轉移劑之單元，並具Tg自40至110℃；以及以選自於壓延、鑄型擠出與射出成形之一或多種製程，將該聚合物摻合物形成膜或片。
  10. 一種製備管之方法，包含：選擇聚合物摻合物，包含：(1)20至90份重之聚氯乙烯樹脂，以該聚合物摻合物之總重量為基準；以及(2)10至80份重之撓性丙烯酸聚合物，以該聚合物摻合物之總重量為基準，係包含：(a)交聯核心，係包含大於95重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基)丙烯酸酯單體組成之群組、0.1至5重量%衍生自交聯單體、接枝交聯單體或其組合之單元，其中該交聯單體及該接枝交聯單體係選自於由丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙烯基苯、二乙二醇二(甲基)丙烯酸酯、二烯丙基馬來酸酯、烯丙基甲基丙烯酸酯、二烯丙基酞酸 酯、三烯丙基酞酸酯、三甲醇基丙烷三(甲基)丙烯酸酯、其摻合物，以及其二或多者之組合所組成之群組，以及該交聯核心具Tg自-85至-10℃；(b)中間區域，係包含一或多個中間層，其中該中間層之每一者包含88.5至100重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基)丙烯酸酯單體組成之群組、0至5重量%衍生自交聯單體、接枝交聯單體或其二或多者組合之單元，其中該交聯單體及該接枝交聯單體係選自於由丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙烯基苯、二乙二醇二(甲基)丙烯酸酯、二烯丙基馬來酸酯、烯丙基甲基丙烯酸酯、二烯丙基酞酸酯、三烯丙基酞酸酯、三甲醇基丙烷三(甲基)丙烯酸酯、其摻合物，以及其二或多者之組合所組成之群組，0.5至2.0重量%衍生自一或多個鏈轉移劑之單元；其中在各中間層間具有組成梯度，以及該組成梯度在較低Tg與較高Tg間轉移，其中該較低Tg為至少-30℃，以及該較高Tg為70℃或更低，以及(c)最外層，係包含98.5至100重量%衍生自一或多個單體之單元，該單體係選自於由烷基(甲基)丙烯酸酯、苯乙烯單體與其二或多者之組合組成之群組、0至1.5重量%衍生自一或多個選自於由烷基硫醇、含硫醇基之酸、醇類，以及鹵化化 合物所組成之群組之鏈轉移劑之單元，並具Tg自40至110℃；以及以選自於由擠出與射出成形組成群組之一或多種製程，將該聚合物摻合物形成管。
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EP3209709B1 (en) 2020-02-19

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