CN114437474A - 包含聚氯乙烯和柔性丙烯酸类聚合物的聚合物共混物以及由其制成的薄膜、片材和管材 - Google Patents
包含聚氯乙烯和柔性丙烯酸类聚合物的聚合物共混物以及由其制成的薄膜、片材和管材 Download PDFInfo
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- CN114437474A CN114437474A CN202210224620.8A CN202210224620A CN114437474A CN 114437474 A CN114437474 A CN 114437474A CN 202210224620 A CN202210224620 A CN 202210224620A CN 114437474 A CN114437474 A CN 114437474A
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- 239000000203 mixture Substances 0.000 claims description 39
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Abstract
提供一种聚合物共混物,所述聚合物共混物包含以所述聚合物共混物的总重量计20至90重量份的聚氯乙烯树脂;以及以所述聚合物共混物的总重量计10至80重量份的柔性丙烯酸类聚合物。还提供由所述聚合物共混物制成的薄膜或片材或管材、由所述薄膜制成的覆盖材料以及制备薄膜的方法。
Description
技术领域
本发明涉及聚合物共混物、由所述聚合物共混物制成的薄膜或片材或管材、由所述薄膜或片材制成的物品以及制备薄膜或片材的方法。
背景技术
聚氯乙烯(PVC)为已用于各种细分市场的通用材料,所述细分市场的范围为建筑构造、医疗和消费者护理、商业石墨印刷到用于汽车、住宅和商业建筑的内部或外部装饰。为了提高PVC材料的柔性,通常将增塑剂并入到PVC制剂中。然而,通常用于柔性PVC制剂中的增塑剂为邻苯二甲酸酯化合物,并且常常随着时间迁出。
可提供机械强度、柔性、尺寸稳定性和耐气候性的替代性添加剂可适用于本领域。
发明内容
本发明为聚合物共混物、由所述聚合物共混物制成的薄膜或片材或管材、由所述薄膜或片材或管材制成的物品以及制备薄膜或片材的方法。
在一个实施例中,本发明提供一种包含以下各项的聚合物共混物:(1)以聚合物共混物的总重量计20至90重量份的聚氯乙烯;以及(2)以聚合物共混物的总重量计10至80重量份的柔性丙烯酸类聚合物,所述丙烯酸类聚合物包含(a)交联芯,所述交联芯包含大于95重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0.1重量百分比至5重量百分比的衍生自交联单体或接枝连接单体或其组合的单元,并且所述交联芯具有-85℃至-10℃的Tg;(b)中间区域,所述中间区域包含一或多个中间层,其中每个中间层包含88.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0重量百分比至5重量百分比的衍生自交联单体或接枝连接单体或其两种或更多种的组合的单元、任选地0重量百分比至2.0重量百分比的衍生自一种或多种链转移剂的单元;其中在中间层之间存在组成梯度并且在下限Tg与上限Tg之间存在所述组成梯度转变,其中所述下限Tg为至少-30℃并所述上限Tg为70℃或更低;以及(c)最外层,所述最外层包含98.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯单体、苯乙烯类单体以及其两种或更多种的组合组成的群组的一或多种单体所衍生的单元、0重量百分比至1.5重量百分比的衍生自一种或多种链转移剂的单元,并且具有40℃至110℃的Tg。
在另一个实施例中,本发明提供一种由本文所揭露的聚合物共混物的任何实施例产生的薄膜或片材或管材。
在另一方面,本发明提供一种由本文所揭露的薄膜或片材的任何实施例制备的覆盖材料(capstock)。
在另一个实施例中,本发明提供一种制备薄膜或片材或管材的方法,所述方法包括选择包含以下各项的聚合物共混物:(1)以聚合物共混物的总重量计20重量百分比至90重量百分比的聚氯乙烯;以及(2)以聚合物共混物的总重量计10重量百分比至80重量百分比的柔性丙烯酸类聚合物,所述丙烯酸类聚合物包含(a)交联芯,所述交联芯包含大于95重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0.1重量百分比至5重量百分比的衍生自交联单体或接枝连接单体或其组合的单元,并且所述交联芯具有-85℃至-10℃的Tg;(b)中间区域,所述中间区域包含一或多个中间层,其中每个中间层包含88.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0重量百分比至5重量百分比的衍生自交联单体、接枝连接单体或其两种或更多种的组合的单元、任选地0重量百分比至2.0重量百分比的衍生自一种或多种链转移剂的单元;其中在中间层之间存在组成梯度并且所述组分梯度在下限Tg与上限Tg之间转变,其中所述下限Tg为至少-30℃并所述上限Tg为70℃或更低;以及(c)最外层,所述最外层包含98.5重量百分比至100重量百分比的衍生自选自由(甲基)丙烯酸烷基酯单体、苯乙烯类单体以及其两种或更多种的组合组成的群组的一或多种单体的单元、0重量百分比至1.5重量百分比的衍生自一种或多种链转移剂的单元,并且具有40℃至110℃的Tg;以及通过选自由以下组成的群组的一种或多种工艺将聚合物共混物形成为薄膜或片材或管材:压延、铸挤或注塑。
具体实施方式
本发明提供一种聚合物共混物、由所述聚合物共混物制成的薄膜或片材或管材、由所述薄膜或片材制成的物品以及制备薄膜或片材或管材的方法。
如本文所用的,聚氯乙烯树脂意指包含衍生自氯乙烯的单元的任何聚合物。
如本文所用的,术语“(甲基)丙烯酸酯”意指丙烯酸酯或甲基丙烯酸酯。
如本文所用的,术语“薄膜或片材”意指厚度小于约0.50mm的聚合物片材。
本发明提供了一种聚合物共混物、薄膜或片材、由所述薄膜或片材形成的覆盖材料以及制备薄膜或片材的方法,其中所述聚合物共混物包含以聚合物共混物的总重量计20至90重量份的聚氯乙烯树脂;以及以聚合物共混物的总重量计10至80重量份的柔性丙烯酸类聚合物。在本文中包括并揭露了20至90重量份的聚氯乙烯树脂的所有单个值和子范围;例如,聚氯乙烯树脂的量的范围可以是以聚合物共混物的总重量计从下限20、40、60或80重量份到上限30、50、70或90重量份。例如,聚合物共混物中的聚氯乙烯树脂的重量可以是20至90重量份,或者在替代方案中是20至60重量份,或者在替代方案中是50至90重量份,或者在替代方案中是40至70重量份。在本文中包括并揭露了10至80重量份的柔性丙烯酸类聚合物的所有单个值和子范围;例如,在聚合物共混物中的柔性丙烯酸类聚合物的量的范围可以是以聚合物共混物的总重量计从下限10、30、50、60或70重量份到上限20、40、60或80重量份。例如,聚合物共混物中的柔性丙烯酸类聚合物的重量的范围可以是10至80重量份,或者在替代方案中是10至50重量份,或者在替代方案中是40至80重量份,或者在替代方案中是20至70重量份。
示范性聚氯乙烯树脂包括以名称FORMOLON销售的那些树脂,它们可从FormosaPlastics Corporation,U.S.A.(Livingston,NJ,USA)商购获得;或者以名称OXYVINYLS销售的那些树脂,它们可从Occidental Petroleum Corporation,U.S.A(Houston,TX,USA)商购获得。在一些实施例中,PVC树脂可与常规添加剂诸如热稳定剂、润滑剂、增塑剂、填充剂、加工助剂、抗冲击改性剂、UV和光稳定剂、染料以及颜料共混。
柔性丙烯酸类聚合物包含交联芯,所述交联芯包含大于95重量百分比(wt%)的选自由(甲基)丙烯酸烷基酯组成的群组的一或多种单体所衍生的单元、0.1重量百分比至5重量百分比的衍生自交联单体、接枝连接单体或其组合的单元,并且其中所述交联芯具有-85℃至-10℃的Tg。本文中包括并揭露了大于95重量百分比的选自由(甲基)丙烯酸烷基酯组成的群组的一或多种单体所衍生的单元的所有单个值和子范围。例如,衍生自一种或多种(甲基)丙烯酸烷基酯单体的单元可以大于95wt%,或者在替代方案中大于96wt%,或者在替代方案中大于97wt%,或者在替代方案中大于98wt%,或者在替代方案中大于99wt%。示范性(甲基)丙烯酸烷基酯单体包括C1-C18(甲基)丙烯酸酯单体单元及其组合,包括但不限于丙烯酸丁酯、乙基丙烯酸酯、丙烯酸2-乙基己基酯、丙烯酸丙酯、丙烯酸甲酯、丙烯酸己酯、丁基甲基丙烯酸酯、甲基甲基丙烯酸酯、甲基丙烯酸乙基己基酯、丙烯酸硬脂酸酯、丙烯酸苄基酯、其共混物以及其组合。
柔性丙烯酸类聚合物的交联芯还包含0.1重量百分比至5重量百分比的衍生自交联单体或接枝连接单体或其组合的单元。本文中包括并揭露了0.1重量百分比至5重量百分比的所有单个值和子范围;例如,衍生自交联单体或接枝连接单体或其组合的单元的量的范围可以是下限0.1wt%、0.5wt%、1wt%、3wt%或4wt%至上限0.2wt%、0.7wt%、2wt%、4wt%或5wt%。例如,衍生自交联单体或接枝连接单体或其组合的单元的量的范围可以是0.1wt%至5wt%,或者在替代方案中是0.1wt%至2.5wt%,或者在替代方案中是2.4wt%至5wt%,或者在替代方案中是1wt%至3wt%。适用于交联芯中的交联单体和/或接枝连接单体示范性但不限于包括丁二醇二(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、马来酸二烯丙酯、甲基丙烯酸烯丙酯、邻苯二甲酸二丙烯酯、邻苯二甲酸三烯丙基酯、三羟甲基丙烷三(甲基)丙烯酸酯、其共混物以及其两种或更多种的组合。在一个具体实施例中,交联芯包含至少95重量百分比的丙烯酸丁酯单元和0.1重量百分比至5.0重量百分比的丁二醇二丙烯酸酯和甲基丙烯酸烯丙酯的组合的单元。
柔性丙烯酸类聚合物的交联芯具有-85℃至-10℃的Tg。本文中包括并揭露了-85℃至-10℃的所有单个值和子范围;例如,交联芯的Tg的范围可以是下限-85℃、-65℃、-45℃、-25℃或-15℃至上限-10℃、-30℃、-50℃、-70℃或-80℃。例如,交联芯的Tg的范围可以是-10℃至-85℃,或者在替代方案中是-10℃至-50℃,或者在替代方案中是-45℃至-75℃,或者在替代方案中是-25℃至-75℃。
柔性丙烯酸类聚合物还包含中间区域,所述中间区域包含一个或多个中间层,其中每个中间层包含88.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0重量百分比至5重量百分比的衍生自交联单体或接枝连接单体或其两种或更多种的组合的单元、任选地0重量百分比至2.0重量百分比的衍生自一种或多种链转移剂的单元;其中在中间层之间存在组成梯度并且在下限Tg与上限Tg之间存在所述组成梯度转变,其中所述下限Tg为至少-30℃并且所述上限Tg为70℃或更小。
中间层包含88.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元。本文中包括并揭露了88.5wt%至100wt%的衍生自一种或多种(甲基)丙烯酸烷基酯单体的单元的所有单个值和子范围;例如,在中间层中衍生自一种或多种(甲基)丙烯酸烷基酯单体的单元的量的范围可以是下限88.5wt%、90wt%、92wt%、94wt%、96wt%、98wt%或99.5wt%至上限88.7wt%、91wt%、93wt%、95wt%、97wt%、99wt%或100wt%。中间层中衍生自(甲基)丙烯酸烷基酯单体的单元的量的范围可以是88.5wt%至100wt%,或者在替代方案中是88.5wt%至95wt%,或者在替代方案中是94wt%至100wt%,或者在替代方案中是91wt%至99wt%。适用于中间层中的(甲基)丙烯酸烷基酯单体示范性但不限于包括丙烯酸丁酯、丙烯酸乙基己酯、丙烯酸乙酯、甲基丙烯酸甲酯、环己基(甲基)丙烯酸酯、甲基丙烯酸环戊酯、甲基丙烯酸四氢呋喃酯以及(甲基)丙烯酸苄酯。在一个具体实施例中,本发明提供根据本文所揭露的任何实施例的聚合物共混物、由所述聚合物共混物制成的薄膜或片材或管材、由所述薄膜或片材制备的物品以及制备薄膜或片材或管材的方法,除了中间区域包含含有衍生自丙烯酸丁酯和甲基丙烯酸甲酯的单元的一个或多个层之外。在另一个实施例中,本发明提供根据本文所揭露的任何实施例的聚合物共混物、由所述聚合物共混物制成的薄膜或片材或管材、由所述薄膜或片材制备的物品以及制备薄膜或片材或管材的方法,除了中间区域包含含有衍生自丙烯酸乙酯和甲基丙烯酸甲酯的单元的一个或多个层之外。
中间层还包含0重量百分比至5重量百分比的衍生自交联单体或接枝连接单体或其两种或更多种的组合的单元。本文中包括并揭露了0wt%至5wt%的衍生自交联单体或接枝连接单体或其两种或更多种的组合的单元的所有单个值和子范围;例如,衍生自交联单体或接枝连接单体或其两种或更多种的组合的单元的量的范围可以是下限0wt%、1wt%、3wt%或4wt%至上限0.5wt%、2wt%、3.5wt%或5wt%。例如,衍生自交联单体或接枝连接单体或其两种或更多种的组合的单元的量的范围可以是0wt%至5wt%,或者在替代方案中是0wt%至2.5wt%,或者在替代方案中是2.5wt%至5wt%,或者在替代方案中是1wt%至4wt%。适用于中间层中的交联单体和/或接枝连接单体示范性但不限于包括丁二醇二(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、马来酸二烯丙酯、甲基丙烯酸烯丙酯、邻苯二甲酸二丙烯酯、邻苯二甲酸三烯丙基酯、三羟甲基丙烷三(甲基)丙烯酸酯、其共混物以及其两种或更多种的组合。
中间层还任选地包含0重量百分比至2.0重量百分比的衍生自一种或多种链转移剂的单元。本文中包括并揭露了2wt%至2.0wt%的衍生自一种或多种链转移剂的单元的所有单个值和子范围;例如,衍生自一种或多种链转移剂的单元的量的范围可以是下限0wt%、0.5wt%、1wt%或1.5wt%至上限0.25wt%、0.75wt%、1.25wt%、1.5wt%或2wt%。例如,衍生自一种或多种链转移剂的单元的量的范围可以是0wt%至2.0wt%,或者在替代方案中是0wt%至1wt%,或者在替代方案中是1wt%至2wt%,或者在替代方案中是0.75wt%至1.75wt%。适用于中间层中的链转移剂示范性但不限于包括烷基硫醇,例如乙硫醇、正丙硫醇、正丁硫醇、异丁硫醇、叔戊硫醇、正己基硫醇、环己硫醇、正辛硫醇、正癸硫醇、正-十二烷硫醇;含有巯基基团的酸,例如3-巯基丙酸;2-羟乙基硫醇;醇类,例如异丙醇、异丁醇、月桂醇以及叔辛醇;以及卤化化合物,诸如四氯化碳、四氯乙烯和三氯溴乙烷。
中间区域还进一步表征为在中间层之间存在组成梯度并且在下限Tg与上限Tg之间存在所述组成梯度转变,其中所述下限Tg为至少-30℃并且所述上限Tg为70℃或更小的。本文中包括并揭露了每个下限Tg和上限Tg的所有单个值和子范围。例如,下限Tg可以是-30℃,或者在替代方案中是-20℃,或者在替代方案中是-10℃。上限Tg可以是70℃,或者在替代方案中是60℃,或者在替代方案中是50℃。即,在中间区域的组成梯度上的Tg变化(ΔTg)可以是大于0℃至100℃。本文中包括并揭露了从大于0℃至100℃的ΔTg的所有单个值和子范围;例如,ΔTg可以是下限大于0℃、20℃、40℃、60℃或80℃至上限10℃、30℃、50℃、70℃、90℃或100℃。例如,ΔTg可以是从大于0℃至100℃,或者在替代方案中是大于0℃至50℃,或者在替代方案中是50℃至100℃,或者在替代方案中是25℃至75℃。
柔性丙烯酸类聚合物还包含最外层,所述最外层包含98.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯、苯乙烯类单体及其两种或更多种的组合组成的群组的一或多种单体所衍生的单元、0重量百分比至1.5重量百分比的衍生自一种或多种链转移剂的单元,并且具有40℃至110℃的Tg。在本文中包括并揭露了98.5wt%至100wt%的选自由(甲基)丙烯酸烷基酯、苯乙烯类单体及其两种或更多种的组合组成的群组的一或多种单体衍生的单元的所有单个值和子范围。例如,衍生自选自由(甲基)丙烯酸烷基酯、苯乙烯类单体及其两种或更多种的组合组成的群组的一或多种单体的单元的量的范围可以是下限98.5wt%、99wt%或99.5wt%至上限98.75wt%、99.25wt%、99.75wt%或100wt%。例如,衍生自选自由(甲基)丙烯酸烷基酯、苯乙烯类单体及其两种或更多种的组合组成的群组的一或多种单体的单元的量的范围可以是98.5wt%至100wt%,或者在替代方案中是98.5wt%至99.5wt%,或者在替代方案中是99.5wt%至100wt%,或者在替代方案中是98.75wt%至99.75wt%。适用于最外层中的(甲基)丙烯酸烷基酯单体示范性但不限于包括丙烯酸丁酯、丙烯酸乙基己酯、丙烯酸乙酯以及甲基丙烯酸甲酯。在一个具体实施例中,最外层包含大于95重量百分比的衍生自丙烯酸乙酯和甲基丙烯酸甲酯单体的组合的单元。适用于最外层中的苯乙烯类单体示范性但不限于包括苯乙烯、α-甲基苯乙烯和乙烯基甲苯。
柔性丙烯酸类聚合物外层还包含0重量百分比至1.5重量百分比的衍生自一种或多种链转移剂的单元。本文中包括并揭露了0wt%至1.5wt%的衍生自一种或多种链转移剂的单元。例如,外层中衍生自一种或多种链转移剂的单元的量的范围可以是下限0wt%、0.5wt%或1wt%至上限0.25wt%、0.75wt%、1.25wt%或1.5wt%。例如,外层中衍生自一种或多种链转移剂的单元的量可以是0wt%至1.5wt%,或者在替代方案中是0wt%至0.75wt%,或者在替代方案中是0.75wt%至1.5wt%,或者在替代方案中是0.25wt%至1.25wt%。
柔性丙烯酸类聚合物的外层具有40℃至110℃的Tg。40℃至110℃的所有单个值和子范围。本文中包括并揭露了40℃至110℃的所有单个值和子范围;例如,柔性丙烯酸类聚合物的外层的Tg的范围可以是下限40℃、60℃、80℃或100℃至上限50℃、70℃、90℃或110℃。例如,外层的Tg的范围可以是40℃至110℃,或者在替代方案中是40℃至77℃,或者在替代方案中是76℃至110℃,或者在替代方案中是60℃至90℃。
制备具有如本文所述的中间区域的柔性丙烯酸类聚合物的方法例如在美国专利申请公布2013/053544中描述,所述专利申请的揭露内容以引用的方式并入本文。
在一个具体实施例中,本发明提供根据本文所揭露的任何实施例的聚合物共混物、由所述聚合物共混物制成的薄膜或片材或管材、由所述薄膜或片材制备的物品以及制备薄膜或片材的方法,除了柔性丙烯酸类聚合物表现出一种或多种以下特性:(a)Tg为50℃至97℃的最外层;以及(b)Tg为-55℃至-30℃的交联芯。
薄膜或片材可由本文揭露的聚合物共混物的任何实施例产生。用于制备薄膜或片材或管材的产生方法为已知的并且包括例如压延、(铸造)挤压以及注塑。
管材可由本文揭露的聚合物共混物的任何实施例产生。可使用用于制备聚合物管材的任何适合的产生方法,包括例如挤出和注塑成型。
典型的覆盖材料可以是0.1至1.0mm厚的,而结构性塑料可以是约0.8至1.2mm厚的,以用于PVC板壁应用,并且是1.2至3.0mm,以用于PVC轮廓应用(例如,PVC窗框、栅栏、甲板和雨水槽)。
实例
以下实例说明了本发明但并不旨在限制本发明的范围。
表1提供了用于制备实例的组分组成。
表1
本发明柔性丙烯酸类聚合物实例1:
向装备有搅拌器和冷凝器并用氮气清空的反应器中装入混合物A。在85℃下向搅拌反应器中添加混合物B、7%的混合物C、1.7%的混合物D和10.4%的混合物E。在发生放热反应并且反应器达到峰值温度之后,在85℃下继续加热和搅拌5分钟。在90分钟内将其余的混合物C和8.7%的混合物D逐渐添加到反应器中。在添加完成后,将反应器在85℃下保持15分钟。将24.3%的混合物E添加到反应器中。在90分钟内将混合物F和24.3%的混合物D逐渐添加到反应器中。在添加完成后,将反应器在85℃下保持15分钟。将21.9%的混合物E添加到反应器中。在60分钟内将混合物G和21.9%的混合物D逐渐添加到反应器中。在添加完成后,将反应器在85℃下保持15分钟。将其余的混合物E添加到反应器中。在60分钟内将混合物H和其余的混合物D逐渐添加到反应器中。在添加完成后,将反应器在85℃下保持15分钟,然后冷却至环境温度。
本发明柔性丙烯酸类聚合物实例1具有200nm的平均粒度、39.3%的固体含量和42,400的重均分子量。
使用真空泵将由以上本发明柔性丙烯酸类聚合物实例1制备的乳液冷冻干燥,并且将所得粉末连同PVC色母粒以表2中所列出的比率在Henschel掺混机(可获自HenschelMixers Americas,Houston,Texas)中混合。
PVC色母粒的制备(PVC MB):来自Formosa Plastics的PVC树脂Formolon 614(100phr)、Dow Chemical Company的Advastab TM-181(2.0phr)、Advalube F-1005(0.8phr)和Advalube E-2107(0.2phr)。利用Henschel掺混机(可获自Henschel MixersAmericas,Houston,Texas)将这些成分混合。
在任何柔性丙烯酸类聚合物不存在下,使用PVC色母粒制备比较性片材实例1。
通过将PVC MB与本发明柔性丙烯酸类聚合物实例1(FA)以表2中所示的比率混合来制备本发明片材实例1和2。通过振摇袋中的粉末共混物的组分来制成PVC MB和FA共混物。
本发明片材实例的制备。首先使用Collin Mill(W.H.Collin GmbHMaschienefabrik,Aichach,Germany)在190°℃下研磨共混的PVC MB和FA(用于本发明实例)或PVC MB(用于比较性实例),持续3分钟。在研磨完成后,将熔化的聚合物从金属辊中剥离并且将其置于金属模具中,以压制成具有1/8英寸的厚度的板。使用CARVER压制机(Carver Press Inc.,Menomonee Falls,Wisconsin),其中操作温度为190°℃并且压制条件为2.268吨持续3分钟,接着用9.07吨的压制条件进行2分钟并且在9.07吨下持续5分钟冷却时间段(室温)。
表2中示出了比较性和本发明片材实例的机械特性。
表2
测试方法
测试方法包括以下各项:
根据ASTM D882获得拉伸强度、屈服强度和杨氏模量值。根据ASTM D790获得弯曲模量值。根据ASTM D256获得悬臂梁缺口冲击值。
丙烯酸类聚合物的玻璃转化温度Tg是在TA仪器Q1000示差扫描热量计中使用在小铝盘中密封的聚合物小样品(5-20mg)来进行的。将所述盘置于DSC装置中,并且通过以10℃/min的速率从室温升高到180℃扫描来记录其热流反应。玻璃转化温度作为热流曲线中的不同偏移来观察。
在不偏离本发明的精神和基本属性的情况下,可以将其体现为其它形式,并且因此应该参考指明本发明的范围的所附权利要求书,而非参考上述说明书。
Claims (13)
1.一种聚合物共混物,其包含:
(1)以所述聚合物共混物的总重量计50至90重量份的聚氯乙烯树脂;以及
(2)以所述聚合物共混物的总重量计10至40重量份的柔性丙烯酸类聚合物,所述柔性丙烯酸类聚合物包含
(a)交联芯,所述交联芯包含大于95重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0.1重量百分比至5重量百分比的衍生自交联单体、接枝连接单体或其组合的单元,并且其中所述交联芯具有-85℃至-10℃的Tg;
(b)中间区域,所述中间区域包含一或多个中间层,其中每个所述中间层包含88.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0重量百分比至5重量百分比的衍生自交联单体、接枝连接单体或其两种或更多种的组合的单元、任选地0重量百分比至2.0重量百分比的衍生自一或多种链转移剂的单元;其中所述一或多个中间层包含衍生自丙烯酸乙酯和甲基丙烯酸甲酯的单元或衍生自丙烯酸丁酯和甲基丙烯酸甲酯的单元;其中在所述中间层之间存在组成梯度并且在下限Tg与上限Tg之间存在所述组成梯度转变,其中所述下限Tg为至少-30℃并且所述上限Tg为70℃或更小,以及
(c)最外层,所述最外层包含98.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯、苯乙烯类单体以及其两种或更多种的组合组成的群组的一或多种单体所衍生的单元、0重量百分比至1.5重量百分比的衍生自一或多种链转移剂的单元,并且具有40℃至110℃的Tg。
2.根据权利要求1所述的聚合物共混物,其中所述柔性丙烯酸类聚合物表现出一或多种以下特性:(a)所述最外层Tg为50℃至97℃;(b)所述交联芯的Tg为-55℃至-30℃。
3.根据前述权利要求中任一权利要求所述的聚合物共混物,其中所述交联芯的所述(甲基)丙烯酸烷基酯单体选自由以下组成的群组:丙烯酸丁酯、丙烯酸乙基己基酯、丙烯酸乙酯、甲基丙烯酸甲酯以及其两种或更多种的组合。
4.根据前述权利要求中任一权利要求所述的聚合物共混物,其中所述中间层的所述(甲基)丙烯酸烷基酯单体选自由以下组成的群组:丙烯酸丁酯、丙烯酸乙基己基酯、丙烯酸乙酯、甲基丙烯酸甲酯、(甲基)丙烯酸环己酯、甲基丙烯酸环戊基酯、甲基丙烯酸四氢呋喃酯、(甲基)丙烯酸苄酯及其两种或更多种的组合。
5.根据前述权利要求中任一权利要求所述的聚合物共混物,其中所述最外层的所述(甲基)丙烯酸烷基酯单体选自由以下组成的群组:丙烯酸丁酯、丙烯酸乙基己基酯、丙烯酸乙酯、甲基丙烯酸甲酯及其两种或更多种的组合。
6.根据前述权利要求中任一权利要求所述的聚合物共混物,其中所述交联芯包含至少95重量百分比的丙烯酸丁酯单元和0.1重量百分比至5.0重量百分比的丁二醇二丙烯酸酯和甲基丙烯酸烯丙酯的组合的单元。
7.根据前述权利要求中任一权利要求所述的聚合物共混物,其中所述最外层包含大于95重量百分比的衍生自丙烯酸乙酯和甲基丙烯酸甲酯单体的组合的单元。
8.一种薄膜或片材,其由根据前述权利要求中任一权利要求所述的聚合物共混物产生。
9.根据权利要求8所述的薄膜或片材,其中所述薄膜或片材具有200至400微米的厚度。
10.一种覆盖材料,其由根据权利要求8所述的薄膜或片材形成。
11.一种管材,其由根据权利要求1到权利要求7中任一权利要求所述的聚合物共混物制得。
12.一种制备薄膜或片材的方法,其包含:
选择聚合物共混物,所述聚合物共混物包含:
(1)以所述聚合物共混物的总重量计50重量百分比至90重量百分比的聚氯乙烯树脂;以及
(2)以所述聚合物共混物的总重量计10重量百分比至40重量百分比的柔性丙烯酸类聚合物,所述柔性丙烯酸类聚合物包含
(a)交联芯,所述交联芯包含大于95重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0.1重量百分比至5重量百分比的衍生自交联单体、接枝连接单体或其组合的单元,并且其中所述交联芯具有-85℃至-10℃的Tg;
(b)中间区域,所述中间区域包含一或多个中间层,其中每个所述中间层包含88.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0重量百分比至5重量百分比的衍生自交联单体、接枝连接单体或其两种或更多种的组合的单元、任选地0重量百分比至2.0重量百分比的衍生自一或多种链转移剂的单元;其中所述一或多个中间层包含衍生自丙烯酸乙酯和甲基丙烯酸甲酯的单元或衍生自丙烯酸丁酯和甲基丙烯酸甲酯的单元;其中在所述中间层之间存在组成梯度并且在下限Tg与上限Tg之间存在所述组成梯度转变,其中所述下限Tg为至少-30℃并且所述上限Tg为70℃或更小,以及
(c)最外层,所述最外层包含98.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯、苯乙烯类单体以及其两种或更多种的组合组成的群组的一或多种单体所衍生的单元、0重量百分比至1.5重量百分比的衍生自一或多种链转移剂的单元,并且具有40℃至110℃的Tg;以及
通过选自由以下组成的群组的一或多种工艺将所述聚合物共混物形成薄膜或片材:压延、铸造挤压和注塑成型。
13.一种制备管材的方法,其包含:
选择聚合物共混物,所述聚合物共混物包含:
(1)以所述聚合物共混物的总重量计50重量百分比至90重量百分比的聚氯乙烯树脂;以及
(2)以所述聚合物共混物的总重量计10重量百分比至40重量百分比的柔性丙烯酸类聚合物,所述柔性丙烯酸类聚合物包含
(a)交联芯,所述交联芯包含大于95重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0.1重量百分比至5重量百分比的衍生自交联单体、接枝连接单体或其组合的单元,并且其中所述交联芯具有-85℃至-10℃的Tg;
(b)中间区域,所述中间区域包含一或多个中间层,其中每个所述中间层包含88.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯单体组成的群组的一或多种单体所衍生的单元、0重量百分比至5重量百分比的衍生自交联单体、接枝连接单体或其两种或更多种的组合的单元、任选地0重量百分比至2.0重量百分比的衍生自一或多种链转移剂的单元;其中所述一或多个中间层包含衍生自丙烯酸乙酯和甲基丙烯酸甲酯的单元或衍生自丙烯酸丁酯和甲基丙烯酸甲酯的单元;其中在所述中间层之间存在组成梯度并且在下限Tg与上限Tg之间存在所述组成梯度转变,其中所述下限Tg为至少-30℃并且所述上限Tg为70℃或更小,以及
(c)最外层,所述最外层包含98.5重量百分比至100重量百分比的选自由(甲基)丙烯酸烷基酯、苯乙烯类单体以及其两种或更多种的组合组成的群组的一或多种单体所衍生的单元、0重量百分比至1.5重量百分比的衍生自一或多种链转移剂的单元,并且具有40℃至110℃的Tg;以及
通过选自由以下组成的群组的一或多种工艺将所述聚合物共混物形成管材:挤出和注塑成型。
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