CN101151312A - 包含纳米微粒TiO2和乙烯共聚物的组合物 - Google Patents

包含纳米微粒TiO2和乙烯共聚物的组合物 Download PDF

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CN101151312A
CN101151312A CNA2006800098817A CN200680009881A CN101151312A CN 101151312 A CN101151312 A CN 101151312A CN A2006800098817 A CNA2006800098817 A CN A2006800098817A CN 200680009881 A CN200680009881 A CN 200680009881A CN 101151312 A CN101151312 A CN 101151312A
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acid
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ethylene copolymer
alkyl
acrylate
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C·特雷尔茨施
J·W·保罗
A·H·小赖德
M·D·韦策尔
D·E·斯帕尔
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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    • B32—LAYERED PRODUCTS
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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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
    • C08L23/04—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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Abstract

本发明公开了一种组合物，所述组合物包含或制备自纳米微粒大小的TiO2、乙烯共聚物或乙烯共聚物的离聚物和任选的第二聚合物。本发明也公开了由所述组合物制造的薄膜和其它成形制品。可用具有紫外线屏蔽的所述组合物保护可能对紫外线敏感的产品，如食品。

Description

包含纳米微粒TiO2和乙烯共聚物的组合物
本发明涉及一种包含纳米微粒大小的TiO2(纳米TiO2)和乙烯共聚物的组合物，其制备方法及用其制造的产物。
发明背景
乙烯共聚物也被本领域的技术人员称为包含衍生自乙烯和极性单体的重复单元的聚合物，如乙烯-酸共聚物，乙烯共聚物包括其离聚物。它们可用作包装材料。这些聚合物为本领域的技术人员所熟悉，并且由于这些聚合物包含衍生自极性单体的重复单元，它们具有不同于没有衍生自极性单体的重复单元的其它聚合物(如聚乙烯、聚丙烯和其它聚烯烃)的性质。
聚合物树脂中存在填料能够改善树脂的机械和化学性能为我们所熟悉。虽然填料可以改善树脂的抗拉强度或模量，但可能降低树脂的韧度、断裂伸长或挠曲模量。通过增加表面积∶体积比，例如利用纳米微粒，可减少所需的填料量，从而降低填料的负面影响，同时保持或增加所需的性能改善。
纳米微粒经常能够获得大块材料不能获得的性能，如吸收或透射的波长。例如，二氧化钛为一种熟知的白色颜料(一般具有100nm至1000nm级的大小)，并且可吸收和散射可见区域的光线。
纳米TiO2微粒(指具有约1nm至约100nm级微粒大小的TiO2)可在水中分散，同时保持透明外观。虽然纳米TiO2不吸收或散射可见区域的光线，但它在紫外区域吸收。
例如，WO 2003/099911公开了在聚烯烃中混入纳米TiO2微粒；US 6,667,360公开了在聚合物树脂中混入TiO2微粒以改善机械性能；而US 6,479,576公开了将TiO2微粒混入聚乙烯或乙烯共聚物。
很多包装应用需要透明的紫外线屏蔽薄膜。例如，一种保持透明的包装材料引起了用户的兴趣。此类包装材料可用于食品、药物、医疗器械和化妆品。这些紫外屏蔽薄膜可增加保存期限，并减少保存被包装物质的其它措施。
可将增塑的聚乙烯醇缩丁醛片材用于制造层压结构，例如包括汽车、摩托车、船和飞机的交通工具的挡风玻璃；住所和建筑；柜橱和陈列橱窗中的搁板；和在玻璃片中需要结构强度的其它制品。在很多应用中，层压材料屏蔽不良作用的紫外线和/或透明合乎需要。此外，可在多种应用中使用多种装饰性玻璃层压材料；使用装饰性玻璃层压材料在产品用途(如家具、橱柜、工作台面、桌面等)中不普遍。
因此，仍需要改善用于包装、瓶、层压玻璃的聚合物性能而不牺牲当前的性能，尤其是对紫外线透射显示屏蔽的透明乙烯共聚物薄膜。
发明概述
本发明包括一种组合物，所述组合物包含或制备自纳米TiO2和聚合物，所述聚合物包括乙烯共聚物或乙烯共聚物的离聚物、聚酯、聚乙烯醇缩丁醛或其两种或多种的组合。
本发明还包括一种制备所述组合物的方法。
本发明进一步包括一种由所述组合物制造的成形制品。
发明详述
一种乙烯共聚物为一种可包含衍生自以乙烯共聚物的总重量计约5至约50％重量，或约10至约19％重量，或12至15％重量极性单体的重复单元的聚合物，所述极性单体如丙烯酸、烷基丙烯酸或丙烯酸烷基酯或其两种或多种的组合。烷基可包含最多约20个碳原子，如甲基、乙基、丁基、异丁基、戊基、己基及其两种或多种的组合。
此类极性单体的实例包括丙烯酸、甲基丙烯酸、乙基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸辛酯、甲基丙烯酸辛酯、丙烯酸十一烷酯、甲基丙烯酸十一烷酯、丙烯酸十八烷酯、甲基丙烯酸十八烷酯、丙烯酸十二烷酯、甲基丙烯酸十二烷酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、聚丙烯酸乙二醇酯、聚甲基丙烯酸乙二醇酯、聚甲基醚丙烯酸乙二醇酯、聚甲基醚甲基丙烯酸乙二醇酯、聚山萮基醚丙烯酸乙二醇酯、聚山萮基醚甲基丙烯酸乙二醇酯、聚4-壬基苯基醚丙烯酸乙二醇酯、聚4-壬基苯基醚甲基丙烯酸乙二醇酯、聚苯基醚丙烯酸乙二醇酯、聚苯基醚甲基丙烯酸乙二醇酯、马来酸二甲酯、马来酸二乙酯、马来酸二丁酯、富马酸二甲酯、富马酸二乙酯、富马酸二丁酯、富马酸二甲酯、乙烯基乙酸、乙酸乙烯酯、丙酸乙烯酯及其两种或多种的组合。
乙烯共聚物可包含最多35％重量任选的共聚单体，如一氧化碳、二氧化硫、丙烯腈、马来酸酐、马来酸二酯、(甲基)丙烯酸、马来酸、马来酸单酯、衣康酸、富马酸、富马酸单酯、这些酸的盐、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯和缩水甘油基乙烯基醚及其两种或多种的组合。
乙烯共聚物的酸部分可用阳离子中和以产生离聚物。可用金属离子中和基于羧酸总含量的约0.1至约100％，或约10至约90％，或约20至80％，或约20至约40％。金属离子可为单价、二价、三价、多价或其两种或多种的组合。实例包括Li、Na、K、Ag、Hg、Cu、Be、Mg、Ca、Sr、Ba、Cd、Sn、Pb、Fe、Co、Zn、Ni、Al、Sc、Hf、Ti、Zr、Ce及其两种或多种的组合。如果金属离子为多价，则可包含络合剂，如硬脂酸根、油酸根、水杨酸根和酚根，如US 3,404,134所公开。
离聚物也可以为具有大于20％中和度的离聚物与例如乙烯-(甲基)丙烯酸共聚物的共混物，以取得所需的中和度。
例如，乙烯-丙烯酸烷基酯共聚物可包含1至30％重量的至少一种E/X/Y共聚物，其中E包括乙烯；X为选自乙酸乙烯酯和(甲基)丙烯酸烷基酯的单体；Y为一种或多种以上公开的任选共聚单体；X为E/X/Y共聚物的0至50％重量；Y为E/X/Y共聚物的0至35％重量，其中X和Y的％重量不能同时为0，E为其余部分。
乙烯共聚物的实例包括但不限于乙烯/丙烯酸甲酯(EMA)、乙烯/丙烯酸乙酯(EEA)、丙烯酸乙酯(EA)、乙烯/丙烯酸丁酯(EBA)、乙烯/丙烯酸异丁酯/甲基丙烯酸、乙烯/丙烯酸甲酯/马来酸酐、乙烯/丙烯酸丁酯/甲基丙烯酸缩水甘油酯(EBAGMA)和乙烯/丙烯酸丁酯/一氧化碳(EBACO)和丙烯酸丁酯(BA)。
市售乙烯共聚物的实例包括自E.I.du Pont de Nemours andCompany(DuPont)，Wilmington，Delaware购得的商标为Surlyn、Nucrel、Appeel、Bvnel和Elvaloy和Elvax的那些产品。
此类乙烯共聚物可由本领域技术人员已知的任何方法用高压釜或管式反应器制备(例如US 3,404,134、US 5,028,674、US 6,500,888和US 6,518,365)。
例如，可在高压和升高的温度在管式反应器中制备乙烯共聚物。乙烯和(甲基)丙烯酸烷基酯(例如丙烯酸甲酯)共聚单体各自的不同反应动力学的固有结果通过在管式反应器内沿着反应流动路径有意引入单体得以缓解或部分补偿。这种管式反应器制备的乙烯共聚物比以相同共聚单体比率在高压搅拌式高压釜反应器制备的共聚物具有沿着聚合物主链更高的相对不均匀度(更不均匀的共聚单体分布)，降低的长链分支和更高的熔点。关于管式反应器和高压釜制备的乙烯共聚物的其它资料，请参阅Richaard T.Chou，Mimi Y.Keating和LesterJ.Hughes，“High Flexibility EMA made from High Pressure TubularProcess”，Annual Technical Conference-Society of Plastics Engineers(2002)，60th(Vol.2)，1832-1836。管式反应器制备的乙烯共聚物可购自DuPont。购自DuPont的某些此类乙烯共聚物具有约0.1至约10的熔体流动(克/10分钟)，并且包含约5至约30％重量衍生自丙烯酸烷基酯的重复单元。
聚酯为醇和有机酸或其盐或其酯的缩聚反应产物。聚酯及其制备的实例已普遍公开于例如美国专利6,166,170；6,075,115；6,080,834；和6,255,442。由于聚酯为本领域的技术人员所熟悉，在本文为简洁起见将其说明省略。
聚乙烯醇缩丁醛(PVB)可以购自例如DuPont或Solutia，St.Louis，MO。PVB也可以根据任何本领域技术人员已知的方法制备，如美国专利3,153,009所公开。通过在约5℃至100℃在酸或酸的混合物存在下在含水介质中混合聚乙烯醇(PVA)与丁醛，可制备PVB树脂。PVA与丁醛之比可取决于残余羟基官能度，例如在全部混合物中约10至约50，或约15至约25，或约15至约20，或约17至约19％重量的PVA。残余％重量PVA可根据ASTM D1396-92测定。
在组合物中可存在约0.1至约50％重量，或约0.5至约30％重量，或约0.5至约10％重量，或约0.5至2％重量的纳米TiO2(基于组合物的总重量)。
纳米TiO2可具有小于或等于约125nm，或≤100nm，或≤50nm，或≤40nm，或≤20nm的平均大小分布。纳米TiO2优选用酸、硅化合物、另一种金属氧化物或其两种或多种的组合涂覆。涂层可为约0.1至约25％重量，或0.1至约10％重量，或约0.3至约5％重量，或约0.7至约2％重量。
酸可以为羧酸，例如己二酸、对苯二甲酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸、水杨酸及其酯或盐。
硅化合物的实例可以为硅酸盐或有机硅烷或硅氧烷，包括硅酸盐、有机烷氧基硅烷、氨基硅烷、环氧基硅烷和巯基硅烷，如己基三甲氧基硅烷、辛基三乙氧基硅烷、壬基三乙氧基硅烷、癸基三乙氧基硅烷、十二烷基三乙氧基硅烷、十三烷基三乙氧基硅烷、十四烷基三乙氧基硅烷、十五烷基三乙氧基硅烷、十六烷基三乙氧基硅烷、十七烷基三乙氧基硅烷、十八烷基三乙氧基硅烷、N-(2-氨基乙基)3-氨基丙基甲基二甲氧基硅烷、N-(2-氨基乙基)3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、3-缩水甘油氧基丙基甲基二甲氧基硅烷、3-巯基丙基三甲氧基硅烷及其两种或多种的组合。
金属氧化物的实例包括Al2O3、SiO2、ZrO2或其两种或多种的组合。
组合物可进一步包含增塑剂、荧光增白剂、粘合促进剂、稳定剂(例如水解稳定剂、辐射稳定剂、热稳定剂和紫外(UV)稳定剂)、抗氧化剂、紫外线吸收剂、抗静电剂、着色剂、染料或颜料、消光剂、填料、阻燃剂、润滑剂、增强剂(例如玻璃纤维和片)、加工助剂、防滑剂、增滑剂(例如，滑石粉、防粘连剂)和其它添加剂。
纳米TiO2可以购得或根据任何本领域的技术人员已知的方法制备，如美国专利6,667,360所公开。可用磷酸、金属磷酸盐、金属卤化物、金属碳酸盐、金属硫酸盐或其两种或多种的组合控制纳米TiO2的结晶度、无定形含量或可轧性。金属可以为钠、钾、铝、锡或锌。微粒的表面反应性也可以通过用表面剂涂覆来控制，如以上所公开的金属氧化物、酸或硅烷。
包含乙烯共聚物的组合物可用本领域的技术人员已知的任何方法制备。乙烯共聚物和纳米TiO2可进行干燥混合、干燥共混、熔融共混及本领域的技术人员已知的其它方法。例如，纳米TiO2混入乙烯共聚物或聚乙烯醇缩丁醛可用粉末和浆料二者来完成。可将TiO2的浆料或干燥粉末加入含共聚物高压釜反应器内的乙烯共聚物中。共聚物可以为基础树脂或所需的离聚物。可在开炼机或挤出机中引入，并且作为所需物质或直接组合物中的母料。或者，可用开炼机以10至30％重量的纳米TiO2在挤出机中制备母料，随后在用金属离子中和以羧酸总含量计约10至约90％的同时，挤出到0.5至2％重量。或者，也可以通过具有10至30％重量纳米TiO2的母料将纳米TiO2粉末加入挤出机内的所需离聚物中，随后挤出到0.5至2％重量。
组合物也可包含增塑剂。增塑剂可为本领域的技术人员已知的那些增塑剂。例如，用于制备增塑PVB片材的增塑剂可包括二(2-乙基己酸)三甘醇酯、二庚酸四甘醇酯、癸二酸二丁酯或其两种或多种的组合。
可包含任何量的增塑剂，例如以树脂的总干重计约5至约50份/百份树脂(pph)，或约20至约45pph，或约32至约45pph。可用任何已知的方法进行增塑，如US 3,153,009或US 5,886,075所公开。
组合物也可包含填料，如CaCO3、SiO2、Al2O3、常规颗粒大小的TiO2、ZrO2或其两种或多种的组合。填料也可以约0.01至约5％重量存在于组合物中。
也可以在组合物尤其是PVB组合物中包含表面活性剂。可使用任何已知的表面活性剂，例如月桂基硫酸钠、磺基琥珀酸二辛酯钠、椰油基甲基氨基乙磺酸钠或癸基(磺基苯氧基)苯磺酸二钠盐。
可用组合物制造成形制品。成形制品可以为薄膜、片材、长丝、带、模制制品、热成形制品、容器等形式。制造这些制品的方法为本领域的技术人员所熟悉。例如，薄膜可用本领域的技术人员所熟悉的任何方法制造，例如溶液流延流延薄膜挤出、吹膜挤出和热塑薄膜成形(例如压延或拉伸)。由于这些方法为本领域的技术人员所熟悉，在本文为简洁起见将其说明省略。
薄膜也可以为由共挤出或层压制备的多层薄膜。例如，多层聚合物薄膜可包括两层或更多层，包括最外结构或滥用层、内部阻挡层和最内层，最内层与包装的预定内容物接触和相容，并且能够形成包封被容纳在包装内的产品所需的密封。也可以使含纳米TiO2的薄膜粘合-层压到由以下材料制成或与以下材料共挤出的薄膜或层，如尼龙、聚丙烯、聚乙烯、离聚物、另一种乙烯共聚物、聚酰胺、聚对苯二甲酸乙二醇酯、聚苯乙烯和/或聚乙烯-乙烯醇。例如，多层薄膜可包括纳米TiO2组合物作为粘结(粘合或密封)层，并且以聚乙烯作为最外层。
可用薄膜制造容器，所述容器为用于包装的成形制品，并且包括盒、泡罩包装、瓶、盘、杯和其它容器。可将容器用于饮料、食品(例如肉类、乳酪、鱼、禽肉、坚果和其它食用产品)、香料、调味品、个人护理产品、芳香剂、电子元件、医疗器械、药液、药物和化妆品。
玻璃层压材料可包括至少一片用薄膜层或中间层粘合的玻璃，所述薄膜层或中间层由包含PVB和纳米TiO2的组合物制成。玻璃层压材料可任选地包括其它层间材料，如在透明层压材料中作为中间层已知和常规使用的那些层间材料。玻璃层压材料可为玻璃层压到玻璃(玻璃/玻璃)、玻璃/塑料、塑料/塑料或其它多层的任何组合。玻璃或塑料或玻璃和塑料的其它组合可包括金属、木或石。可使用粘合剂层。此类玻璃层压材料非常有用，如制造柜橱中的装饰性制品、柜橱门、桌面、桌布、台面、进口门、门板、浴室门、地板砖、天花板砖、墙面砖、楼梯踏步板、墙后防溅板、器具门、器具面、房间屏风、搁板和柜橱。例如通过使玻璃片和另一玻璃片或塑料片或薄膜层叠在一起在热和压力下形成层压材料，或通过共挤出PVB与填料和增塑剂，可制造这种玻璃层压材料。挤出可在约175℃至约245℃的温度进行。可将挤出的片材淬火或冷却到低于约40℃并且高于约10℃。
提供以下实施例用于进一步说明，不应将这些实施例解释为对本发明范围的非常限制。
实施例1
本实施例通过将纳米TiO2粉末加入双螺杆挤出机来制备。纳米TiO2购自Sachtleben Chemie Gmbh，Duisburg，Germany，具有约15nm的平均微晶大小，并且用Al2O3和硬脂酸涂覆。制备10％重量TiO2于15％重量甲基丙烯酸/乙烯离聚物(有58％羧酸根被中和)中的母料，然后通过与更多离聚物共混冲淡(稀释)到0.5、1和2％重量样品。将样品收集为粒料，然后吹成薄膜。检测薄膜雾度(ASTM-D-1003方法)和紫外吸收度(表1)。雾度由Gardner Hazemeter Model UX10检测，在ASTM标准中将雾度定义为由表面反射检视，造成物体对比度表观减少的在样品的光泽表面的光线n-散射。
表1
    ％TiO2 ％吸收度，低于350nm     雾度
    00.512     04580100     1.612.638.533.0
实施例2
本实施例通过将10％重量纳米TiO2加入15％重量甲基丙烯酸/乙烯共聚物作为母料来制备。然后用ZnO处理母料以中和58％羧酸，并如实施例1用更多离聚物冲淡到0.5和1％重量样品。然后将样品吹成薄膜，并且如实施例1所公开检测薄膜的雾度。结果显示于表2中。
表2
    TiO2(％)     0     0.5     1
    雾度     2.4     11.3     17.5
实施例3
制备本实施例中的材料是通过在聚合过程中将纳米TiO2的浆料直接注入高压釜反应器，一种高压试验装置，以制备含纳米TiO2的乙烯-甲基丙烯酸共聚物。将所制备的含纳米TiO2的聚合物处理成母料，并用不含纳米TiO2的乙烯-甲基丙烯酸共聚物稀释成0.5和1％重量(纳米TiO2)样品。
表3
    TiO2(％)     0     0.5     1
    雾度     1.9     7.5     11.8

Claims (10)

1.一种组合物，所述组合物包含或制备自纳米TiO2、第一聚合物和任选的第二聚合物，其中所述第一聚合物为聚酯、聚乙烯醇缩丁醛、乙烯共聚物、乙烯共聚物的离聚物或其两种或多种的组合，并且所述乙烯共聚物包含衍生自乙烯和极性单体的重复单元。
2.权利要求1的组合物，其中所述极性单体为丙烯酸、甲基丙烯酸、烷基丙烯酸、烷基甲基丙烯酸、丙烯酸烷基酯、甲基丙烯酸烷基酯、烷基丙烯酸烷基酯、烷基甲基丙烯酸烷基酯、丙烯酸盐、甲基丙烯酸盐、烷基丙烯酸盐、烷基甲基丙烯酸盐或其两种或多种的组合。
3.权利要求1或2的组合物，其中所述乙烯共聚物进一步包含衍生自共聚单体的重复单元，所述共聚单体包括一氧化碳、二氧化硫、丙烯腈、马来酸酐、马来酸二酯、(甲基)丙烯酸、马来酸、马来酸单酯、衣康酸、富马酸、富马酸单酯、这些酸的盐、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯和缩水甘油基乙烯基醚及其两种或多种的组合。
4.权利要求1、2或3的组合物，其中所述极性单体为丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯或其两种或多种的组合，并且优选为甲基丙烯酸或丙烯酸或两者。
5.权利要求4的组合物，所述组合物包含或制备自纳米TiO2和乙烯共聚物或乙烯共聚物的离聚物，并且所述纳米TiO2任选以0.5至10％重量或0.5至10％重量存在于组合物中。
6.一种成形制品，所述成形制品包含或制备自权利要求1、2、3、4或5的组合物。
7.权利要求6的制品，所述制品为薄膜。
8.权利要求6或7的制品，其中所述第一聚合物为聚乙烯醇缩丁醛，并且所述制品为玻璃层压材料。
9.一种容器，所述容器包括或制备自权利要求7的薄膜，并且优选为瓶。
10.权利要求9的容器，所述容器包含饮料、食品、香料、调味品、个人护理产品、芳香剂、电子元件、医疗器械、药液、药物、化妆品或其两种或多种的组合。
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US7265176B2 (en) 2007-09-04
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