CN102802947B - 具有改进氧反应性的聚酰胺-聚二烯共混物 - Google Patents
具有改进氧反应性的聚酰胺-聚二烯共混物 Download PDFInfo
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- CN102802947B CN102802947B CN201080026351.XA CN201080026351A CN102802947B CN 102802947 B CN102802947 B CN 102802947B CN 201080026351 A CN201080026351 A CN 201080026351A CN 102802947 B CN102802947 B CN 102802947B
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Classifications
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- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本申请公开了聚酰胺-聚二烯共混物用于在离子聚酯增容剂存在下改进氧反应性的用途。
Description
优先权和交叉引用
本申请要求于2009年6月11日提交的美国临时专利申请号61/186271的优先权，其教导以其整体结合到本文中。
背景
本领域公知离子增容剂用于在PET阻透瓶(barrier bottle)中增容尼龙的用途。本领域公知钴和尼龙的用途，以及离子增容剂、钴和尼龙在阻透瓶中的用途。
本领域还公知，在与PET反应的聚丁二烯存在下钴盐用于产生阻透瓶的用途。
WO0183318描述了尼龙与聚丁二烯反应，以产生待与PET和钴共混的除氧化合物。
然而，从2009年2月25日在Research Disclosures电子版发表的“Evaluation of polybutadiene scavengers and nylon scavengers in thepresence of sulfoisopthalic acid(在磺基间苯二甲酸存在下评估聚丁二烯清除剂和尼龙清除剂)”中得知：当离子增容剂存在时，聚酰胺钴盐混合物对与氧反应的诱导期间非常长。还公知的是，在钴盐和离子增容剂存在下，聚丁二烯不能与氧充分反应。依据此公开，SIPA淬灭氧与聚丁二烯的反应以及氧与MXD6尼龙的反应。
因此，存在需要当离子增容剂存在时以较快诱导时间与氧充分反应的体系的需要。
概述
本说明书公开了包含聚酯、离子增容剂、聚酰胺、聚二烯化合物和过渡金属化合物的组合物。还公开了离子增容剂可源自磺基间苯二甲酸或它的二甲基酯的盐。还公开了聚酰胺与聚二烯化合物的比率在4∶1和1000∶1的范围。聚二烯可具有官能团并且这些官能团中的至少一些与聚酰胺反应。聚酯可按总组合物约9至99.8重量百分比的范围存在。
还公开了过渡金属化合物相对聚酰胺加上聚二烯化合物可按约100至15,000ppm金属的范围存在并且过渡金属化合物可为钴化合物。
附图简述
图1是显示本发明各种实施方案和对照制成的包装(package)的氧进入量的图表。
图2是显示本发明各种实施方案和对照制成的包装的氧进入量的图表。
详述
本文描述的是改进的聚酯-聚酰胺组合物，所述组合物在聚酯和离子增容剂存在下通过混合聚酰胺均聚物、共聚物或其共混物以及可氧化聚二烯或聚醚来制备。优选地组合物还包含金属羧酸盐催化剂。聚二烯还可被认为是来自双烯类单体的化合物。
优选的聚酰胺均聚物或共聚物选自数均分子量为约2,000至约100,000的脂族聚酰胺和脂族/芳族聚酰胺。可用于制备聚酰胺的通用方法为本领域熟知。用于制备聚酰胺的有用二酸包括二羧酸，其由通式HOOC-Z-COOH表示，其中Z代表含有至少2个碳原子的二价脂烃基，例如己二酸、癸二酸、十八烷二酸、庚二酸、辛二酸、壬二酸、十二烷二酸和戊二酸。二羧酸可为脂族酸或芳族酸例如间苯二甲酸和对苯二甲酸。用于制备聚酰胺的合适二胺包括具有式H2N(CH2)n NH2的那些，其中n为1-16的整数值并且包括以下化合物例如三亚甲基二胺、四亚甲基二胺、五亚甲基二胺、六亚甲基二胺、八亚甲基二胺、十亚甲基二胺、十二亚甲基二胺、十六亚甲基二胺、芳族二胺例如对-苯二胺、4，4′-二氨基二苯醚、4，4′-二氨基二苯砜、4，4′-二氨基二苯甲烷、烷基化二胺例如2，2-二甲基五亚甲基二胺、2，2，4-三甲基六亚甲基二胺和2，4，4三甲基五亚甲基二胺以及脂环族二胺例如二氨基二环己基甲烷和其它化合物。其它有用的二胺包括七亚甲基二胺、九亚甲基二胺等。
有用的脂族聚酰胺均聚物包括聚(4-氨基丁酸)(尼龙4)、聚(6-氨基己酸)(尼龙6，也称为聚(己内酰胺))、聚(7-氨基庚酸)(尼龙7)、聚(8-氨基辛酸)(尼龙8)、聚(9-氨基壬酸)(尼龙9)、聚(10-氨基癸酸)(尼龙10)、聚(11-氨基十一酸)(尼龙11)、聚(12-氨基十二酸)(尼龙12)、聚(己二酰己二胺)(尼龙6，6)、聚(癸二酰己二胺)(尼龙6，10)、聚(庚二酰庚二胺)(尼龙7，7)、聚(辛二酰辛二胺)(尼龙8，8)、聚(壬二酰己二胺)(尼龙6，9)、聚(壬二酰壬二胺)(尼龙9，9)、聚(壬二酰癸二胺)(尼龙10，9)、聚(己二酰丁二胺(尼龙4，6)、己内酰胺/己二酰己二胺共聚物(尼龙6，6/6)、己二酰己二胺/己内酰胺共聚物(尼龙6/6，6)、己二酰丙二胺/壬二酰己二胺共聚物(尼龙三甲基6，2/6，2)、己二酰己二胺-壬二酰己二胺己内酰胺共聚物(尼龙6，6/6，9/6)、聚(四亚甲基二胺-共-草酸)(尼龙4，2)、正-十二烷二酸和六亚甲基二胺的聚酰胺(尼龙6，12)、十二亚甲基二胺和正-十二烷二酸的聚酰胺(尼龙12，12)以及它们的共混物和共聚物和此处未具体限定的其它聚酰胺。
这些聚酰胺中，优选的聚酰胺包括聚己内酰胺(其通常还称为尼龙6)和聚己二酰己二胺(其通常还称为尼龙6，6)以及它们的混合物。在这些当中，聚己内酰胺是最优选的。
用于实施本发明的聚酰胺可获自市售来源或依据公知制备技术而制备。例如，聚(己内酰胺)可获自商标为CAPRON的HoneywellInternational Inc.，Morristown，N.J。用作本发明第一聚酰胺的合适CAPRON变体包括CAPRON8200尼龙、甲酸粘度(FAV)为75的平衡尼龙6、CAPRON1767尼龙、FAV为35的平衡尼龙6和CAPRON8224HSL尼龙、FAV为60的热稳定润滑性尼龙6。用作第二聚酰胺的合适CAPRON尼龙变体包括CAPRON1250尼龙、FAV为60并且具有70-78毫当量每克末端氨基的胺封端尼龙6。
脂族/芳族聚酰胺实例包括聚(对苯二甲酰2，2，2-三甲基己二胺)(poly(2，2，2-trimethyl hexamethylene terephthalamide))、聚(己二酰间苯二甲胺)(MXD6)、聚(己二酰对苯二甲胺)、聚(对苯二甲酰己二胺)(尼龙6，T)、聚(间苯二甲酰己二胺)(尼龙6，I)、聚(对苯二甲酰十二烷二胺)、聚酰胺6T/6I、聚(四亚甲基二胺-共-间苯二甲酸)(尼龙4，I)、聚酰胺6/MXDT/I、聚酰胺MXDI、己二酰己二胺/间苯二甲酰己二胺(尼龙6，6/6I)、己二酰己二胺/对苯二甲酰己二胺(尼龙6，6/6T)以及此处未具体限定的其它脂族/芳族聚酰胺。
还可以使用两种或更多种脂族/芳族聚酰胺和/或脂族聚酰胺的共混物。脂族/芳族聚酰胺可通过公知制备技术而制备或可获自市售来源。其它合适的聚酰胺可参见美国专利号4,826,955和5,541,267。
本发明的组合物还包含作为除氧剂的官能的、尼龙反应性的、可氧化聚二烯或聚醚。这些是相容并可均一分散于聚酰胺的低分子量小颗粒。优选地尼龙反应性可氧化聚二烯或聚醚包含环氧或酐官能性使得其与聚酰胺的羧基或氨基末端基团反应。聚二烯或聚醚中的官能性还可与聚酰胺主链中的酰胺基团反应。该官能性可为主链的侧基或在聚二烯或聚醚的链末端。优选官能聚二烯是官能聚链二烯寡聚物，其可具有如下一般主链结构
其中R1、R2、R3和R4可相同或不同并且可选自氢(--H)或任何低级烷基(甲级、乙基、丙基、丁基等)。R2和R3还可为氯(--Cl)基团。说明性的主链结构是聚丁二烯(1，4或1，2或两者的混合物)，聚异戊二烯(1，4或3，4)、聚2，3-二甲基丁二烯、聚氯丁二烯、聚2，3-二氯丁二烯、聚丙二烯、聚1，6-己三烯等。
作为合适除氧剂的官能的可氧化聚二烯的具体非限制性实例包括环氧官能化的聚丁二烯(1，4和/或1，2)、马来酸酐接枝或共聚化的聚丁二烯(1，4和/或1，2)、环氧官能化聚异戊二烯和马来酸酐接枝或和共聚化的聚异戊二烯。
作为除氧剂的官能的、可氧化聚醚的具体非限制性实例包括胺、环氧或酐官能化聚环氧丙烷、聚环氧丁烷(2，3或1，2)和聚氧化苯乙烯。优选除氧剂是环氧官能的聚丁二烯寡聚物。除氧剂作为大量小颗粒存在于聚酰胺组合物中。官能聚二烯或聚醚寡聚物的数均分子量(Mn)的范围可为500至7,000，优选约750至约3000并且最优选约1000至约2000。
其以与所述聚酰胺约0.1％至约10％重量聚酰胺的比率存在，优选相对于聚酰胺重量的约1％至约10％并且更优选约0.5％至约5％。官能的、可氧化聚二烯或聚醚为颗粒的形式，其平均粒度的范围为约10nm至约1000nm，其中颗粒基本均一分布于聚酰胺中。优选地，粒度应介于10nm和400nm之间，更优选10nm至300nm，甚至更优选10nm至200nm，最优选5nm至150nm。
组合物可包含聚酰胺和聚二烯或聚醚的共混物，或聚酰胺与可氧化聚二烯或聚醚的反应产物。
组合物中聚酰胺与二烯的比例为约4∶1至约1000∶1重量，优选地约10∶1至约100∶1并且更优选约18∶1至约49∶1。
优选地组合物还包含金属脂肪酸盐催化剂例如低分子量金属羧酸盐催化剂。合适的金属脂肪酸盐催化剂具有反离子，其为醋酸根、硬脂酸根、丙酸根、己酸根、辛酸根、苯甲酸根、水杨酸根和肉桂酸根或它们的组合。优选地金属脂肪酸盐催化剂是钴、铜或钌，醋酸盐、硬脂酸盐、丙酸盐、己酸盐、辛酸盐、苯甲酸盐、水杨酸盐和肉桂酸盐或它们的组合。优选金属羧酸盐是羧酸钴、羧酸锰、羧酸钌或羧酸铜。在这些当中，更优选的是羧酸钴或羧酸锰并且最优选的是羧酸钴。其在整体组合物中存在量为聚酰胺重量加上二烯重量的约0.0001％至约10％重量，优选为聚酰胺重量加上二烯重量的约0.001％至约5％重量，更优选为聚酰胺重量加上二烯重量的约0.005％至约0.5％重量。最优选范围是聚酰胺重量加上二烯重量的约0.01％至约0.1％重量。
本发明的聚酯可通过本领域熟知的聚合方法制备。由于工业总在不断发展，聚酯可通过尚未公知的发明或创造而制备。制备聚酯聚合物和共聚物的传统方法是熔融聚合，这涉及二醇与二羧酸或其相应酯的反应。还可使用多种二醇和二酸的各种共聚物。
通常，例如可通过熔融聚合制备聚酯聚合物和共聚物，这涉及二醇与二羧酸或其相应酯的反应。还可使用从多种二醇和二酸的使用得到的各种共聚物。包含仅一个化学组成重复单元的聚合物是均聚物。在同一大分子中含有两个或更多个化学上不同重复单元的聚合物被称为共聚物。重复单元的多样性取决于存在于起始聚合反应中不同类型单体的数目。就聚酯而言，共聚物包括将一种或更多种二醇与一种或多种二酸反应，并且有时被称为三元共聚物。
如上文所述，合适的二羧酸包括含约4至约40个碳原子的那些。具体的二羧酸包括但不限于对苯二甲酸、间苯二甲酸、萘2，6-二甲酸、环己烷二甲酸、环己烷二乙酸、二苯基-4，4′-二甲酸、1，3-亚苯基二氧基二乙酸、1，2-亚苯基二氧基二乙酸、1，4-亚苯基二氧基二乙酸、琥珀酸、戊二酸、己二酸、壬二酸、癸二酸等。具体酯类包括但不限于邻苯二甲酸酯和萘二甲酸二酯。如后面所解释的，磺基间苯二甲酸金属盐例如锂、钠和钙也是合适的二羧酸。
这些酸或酯类可与下列物质反应：优选具有约2至约24个碳原子的脂族二醇，具有约7至约24个碳原子的脂环族二醇，具有约6至约24个碳原子的芳族二醇，或具有4至24个碳原子的二醇醚。合适的二醇包括但不限于乙二醇、1，4-丁二醇、1，3-丙二醇、1，6-己二醇、1，4-环己烷二甲醇、二乙二醇、间苯二酚、1，3-丙二醇和氢醌。
有用的聚酯是可结晶聚酯，其超过85％的酸单元源自对苯二甲酸。通常认为，共聚单体改性超过15％的聚酯难以结晶。然而，本发明包括可结晶并且具有超过15％共聚单体含量的聚酯。本发明还包括不结晶和/或具有超过15％共聚单体含量的聚酯。
还可使用多官能共聚单体，通常量为约0.01至约3摩尔百分比。合适的共聚单体包括但不限于偏苯三酸酐、三羟甲基丙烷、均苯四酸二酐(PMDA)和季戊四醇。还可使用形成聚酯的多元酸或多元醇。聚酯和共聚酯的共混物也可用于本发明。
一种合适的可结晶聚酯是聚对苯二甲酸乙二酯(PET)或共聚物，所述共聚物是由间苯二甲酸酯磺酸锂(lithium sulfoisophthalate)的二酯或二羧酸在酸或它们的二酯与乙二醇约1∶1化学计量反应中形成的间苯二甲酸酯磺酸锂改性的共聚物。共聚物也是合适的。具体的感兴趣共聚物和三元共聚物是可结晶聚酯，包括间苯二甲酸酯磺酸锂联合间苯二甲酸或它的二酯、2，6萘二甲酸或它的二酯、和/或环己烷二甲醇。基于聚合物中的酸部分，间苯二甲酸酯磺酸锂最佳水平在0.1和2.0摩尔百分比范围内。尽管大于2.0摩尔百分比对增加聚酯中聚酰胺的分散没有损害，但大于2.0摩尔百分比只取得少许改进或没有额外的改进。
磺酸盐特别例如间苯二甲酸酯磺酸锂(源自5-磺基间苯二甲酸单锂盐)的量，为约0.05至10.0摩尔百分比，其中优选量的范围为约0.1至约2.0摩尔百分比，更优选的范围为约0.1至约1.1摩尔百分比并且甚至更优选为约0.18至约0.74，最优选范围为约0.18至约0.6摩尔百分比。
羧酸或酯类与二醇的酯化反应或缩聚反应通常在催化剂存在下发生。合适的催化剂包括但不限于氧化锑、三乙酸锑、乙二醇锑、有机镁、氧化锡、醇化钛、二月桂酸二丁基锡和氧化锗。这些催化剂可与锌、锰或镁的乙酸盐或苯甲酸盐联合使用。含有锑的催化剂为优选的。
另一种优选的基础聚酯(base polyester)是聚对苯二甲酸丙二酯(PTT)。其可以例如通过使1，3-丙二醇与至少一种芳族二酸或其烷基酯反应制备。优选的二酸和烷基酯包括对苯二甲酸(TPA)或对苯二甲酸二甲酯(DMT)。因此，所述PTT优选包含至少约80摩尔百分比的TPA或DMT。可在这样的聚酯中共聚的其他二醇包括，例如乙二醇、二乙二醇、1，4-环己烷二甲醇和1，4-丁二醇。除了离子增容剂例如磺基间苯二甲酸之外，可同时使用以制备共聚物的其他芳族和脂族酸包括，例如间苯二甲酸和癸二酸。
用于制备PTT的优选的催化剂包括钛和锆化合物。合适的催化钛化合物包括但不限于，钛烷基化物和它们的衍生物、钛络盐、与羟基羧酸的钛络合物、二氧化钛-二氧化硅共沉淀物和水合含碱二氧化钛。具体实例包括钛酸四-(2-乙基己基)酯、钛酸四硬脂基酯、二异丙氧基-双(乙酰丙酮)合钛(diisopropoxy-bis(acetyl-acetonato)-titanium)、二-正-丁氧基-双(三乙醇氨基)合钛(di-n-butoxy-bis(triethanolaminato)-titanium)、单乙酰基钛酸三丁基酯、单乙酰基钛酸三异丙基酯、四苯甲酸钛酸酯、碱性钛草酸盐和丙二酸盐、六氟钛酸钾和与酒石酸、柠檬酸或乳酸的钛络合物。优选的催化钛化合物为四丁醇钛(titanium tetrabutylate)和四异丙醇钛(titaniumtetraisopropylate)。还可使用相应的锆化合物。
聚酯还可包含少量的含磷化合物，例如磷酸酯和亚磷酸酯，和催化剂例如钴化合物，其倾向于赋予蓝色调。此外，在连续基质中可容忍少量其它聚合物例如聚烯烃。亚磷酸三乙基酯是亚磷酸酯的实例。
熔融聚合完成后，将聚合物制成例如膜或部件(part)的形式或丝条化(strand)并切成较小切片例如粒料。通常随后使聚合物结晶并且进行固相(固态)聚合(SSP)步骤，以达到制备某些制品例如瓶必需的特性粘度。结晶和聚合可在间歇式系统中滚筒干燥器反应器进行。固相聚合可在同一滚筒干燥器中继续进行，在干燥器中，使聚合物经受高真空以提取聚合副产物。
或者，结晶和聚合可在连续的固相聚合过程中完成，其中聚合物在每一容器中的预定处理后从一个容器流至另一个容器。结晶条件与聚合物的结晶和粘性趋势有关。然而，优选温度为约100℃至约235℃。在可结晶聚酯的情况下，固相聚合条件通常比聚合物熔点低10℃。在非结晶聚酯的情况下，固相聚合温度通常比聚合物开始自身粘附的温度低约10℃。对于可结晶聚合物，尽管传统固相聚合温度为约200℃至约232℃，许多操作温度均为约215℃至约232℃。本领域技术人员将意识到，最佳固相聚合温度是聚合物特异性的并且取决于产物中共聚物的类型和量。然而，最佳固相聚合条件的确定常常在工业上完成并且无需过度实验可容易地进行。
固相聚合可进行足够的时间以使特性粘度提高至所需水平，这将取决于应用。对于典型的瓶应用，优选特性粘度(I.V.)为约0.65至约1.0分升/克。达到此I.V.所需的时间为约8至约21小时。
在本发明的一个实施方案中，本发明的可结晶聚酯可包含再循环聚酯或来自再循环聚酯的材料，例如聚酯单体、催化剂和寡聚物。
术语可结晶的意指聚对苯二甲酸乙二酯通过取向或热诱导的结晶性可变成半结晶的。熟知的是没有塑料是完全结晶的并且更准确地是将结晶形式描述为半结晶的。术语半结晶的是现有技术中熟知的并且意在描述展现出具有结晶区的明显特征(sharp features)和无定形区域特有的弥散特征(diffuse features)的X-射线图案的聚合物。本领域中还熟知半结晶应与纯晶体和无定形状态区分开。
不能变成晶体的对苯二酸酯聚合物是非可结晶聚酯并且认为其也适用于本发明。
聚酰胺的优选量为1-15份/100份聚酯加上聚酰胺，优选3-8份/100份聚酯加上聚酰胺，最实用的是3-7份聚酰胺/100份聚酯加上聚酰胺。
还优选的是，聚酰胺含有稳定剂例如次磷酸钠或其它无机亚磷酸盐稳定剂。稳定剂的水平基于聚酰胺应介于10和500ppm之间。然而，聚酰胺还可不含亚磷酸盐稳定剂。
优选地，离子增容剂源自已反应到聚合物链中的共聚单体。为成为共聚单体，离子增容剂与至少一个端基官能化，这使得离子增容剂与组合物中其它聚合物或聚合物共聚单体的至少一种反应。
就聚酯而言，这些可为用于产生聚酯离聚物的极性共聚单体，就聚酰胺而言，离子增容剂可为用于产生聚酰胺离聚物的极性共聚单体。这些共聚单体的实例是描述在美国专利号6,500,895(B1)中的各自磺酸根的一价和/或二价盐，该专利的教导结合到本文中。还包括一价或二价金属盐，这可参见日本专利申请0 3281246 A中下式所描述的。
描述各种金属盐的一种方式是使用术语官能化金属磺酸盐来描述R-SO3M形式的化合物，其中M是金属离子并且R是具有至少一个官能团的脂族、芳族或环状化合物，其允许官能化金属盐与聚酯或聚酰胺或它们相应的单体或寡聚物反应，其中M表示金属离子。包括在本发明中的官能化金属磺酸盐是磺化共聚单体的锂、钠和钾盐，包括脂族和芳族醇、羧酸、二醇、二羧酸和多官能醇、羧酸、胺和二胺。相反，非官能的金属磺酸盐是R-SO3M的那些，并且R不具有官能团。因此，短语金属磺酸盐是指官能的和非官能的金属磺酸盐。其一个例子是磺化的聚苯乙烯或聚烯烃，其已知在聚酯-聚酰胺体系中充当离子增容剂。
一般而言，离子增容剂从X-R形式的官能化形式加入，其中X是醇、羧酸或环氧，最优选二羧酸或二醇，并且R是-SO3M、-COOM、-OM、-PO3(M)2，M是+1或+2价态的金属，其可以选自Li、Na、Zn、Sn、K和Ca，并且X-R被共聚到聚酯聚合物中以改变界面张力。相对于聚合物组合物中相应二羧酸或二醇摩尔总数，所需的X-R的量将超过0.01摩尔百分比。X-R可能包括二醇或二羧酸两者。在该情形下，摩尔百分比基于相应二醇、二羧酸或聚合物重复单元的摩尔总数。
官能化的离子增容剂可含有2个或更多个R基团。R直接结合到X的芳环上，其可以是二醇、二羧酸、或侧链例如亚甲基。
其中R是-SO3M、-COOM、-OM、-PO3(M)2，M表示+1或+2价态的金属，其可选自Li、Na、Zn、Sn、Ca和K。
由X表示的二羧酸可以各自为邻、间或对位。它们包括例如芳族二羧酸，例如对苯二甲酸、间苯二甲酸、邻苯二甲酸、萘二甲酸、二苯醚二羧酸、二苯基-4，4-二羧酸等。
X还可以是脂族的。在该情形下，脂族二羧酸例如草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸等是合适的。可使用环脂族二羧酸例如环己烷二甲酸和这些中的一种或多种。还包括的是羟乙基磺酸。还特别考虑二羧酸的混合物。
X还可表示醇，优选以下结构的二醇：
其中R是-SO3M、-COOM、-OM、-PO3(M)2，其中M是+1或+2价态的金属，其可以选自Li、Na、Zn、Sn、K和Ca。
由X表示的二醇还可以是脂族二醇例如乙二醇、1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、1，9-壬二醇、二乙二醇、丙二醇和环脂族二醇例如环己烷二醇、环己烷二甲醇，并且可以组合使用一种或多种。在这些当中，优选乙二醇、二乙二醇和环己烷二醇。
其他可用的官能化离子增容剂包括羟基封端的聚醚例如聚乙二醇(Carbowax)和环状酰胺例如乙氧基化的二甲基乙内酰脲。另外，聚酯可以与环氧封端的化合物，包括环氧封端的聚醚反应以产生与聚合物相连的聚醚侧链。
尽管许多金属起作用并且现有技术教导优选双金属，但出乎意料地发现，一价金属锂比钠的性能好得多。事实上，锂盐产生具有低于先前测量水平的平均域(average domain)的分散体。如下面所述，没有钴化合物的间苯二甲酸酯磺酸锂具有比在钴盐存在下与相同量的MXD6共混的间苯二甲酸酯磺酸钠更好的颜色，如在WO2005/023530 A1中所述。
间苯二甲酸磺酸锂(lithium sulfoisophthalic acid)的分子结构是：
间苯二甲酸磺酸锂(LiSIPA)或磺酸锂盐改性的间苯二甲酸。
从以上图示可以清楚地看出，间苯二甲酸磺酸锂是磺酸锂并且包括间苯二甲酸酯磺酸锂。该间苯二甲酸酯磺酸锂是指看上去引入聚合物链中的化合物。它也已知为间苯二甲酸磺酸锂的重复单元。间苯二甲酸酯磺酸锂因此是少一个水分子的间苯二甲酸磺酸锂，其中从一个羧基端基除去一个羟基和从另一个羧基端基中除去氢。该分子然后连接于聚合物主链中的一个或更多个单体(R1和R2)。
该磺酸盐，在这种情况下为间苯二甲酸酯磺酸锂，是在两个R基团之间的分子。再次，R可为相同的单体，对于PET的情况，R有可能与已反应到聚合物链中的乙二醇部分相同。
在盐形式中，间苯二甲酸酯磺酸锂的二羧酸、二酯或预反应的低分子量寡聚物例如双羟乙基酯是优选的。还有可能的是，离子增容剂，在这种情况下为磺酸锂，同样以二醇形式存在。可能的备选物是在侧链的末端有磺酸酯基的乙二醇。甚至已建议将磺酸酯基置于聚酯分子的末端。这可通过聚酯与苯甲酸的磺化盐或其它单官能物质如羟乙基磺酸，在熔融反应器中或在挤出机中进行反应或共聚来实现。
为了反应到聚合物中，改性剂必须具有至少一个官能团。这些官能团是羧酸(-COOH)、醇(-OH)、羧酸的酯、环氧端基(epoxytermination)、二胺或胺端基。
因为高I.V.聚酯具有两个官能端基，当与不含金属磺酸盐的聚酰胺和聚酯共混时在其主链中含有金属磺酸盐的高I.V.聚酯是离子增容剂。如果该高I.V.聚酯的两端都封端，则它被认为是非官能化的离子增容剂。
非官能化离子增容剂是含有极性基团特别为锂盐、但不具有允许该离子增容剂与聚酯或聚酰胺反应的任何官能端基的那些化合物。磺化聚苯乙烯的锂盐是一个实例。在该三组分体系中，离子增容剂的摩尔百分比基于聚酯的全部酸基团的摩尔百分比。
正如下面所教导，聚合物优选用离子增容剂改性。该改性是通过离子增容剂共聚合到聚合物链中来实现的。
组合物可按双组分的形式存在。在双组分形式中，离子增容剂被引入聚酯主链中使得该聚酯同时成为聚酯和离子增容剂。因此该单个聚酯分子含有权利要求的两种要素-聚酯和离子增容剂。
组合物也可按两种以上组分存在。例如，不含离子增容剂的聚酯，含离子增容剂的聚酯和聚酰胺。
减少界面张力所需要的离子增容剂的水平是相对于在组合物中各自酸或二醇部分的总摩尔数的0.01摩尔百分比-15摩尔百分比。例如，典型的均聚物聚酯具有100摩尔百分比的来源于对苯二甲酸的对苯二甲酸酯和几乎100摩尔百分比的来源于乙二醇的亚乙基，其中剩余的二醇来源于在制造过程中原位获得的二乙二醇的二亚乙基。100摩尔的具有5摩尔百分比的离子二羧酸共聚单体(例如间苯二甲酸磺酸锂)的聚合物将含有95摩尔的来源于对苯二甲酸的对苯二甲酸酯，5摩尔的间苯二甲酸酯磺酸锂和约100摩尔的来源于乙二醇的亚乙基。类似地，有利的是使用另一种共聚单体如间苯二甲酸。例如，如果用2摩尔的间苯二甲酸酯替代2摩尔的对苯二甲酸酯，则产生具有2摩尔间苯二甲酸酯、93摩尔对苯二甲酸酯、5摩尔磺基间苯二甲酸酯和约100摩尔亚乙基的聚合物，以构成100摩尔的聚合物重复单元。
在三组分共混物体系中，酸的摩尔数是在改性聚合物中酸的摩尔数加上在相容的未改性聚合物中酸的摩尔数。例如，如果有两种聚酯存在，一种含有磺基间苯二甲酸酯，和另一种不含，则磺基间苯二甲酸酯的摩尔百分比将是磺基间苯二甲酸酯的摩尔数除以两种聚酯的加在一起的酸部分的摩尔数。
还熟知的是，二乙二醇是在聚酯的制造过程中原位形成的并且二醇来源的重复单元的总摩尔数的约1-3％将是源自二乙二醇的二亚乙基。因此，聚酯组合物通常为97摩尔百分比的亚乙基和3摩尔百分比的二亚乙基。
凭经验确定所需要的离子增容剂的量。通常，需要少量并且接近一个临界量，超过该临界量时附加的量几乎没有或没有影响。与其它盐不同，锂盐尤其显示出约在0.3-1.0摩尔/每100摩尔聚合物重复单元之间的最佳水平。这也可表示为0.2-1.0摩尔百分比的该锂盐连接于它之上的酸或二醇部分。
用于本发明中的离子增容剂改性的聚酯可通过聚合方法来制备。可将传统技术分为酯，酸和改性工艺。在该酯工艺中，羧酸或酸的二甲酯与一种或多种二醇在热的作用下进行反应，除去甲醇，得到该酸的双羟乙基酯。双羟乙基酯然后以其液态进行聚合，该聚合是通过让该物质接受真空和加热以除去二醇并且提高分子量来实现的。目标聚合物与离子增容剂的通常工艺将从下面这些比率开始：98摩尔的对苯二甲酸二甲酯、2摩尔的磺基间苯二甲酯的二甲基钠盐和220摩尔的二醇(通常为乙二醇)。在220摩尔的二醇当中，120是过量的，在处理过程中将其除去。应指出的是，有可能获得双-(羟乙基)酯或二甲酯形式的磺化共聚单体。
为了清楚起见，短语“与至少X％的特定酸共聚合”指化合物被认为是聚合物的酸基团一部分，例如对苯二甲酸或间苯二甲酸。它为确定使用多少摩尔的化合物提供参考。该短语并不是指化合物必须作为酸被添加到该方法中。例如，间苯二甲酸磺酸锂能够作为具有两个羧基端基的酸、作为羧酸的二甲酯、作为二甲酯的双羟基酯、作为二醇酸聚合物的极低分子量寡聚物(其中酸部分至少部分地是间苯二甲酸酯磺酸盐)、或作为二醇共聚合到聚对苯二甲酸乙二酯中。
短语“酸的共聚合盐”不应该将权利要求限于仅仅使用酸形式，而应认为该化合物是聚合物中酸衍生基团中的一种。
短语“与......共聚合”是指化合物已经与该聚合物进行化学反应，如在聚合物链中或作为侧基。例如，与间苯二甲酸酯磺酸盐共聚合的、或通过将至少0.01摩尔百分比磺基间苯二甲酸酯共聚合到聚酯中被改性的聚酯，是指磺基间苯二甲酸酯用至少一个化学键键接于聚合物上，包括键接于聚合物链中。该短语不关注该物质如何引入到聚合物中。与间苯二甲酸酯磺酸锂共聚合的聚酯或通过将至少0.01摩尔百分比间苯二甲酸酯磺酸锂共聚合到聚酯中而改性的聚酯，是指含有间苯二甲酸酯磺酸锂的聚酯，不论该间苯二甲酸酯磺酸锂是否通过使用(但不限于)以下物质引入：间苯二甲酸磺酸锂、苯甲酸磺酸锂、间苯二甲酸磺酸锂的二甲酯、苯甲酸磺酸锂的甲基酯、间苯二甲酸酯磺酸锂的二醇、磺基羟基苯锂、羟基苯磺酸的锂盐、或含有间苯二甲酸酯磺酸锂的寡聚物或聚合物。
尽管前述段落使用锂作为例子，但对于钠和其他金属盐也适用。应该注意的是，在本说明书中对于锂的提及不应该将权利要求仅仅限于锂盐。尽管锂是优选的金属，但是在规定的氨基与酸端基比率内聚酰胺的使用已经用其它金属有效地证明，正如在实施例中所述。
短语“和衍生物”和“和其衍生物”是指可共聚合到聚合物中的界面还原剂的各种官能化形式。例如，间苯二甲酸酯磺酸锂“和其衍生物”一起是指并且不限于间苯二甲酸磺酸锂、间苯二甲酸磺酸锂的二甲基酯、间苯二甲酸磺酸锂的双羟乙基酯、间苯二甲酸酯磺酸锂的二醇、低分子量寡聚物和在聚合物链中含有间苯二甲酸酯磺酸锂的高I.V.聚合物。
相同的命名法适用于含有离子增容剂的二醇或醇。
在酸工艺中，起始原料是二羧酸，水是主要副产物。在典型的酸工艺中的进料比是98摩尔对苯二甲酸、2摩尔的磺基间苯二甲酸的金属盐(例如间苯二甲酸磺酸锂-LiSIPA)和120摩尔的二醇(通常为乙二醇)。在二醇与酸的反应后，该物质经历与酯工艺同样的聚合工艺条件。在实践中，许多的盐降解并且因此作为预反应的双-羟基酯形式加入，如在实施例中所述。
经改变的工艺是任何一种工艺的变型；在某些步骤中结合中间产物。例如，酸工艺可以仅使用对苯二甲酸来产生它的低分子量中间体，以及酯工艺用于产生均聚物磺化聚酯的双羟乙基酯。然后将这两种中间体合并和聚合成更无规的共聚物。另一个变型是将成品改性聚合物添加到熔融反应器中并让熔融工艺解聚该改性聚合物，然后形成无规共聚物。尽管PET、PET-离聚物和聚酰胺的三组分体系没有发现与双组分体系(PET-离聚物，聚酰胺)的更无规共聚物一样有效，但是该三组分体系被认为是本发明的一部分。
制备改性聚合物的另一种技术是把具有大量离子增容剂部分的改性聚酯完全酯交换成未改性的聚酯以生成嵌段共聚物。这可以使用其他技术例如长停留时间和/或高温挤出进行。
引入类似的共聚单体的其它方法已提供在美国专利号3,936,389、3,899,470、5,178,950和美国Statutory InventionRegistration H1760中。
在制备组合物的过程中，聚酯、聚酰胺和离子增容剂通过任何已知技术来进行熔融共混，然后模塑，成形或铸塑成制品。熔融共混包括将单独的物质加热，以使至少聚酯和聚酰胺液化并让该液体接受剪切应力。这可在挤出机或加热容器中进行，并且可连续地进行或在间歇操作中进行。如果离子增容剂没有结合到聚酰胺或聚酯中，则温度应同样足以将其液化。实际的共混可在搅拌容器或挤出机(例如注塑机)中进行。在材料进行熔融共混之后，成形为制品。
制品的实例是膜、纤维、粒料、预成形体(preform)和注塑形状。常常将这些制品进一步处理来制造不同的制品例如瓶、容器、盘、或拉伸膜。在一些情况下，该组合物作为在制品中的层被引入并且成为在最终产生的制品中的层。
为了制造制品，熔融共混物将通过喷嘴或模头。对于膜或片材的情况，共混的组合物被推挤通过模头并通常挤出到辊上。对于预成形体或注塑部件，熔融共混组合物被推挤到模具中并呈现模具的形状。对于粒料的情况，熔融共混的组合物被推挤通过孔，形成丝条，该丝条被切粒。对于纤维的情况，该丝条保持未切断并卷绕到筒管(bobbin)之上。
因为聚酰胺和聚酯两者都是吸水性的，优选的是在熔融共混之前将它们两者干燥。通常，待共混的物质所包含的水分量不超过30ppm水，这基于当熔融共混时在组合物中聚酯的总量计算。
实验工作：
可得自Sartomer的Ricon131MA5和可得自Synthomer的LitheneN4-5000-5MA两者均为用马来酐改性的聚丁二烯(PBD)共聚物并用于这些实验。其性质示于表1。
为产生这些改性材料，在Werner ZSK-30双螺杆挤出机中将不同尼龙与PBD(双烯)混合。挤出条件和尼龙/PBD组合物示于表2。测试不同类型的尼龙，包括脂族(尼龙6和66)和MXD6-样尼龙。表3显示所用尼龙的特性。
表I 马来酐改性的PBD
表2尼龙/PBD共混物
表3-尼龙特性
为生产活性阻透瓶，将改性尼龙与PET和Co盐直接在Arburg注塑机中共混。样品制备涉及粒料混合(PET和改性尼龙)、0.05％矿物油的加入以及最后所需量新癸酸钴(20％Co，来自Shepherd)的加入。通常所用PET是标称2摩尔百分比LiSIPA高0.84dl/g IV树脂。比较实施例使用间苯二甲酸改性的具有0.80dl/g IV的PET共聚物。
将28g预成型体吹进500ml直壁瓶。对瓶进行Fibox，用于氧阻透评估。Fibox是测量液体中溶解氧量的测试方法。渗透率低与随时间的溶解氧量低相关。
预成型体的组成示于表4
表4.预成型体和瓶组合物
C＝比较实例，W＝工作实例
结果分析
图1显示用少量PBD加上100ppm Co改性的尼龙RadilonS(PA 6)和MXD6 6007的Fibox结果。包括一些比较的钝化和活性阻透材料用于比较。
样品998-3和1157-6具有突出的性能，从第一天开始氧渗透率为零。这两个瓶用分别含有5％和2％PBD的3％MXD6-6007制造，这通过尼龙含量而计算(对应预成型体中总PBD的0.15％和0.06％)。
用PBD(尼龙含量为5％；总量的0.15％)改性的含有3％PA6的样品1157-5，比仅用PBD或用7％6007钝化阻透物制备的样品的渗透率低得多。
图2比较含有和不含PBD的3％6007瓶的Fibox结果，其与一些其它用于比较的样品(包括含有PBD/Co无任何尼龙的样品)一起，严格在相同条件下产生。
用新癸酸钴的低尼龙含量瓶的通常诱导行为在样品1293-1中观察到(不含PBD)。在此情形中，仅在约100天后，并且超调量0.9ppm，清除系统变得足够活跃，以降低瓶内部的氧浓度。在约480天中氧浓度达到1ppm。对于含有PBD和相同量6007/Co(998-3)的样品，完全没有氧气进入达约250天，仅在700天内达到1ppm。在离子增容剂LiSIPA存在下，MXD6和PBD之间的协同作用是明显的，这是因为仅通过将PBD和MXD6的各自性能相加，我们不能预计到该结果。
Claims (10)
1.由包含聚酯、离子增容剂、聚酰胺、聚二烯化合物和过渡金属化合物的组合物制成的容器，其中所述离子增容剂源自磺基间苯二甲酸或它的二甲基酯的盐并且共聚为聚酯；
所述聚二烯化合物包含环氧或酐官能性使得其与所述聚酰胺的羧基或氨基末端基团反应，或者与聚酰胺主链中的酰胺基团反应；
所述过渡金属化合物是钴化合物；并且
所述聚酰胺与所述聚二烯化合物的重量比范围为4:1至1000:1。
2.权利要求1的容器，其中所述离子增容剂是锂盐。
3. 权利要求1或2的容器，其中相对所述聚酰胺，所述聚二烯以与所述聚酰胺0.1%至10%重量的比率存在。
4. 权利要求1或2的容器，其中所述聚酯以总组合物的9至99.8重量百分比的范围存在。
5. 权利要求1或2的容器，其中所述过渡金属化合物相对所述聚酰胺加上聚二烯化合物以100至15,000 ppm金属的范围存在。
6. 权利要求1或2的容器，其中所述聚二烯化合物是聚丁二烯。
7. 权利要求6的容器，其中所述聚丁二烯的数均分子量范围为500至7000。
8. 权利要求1或2的容器，其中所述聚酰胺选自MXD6和尼龙6。
9. 权利要求1或2的容器，其中所述聚酯是可结晶聚酯，其酸单元的至少85%源自对苯二甲酸。
10. 权利要求1的容器，其中所述容器包括拉伸壁。
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- 2010-06-11 EP EP10722143.4A patent/EP2440407B8/en active Active
- 2010-06-11 CA CA2763121A patent/CA2763121C/en not_active Expired - Fee Related
- 2010-06-11 TW TW104107856A patent/TWI605089B/zh active
- 2010-06-11 CN CN201080026351.XA patent/CN102802947B/zh active Active
- 2010-06-11 RU RU2011153692/12A patent/RU2532150C2/ru active
- 2010-06-11 BR BRPI1009680-9A patent/BRPI1009680B1/pt active IP Right Grant
- 2010-06-11 AU AU2010258627A patent/AU2010258627B2/en not_active Ceased
- 2010-06-11 KR KR1020127000762A patent/KR20120061794A/ko not_active Application Discontinuation
- 2010-06-11 PL PL10722143T patent/PL2440407T3/pl unknown
- 2010-06-11 WO PCT/EP2010/058221 patent/WO2010142782A1/en active Application Filing
- 2010-06-11 MX MX2011013301A patent/MX2011013301A/es active IP Right Grant
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2013
- 2013-03-14 US US13/803,528 patent/US20130260071A1/en not_active Abandoned
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2014
- 2014-04-01 HR HRP20140311AT patent/HRP20140311T1/hr unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332688A (zh) * | 1998-12-22 | 2002-01-23 | Bp北美公司 | 改进的活性氧清除剂包装 |
| US6353050B1 (en) * | 2000-10-13 | 2002-03-05 | General Electric Co. | Thermoplastic blend comprising poly(arylene ether) and polyamide |
| CN101048275A (zh) * | 2004-08-31 | 2007-10-03 | 因维斯塔技术有限公司 | 具有低雾度的聚酯－聚酰胺共混物 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20130260071A1 (en) | 2013-10-03 |
| WO2010142782A1 (en) | 2010-12-16 |
| TW201529711A (zh) | 2015-08-01 |
| TW201107408A (en) | 2011-03-01 |
| EP2440407B8 (en) | 2014-06-04 |
| US8409680B2 (en) | 2013-04-02 |
| ES2458109T3 (es) | 2014-04-29 |
| TWI486394B (zh) | 2015-06-01 |
| AU2010258627A1 (en) | 2011-12-22 |
| CA2763121A1 (en) | 2010-12-16 |
| MX2011013301A (es) | 2012-01-12 |
| CN102802947A (zh) | 2012-11-28 |
| EP2440407A1 (en) | 2012-04-18 |
| CA2763121C (en) | 2017-04-11 |
| RU2011153692A (ru) | 2013-07-20 |
| PL2440407T3 (pl) | 2014-06-30 |
| KR20120061794A (ko) | 2012-06-13 |
| DK2440407T3 (en) | 2014-03-10 |
| US20100316824A1 (en) | 2010-12-16 |
| HRP20140311T1 (hr) | 2014-05-09 |
| BRPI1009680A2 (pt) | 2016-03-15 |
| BRPI1009680B1 (pt) | 2020-03-24 |
| AU2010258627B2 (en) | 2014-10-09 |
| EP2440407B1 (en) | 2014-01-15 |
| RU2532150C2 (ru) | 2014-10-27 |
| TWI605089B (zh) | 2017-11-11 |
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