CN109153816B - 用于聚酯的水解稳定化的组合物 - Google Patents
用于聚酯的水解稳定化的组合物 Download PDFInfo
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- CN109153816B CN109153816B CN201780027346.2A CN201780027346A CN109153816B CN 109153816 B CN109153816 B CN 109153816B CN 201780027346 A CN201780027346 A CN 201780027346A CN 109153816 B CN109153816 B CN 109153816B
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- terephthalate
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- polyester
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Classifications
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
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- C07C69/82—Terephthalic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08K5/3492—Triazines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
本发明涉及至少一种式(1)的化合物作为聚酯材料中的水解稳定剂的用途,其中,R1和R2相同或不同并且表示C1‑C10‑烷基。
Description
技术领域
本发明涉及耐水解的聚酯膜。
背景技术
聚酯膜是公知的。然而,未稳定化的聚酯膜的不利之处在于它们对水解的敏感性,特别是在高于特定的聚酯的玻璃化转变温度的温度时。对水解的敏感性是聚酯在湿气条件下水解降解的性质,这可以例如在IV值方面的降低中看出。这是使用聚酯膜的限制性因素,特别是在具有高温应力的应用中,如在薄膜电容器、电缆护套、扁平电缆、电动机保护膜、电池薄膜、地板膜、窗户膜、光伏背板中,以及在长期应用中,如在装配玻璃和户外应用中。
在脂族聚酯中观察到特别明显的对水解的敏感性,但采用芳族聚酯如PBT和PET也是如此。当PET的水解倾向对于应用而言过大时,不得不诉诸水解稳定的PEN或甚至诉诸其它聚合物如聚醚或聚酰亚胺。然而,它们比PET明显更昂贵并且因此出于经济的原因是不利的。
因此,已提出通过引入水解稳定剂而改进聚酯膜的水解稳定性。
通过使用碳二亚胺获得的耐水解的聚酯原料是已知的(US-A-5,885,709、EP-A-0838500、CH-A-621135)。然而由这样的聚合物制备的膜在制造中以及在之后的使用中都倾向于放出对粘膜有刺激性的异氰酸酯气体或释放其它有害的副产物和降解产物。基于环氧基的水解稳定剂也提供水解稳定性并且描述于例如EP-A-0292251或US-A-3,657,191中。然而,这些化合物基于借助于表氯醇产生环氧乙烷环,但是显示出裂解低分子量有毒化合物的倾向,从而产生与使用碳二亚胺相关的类似问题。此外,它们到聚酯基质中的引入是不足的,导致长的反应时间和以高浊度的取向的聚酯膜。
此外,已知的水解稳定剂,如碳二亚胺和其它物质,如描述于EP-A-0 292 251中的那些的不利之处在于,它们有时在挤出期间导致聚合物中的分子量方面的急剧增加(粘度上升),因此使得挤出过程不稳定和难于控制。
发明内容
因此,本发明的目的在于提供可获得的耐水解的聚酯原料,其避免了所描述的现有技术的不利之处。
所述目的出人意料地通过含有基于对苯二甲酸酯的水解稳定剂的聚酯制品,优选膜而实现。
本发明涉及至少一种式(1)的化合物作为聚酯材料中的水解稳定剂的用途,
其中,
R1和R2相同或不同并且表示C1-C10-烷基,优选C1-C6-烷基,更优选C1-C4-烷基,最优选C1-C2-烷基。
式(1)的化合物的实例为对苯二甲酸二甲酯、对苯二甲酸二乙酯、对苯二甲酸二丙酯、对苯二甲酸二丁酯、对苯二甲酸二戊酯、对苯二甲酸二己酯、对苯二甲酸二庚酯、对苯二甲酸二辛酯、对苯二甲酸二壬酯或对苯二甲酸二癸酯。
优选的增链剂为式(2)的对苯二甲酸二甲酯(DMT)
该分子可以通过氧化对二甲苯的甲基并且与甲醇反应产生所述甲酯(对苯二甲酸二甲酯)。
水解稳定剂的份额优选在0.1至20.0重量%,更优选1.0至10.0重量%,且特别优选1.5至5重量%范围内,基于聚酯的重量计。
如果引入母料中,则水解稳定剂的份额通常为0.1至50.0重量%,优选1.0至20.0重量%,各自基于母料的总重量计。
合适的聚酯例如为聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸丙二醇酯(PTT)、二苯甲酰聚对苯二甲酸乙二醇酯(PETBB)、二苯甲酰聚对苯二甲酸丁二醇酯(PBTBB)、二苯甲酰聚萘二甲酸乙二醇酯(PENBB)或其混合物。优选的是PET、PBT、PEN和PTT,及其混合物和共聚酯。
合适的聚酯还有脂族聚酯,如聚羟基丁酸酯(PHB)及其与聚羟基戊酸酯(PHV)的共聚物,聚羟基丁酸酯-戊酸酯(PHBV),聚(ε-己内酯)(PCL),SP 3/6,4/6SP(由1,3-丙二醇/己二酸酯或1,4-丁二醇/己二酸酯组成),聚己内酰胺或通常为己二酸聚酯以及其它脂族羧酸的酯。
用于本发明中的聚酯可以另外含有用于调节表面形貌或光学性质所需的无机或有机颗粒,并且在下文将其称为聚酯组合物。颗粒的量取决于用途和它们的粒度。所述粒度通常在0.01至30.0,优选0.1至5.0,且特别是0.3至3.0微米范围内。
获得粗糙度的合适的化合物例如为碳酸钙、硫酸钡、磷灰石、二氧化硅、二氧化钛、氧化铝、交联的苯乙烯、交联的PMMA、沸石以及其它硅酸盐,如硅酸铝。这些化合物通常以0.05至5重量%,优选0.1至0.6重量%(基于聚酯组合物的总重量计)的量使用。
除了前述添加剂以外,聚酯组合物可以另外含有其它组分,如阻燃剂和/或自由基清除剂和/或其它聚合物,如聚醚酰亚胺,颜料和染料、稳定剂、抗氧化剂、抗菌剂、热稳定剂、光稳定剂、中和剂、抗静电剂、防结块剂、光学增亮剂、重金属钝化剂、疏水剂、过氧化物、水清除剂、酸清除剂、水滑石、弹性体、冲击改性剂、激光标记添加剂、加工助剂及其混合物。
优选通过母料技术添加式(1)的水解稳定剂。出于该目的,将水解稳定剂首先分散在载体材料中。合适的载体材料可以为聚酯本身,例如聚对苯二甲酸乙二醇酯或与各个聚酯相容的其它聚合物。取决于载体树脂,母料可以为固体或液体,固体是优选的。在将母料添加至聚酯材料中之后,母料的组分在挤出期间熔化并且溶解或细分散在聚酯中。因为水解稳定剂物理上均匀地分散在载体中,同时将母料与聚酯混合,所以使水解稳定剂的局部较高浓度的可能性最小化。此外,当引入成型设备时,通过增加熔化浓缩物所需要的时间防止了水解稳定剂在冲淡聚合物内的提早反应。这延迟了允许水解稳定剂完全分散在整个聚合物中的反应时间。
可以如下将式(1)的水解稳定剂引入待稳定化的聚酯材料:
将待生产的母料的载体材料和水解稳定剂进料至挤出机,优选双螺杆挤出机中,熔化,混合,然后通过穿孔的模头挤出,急冷和造粒。优选的是其中将聚合物首先在挤出机中熔化,并且在脱气之后将水解稳定剂直接计量添加至熔体中的方法。
便利地将水解稳定化的聚酯材料加工成聚合物制品,例如片材、膜、容器或纤维。片材和膜是特别优选的。
有利地,水解稳定化的聚酯制品,例如膜含有另外的常规聚合物稳定剂,如自由基清除剂、光稳定剂或热稳定剂,其量有利地为50至15,000ppm,优选100至5,000ppm,更优选300至1000ppm,基于制品的总重量计。所添加的聚合物稳定剂可以选自主稳定剂,如空间位阻酚或芳族仲胺,或选自次稳定剂,如硫醚和亚膦酸酯和二丁基二硫代氨基甲酸锌,或主稳定剂与次稳定剂的混合物。优选的是酚稳定剂。酚稳定剂中特别优选的是空间位阻酚、硫代联苯酚、亚烷基联苯酚、烷基酚、羟基苄基化合物、酰基氨基和羟基苯基丙酸酯。
还有利地在用于户外应用的膜中使用UV吸收剂(基于苯并***),如Tinuvin1577、Tinuvin 1600、Tinuvin 360、Tinuvin 234、Cyasob 3638、Cyasorb 1164。这些添加剂可以以在0.1至20.0重量%,优选1.0至10.0重量%,且特别优选1.5至5重量%范围内的量添加,基于膜的总重量计。
除了以母料形式添加水解稳定剂以外,可以在生产聚酯制品,例如膜期间直接添加水解稳定剂。当使用双螺杆挤出机并且将水解稳定剂直接计量添加至各个挤出机的熔体中时,获得特别好的结果。
可以通过用于生产单层和多层膜的常规挤出方法制备膜。水解稳定剂优选存在于所有层中,其中并非将所有层用水解稳定剂改性的实施方案也是可能的。
通常,将各个熔体通过平膜模头挤出,将在一个或更多个辊(冷却辊)上固化的所得的膜作为基本上无定形的预制膜(prefilm)取出,和急冷,然后将膜重新加热并且双轴(双向)拉伸和使经双轴拉伸的膜热固化。在加工方向(=MD)上并且然后横向垂直于加工方向(=TD)上相继进行双轴拉伸。这导致分子链的取向。
进行取向的温度可以在相对宽的范围内变化并且取决于膜的期望的性质。可以任选地与横向拉伸同时进行第一纵向拉伸(同时拉伸)。
以该方式产生的膜具有比未改性的聚酯膜低得多的在室温和高达210℃的温度二者时水解的倾向。稳定化在很大程度上与膜厚度和温度无关。
特别出人意料的是,尽管具有良好的长期水解,但是在挤出机中在膜生产期间不发生不期望的粘度上升并且没有观察到增加的凝胶和斑点水平。
借助于式(1)的水解稳定剂稳定化的膜对于生产包含聚酯膜的产品而言是理想的,所述产品应当具有长寿命(大于1年)并且用于其中存在较高温度(高于80℃)和高湿度的应用中。
式(1)的稳定剂特别可用于生产薄膜电容器(优选的厚度范围为0.3至12微米)。为了制造电容器,已证实当膜在200℃时具有小于4%的纵向收缩率和小于1%的横向收缩率时是有利的,因为其特别好地适合于生产SMD电容器。
另一应用为用于汽车中的扁平电缆。
在以下实施方案中,根据被认可的标准方法测量单个性质。除非另外指明,否则百分数为重量百分比。
测量方法
压力锅测试PCT
该类型的测试提供了快速跟踪形式的关于耐水解性的信息。将样品在高压处理之前进行切割并且在120℃和2巴(绝对压力)储存0、40、50h。对于每个测试测量5个测试样品。
湿热测试DHT
该类型的测试提供了长期过程形式的关于耐水解性的信息。将样品在高压处理之前进行切割并且在85℃和常压储存直至5000h,在每个500h之后测量测试结果。
拉伸试验
采用100mm的铝夹遵照ISO 527-1/2处理拉伸测试,以获得断裂伸长率和拉伸强度。结果为5次测量的平均值。
●测试速率:
-ε<0.25%:1mm/min
-ε>0.25%:100mm/min
●在x h高压处理之后测量断裂伸长率保留率以获得膜的脆度的指示:
特性粘度(I.V.)
将特性粘度(I.V.)的测量用于测量聚合物的分子量,因为特性粘度为聚合物分子量的独特函数。通过使用用于熔体粘度测量(例如用于PET)的Davenport粘度计,在使用高压氮气通过标准化模头挤出的熔融状态下检测I.V.。
标准粘度(S.V.)
标准粘度S.V.基于DIN 53726。通过在25℃在Ubbelohde粘度计中测量在二氯乙酸(DCA)中1%溶液的相对粘度η相对。如下定义S.V.值:
S.V.=(η相对–1)·1000S.V.=(η相对-.1)×1000
实施例
使用以下材料:
PET1:(XPURE 4004,Invista,I.V.0.63)
PET2:重新粒化的RT4027(Invista/Erema)
PET3:RAMAPET R 180GR BB(Indorama Plastics)
PC(聚碳酸酯):Trirex 3022PJ(01)Entec
水解稳定剂:DMT(对苯二甲酸二甲酯)
UV吸收剂:2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己氧基苯酚(TINUVIN 1577ED,BASF)
通过使用双螺杆挤出机Leistritz MASS技术(27mm/40D)生产两个母料(MB)。MBHS含有10%的在PC上的DMT用于水解稳定化。MBUV含有15%的在PET3上的UV吸收剂Tinuvin1577。
实施例1
生产具有ABA结构的三层膜。芯层B的组合物由53%的PET1、15%的PET2、2%的MBHS、30%的MBUV组成。外层A由67%的PET1、3%的MBHS、30%的MBUV组成。在100-170℃预干燥所使用的PET。主挤出机配备有~10mbar真空。共挤出机配备有~20mbar真空。
不同区域的挤出温度显示于表1中。
表1:以℃计的挤出温度:
区域1 | 区域2 | 区域3 | 区域4 | 区域5 | 区域6 | 区域7 | 区域8 | 区域9 |
100 | 102 | 104/105 | 106 | 120/130 | 210 | 210/215 | 220 | 200/190 |
从牵拉辊的喷嘴排出熔融的聚合物。将膜在加工方向上拉伸至3.0倍并且在横向拉伸方向上拉伸至3.4倍。然后,将在225℃热固化和在横向方向上在220-180℃的温度松弛3%。最终膜厚度为50微米。
实施例2(对比)
生产具有ABA结构的三层膜。芯层B的组合物由45%的PET1、25%的PET2、30%的MBUV组成。外层A由70%的PET1、30%的MBUV组成。在100-170℃预干燥所使用的PET。主挤出机配备有~10mbar真空。共挤出机配备有~20mbar真空。
不同区域的挤出温度显示于表2中。
表2:以℃计的挤出温度:
区域1 | 区域2 | 区域3 | 区域4 | 区域5 | 区域6 | 区域7 | 区域8 | 区域9 |
100 | 102 | 104/105 | 106 | 120/130 | 210 | 210/215 | 220 | 200/190 |
从牵拉辊的喷嘴排出熔融的聚合物。将膜在加工方向上拉伸至3.0倍并且在横向拉伸方向上拉伸至3.4倍。然后,将在225℃热固化和在横向方向上在220-180℃的温度松弛3%。最终膜厚度为50微米。
测试结果
表3:试验的结果
含有抗水解添加剂的实施例1的测试结果在模拟聚合物的水解降解的所有测试中都令人信服。在压力锅测试中,所述膜比没有抗水解添加剂的膜明显更久地保持稳定。同样在湿热测试中,配备有抗水解添加剂的材料比未配备的膜耐抗得明显更久。熔体粘度和标准粘度的测量也显示更稳定的材料是配备有抗水解添加剂的材料。实施例1的所有膜还显示出高的UV稳定性。
Claims (14)
2.根据权利要求1所述的用途,其中所述式(1)的化合物为对苯二甲酸二甲酯、对苯二甲酸二乙酯、对苯二甲酸二丙酯、对苯二甲酸二丁酯、对苯二甲酸二戊酯、对苯二甲酸二己酯、对苯二甲酸二庚酯、对苯二甲酸二辛酯、对苯二甲酸二壬酯或对苯二甲酸二癸酯。
3.根据权利要求1或2所述的用途,其中所述式(1)的化合物为对苯二甲酸二甲酯。
4.根据权利要求1或2所述的用途,其中所述聚酯材料中的聚酯为聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、二苯甲酰聚对苯二甲酸乙二醇酯、二苯甲酰聚对苯二甲酸丁二醇酯、二苯甲酰聚萘二甲酸乙二醇酯或其混合物。
5.根据权利要求1或2所述的用途,其中所述聚酯材料中的聚酯为聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯和聚对苯二甲酸丙二醇酯及其混合物和共聚酯。
6.根据权利要求1或2所述的用途,其中所述聚酯材料中的聚酯为脂族聚酯,选自聚羟基丁酸酯及其与聚羟基戊酸酯的共聚物,聚羟基丁酸酯-戊酸酯、聚(ε-己内酯)。
7.根据权利要求1或2所述的用途,其中所述式(1)的化合物的份额为0.1至20.0重量%,基于经稳定化的聚酯材料的重量计。
8.根据权利要求1或2所述的用途,其中所述式(1)的化合物的份额为1.0至10.0重量%,基于经稳定化的聚酯材料的重量计。
9.根据权利要求1或2所述的用途,其中所述式(1)的化合物的份额为1.5至5.0重量%,基于经稳定化的聚酯材料的重量计。
10.根据权利要求1或2所述的用途,其中所述式(1)的化合物与另外的添加剂组合使用,所述另外的添加剂选自自由基清除剂、光稳定剂、热稳定剂、阻燃剂、颜料、染料、抗氧化剂、抗菌剂、中和剂、抗静电剂、防结块剂、光学增亮剂、重金属钝化剂、疏水剂、过氧化物、水清除剂、酸清除剂、水滑石、弹性体、冲击改性剂、激光标记添加剂及其混合物。
11.根据权利要求1或2所述的用途,其中所述式(1)的化合物与另外的添加剂组合使用,所述另外的添加剂为加工助剂。
12.根据权利要求1或2所述的用途,其中所述式(1)的化合物与UV吸收剂组合使用。
13.根据权利要求1或2所述的用途,其中所述式(1)的化合物以母料形式使用。
14.根据权利要求1或2所述的用途,其中所述聚酯材料为膜或片材的形式。
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EP16168305.7 | 2016-05-04 | ||
EP16168305.7A EP3241866A1 (en) | 2016-05-04 | 2016-05-04 | Composition for polyester hydrolytic stabilization |
PCT/EP2017/059848 WO2017190993A1 (en) | 2016-05-04 | 2017-04-26 | Composition for hydrolytic stabilization of polyester |
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CN109153816A CN109153816A (zh) | 2019-01-04 |
CN109153816B true CN109153816B (zh) | 2021-05-14 |
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US (1) | US10808101B2 (zh) |
EP (2) | EP3241866A1 (zh) |
JP (1) | JP7113759B2 (zh) |
KR (1) | KR102404837B1 (zh) |
CN (1) | CN109153816B (zh) |
BR (1) | BR112018070575B1 (zh) |
CA (1) | CA3022923A1 (zh) |
ES (1) | ES2861312T3 (zh) |
MX (1) | MX2018012428A (zh) |
RU (1) | RU2763499C2 (zh) |
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WO (1) | WO2017190993A1 (zh) |
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- 2017-04-26 ES ES17719586T patent/ES2861312T3/es active Active
- 2017-04-26 CN CN201780027346.2A patent/CN109153816B/zh active Active
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- 2017-04-26 BR BR112018070575-6A patent/BR112018070575B1/pt active IP Right Grant
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EP3241866A1 (en) | 2017-11-08 |
US10808101B2 (en) | 2020-10-20 |
BR112018070575A2 (pt) | 2019-02-12 |
CA3022923A1 (en) | 2017-11-09 |
EP3452542B1 (en) | 2021-02-24 |
WO2017190993A1 (en) | 2017-11-09 |
SG11201808508TA (en) | 2018-10-30 |
MX2018012428A (es) | 2019-03-01 |
EP3452542A1 (en) | 2019-03-13 |
RU2018142568A3 (zh) | 2020-08-26 |
RU2018142568A (ru) | 2020-06-04 |
JP2019515102A (ja) | 2019-06-06 |
JP7113759B2 (ja) | 2022-08-05 |
TWI769156B (zh) | 2022-07-01 |
KR20190005922A (ko) | 2019-01-16 |
US20190153195A1 (en) | 2019-05-23 |
KR102404837B1 (ko) | 2022-06-07 |
TW201811888A (zh) | 2018-04-01 |
ES2861312T3 (es) | 2021-10-06 |
BR112018070575B1 (pt) | 2022-09-27 |
CN109153816A (zh) | 2019-01-04 |
RU2763499C2 (ru) | 2021-12-29 |
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