CN104448794A - 基于部分芳族的共聚酰胺的模塑料 - Google Patents
基于部分芳族的共聚酰胺的模塑料 Download PDFInfo
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- CN104448794A CN104448794A CN201410480541.9A CN201410480541A CN104448794A CN 104448794 A CN104448794 A CN 104448794A CN 201410480541 A CN201410480541 A CN 201410480541A CN 104448794 A CN104448794 A CN 104448794A
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- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Landscapes
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Abstract
本发明涉及基于部分芳族的共聚酰胺的模塑料。将模塑料加工成具有改善的耐热老化性的模塑制品,所述模塑料含有至少40重量%的如下组分:a)60-99重量份的共聚酰胺,其基于六亚甲基二胺、对苯二甲酸和具有11或12个C原子的内酰胺和/或ω-氨基羧酸和b)40-1重量份的烯烃共聚物,其含有基于乙烯、基于具有4-8个C原子的1-烯烃、基于脂族不饱和二羧酸酐和任选地基于另一种烯烃的单体单元,其中a)和b)的重量份总和为100。
Description
技术领域
本发明的主题是抗冲改性的聚酰胺模塑料,其含有部分芳族的共聚酰胺和聚烯烃抗冲改性剂,并且其基于各个组分的选择具有高的抗冲击性和断裂伸长率以及高的耐热老化性。由此制备的模塑制品也是本发明的主题。
背景技术
已知的标准聚酰胺如PA6和PA66可以容易加工和具有高的熔点和高的受热尺寸稳定性,尤其是如果它们用玻璃纤维进行增强或含有矿物质填料的话。然而,当存贮在水中时它们一般具有高达10%的高吸水性。对于甚至在潮湿条件下也对尺寸稳定性具有高要求的许多应用来说,不能使用这些脂族聚酰胺。另外,通过吸收水,机械性能也发生变化;刚性和强度通过吸水被数倍降低。
部分芳族聚酰胺与PA6和PA66相比具有降低的吸水性,并且在吸水之后机械性能基本保持。另外,它们具有有时候显著在PA66的熔点以上的熔点并且因此原则上适合用于长期暴露于高温的应用,例如在汽车的发动机舱中。由于PA6T具有如此的高熔点使得其不再可加工,实践中使用共聚酰胺,例如PA6T/6I、PA6T/66或PA6T/6,其熔点已经降低得足以使聚合物可加工。通过合适的组成,该类共聚物是高度结晶的,具有大约300℃左右范围内的熔点和高的刚性;然而,它们通常非常脆和具有非常低的断裂伸长率。
对于聚酰胺模塑料,通常通过与抗冲改性剂混合提高韧性和断裂伸长率。在大多数情况下,使用聚烯烃橡胶作为抗冲改性剂,所述橡胶已经用不饱和二羧酸酐例如马来酸酐接枝以便将分散分布的橡胶与聚酰胺基质进行相结合。特别地,使用含有约0.5重量%接枝马来酸酐的乙烯-丙烯橡胶用于此。
对于基于部分芳族聚酰胺的模塑料,过去还努力通过使用抗冲改性剂提高它们的韧性和断裂伸长率。
EP 1
988 113 A1描述了一种基于共聚酰胺10T/6T的聚酰胺模塑料,该共聚酰胺由1,10-癸二胺、1,6-六亚甲基二胺和对苯二甲酸单体形成。共聚酰胺具有大约300℃范围的相对高的熔点;因此加工窗口相对小。提供了可以加入的一系列抗冲改性剂,其中优选乙烯-丙烯橡胶;然而,没有详细讨论差异并且热老化后机械性能的保持并不是中心话题。我们自己的实验已经表明:对于该类抗冲改性的模塑料,断裂伸长率低。
EP 2
325 260 A1描述了一种基于共聚酰胺的聚酰胺模塑料,该共聚酰胺由1,10-癸二胺、1,6-六亚甲基二胺、对苯二甲酸和至少一种另外的聚酰胺形成单体构成。这里同样,提供了可以加入的一系列抗冲改性剂,其中优选乙烯-丙烯橡胶。这里同样,我们自己的实验已经表明:对于该类抗冲改性的模塑料,断裂伸长率低。
由JP04-202560A已知在暴露于热之后,由六亚甲基二胺-间苯二甲酸-对苯二甲酸共聚物和马来酸酐-官能化的乙烯-1-丁烯橡胶制得的模塑料在其韧性和断裂伸长率上与含有其它橡胶的模塑料没有差异。
在WO 2005/018891和JP2010-202724A中,描述了含有芳族聚酰胺、官能化的抗冲改性剂和铜稳定剂的模塑料。也可加入抗氧化剂。所述模塑料被用于多层管。
然而,由此现有技术已知的模塑料具有许多缺点,特别是不足的耐热老化性。另外,它们的可加工性能较差。它们的机械性能,特别是抗冲击性和断裂伸长率如此之差使得它们在模塑制品中例如汽车发动机舱中的管或在类似条件下的用途是不可取的。
容易地可加工的模塑料由WO2012/106309已知;它们含有部分芳族的聚酰胺,其中主要是脂族含量和脂族聚酰胺与官能化的橡胶。然而,它们的受热尺寸稳定性与完全脂族的聚酰胺相当且对于高要求的应用来说远远不够。US2013/0115401A1类似。
发明内容
本发明的目的是避免这些缺点和特别是提供容易地可加工的、高熔点的、抗冲击的模塑料,其具有高的断裂伸长率和基于部分芳族的聚酰胺,所述模塑料甚至在高温下长期使用之后也基本上保持了它们有利的机械性能。
此目的通过含有至少40重量%,优选至少50重量%,特别优选至少60重量%,尤其优选至少70重量%和非常特别优选至少80重量%的如下组分的模塑料得以实现:
a) 60-99重量份,优选65-98重量份,特别优选68-97重量份和尤其优选70-96重量份的部分芳族的共聚酰胺,其由衍生自如下的重复单元组成:
I. 30-90 mol%,优选40-85 mol%,特别优选45-80 mol%,尤其优选50-75
mol%和非常特别优选大于50至70
mol%的六亚甲基二胺与对苯二甲酸的组合和
II. 70-10 mol%,优选60-15 mol%,特别优选55-20 mol%,尤其优选50-25
mol%和非常特别优选小于50至30
mol%的具有11或12个C原子的内酰胺和/或ω-氨基羧酸,
其中mol%值基于I和II的总和计且其中至多20%,优选至多15%,特别优选至多12%,尤其优选至多8%和非常特别优选至多5%或至多4%的六亚甲基二胺可以被等量的另一种二胺代替和/或其中至多20%,优选至多15%,特别优选至多12%,尤其优选至多8%和非常特别优选至多5%或至多4%的对苯二甲酸可以被等量的另一种芳族二羧酸和/或1,4-环己烷二甲酸代替和/或其中至多20%,优选至多15%,特别优选至多12%,尤其优选至多8%和非常特别优选至多5%或至多4%的具有11或12个C原子的内酰胺和/或ω-氨基羧酸的重复单元可以被等量的衍生自六亚甲基二胺与具有8-19个C原子的直链脂族二羧酸和/或己内酰胺的组合的单元代替,
b) 40-1重量份,优选35-2重量份,特别优选32-3重量份和尤其优选30-4重量份的烯烃共聚物,其含有如下的单体单元:
- 35-94.9重量%,优选40-90重量%和特别优选45-85重量%的基于乙烯的单体单元,
- 5-65重量%,优选10-60重量%和特别优选15-55重量%的基于具有4-8个C原子的1-烯烃的单体单元,
- 0-10重量%的基于另一种烯烃的单体单元,和
- 0.1-2.5重量%的基于脂族不饱和二羧酸酐的单体单元,
其中选择各个含量使得这些重量%值的总和为100,
和其中a)和b)的重量份总和为100。
根据权利要求,部分六亚甲基二胺可以任选地被另一种二胺代替。这里原则上任何二胺都是合适的;作为实例可以提及下面的二胺:1,10-癸二胺、1,12-十二烷二胺、间-苯二甲胺、对-苯二甲胺、双-(4-氨基环己基)-甲烷、2-甲基-1,5-戊二胺和1,4-双-氨基甲基-环己烷。显然,也可使用这些二胺的混合物。然而,优选地,除了六亚甲基二胺之外,不使用其它二胺。
根据权利要求,部分对苯二甲酸也可任选地被另一种芳族二羧酸或被1,4-环己烷二甲酸代替。这里原则上任何芳族二羧酸都是合适的;作为实例可以提及下面的二羧酸:间苯二甲酸、4,4'-二苯基二甲酸、4,4'-二苯基醚二甲酸、2,6-萘二甲酸、1,4-萘二甲酸和1,5-萘二甲酸。显然,也可使用这些二羧酸的混合物。然而,优选地,除了对苯二甲酸之外,不使用其它芳族二羧酸并更优选不使用1,4-环己烷二甲酸。
同样,根据权利要求,部分具有11或12个C原子的内酰胺和/或ω-氨基羧酸的重复单元可以任选地被等量的衍生自六亚甲基二胺与具有8-19个C原子的直链脂族二羧酸和/或己内酰胺的组合的单元代替。具有11或12个C原子的内酰胺或ω-氨基羧酸是十一烷基内酰胺、ω-氨基十一烷酸、十二烷基内酰胺和ω-氨基十二烷酸。如下化合物可以作为具有8-19个C原子的直链脂族二羧酸:辛二酸(软木酸;C8)、壬二酸(杜鹃花酸;C9)、癸二酸(癸二酸;C10)、十一烷二酸(C11)、十二烷二酸(C12)、十三烷二酸(C13)、十四烷二酸(C14)、十五烷二酸(C15)、十六烷二酸(C16)、十七烷二酸(C17)、十八烷二酸(C18)和十九烷二酸(C19)。
有利地选择部分芳族的共聚酰胺的组成使得根据ISO 11357在第二次加热后测量的其微晶熔点Tm位于240-300℃范围内,优选在250-295℃范围内并特别优选在260-290℃范围内。如果出现若干熔融峰,则Tm由主熔融峰测定。
所述共聚酰胺通常通过熔融缩聚制备。合适的方法是现有技术。替代性地,也可以使用任何其它已知的聚酰胺合成法。
如果确保这些单体可以以1:1的摩尔比反应,则必须存在六亚甲基二胺与对苯二甲酸的等摩尔组合。这里可以指出的是六亚甲基二胺是相对易挥发性的并且为此在缩聚期间会出现损失,其必须通过增加初始称重的量进行补偿。另外需要稍微偏离确切的化学计量以便建立规定的端基比率。
在一个优选的实施方案中,在所述部分芳族的聚酰胺中,氨基端基与氨基和羧基端基之和的比率为0.3-0.7并特别优选为0.35-0.65。氨基端基的含量可以通过本领域技术人员已知的方法调整缩聚反应进行调节。所述调整可以例如通过加入一元羧酸或加入一元胺改变使用的二胺与使用的二羧酸的比率来进行。另外,氨基端基的含量也可以通过混合两种颗粒或熔体形式的共聚酰胺进行调节,其中所述两种共聚酰胺一种富含氨基端基而另一种氨基端基含量低。
氨基含量可以通过用高氯酸滴定共聚酰胺在间-甲酚中的溶液进行测定。羧基含量的测定可以通过用在乙醇中的KOH滴定共聚酰胺在邻-甲酚中的溶液进行。这些方法是本领域技术人员熟悉的。
在烯烃共聚物中,下面的化合物可以作为具有4-8个C原子的1-烯烃:1-丁烯、1-戊烯、1-己烯、1-庚烯和1-辛烯。显然,基于具有4-8个C原子的1-烯烃的单体单元也可以由这些化合物的混合物衍生。
对所述其它烯烃的特征没有限制,在所述烯烃共聚物中可以含有0-10重量%的其单体单元。例如可以是非共轭的二烯、单烯如丙烯、4-甲基-1-戊烯或苯乙烯或其混合物。
在第一个实施方案中,所述其它烯烃不是非共轭二烯,在所述烯烃共聚物中可以含有0-10重量%的其单体单元。
在第二个实施方案中,此其它烯烃不是苯乙烯和/或不是丙烯。
在第三个实施方案中,所述烯烃共聚物仅含有衍生自乙烯、具有4-8个C原子的1-烯烃和脂族不饱和二羧酸酐的单体单元。
在第四个实施方案中,所述具有4-8个C原子的1-烯烃是1-丁烯。
在第五个实施方案中,所述具有4-8个C原子的1-烯烃是1-己烯。
在第六个实施方案中,所述具有4-8个C原子的1-烯烃是1-辛烯。
这些实施方案可以不受限制地相互组合。
所述脂族不饱和二羧酸酐可以例如是马来酸酐,然而其它类似的化合物例如乌头酸酐、柠康酸酐或衣康酸酐也是合适的。
根据权利要求的烯烃共聚物可以以已知的方式制备,其中所述脂族不饱和二羧酸酐或其前体,例如相应的酸或半酯,与预形成的共聚物加热地或优选通过自由基反应进行反应。这里所述脂族不饱和二羧酸酐也可以与其它单体,例如与富马酸二丁酯或苯乙烯组合进行反应。根据权利要求的烯烃共聚物以多种类型市购可得。
所述烯烃共聚物通常是橡胶类的,但是也可以具有相对高的结晶含量。这一点特别通过较高含量的衍生自乙烯的单体单元和各单体单元的不完全无规分布可以看出。
根据本发明的模塑料,除了组分a)和b)之外,任选地含有其它添加剂,其补足余量至100重量%,并优选为至少其0.01重量%。这些其它添加剂例如是:
a) 稳定剂,
b) 其它聚合物,
c) 纤维状增强材料,
d) 填料,
e) 增塑剂,
f) 颜料和/或染料,
g) 阻燃剂,和
h) 加工助剂。
在一个优选的实施方案中,所述模塑料含有有效量的含铜稳定剂。这特别是溶于聚酰胺基质中的铜化合物。所述铜化合物优选与碱金属组合。
在某些实施方案中,所述稳定剂是铜(I)盐,例如与碱金属卤化物组合的乙酸铜、硬脂酸铜、有机铜配合物例如乙酰丙酮化铜、卤化铜等。
在某些实施方案中,所述含铜稳定剂包含选自碘化铜和溴化铜的卤化铜和选自锂、钠和钾的碘化物与溴化物的碱金属卤化物。
优选地,所述含铜稳定剂这样计量加入,其使得所述模塑料含有20-2000 ppm的铜,特别优选30-1500 ppm的铜和尤其优选40-1000 ppm的铜。
另外,优选所述含铜稳定剂的构成使得碱金属卤化物与铜化合物的重量比位于2.5-12范围内并特别优选位于6-10范围内。在模塑料中通常含有大约0.01重量%-大约2.5重量%的碱金属卤化物与铜化合物的组合。
含铜稳定剂提供了针对长期热老化的保护,例如在汽车的发动机罩下的应用中。
在一个另外优选的实施方案中,所述模塑料含有有效量的氧化稳定剂并特别优选与有效量的含铜稳定剂组合的有效量的氧化稳定剂。合适的氧化稳定剂例如是芳族胺、立体位阻酚、亚磷酸盐/酯、亚膦酸盐/酯、硫增效剂、羟基胺、苯并呋喃酮衍生物、丙烯酰氧基改性的酚等。该类氧化稳定剂是以多种类型市购可得的,例如以商标名Naugard 445、Irganox 1010、Irganox 1098、Irgafos 168、P-EPQ或Lowinox
DSTDP。通常,所述模塑料含有大约0.01-大约2重量%和优选大约0.1-大约1.5重量%的氧化稳定剂。
另外,所述模塑料也可以含有UV稳定剂或HALS型的光稳定剂。合适的UV稳定剂首先是有机UV吸收剂,例如二苯甲酮衍生物、苯并三唑衍生物、N,N'-二苯基乙二酰胺或苯基三嗪。HALS型的光稳定剂是四甲基哌啶衍生物;它们是抑制剂,充当自由基清除剂。UV稳定剂和光稳定剂可以有利地组合使用。二者都是可以多种类型市购可得的;关于剂量,可以遵从制造商的说明。
所述模塑料可以另外含有水解稳定剂例如单体的、低聚的或聚合的碳二亚胺或双噁唑啉。
可以作为添加剂含在所述模塑料中的其它聚合物例如是脂族聚酰胺、聚醚酰胺、聚四氟乙烯(PTFE)或聚亚苯基醚。
合适的脂族聚酰胺例如是PA46、PA66、PA68、PA610、PA612、PA613、PA410、PA412、PA810、PA1010、PA1012、PA1013、PA1014、PA1018、PA1212、PA6、PA11和PA12以及由这些类型衍生的共聚酰胺。优选地,所述模塑料的聚酰胺部分含有小于10重量%,特别优选小于8重量%,尤其优选小于5重量%和非常特别优选小于3重量%的脂族聚酰胺或优选小于10重量%,特别优选小于8重量%,尤其优选小于5重量%和非常特别优选小于3重量%的脂族聚酰胺和聚醚酰胺的总和,所述聚酰胺部分由部分芳族的共聚酰胺、任选的脂族聚酰胺和任选的聚醚酰胺组成。
合适的聚亚苯基醚通过常规的方法由在邻位被烷基双取代的苯酚氧化偶联制备。特别优选的聚亚苯基醚是聚(2,6-二甲基-1,4-亚苯基)醚,任选地与2,3,6-三甲基苯酚单元组合。根据现有技术,所述聚亚苯基醚含有用于结合到聚酰胺基质上的官能团;这些官能团例如通过用马来酸酐处理而引入。
作为其它的聚合物,在所述模塑料中含有优选至多4重量%和特别优选没有选自乙烯/乙烯基醇共聚物和聚乙烯基醇的多羟基聚合物并特别优选同时也不含脂族聚酰胺。
所述模塑料优选含有至多40重量%,特别优选至多30重量%和尤其优选至多25重量%的其它聚合物。
作为纤维状增强材料,例如使用玻璃纤维。为此,可以使用短纤维(例如长度0.2-50mm的短切玻璃纤维)或连续纤维(粗纱)。玻璃纤维的横截面可以是十字形的,但是也可以是卵形、椭圆形、收缩的椭圆形(蚕丝)、多边形、长方形或近似长方形。长纤维增强的模塑料可以通过已知用于制备长纤维增强的棒形颗粒的方法,特别是通过拉挤法制备,其中连续的纤维条带(粗纱)完全被聚合物熔体浸透并接着冷却和切断。
其它合适的纤维状增强材料例如是碳纤维、石墨纤维、碳化硅纤维、硼纤维、芳族聚酰胺纤维、不锈钢纤维或钛酸钾晶须。
合适的填料例如是滑石、云母、硅酸盐、石英、石墨、二硫化钼、二氧化钛、硅灰石、高岭土、无定形硅酸、碳酸镁、白垩、石灰石、长石、硫酸钡、导电碳黑、石墨原纤、实心或空心玻璃珠或磨砂玻璃。
模塑料中纤维状增强材料和填料的含量总的来说至多60重量%,优选至多50重量%和优选至少0.1重量%。
增塑剂及其在聚酰胺中的用途是已知的。适合用于聚酰胺的增塑剂的一般综述可以由 Gächter/Müller, Kunststoffadditive (Plastics Additives), C. Hanser Verlag, 第2版,第296页得到。
适合作为增塑剂的常用化合物例如是在醇组分中具有2-20个C原子的对-羟基苯甲酸的酯或在胺组分中具有2-12个C原子的芳基磺酸的酰胺,优选苯磺酸的酰胺。
作为增塑剂,尤其可以是对-羟基苯甲酸乙酯、对-羟基苯甲酸辛酯、对-羟基苯甲酸异十六烷基酯、甲苯磺酸正辛基酰胺、苯磺酸正丁基酰胺或苯磺酸2-乙基己基酰胺。
合适的颜料和/或染料例如是炭黑、氧化铁、硫化锌、群青、苯胺黑、珠光颜料和金属闪光片(Metallflitter)。
合适的阻燃剂例如是三氧化锑、六溴代环十二烷、四溴代双酚、硼酸盐、红磷、氢氧化镁、氢氧化铝、氰尿酸三聚氰胺及其缩合产物例如蜜白胺、蜜勒胺和Melon;三聚氰胺化合物如三聚氰胺焦磷酸盐和多磷酸盐、多磷酸铵和有机磷化合物或其盐例如间苯二酚二苯基磷酸酯、膦酸酯或金属亚膦酸盐。
合适的加工助剂例如是石蜡、脂肪醇、脂肪酸酰胺、硬脂酸盐如硬脂酸钙、石蜡、褐煤酸盐或聚硅氧烷。
所述模塑料由各组分以本领域技术人员已知的方式通过在熔体中混合制备。
根据本发明的模塑料可以例如通过注塑、挤出或吹塑加工成模塑制品。该类模塑制品的实例为用于泵、齿轮、阀门和水表、节流阀、前灯罩、反射器、转向灯调节器(Kurvenlichtverstellung)、大齿轮、插头和插座型连接器、连接器、型材、多层膜的膜或层、电子组件、电子组件罩壳、工具、复合材料、塑料橡胶复合材料、连接件和用于连接软管或管的配件。
特别是单层或多层空心体可以由根据本发明的模塑料制备,尤其是管或容器。这些包括例如汽车的充电气道、单层或多层流体进料管,其可以是光滑的或波纹状的,如燃料管、液压管、制动液管、车钩连接线或冷冻剂管、制动液容器或燃料容器。其它应用例如是油或气提取工业中用于刚性或柔性管的衬里、用于海上提取的柔性管或其中输送热流体的脐带管上的抗磨胶带。
在多层膜、多层管和多层容器中,至少一层由根据本发明的模塑料组成,其与由另一种模塑料组成的至少一个其它层结合。在不充分的层粘附的情况下,可以使用中间增粘层。
根据本发明的模塑料的模塑制品在其中常规地主要是高温的地方都可以使用,而它们的抗冲击性和断裂伸长率没有大程度地损害。
具体实施方式
本发明将通过下面的实施例进行说明。
在所述实施例中,使用下面的材料:
PA6T/12: 参见制备实施例1
AMODEL A-1006: PA6T/6I/66,来自Solvay Specialty Polymers,含有大约65
mol% 6T、大约25 mol% 6I和大约10
mol% 66
PA10T/TMDT:
参见制备实施例2
彩色批料:
80重量% PA12和20重量%炭黑的混合物
TAFMER MH7010:
酸改性的乙烯-丁烯橡胶,来自Mitsui
Chemicals
EXXELOR VA1803:
酸改性的乙烯-丙烯橡胶,来自ExxonMobil
Chemical
硬脂酸钙:
加工助剂
Polyad PB201碘化物: 基于碘化铜和碱金属卤化物的含铜的稳定剂
Naugard 445:
氧化稳定剂(芳族胺)。
制备实施例1(PA6T/12 60:40;根据本发明):
将19.118 kg的六亚甲基二胺、20.898 kg的对苯二甲酸、34.953 kg的ω-氨基月桂酸、32.130 kg蒸馏水和7.46 g的50重量%的次磷酸水溶液放入缩聚反应器中。将起始材料在180℃下熔融并在220℃/22 bar下搅拌3小时。通过连续的压力释放至2 bar,将所述混合物加热到300℃并在此温度下再次进行压力释放。在达到0.6 bar时,排空反应器并将产物造粒。使所述颗粒在转动干燥器中经历进一步缩合并由此达到需要的分子量。
微晶熔点Tm:269.5℃(主峰)。
制备实施例2(PA10T/TMDT 85:15;不是根据本发明):
用US 2361717图2中示出的设备进行制备,然而其中部件23、 24和25被耐高压的高压釜代替,其通过惰性气体叠加确保了通过反应器的恒定加料压力。两个反应器都通过360℃的进油操作。
将24.70 kg的对苯二甲酸、21.775 kg的十亚甲基二胺、3.53
kg的2,2,4-与2,4,4-三甲基-六亚甲基二胺(TMD)的混合物、14.0 kg完全去离子水(VE水)和10.0 g的50重量%的次磷酸水溶液放入高压釜中,用氮气惰化三次,并将高压釜密封和在230℃的进油温度下加热。结果,形成透明的均匀盐溶液。用氮气调节高压釜至恒定的44 bar总压力;此压力将所述材料输送通过装置。使获得的产物在转动干燥器中进一步缩合并由此达到需要的分子量。
微晶熔点Tm:285℃。
制备模塑料
所述模塑料由各组分通过在捏合单元中熔体混合制备,作为条带排出、造粒和干燥。
接下来,通过注塑制备试样。使这些试样中的一部分在新鲜模塑的状态下,一部分在180℃下在空气中4小时热老化之后和另一部分在180℃在空气中295小时热老化之后经历根据ISO 527的拉伸试验。组成和试验结果示于表1中。
在180℃下4小时后,期望尚无严重的热老化。这里测量值的变化主要归因于样品的后结晶。
在对比实施例2-5中,从一开始就不可测量屈服应力或屈服伸长率。这是因为仅有低的断裂伸长率。
在新鲜模塑状态下和在后结晶之后的断裂伸长率在实施例1中以及特别是在对比实施例1中最大。热老化之后,在此所述比率颠倒;在实施例1中保持了40.5%的初始断裂伸长率,而在对比实施例1中断裂伸长率降到只有初始值的13.3%。
结果显示存在组合的效果。这既取决于正确的部分芳族聚酰胺的选择又取决于匹配的烯烃共聚物的选择。此双重选择由现有技术不是显而易见的。
Claims (13)
1.模塑料,其含有至少40重量%的如下组分:
a) 60-99重量份的部分芳族的共聚酰胺,其由衍生自如下的重复单元组成:
I. 30-90 mol%的六亚甲基二胺与对苯二甲酸的组合和
II. 70-10 mol%的具有11或12个C原子的内酰胺和/或ω-氨基羧酸,
其中mol%值基于I和II的总和计和其中至多20%的六亚甲基二胺可以被等量的另一种二胺代替和/或其中至多20%的对苯二甲酸可以被等量的另一种芳族二羧酸和/或1,4-环己烷二甲酸代替和/或其中至多20%的具有11或12个C原子的内酰胺和/或ω-氨基羧酸的重复单元可以被等量的衍生自六亚甲基二胺与具有8-19个C原子的直链脂族二羧酸和/或己内酰胺的组合的单元代替,
b) 40-1重量份的烯烃共聚物,其含有下面的单体单元:
- 35-94.9重量%的基于乙烯的单体单元,
- 5-65重量%的基于具有4-8个C原子的1-烯烃的单体单元,
- 0-10重量%的基于另一种烯烃的单体单元,和
- 0.1-2.5重量%的基于脂族不饱和二羧酸酐的单体单元,
其中选择各含量使得这些重量%值的总和为100,
和其中a)和b)的重量份总和为100。
2.根据权利要求1的模塑料,其特征在于:根据ISO 11357在第二次加热过程中测量的所述共聚酰胺的微晶的熔点Tm位于240℃-300℃范围内。
3.根据前述权利要求之一的模塑料,其特征在于:在所述部分芳族共聚酰胺中氨基端基与氨基和羧基端基之和的比率为0.3-0.7。
4.根据前述权利要求之一的模塑料,其特征在于:在根据b)的烯烃共聚物中,所述其它烯烃不是非共轭的二烯。
5.根据前述权利要求之一的模塑料,其特征在于:在根据b)的烯烃共聚物中,所述其它烯烃不是苯乙烯和/或不是丙烯。
6.根据权利要求1-3之一的模塑料,其特征在于:所述烯烃共聚物仅含有衍生自乙烯、具有4-8个C原子的1-烯烃和脂族不饱和二羧酸酐的单体单元。
7.根据前述权利要求之一的模塑料,其特征在于:所述具有4-8个C原子的1-烯烃是1-丁烯、1-己烯、1-辛烯或其混合物。
8.根据前述权利要求之一的模塑料,其特征在于:其含有0.01-60重量%的其它添加剂。
9.根据权利要求8的模塑料,其特征在于:所述其它添加剂之一是含铜的稳定剂。
10.根据权利要求8和9之一的模塑料,其特征在于:所述其它添加剂之一是氧化稳定剂。
11.模塑制品,其使用根据前述权利要求之一的模塑料制备。
12.根据权利要求11的模塑制品,其特征在于:其为单层管或多层管。
13.根据权利要求11的模塑制品,其特征在于:其为单层容器或多层容器。
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CN114514263A (zh) * | 2019-10-11 | 2022-05-17 | 赢创运营有限公司 | 含有聚醚酰胺(pea)的模塑料 |
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CN111511551A (zh) * | 2017-12-22 | 2020-08-07 | Ems 专利股份公司 | 柔性塑料管路以及用于其制造的方法和其应用 |
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CN114514263A (zh) * | 2019-10-11 | 2022-05-17 | 赢创运营有限公司 | 含有聚醚酰胺(pea)的模塑料 |
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CN104448794B (zh) | 2019-04-23 |
US20150086738A1 (en) | 2015-03-26 |
BR102014023206B1 (pt) | 2020-08-25 |
JP6463057B2 (ja) | 2019-01-30 |
RU2014137952A (ru) | 2016-04-10 |
KR20150032812A (ko) | 2015-03-30 |
BR102014023206A2 (pt) | 2015-09-08 |
KR102154551B1 (ko) | 2020-09-10 |
EP2860220A1 (de) | 2015-04-15 |
RU2663174C2 (ru) | 2018-08-01 |
JP2015059222A (ja) | 2015-03-30 |
DE102013218964A1 (de) | 2015-03-26 |
EP2860220B1 (de) | 2016-05-25 |
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