CN1900163B - 具有高熔体刚度的聚酰胺模塑物料用于与高熔点聚合物共挤出的用途 - Google Patents
具有高熔体刚度的聚酰胺模塑物料用于与高熔点聚合物共挤出的用途 Download PDFInfo
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Abstract
本发明使用包含如下成分的模塑物料,与具有至少255℃的晶体熔点Tm和/或至少180℃的玻璃化转变温度Tg的基于高熔点聚合物的模塑物料共挤出,a)100重量份的聚酰胺以及b)0.005至10重量份的具有至少两个碳酸酯单元的化合物,这其中可得到具有良好品质、特别是具有好的层厚和壁厚分布的多层复合体。
Description
技术领域
本发明的主题在于具有高熔体刚度的聚酰胺模塑物料用于与基于高熔点聚合物的模塑物料一起共挤出的用途。本发明的主题还在于由具有高熔体刚度的聚酰胺模塑物料和基于高熔点聚合物的模塑物料组成的多层复合体的共挤出方法,以及由此制得的多层复合体。
背景技术
高熔点聚合物在本发明范畴内是指只能在高温下才可加工的那些。这就涉及到晶体熔点Tm(根据ISO 11357利用DSC测得)为至少270℃的部分结晶的聚合物。如果是非晶态聚合物,则玻璃化转变点Tg(同样根据ISO 11357利用DSC测得)应在至少190℃。两种类型的聚合物都只能在约300℃或者更高的温度下以经济上足够的速率进行挤出。
在共挤出聚酰胺如PA12和这种的HT聚合物时,由于高挤出温度和由此而引起的强烈下降的聚酰胺熔体刚度,使得出现各种各样的困难。过高的熔体粘度差会导致层间界不稳定,导致层厚和壁厚分布变差并总体造成不令人满意的挤出质量。
由于此原因,在过去曾有一些改进措施,其中是将例如ETFE的熔点(晶体熔点Tm为约270℃;加工温度300至340℃)降低以获得与低熔点聚合物(例如PA12)的可共挤出性。这种改进的结果是,例如得到了晶体熔点为约255℃和具有推荐的280至290℃的加工温度的软ETFE(例如Neoflon RP7000,Daikin公司,日本),或者是一种具有约195℃的晶体熔点和在约240至285℃下加工的聚合物型EFEP(例如Neoflon RP5000,Daikin公司)。基于PA12的挤出模塑物料的熔体刚度在这一加工温度范围内已经足以以足够好的品质实现与软ETFE或EFEP的可共挤出性。但是在对ETFE改性时,人们则不得不容忍其工业应用性能(例如对于燃料的阻隔作用)变差。
特定的研究表明,由于有着上述的困难,与其他高熔点聚合物如PPS的共挤出很难实现。
发明内容
本发明的任务在于避免上述缺陷。
本发明的任务的解决方法在于使用一种包含如下成分的模塑物料,与基于具有至少270℃的晶体熔点Tm和/或至少190℃的玻璃化转变温度Tg的高熔点聚合物的模塑物料共挤出:
a)100重量份的聚酰胺,以及
b)0.005至10重量份的具有至少两个碳酸酯单元的化合物。
这种聚酰胺模塑物料公开于WO 00/66650中。其中记载了使用具有至少两个碳酸酯单元的化合物来缩合聚酰胺,该过程中可以可靠而稳定地调节性能并提供了对缩合的材料进行多次加工而不会形成凝胶或造成不均匀的可能性。基于该原理的用于调节聚酰胺分子量的添加剂可从Brüggemann KG公司以Brüggolen M1251的牌号购得。主要应用是在PA6或PA66的回收物的粘度调节领域,该回收物可在挤出模塑物料中重新加以利用。所谓添加剂BrüggolenM1251指的是低粘度聚碳酸酯,例如Lexan 141在酸封端的PA6中形成的母料。分子量增加的原因是在要缩合的材料中所含的氨端基与聚碳酸酯进行反应。
适于本发明范畴的聚酰胺是基于己内酰胺、氨基羧酸、二胺或二羧酸结构的。此外也可以含有具支化作用的结构单元,例如衍生自三羧酸、三胺或聚乙烯亚胺的那些。分别作为均聚物或共聚物的形式,合适的类型有例如PA6、PA66、PA610、PA66/6以及特别是PA612、PA1010、PA1012、PA1212、PA613、PA614、PA1014、PA11、PA12或透明聚酰胺。作为透明聚酰胺可考虑以下例子:
-由对苯二甲酸与2,2,4-和2,4,4-三甲基-1,6-己二胺组成的异构体混合物形成的聚酰胺,
-由间苯二甲酸和1,6-己二胺形成的聚酰胺,
-由对苯二甲酸/间苯二甲酸混合物和1,6-己二胺形成的共聚酰胺,
-由间苯二甲酸、3,3’-二甲基-4,4’-二氨基二环己基甲烷和月桂内酰胺或己内酰胺形成的共聚酰胺,
-由1,12-十二双酸、3,3’-二甲基-4,4’-二氨基二环己基甲烷和任选地月桂内酰胺或己内酰胺形成的(共)聚酰胺,
-由间苯二甲酸、4,4-二氨基二环己基甲烷和月桂内酰胺或己内酰胺形成的共聚酰胺,
-由1,12-十二双酸和4,4’-二氨基二环己基甲烷形成的聚酰胺,
-由对苯二甲酸/间苯二甲酸混合物、3,3’-二甲基-4,4’-二氨基二环己基甲烷和月桂内酰胺形成的共聚酰胺。
此外,合适的还有基于内酰胺、氨基羧酸、二胺、二羧酸和聚醚二胺和/或聚醚二醇的聚醚酰胺。
优选原料化合物具有大于5000,特别是大于8000的分子量Mn。这里使用其端基至少部分以氨基形式存在的聚酰胺。例如,至少30%、至少40%、至少50%、至少60%、至少70%、至少80%或至少90%的端基以氨端基形式存在。现有技术中,使用二胺或多胺作为调节剂来制备具有更高氨端基含量的聚酰胺。在本发明情况下,在制备聚酰胺时优选使用具有4至44个C原子的脂族、脂环族或芳脂族的二胺作为调节剂。合适的二胺是例如己二胺、癸二胺、2,2,4-或2,4,4-三甲基-1,6-己二胺、1,12-十二烷二胺、1,4-二氨基环己烷、1,4-或1,3-二甲基氨基环己烷、4,4’-二氨基二环己基甲烷、4,4’-二氨基-3,3’-二甲基二环己基甲烷、4,4’-二氨基二环己基丙烷、异佛尔酮二胺、间苯二甲胺或对苯二甲胺。
在另一个优选实施方式中,制备聚酰胺时使用多胺作为调节剂并同时作为支化剂。此类例子是二亚乙基三胺、1,5-二氨基-3-(β-氨基乙基)戊烷、三(2-氨基乙基)胺、N,N-双(2-氨基乙基)-N’,N’-双[2-[双(2-氨基乙基)氨基]-乙基]-1,2-乙二胺、枝状聚合物以及聚乙烯亚胺,特别是通过氮丙啶聚合得到的支化的聚乙烯亚胺(Houben-Weyl,Methoden der Organischen Chemie,第E20卷,第1482-1487页,Georg Thieme出版社,斯图加特,1987)并且通常其具有以下氨基分布:
25至46%的伯氨基,
30至45%的仲氨基,
16至40%的叔氨基。
在本发明方法中使用至少一种具有至少两个碳酸酯单元的化合物且其用量比例为0.005至10重量%,相对于所用聚酰胺计算。优选这一比例在0.01至5.0重量%、特别优选在0.05至3重量%的范围内。术语“碳酸酯”在此指的是碳酸特别与酚或醇形成的酯。
具有至少两个碳酸酯单元的化合物可以是小分子、低聚物和聚合物。其可以完全由碳酸酯单元构成或者其还可含有其他单元。它们优选是低聚或聚合的酰胺、酯、醚、醚酯酰胺或醚酰胺单元。这些化合物可以通过已知的低聚法或高聚法或者通过与聚合类似的反应制得。
在一个优选实施方式中,具有至少两个碳酸酯单元的化合物是指例如基于双酚A的聚碳酸酯,或者是含有这种聚碳酸酯嵌段的嵌段共聚物。
合适的具有至少两个碳酸酯单元的化合物以及合适的母料详细记载于WO00/66650中,在此明确引用该文献内容。
以母料形式计量加入作为添加剂用的具有至少两个碳酸酯单元的化合物可以实现添加剂的更精确加料,因为所用的量更大了。另外还发现通过使用母料可以获得更好的挤出质量。母料包含优选作为基质材料的且在本发明方法中也可被缩合的聚酰胺,或者与此相容的聚酰胺,但是在反应条件下,不相容的聚酰胺也可以部分地连接在将缩合的聚酰胺上,这就起到了相容作用。在母料中作为基体材料使用的聚酰胺优选具有大于5000且特别优选大于8000的分子量Mn。这里优选是那种其端基主要以羧酸基形式存在的聚酰胺。例如至少80%、至少90%或至少95%的端基以酸基形式存在。
母料中,具有至少两个碳酸酯单元的化合物的浓度优选为0.15至50重量%、更优选0.2至25重量%且特别优选0.3至15重量%。这种母料的制备以通常的、技术人员所公知的方法进行。
本发明可应用于由于制备条件而含有至少5ppm酸性化合物形式的磷的聚酰胺。在这种情况下,聚酰胺模塑物料在配混前或者在配混时要添加0.001至10重量%的弱酸盐,以聚酰胺量计。合适的盐公开于DE-A-10337707中,在此明确引入该文献的内容。
但是,本发明可同样好地用于由于制备条件而含有少于5ppm酸性化合物形式的磷甚至不含磷的聚酰胺。在这种情况下也就可以、但不必添加弱酸的相应盐。
根据本发明可以使用常规的在制备聚酰胺模塑物料时使用的添加剂。说明性的例子有着色剂、燃烧延迟剂和阻燃剂、稳定剂、填料、润滑改良剂、脱模剂、冲击改性剂、增塑剂、结晶促进剂、抗静电剂、润滑剂、加工助剂以及其他通常可与聚酰胺配混的聚合物。
这些添加剂的实例有以下:
着色剂:二氧化钛、铅白、锌白、Liptone、锑白、炭黑、氧化铁黑、锰黑、钴黑、锑黑、铬酸铅、铅丹、锌黄、锌绿、镉红、钴蓝、柏林蓝、群青、锰紫、镉黄、施韦因福特绿、钼橙和钼红、铬橙和铬红、氧化铁红、氧化铬绿、锶黄、钼蓝、白垩、赭石、杂铁锰胶块土、绿土、经锻烧赭土、石墨或可溶性的有机色料。
燃烧延迟剂和防火剂:三氧化锑,六溴环十二烷,四氯或四溴双酚,卤代磷酸盐,硼酸盐,氯化石蜡以及红磷,此外还有锡酸盐,氰尿酸蜜胺酯和它们的缩合产物如蜜白胺、蜜勒胺、氰尿酰胺,蜜胺化合物如蜜胺焦磷酸盐和蜜胺多磷酸盐,多磷酸铵,氢氧化铝,氢氧化钙以及不含卤素的有机磷化合物,如间苯二酚二苯基磷酸酯或膦酸酯。
稳定剂:金属盐,特别是铜盐和钼盐以及铜络合物,亚磷酸盐,空间位阻酚,仲胺,UV吸收剂和HALS稳定剂。
润滑改良剂和润滑剂:MoS2、石蜡、脂肪醇以及脂肪酸酰胺。
脱模剂和加工助剂:蜡(褐煤酸酯)、褐煤酸蜡、褐煤酸酯蜡、聚硅氧烷、聚乙烯醇、SiO2、硅酸钙以及全氟聚醚。
增塑剂:BBSA,POBO。
冲击韧性改性剂:聚丁二烯、EPM、EPDM、HDPE、丙烯酸酯橡胶。
抗静电剂:炭黑、碳纤维、石墨纤丝、多元醇、脂肪酸酯、胺、酰胺、季铵盐。
其他聚合物:ABS、聚丙烯。
这些添加剂可以以常规的、技术人员所熟知的量使用。
高熔点聚合物优选具有分别为至少255℃、260℃、265℃、270℃、275℃、280℃、285℃、290℃、295℃或300℃的晶体熔点Tm,和/或分别为至少180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃、220℃、225℃、230℃、235℃、240℃或245℃的玻璃化转变温度。在基于这种聚合物的模塑物料中,其含有量为至少50重量%、至少55重量%、至少60重量%、至少65重量%、至少70重量%、至少75重量%或至少80重量%。
合适的高熔点聚合物是例如:
-含氟聚合物,如聚四氟乙烯(PTFE)、四氟乙烯-六氟丙烯共聚物(FEP)或乙烯-四氟乙烯共聚物(ETFE);
-聚酰胺和共聚酰胺,如PA46、PA66、PA9T、PA12T、PA66/6T、PA6/6T或PA6T/MPMDT(MPMD表示2-亚甲基-1,5-戊二胺);
-聚醚酮,如PEEK、PEKK或PEK;
-液晶聚合物(LCP),如液晶聚酯;
-聚苯硫(PPS);
-聚砜;
-聚醚砜;
-聚醚酰亚胺,以及
-间同立构聚苯乙烯。
需要时可通过使用合适的粘结剂而在聚酰胺模塑物料和基于高熔点聚合物的模塑物料之间实现层间粘结。
由聚酰胺和具有至少两个碳酸酯单元的化合物构成的模塑物料可以事先制备出来并以这种形式用于共挤出中。但是在一个优选实施方式中也可以将该模塑物料在加工过程中原位制得。
因此,本发明的主题还在于制备多层复合体的方法,其中,
a)提供聚酰胺模塑物料,
b)制备聚酰胺模塑物料和以100重量份聚酰胺计为0.005至10重量份的、具有至少两个碳酸酯单元的化合物组成的预混物,
c)视需要存放和/或运输所述混合物,和
d)接着将此混合物与基于高熔点的聚合物的模塑物料一起共挤出。
现已惊人地发现,在这种添加方式下,在加工时会出现熔体刚度显著提高的现象,同时加工压力适中且电机负载小。因此,尽管有着高熔体粘度,但是在加工时还是可获得高物料通量,由此实现生产工艺经济性的改善。
在根据权利要求的方法中,具有至少两个碳酸酯单元的化合物以其本身形式或者母料形式在配混后才添加,但也可之后在加工过程中进行添加。优选在加工过程中混合待缩合的聚酰胺或颗粒形式的待缩合聚酰胺模塑物料与具有至少两个碳酸酯单元的化合物的颗粒或相应的母料。但是也可以制备配混后的聚酰胺模塑物料与具有至少两个碳酸酯单元的化合物或母料的颗粒混合物,接着进行运输或存放,然后进行加工。相应地,自然也可利用粉末混合物来进行。关键点是混合物只在加工时才熔融。值得推荐的是加工时,熔体彻底混合。但是,母料也可以很好地以熔体流形式利用所提供的挤出机计量添加到待加工的聚酰胺模塑物料的熔体中,然后进行彻底混合。
本发明的主题还在于使用根据权利要求的聚酰胺模塑物料或根据本发明方法所制得的多层复合体。这些多层复合体是,例如,型材,平面型材,中空型材,供给管道,如加油站供油管,通风管,抽气管,油箱填充架,燃料管,油箱排气管,曲轴箱排气管,冷却剂导管,压缩空气制动管,水压管(耦合器和制动器),缆道,电缆套,平面膜,吹塑膜,片材,存储容器,瓶子或燃料罐。这些成形部件和包覆体都可例如通过共挤出方法制得,包括连续的共挤或共挤吹塑,如抽气吹塑成型,3-D吹塑成型,内胎植入法和内胎操作法。这些方法都是现有技术。另外还可以利用所谓的Conex法来制备多层复合体。其指的是一种共挤出方法,其中各个层都可以相当于缠绕法中那样重叠覆盖上去(WO 97/28949)。
具体实施方式
在一个有益实施方式中,可以在本发明的多层管上设置两个覆层,就像在实用新型DE 202004004753U1中所述的那样。接着用含有玻璃纤维或芳酰胺纤维的带子或粗纱来缠绕管子。由此就形成了一种轻质且降低渗透的气体和液体存储容器。
对于本发明的管,合适的层结构由外向内有例如以下这些,其中PA表示根据权利要求的聚酰胺模塑物料,HT表示基于高熔点聚合物的模塑物料,而HV表示粘结剂:
PA/HT
HT/PA
PA/HV/HT
HT/HV/PA
PA/HT/PA
HT/PA/HT
PA/HV/HT/HV/PA
PA/HT/HT(具导电能力)
PA/HT/PA/PA(具有导电能力)
内层的导电能力可以根据现有技术,例如通过向各个模塑物料中配混入有效量的导电炭黑、石墨纤丝或其他导电添加剂而获得。
以下示例性阐释发明。在试验中用到了以下材料:
胺调节的PA12,具有50毫当量/kg的NH2基团和9毫当量/kg的COOH基团,ηrel约为2.15。
酸调节的PA12,具有8毫当量/kg的NH2基团和50毫当量/kg的COOH基团,ηrel约为2.15。
在Wemer&Pfleiderer ZSK 30型双螺杆挤出机上制备表1中所列的组合物。
表1:接着要继续使用的组合物的制备
配混物A | 母料1 | 母料2 | 母料3 | 母料4 | |
胺调节的PA12[重量%] | 60 | 99.9 | 0 | 0 | 0 |
酸调节的PA12[重量%] | 40 | 0 | 98.9 | 98.4 | 97.4 |
BrüggolenM1251[重量%] | 0 | 0 | 1 | 1.5 | 2.5 |
Ceasit PC[重量%] | 0 | 0.1 | 0.1 | 0.1 | 0.1 |
物料通量[kg/h] | 10 | 10 | 10 | 10 | 10 |
剪切速率[l/min] | 250 | 250 | 250 | 250 | 250 |
熔融温度[℃] | 251 | 249 | 251 | 251 | 251 |
熔体压力[bar] | 33 | 35 | 34 | 34 | 34 |
电机功率[%] | 73 | 78 | 72 | 72 | 72 |
η<sub>rel</sub>,根据DIN EN ISO307 | 2.11 | 2.10 | 2.12 | 2.12 | 2.12 |
比较例1以及实施例1至3:
在240℃或300℃下利用扭矩流变仪(Drehrehometer)来测量表2中所述的组合物的熔体刚度。
扭矩流变仪用以测量恒定的抽出速率条件下或者恒定或指数加速抽出条的条件下熔体的膨胀能力(M.H.Wagner,A.Bernat,V.Schulze,Kautschuk GummiKunststoffe 50年度,9/97号;M.H.Wagner,V.Schulze,A.Gttfert,PolymerEngineering and Science,四月中,1996,36卷,第7号)。
这里所用的设备是Gttfert公司的最高为30转/分的单螺杆实验室用挤出机且其后连接着抽出装置。在挤出机内,从颗粒或颗粒混合物出发对表2中所列的原料进行加工。利用抽出装置,以不同的速度拉伸所排出的股线直至断裂,同时测量此时所需的转矩;由此计算出抽出力。结果列于表2中。
可以看出,根据本发明,在300℃下可以得到与在典型的240℃的加工温度下传统的PA12模塑物料相比,大略相同甚或更高的熔体刚度。因此,本发明所制得的聚酰胺模塑物料可以在300℃且更高的温度范围内使用,优选用于与高熔点的聚合物一起共挤出。
表2:用扭矩流变仪进行测量
比较例1 | 实施例1 | 实施例2 | 实施例3 | |
配混物A[重量%] | 100 | 0 | 0 | 0 |
母料1[重量%] | 0 | 60 | 60 | 60 |
母料2[重量%] | 0 | 40 | 0 | 0 |
母料3[重量%] | 0 | 0 | 40 | 0 |
母料4[重量%] | 0 | 0 | 0 | 40 |
物料通量[g/min] | 12 | 12 | 12 | 12 |
最大抽出力[cN]240℃ | 4.5 | 18.5 | 29.2 | 42.1 |
300℃ | 2.4 | 4.1 | 5.4 | 7.4 |
Claims (7)
1.包含如下成分的模塑物料用于与基于具有至少255℃的晶体熔点Tm和/或至少180℃的玻璃化转变温度Tg的高熔点聚合物的模塑物料共挤出用于制造多层复合材料的用途,
a)100重量份的聚酰胺,以及
b)0.005至10重量份的具有至少两个碳酸酯单元的化合物。
2.权利要求1的用途,其特征在于,所述高熔点聚合物具有至少270℃的晶体熔点Tm和/或至少190℃的玻璃化转变温度Tg。
3.权利要求1或2的用途,其特征在于,使用二胺或多胺作为调节剂来制备聚酰胺。
4.制备多层复合材料的方法,其中
a)提供聚酰胺模塑物料,
b)制备由聚酰胺模塑物料和以100重量份聚酰胺计0.005至10重量份的、具有至少两个碳酸酯单元的化合物组成的预混物,
c)视需要存放和/或运输所述混合物,和
d)接着将此混合物与基于高熔点聚合物的模塑物料一起共挤出,所述高熔点聚合物具有至少255℃的晶体熔点Tm和/或至少180℃的玻璃化转变温度Tg。
5.权利要求4的方法,其特征在于,所述高熔点聚合物具有至少270℃的晶体熔点Tm和/或至少190℃的玻璃化转变温度Tg。
6.权利要求4或5的方法,其特征在于,以母料形式使用具有至少两个碳酸酯单元的化合物。
7.多层复合材料,其根据权利要求4-6之一的方法制得。
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Publication number | Priority date | Publication date | Assignee | Title |
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DE102005007663A1 (de) | 2005-02-19 | 2006-08-24 | Degussa Ag | Transparente, dekorierbare mehrschichtige Folie |
DE102005007664A1 (de) * | 2005-02-19 | 2006-08-31 | Degussa Ag | Transparente Formmasse |
DE102005026264A1 (de) | 2005-06-08 | 2006-12-14 | Degussa Ag | Transparente Formmasse |
DE102006038108A1 (de) | 2006-08-14 | 2008-02-21 | Evonik Degussa Gmbh | Verwendung eines Formteils aus einer Polyamidformmasse als Inliner für eine Rohrleitung |
DE102007040683A1 (de) * | 2007-08-29 | 2009-03-05 | Evonik Degussa Gmbh | Umhüllte Rohrleitung |
DE102007041488A1 (de) * | 2007-08-31 | 2009-03-05 | Evonik Degussa Gmbh | Fügen von Formteilen aus unterschiedlichen Polyamidformmassen |
DE102008001678A1 (de) * | 2007-10-17 | 2009-04-23 | Evonik Degussa Gmbh | Verwendung einer Polyamidformmasse zur Auskleidung von Rohrleitungen |
DE102008001873A1 (de) * | 2008-05-20 | 2009-11-26 | Evonik Degussa Gmbh | Kerbschlagzähe Polyarylenetherketon-Formmasse |
DE102008002599A1 (de) * | 2008-06-24 | 2009-12-31 | Evonik Degussa Gmbh | Bauteil mit Deckschicht aus einer PA613-Formmasse |
DE102008044225A1 (de) * | 2008-12-01 | 2010-06-02 | Evonik Degussa Gmbh | Verfahren zur Herstellung einer Formmasse oder eines Formteils mit erhöhter Schmelzesteifigkeit |
DE102008044224A1 (de) * | 2008-12-01 | 2010-06-02 | Evonik Degussa Gmbh | Verwendung einer Zusammensetzung für den Kontakt mit überkritischen Medien |
DE102009001001A1 (de) | 2009-02-19 | 2010-09-02 | Evonik Degussa Gmbh | Verwendung eines Leitungsrohrs zur Herstellung einer im Wasser verlegten Rohrleitung |
US9592648B2 (en) * | 2009-06-01 | 2017-03-14 | Gates Corporation | Low-permeation flexible fuel hose |
DE102010003916A1 (de) | 2010-04-13 | 2011-10-13 | Evonik Degussa Gmbh | Flexibles Rohr und Verfahren zu dessen Herstellung |
DE102010003920A1 (de) * | 2010-04-13 | 2011-10-13 | Evonik Degussa Gmbh | Flexibles Rohr mit höherer Temperaturbeständigkeit |
DE102010003909A1 (de) | 2010-04-13 | 2011-10-13 | Evonik Degussa Gmbh | Flexibles Rohr mit mehrschichtigem Aufbau |
CN111098491A (zh) * | 2010-04-25 | 2020-05-05 | 斯特塔西有限公司 | 带外壳物体的实体无模制造 |
DE102011004305A1 (de) * | 2011-02-17 | 2012-08-23 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Stäben |
US20140377487A1 (en) * | 2013-06-24 | 2014-12-25 | Hamilton Sundstrand Corporation | Suction-blow-molded aircraft ducting |
DE102013218957A1 (de) | 2013-09-20 | 2015-03-26 | Evonik Industries Ag | Formmasse auf Basis eines teilaromatischen Copolyamids |
CA2941018A1 (en) * | 2014-04-10 | 2015-10-15 | Mitsubishi Gas Chemical Company, Inc. | Molded body and manufacturing method thereof |
US9422398B2 (en) | 2014-05-30 | 2016-08-23 | Industrial Technology Research Institute | Copolymer, and method for preparing a monomer used to form the copolymer |
EP3477176A1 (de) | 2017-10-25 | 2019-05-01 | Evonik Degussa GmbH | Verfahren zur herstellung eines mit einem inliner ausgekleideten rohres |
KR102480392B1 (ko) * | 2019-12-30 | 2022-12-26 | 세메스 주식회사 | 기판 처리 장치 및 방법 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1406739A (zh) * | 2001-09-06 | 2003-04-02 | Ti集团车辆系统(富尔达布吕克)公司 | 通过共挤出制成的油料等用的汽车管路 |
WO2003047857A1 (en) * | 2001-11-30 | 2003-06-12 | General Electric Company | Multilayer articles comprising resorcinol arylate polyester and method for making thereof |
CN1590460A (zh) * | 2003-08-16 | 2005-03-09 | 德古萨公司 | 增加聚酰胺分子量的方法 |
Family Cites Families (81)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1289297C2 (de) * | 1965-04-02 | 1973-09-06 | Kalle Ag | Verfahren und Vorrichtung zur kontinuierlichen Herstellung mehrschichtiger Schlaeuche aus thermoplastischen Kunststoffen nach dem Extrusionsverfahren |
GB1180403A (en) * | 1966-02-11 | 1970-02-04 | Toyo Rayon Co Ltd | Polyamide Resin Composition |
ZA693804B (en) | 1968-06-13 | 1971-01-27 | Colgate Palmolive Co | Detergents |
JPS5519948B2 (zh) * | 1973-02-06 | 1980-05-29 | ||
CA1074049A (en) | 1974-11-13 | 1980-03-18 | Russell Van Cleve | Polymer/polyols and polyurethane derivatives thereof |
US4482695A (en) * | 1983-11-14 | 1984-11-13 | Eastman Kodak Company | Polyamide containers having improved gas barrier properties |
US4732934A (en) * | 1986-12-08 | 1988-03-22 | General Electric Company | Functionalized thermoplastic polymers, blends prepared therefrom, and methods for preparing blends |
US5248720A (en) * | 1988-09-06 | 1993-09-28 | Ube Industries, Ltd. | Process for preparing a polyamide composite material |
US5068284A (en) * | 1990-08-03 | 1991-11-26 | General Electric Company | Blocked amine terminated polycarbonates and products obtained therefrom |
EP0598836B1 (en) * | 1991-08-12 | 1997-10-15 | AlliedSignal Inc. | Melt process formation of polymer nanocomposite of exfoliated layered material |
DE4130486A1 (de) * | 1991-08-23 | 1993-02-25 | Wolff Walsrode Ag | 5-schichtige, coextrudierte biaxial gereckte schlauchfolie mit mindestens 3 pa-schichten |
DE4317189A1 (de) | 1993-05-22 | 1994-11-24 | Huels Chemische Werke Ag | Schmelzflüssige, aliphatische Dicarbonsäuren |
ATE177053T1 (de) * | 1993-09-28 | 1999-03-15 | Inventa Ag | Mehrschicht-polymerrohrleitung |
DE19510314A1 (de) | 1995-03-22 | 1996-09-26 | Huels Chemische Werke Ag | Polyester für das Verkleben von Textilien |
DE19536056A1 (de) | 1995-09-28 | 1997-04-03 | Huels Chemische Werke Ag | Flüssige Lösungen von Dicarbonsäuren |
CA2221266A1 (en) * | 1996-12-10 | 1998-06-10 | Achim Grefenstein | Laminated sheets or films and moldings thereof |
DE19708946A1 (de) | 1997-03-05 | 1998-09-10 | Huels Chemische Werke Ag | Herstellung von Polyamid-Fällpulvern mit enger Korngrößenverteilung und niedriger Porosität |
DE19746834A1 (de) | 1997-10-23 | 1999-04-29 | Huels Chemische Werke Ag | Polyethylenwachs als Verarbeitungshilfe für Schmelzklebermassen |
DE19808809A1 (de) | 1998-03-03 | 1999-09-09 | Degussa | Vernetzende Basisschicht für Fixiereinlagen nach dem Doppelpunktverfahren |
DE19830976A1 (de) * | 1998-07-10 | 2000-01-13 | Wolff Walsrode Ag | Mehrschichtige, coextrudierte, wärmestabile Tiefziehfolie für Verpackungsanwendungen |
DE19830977A1 (de) * | 1998-07-10 | 2000-01-13 | Wolff Walsrode Ag | Mehrschichtige, symmetrische, rollneigungsfreie, coextrudierte Tiefziehfolie |
US6525099B1 (en) * | 1998-07-31 | 2003-02-25 | Eli Lilly And Company | N-substituted sulfonamide derivatives |
US6232388B1 (en) * | 1998-08-17 | 2001-05-15 | Amcol International Corporation | Intercalates formed by co-intercalation of onium ion spacing/coupling agents and monomer, oligomer or polymer MXD6 nylon intercalants and nanocomposites prepared with the intercalates |
AU6416399A (en) * | 1998-10-01 | 2000-04-17 | Airtech International, Inc. | Method of molding or curing a resin material at high temperatures using a multilayer release film |
DE19854819A1 (de) | 1998-11-27 | 2000-05-31 | Degussa | Hohler Artikel mit antistatischen Eigenschaften |
US6589615B1 (en) * | 1999-01-04 | 2003-07-08 | William W. Yen | Thermoplastic food casing |
DE19908640A1 (de) | 1999-02-27 | 2000-08-31 | Degussa | Mehrschichtverbund |
DE19920336C2 (de) * | 1999-05-03 | 2002-10-24 | Brueggemann Kg Sprit Und Chem | Verfahren zur Aufkondensierung von Polyamiden |
US6632868B2 (en) * | 2000-03-01 | 2003-10-14 | Amcol International Corporation | Intercalates formed with polypropylene/maleic anhydride-modified polypropylene intercalants |
DE10010669A1 (de) * | 2000-03-04 | 2001-09-06 | Degussa | Verfahren zur Herstellung eines extrusionsbeschichteten Metallgegenstands |
JP4096556B2 (ja) * | 2000-03-23 | 2008-06-04 | ダイキン工業株式会社 | 多層積層体の製造方法 |
JP2003535204A (ja) * | 2000-05-30 | 2003-11-25 | ユニバーシティ オブ サウスカロライナ リサーチ ファウンデーション | マトリックスポリマーおよび抽出可能な物質のレベルが改善された層状粘土物質を含むポリマーナノ複合材 |
DE10030716A1 (de) | 2000-06-23 | 2002-01-03 | Degussa | Tieftemperaturschlagzähe Polymerlegierung |
DE10032075A1 (de) | 2000-07-01 | 2002-01-10 | Degussa | Elektrostatische Beschichtung von Formteilen mit thermoplastischen und vernetzbaren Copolyamidschmelzklebern |
JP2002018999A (ja) * | 2000-07-06 | 2002-01-22 | Toyoda Gosei Co Ltd | 樹脂積層体 |
DE10050231A1 (de) | 2000-10-11 | 2002-04-25 | Degussa | Vernetzende Basisschicht für Fixiereinlagen nach dem Doppelpunkt- und Pastenverfahren |
DE10064338A1 (de) | 2000-12-21 | 2002-06-27 | Degussa | Formmasse mit guter Blasformbarkeit |
JP4961632B2 (ja) * | 2001-02-01 | 2012-06-27 | 三菱瓦斯化学株式会社 | ポリアミド延伸フィルム |
DE10161038A1 (de) | 2001-12-12 | 2003-06-26 | Degussa | pH-Wert geregeltes Polyamidpulver für Kosmetikanwendungen |
DE10164408A1 (de) | 2001-12-28 | 2003-07-17 | Degussa | Flüssigkeits- oder dampfführendes System mit einer Fügezone aus einem coextrudierten Mehrschichtverbund |
DE10201903A1 (de) | 2002-01-19 | 2003-07-31 | Degussa | Formmasse auf Basis von Polyetheramiden |
CA2417485C (en) * | 2002-01-29 | 2010-08-17 | Kuraray Co., Ltd. | Thermoplastic polyurethane composition and process for producing the same |
US6803113B2 (en) * | 2002-09-13 | 2004-10-12 | Honeywell International Inc. | High barrier antifog laminate for case ready meat packaging |
DE10228439A1 (de) | 2002-06-26 | 2004-01-22 | Degussa Ag | Kunststoff-Lichtwellenleiter |
US20070167552A1 (en) * | 2002-08-27 | 2007-07-19 | Georg Stoeppelmann | Polyamide moulding materials for the production of moulded articles having reduced surface carbonization |
DE50309009D1 (de) | 2002-09-21 | 2008-03-06 | Evonik Degussa Gmbh | Verfahren zur Herstellung eines dreidimensionalen Objektes |
DE10245355A1 (de) | 2002-09-27 | 2004-04-08 | Degussa Ag | Rohrverbindung |
DE10248406A1 (de) | 2002-10-17 | 2004-04-29 | Degussa Ag | Laser-Sinter-Pulver mit Titandioxidpartikeln, Verfahren zu dessen Herstellung und Formkörper, hergestellt aus diesem Laser-Sinterpulver |
EP1413594A2 (de) | 2002-10-17 | 2004-04-28 | Degussa AG | Laser-Sinter-Pulver mit verbesserten Recyclingeigenschaften, Verfahren zu dessen Herstellung und Verwendung des Laser-Sinter-Pulvers |
DE10250330A1 (de) | 2002-10-29 | 2004-05-13 | Degussa Ag | Biegeelement mit drehsinnabhängigem Verhalten |
DE10251790A1 (de) | 2002-11-07 | 2004-05-19 | Degussa Ag | Polyamidpulver mit dauerhafter, gleichbleibend guter Rieselfähigkeit |
EP1424354B1 (de) | 2002-11-28 | 2006-03-15 | Degussa AG | Laser-Sinter-Pulver mit Metallseifen, Verfahren zu dessen Herstellung und Formkörper, hergestellt aus diesem Laser-Sinter-Pulver |
US7534494B2 (en) * | 2002-12-02 | 2009-05-19 | Daicel-Evonik Ltd. | Composite formed body and method for producing same |
EP1459871B1 (de) | 2003-03-15 | 2011-04-06 | Evonik Degussa GmbH | Verfahren und Vorrichtung zur Herstellung von dreidimensionalen Objekten mittels Mikrowellenstrahlung sowie dadurch hergestellter Formkörper |
DE10311437A1 (de) | 2003-03-15 | 2004-09-23 | Degussa Ag | Laser-Sinter-Pulver mit PMMI, PMMA und/oder PMMI-PMMA-Copolymeren, Verfahren zu dessen Herstellung und Formkörper, hergestellt aus diesem Laser-Sinterpulver |
JP4619624B2 (ja) * | 2003-03-31 | 2011-01-26 | 旭硝子株式会社 | 積層ホース |
US20040209021A1 (en) * | 2003-04-18 | 2004-10-21 | Shih Keith S. | Multi-layer laminate structure |
DE10318321A1 (de) | 2003-04-19 | 2004-10-28 | Degussa Ag | Verfahren zum Ultraschallschweißen von Kunstoffkomponenten |
DE602004002949T2 (de) * | 2003-05-07 | 2007-05-03 | Topas Advanced Polymers Gmbh | Siegelbarer mehrschichtiger koextrudierter verpackungsfilm, seine verwendung sowie verfahren zu dessen herstellung |
KR101046555B1 (ko) * | 2003-06-18 | 2011-07-05 | 산요가세이고교 가부시키가이샤 | 투명성 수지 조성물 |
DE10333005A1 (de) | 2003-07-18 | 2005-02-03 | Degussa Ag | Formmasse auf Basis von Polyetheramiden |
DE10334497A1 (de) | 2003-07-29 | 2005-02-24 | Degussa Ag | Polymerpulver mit phosphonatbasierendem Flammschutzmittel, Verfahren zu dessen Herstellung und Formkörper, hergestellt aus diesem Polymerpulver |
DE10334496A1 (de) | 2003-07-29 | 2005-02-24 | Degussa Ag | Laser-Sinter-Pulver mit einem Metallsalz und einem Fettsäurederivat, Verfahren zu dessen Herstellung und Formkörper, hergestellt aus diesem Laser-Sinterpulver |
JP3783057B2 (ja) * | 2003-08-29 | 2006-06-07 | 独立行政法人物質・材料研究機構 | 電界電子放出特性を利する自己造形的表面形状を有するsp3結合性窒化ホウ素薄膜とその製造方法及びその用途 |
JP2005119017A (ja) * | 2003-10-14 | 2005-05-12 | Ube Ind Ltd | 積層構造体 |
US7786189B2 (en) * | 2003-12-22 | 2010-08-31 | Amcol International Corp. | Oligomer-modified layered inorganic compounds and their use in nanocomposites |
DE502004005258D1 (de) * | 2004-02-03 | 2007-11-29 | Ems Chemie Ag | Werkstoffverbunde aus einem Formteil aus transparenten oder transluzenten, einfärbbaren Kunststoffformmassen |
CN1964844A (zh) * | 2004-04-08 | 2007-05-16 | 陶氏环球技术公司 | 具有改进的组件间粘合性的多组件结构 |
DE102004025001A1 (de) * | 2004-05-21 | 2005-12-08 | Lanxess Deutschland Gmbh | Extrusionsverfahren mit Polyamiden |
CN100564029C (zh) * | 2004-06-21 | 2009-12-02 | 纳幕尔杜邦公司 | 包含聚酯多层薄膜的制品 |
US7833450B2 (en) * | 2004-06-22 | 2010-11-16 | Arkema France | Use of a microcrystalline polyamide to obtain a particular surface finish |
DE102004047876A1 (de) | 2004-10-01 | 2006-04-06 | Degussa Ag | Pulver mit verbesserten Recyclingeigenschaften, Verfahren zu dessen Herstellung und Verwendung des Pulvers in einem Verfahren zur Herstellung dreidimensionaler Objekte |
US8741433B2 (en) * | 2004-12-10 | 2014-06-03 | Curwood, Inc. | Packaging films comprising nylon blend compositions |
DE102004062761A1 (de) | 2004-12-21 | 2006-06-22 | Degussa Ag | Verwendung von Polyarylenetherketonpulver in einem dreidimensionalen pulverbasierenden werkzeuglosen Herstellverfahren, sowie daraus hergestellte Formteile |
DE102005026264A1 (de) * | 2005-06-08 | 2006-12-14 | Degussa Ag | Transparente Formmasse |
US7619024B2 (en) * | 2005-08-31 | 2009-11-17 | Amcol International Corporation | Resin compositions, intercalates, nanocomposites and laminates prepared with aromatic polyamide and polyphenoxy polymers |
US20070134411A1 (en) * | 2005-12-14 | 2007-06-14 | General Electric Company | Method for making compositions containing microcapsules and compositions made thereof |
CN101688032A (zh) * | 2007-05-09 | 2010-03-31 | 陶氏环球技术公司 | 基于乙烯的聚合物组合物、制备其的方法和由其制备的制品 |
US20090117399A1 (en) * | 2007-11-01 | 2009-05-07 | Next Generation Films, Inc. | Multi-layer polymer nanocomposite packaging films |
US20100151180A1 (en) * | 2008-10-13 | 2010-06-17 | Bravet David J | Multi-layer fluoropolymer film |
US20100108778A1 (en) * | 2008-10-30 | 2010-05-06 | Greenland Steven J | Device for containing and releasing a volatile substance |
-
2005
- 2005-07-04 DE DE200510031491 patent/DE102005031491A1/de not_active Withdrawn
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- 2006-06-06 ES ES06114974T patent/ES2714562T3/es active Active
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1406739A (zh) * | 2001-09-06 | 2003-04-02 | Ti集团车辆系统(富尔达布吕克)公司 | 通过共挤出制成的油料等用的汽车管路 |
WO2003047857A1 (en) * | 2001-11-30 | 2003-06-12 | General Electric Company | Multilayer articles comprising resorcinol arylate polyester and method for making thereof |
CN1590460A (zh) * | 2003-08-16 | 2005-03-09 | 德古萨公司 | 增加聚酰胺分子量的方法 |
Also Published As
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JP5080033B2 (ja) | 2012-11-21 |
BRPI0602498B1 (pt) | 2016-06-07 |
JP2007016234A (ja) | 2007-01-25 |
US8303873B2 (en) | 2012-11-06 |
KR101316555B1 (ko) | 2013-10-15 |
KR20070004440A (ko) | 2007-01-09 |
ES2714562T3 (es) | 2019-05-29 |
CN1900163A (zh) | 2007-01-24 |
US20070036998A1 (en) | 2007-02-15 |
RU2006123683A (ru) | 2008-01-20 |
EP1741540A1 (de) | 2007-01-10 |
EP1741540B1 (de) | 2018-12-05 |
BRPI0602498A (pt) | 2007-03-06 |
DE102005031491A1 (de) | 2007-01-11 |
RU2429260C2 (ru) | 2011-09-20 |
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