CN1539882A - 含有碳纳米管的聚酰胺/聚烯烃共混物 - Google Patents
含有碳纳米管的聚酰胺/聚烯烃共混物 Download PDFInfo
- Publication number
- CN1539882A CN1539882A CNA2004100052248A CN200410005224A CN1539882A CN 1539882 A CN1539882 A CN 1539882A CN A2004100052248 A CNA2004100052248 A CN A2004100052248A CN 200410005224 A CN200410005224 A CN 200410005224A CN 1539882 A CN1539882 A CN 1539882A
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- Prior art keywords
- layer
- blend
- polyamide
- polyolefine
- acid
- Prior art date
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000004952 Polyamide Substances 0.000 title claims abstract description 57
- 229920002647 polyamide Polymers 0.000 title claims abstract description 57
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 98
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 12
- 229920000571 Nylon 11 Polymers 0.000 claims abstract description 12
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 12
- 150000001408 amides Chemical class 0.000 claims description 68
- 239000000126 substance Substances 0.000 claims description 26
- 239000002071 nanotube Substances 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 5
- 238000010561 standard procedure Methods 0.000 abstract description 4
- 229920001169 thermoplastic Polymers 0.000 abstract description 4
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 4
- 238000001746 injection moulding Methods 0.000 abstract description 2
- 238000010101 extrusion blow moulding Methods 0.000 abstract 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 34
- -1 aminocaproic acid Chemical class 0.000 description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 29
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- 239000005977 Ethylene Substances 0.000 description 21
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 19
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 18
- 229920000570 polyether Polymers 0.000 description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 16
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- 239000004721 Polyphenylene oxide Substances 0.000 description 15
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
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- 239000004711 α-olefin Substances 0.000 description 8
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Chemical group 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 229920006132 styrene block copolymer Polymers 0.000 description 6
- YDBHSDRXUCPTQQ-UHFFFAOYSA-N 1-methylcyclohexan-1-amine Chemical compound CC1(N)CCCCC1 YDBHSDRXUCPTQQ-UHFFFAOYSA-N 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
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- 239000000155 melt Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 4
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- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 4
- 229920000572 Nylon 6/12 Polymers 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
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- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
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- 238000002156 mixing Methods 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
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- HWRRQRKPNKYPBW-UHFFFAOYSA-N 2,4-dimethylcyclohexan-1-amine Chemical compound CC1CCC(N)C(C)C1 HWRRQRKPNKYPBW-UHFFFAOYSA-N 0.000 description 2
- MSWZFWKMSRAUBD-UHFFFAOYSA-N 2-Amino-2-Deoxy-Hexose Chemical compound NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 2
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- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及含碳纳米管的聚酰胺(A)/聚烯烃(B)共混物。及包含至少一层该共混物和视情况的至少一层另一种材料的构件。该构件可呈任意的瓶、罐、槽、软管、筒管和壶形状。该构件可使用热塑性塑料的标准技术,如注塑、挤出-吹塑和共挤出来生产。按照一个实施方案,本发明多层管,以其径向由外到内包含:·由选自于PA-11和PA-12的聚酰胺形成的外层(1);·由结合物形成的层(2);·由EVOH形成的任选层(3);·视具体情况而定的粘结层(不存在层(3)时,则该层不存在);·由具有聚酰胺基质和碳纳米管的聚酰胺(A)/聚烯烃(B)共混物形成的内层(4);·所述层是连续的且在它们相应的接触表面互相粘合。
Description
[发明领域]
本发明涉及含有碳纳米管的聚酰胺/聚烯烃共混物。这些共混物可用于生产传递流体用单层或多层管。
作为传递流体用管的例子,可以提及的是燃料管,特别是将燃料从油箱中加入到机动车发动机中的那些。作为传递流体的其他例子,可以提及的是用于燃料电池、以CO2-为基的冷却和空气调节系统、液压系统、冷却回路系统、空气调节和中压动力传送系统中的流体。
为了安全和环境的原因,机动车生产商要求这些管材不仅具有机械性能,诸如爆破强度和挠曲性,同时无论在低温(-40℃)和高温(125℃)下都具有良好的抗冲击强度,而且具有对于烃类及其添加剂特别是对于醇类诸如甲醇和乙醇的非常低的渗透性。这些管材也必须具有良好的对发动机燃料和润滑油的耐受性。
在机动车中,汽油在注射泵作用下在连接发动机与油箱的管道中高速流动。在某些情况下,燃料与管内壁之间的摩擦可能产生静电荷,静电荷的累积会导致放电(电火花),这会点燃汽油造成灾难性后果(爆炸)。因而需要使与汽油接触的管的内表面导电。
使用用于热塑性塑料的标准技术,通过共挤出各种层状物来生产这些管材。
已经发现,这些含有碳纳米管的聚酰胺/聚烯烃共混物既具有良好的阻挡性又具有抗静电性。
[现有技术和技术问题]
专利EP 470606公开了具有抗静电聚酰胺层的管。该抗静电层由填充有20wt%炭黑的聚酰胺构成。的确获得了抗静电层,然而20%炭黑的加入提高了聚酰胺的弯曲模量,管材无法通过抗冲击试验。
碳纳米管的好处是,向聚酰胺中加入2-6wt%的碳纳米管使其具有抗静电性是足够的,同时在该含量下,聚酰胺保持了其机械性能。特别地,包含该层的管没有被削弱,其通过了抗冲击试验。专利US 6090459公开了包含尼龙-12(PA-12)和/或PVDF层、也包含抗静电PA-12或PVDF层的管材。这些抗静电层通过向PA-12或PVDF中引入直径约10纳米的晶态石墨纤维而获得。这些纤维在PA-12或PVDF中的量介于3-5wt%之间。
该解决办法提供了比现有技术EP 470606更好的技术优势,然而这些纤维的成本很高。目前已经发现,在含有碳纳米管的聚酰胺/聚烯烃共混物中,碳纳米管集中在聚酰胺上。于是,含有碳纳米管且具有聚酰胺基质的聚酰胺/聚烯烃共混物与含有碳纳米管的聚酰胺共混物具有相同的抗静电性;而且由于含有更少的碳纳米管,因而其相对便宜。另外,与不含碳纳米管的聚酰胺/聚烯烃共混物相比,这些含有碳纳米管的聚酰胺/聚烯烃共混物对于含醇燃料形成更强的阻挡性。
[发明概述]
本发明涉及含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物。
理想地,碳纳米管的量足以满足表面电阻系数约为106-107Ω。
本发明也涉及包含至少一层该共混物和视具体情况而定的至少一层另一种材料的构件。这些构件可呈任意类型的瓶、罐、槽、软管、筒管和壶形状。这些构件可通过使用用于热塑性塑料的标准技术,诸如注塑、挤出-吹塑和共挤出来生产。
按照一个实施方案,本发明涉及一多层管,该管以其径向方向由外到内包含:
●由选自于PA-11和PA-12的聚酰胺形成的外层(1);
●由结合物形成的层(2);
●由EVOH形成的任选层(3);
●视具体情况而定的粘结层(如果不存在层(3)的话,则该层不存在);
●由具有聚酰胺基质且含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物所形成的内层(4);
●所述层是连续的且在它们相应的接触表面互相粘合。
按照一种变化形式,用层(4a)和层(5)代替层(4),使得:
●层(4a)由聚酰胺(A1)或具有聚酰胺基质但不含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物所形成;
●层(5)处于管的内面上并且由具有聚酰胺基质且含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物形成;
●处于层(4a)和(5)之间的任选粘结层。
也就是说,按照该变化形式,本发明涉及一多层管,该管以其径向方向由外到内包含:
●由选自于PA-11和PA-12的聚酰胺形成的外层(1);
●由结合物形成的层(2);
●由EVOH形成的任选层(3);
●视具体情况而定的粘结层(如果不存在层(3)的话,则该层不存在);
●由聚酰胺(A1)或具有聚酰胺基质且不含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物所形成的层(4a);
●视具体情况而定的粘结层;
●处于管的内面上并且由具有聚酰胺基质且含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物形成的层(5);
●所述层是连续的且在它们相应的接触表面互相粘合。
理想地,碳纳米管的量足以满足管内层(与传输流体接触的层)的表面电阻系数约为106-107Ω。
[附图说明]
图1示出有机合金1中CNT%含量与电阻系数的关系。
[发明详述]
关于含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物,应该理解术语“聚酰胺”指的是由下面物质缩合得到的产物:
-一种或多种氨基酸,诸如氨基己酸、7-氨基庚酸、11-氨基十一(烷)酸和12-氨基十二(烷)酸,或一种或多种内酰胺,诸如己内酰胺、庚内酰胺和十二烷基内酰胺;
-二胺诸如六亚甲基二胺、十二甲撑二胺、间-苯二甲胺、双-对(氨基环己基)甲烷和三甲基六亚甲基二胺与二酸诸如间苯二甲酸、对苯二甲酸、己二酸、壬二酸、辛二酸、癸二酸和十四双酸的一种或多种盐或混合物。
作为聚酰胺的例子,可以提及的是PA-6和PA-6,6。
使用共聚酰胺也是有利的。可以提及的是由至少两种α,ω-氨基羧酸或两种内酰胺或一种内酰胺与一种α,ω-氨基羧酸的缩合而得到的共聚酰胺。也可以提及的是由至少一种α,ω-氨基羧酸(或内酰胺)、至少一种二胺和至少一种二羧酸的缩合而得到的共聚酰胺。
作为内酰胺的例子,可以提及的是在主环中具有3-12个碳原子且可能被取代的那些。例如可以提及的是,β,β-二甲基丙内酰胺、α,α-二甲基丙内酰胺、戊内酰胺、己内酰胺、辛内酰胺和十二烷基内酰胺。
作为α,ω-氨基羧酸的例子,可以提及的是氨基十一(烷)酸和氨基十二(烷)酸。作为二羧酸的例子,可以提及的是己二酸、癸二酸、间苯二甲酸、丁二酸、1,4-环己基二羧酸、对苯二甲酸、磺基间苯二甲酸的钠或锂盐、二聚脂肪酸(这些二聚脂肪酸的二聚体含量是至少98%且优选被氢化)和十二烷二酸HOOC-(CH2)10-COOH。
二胺可以是具有6-12个碳原子的脂族二胺,或可以是芳基二胺和/或饱和环二胺。作为例子,可以提及的是六亚甲基二胺、哌嗪、四亚甲基二胺、八亚甲基二胺、十亚甲基二胺、十二甲撑二胺、1,5-二氨基己烷、2,2,4-三甲基-1,6-二氨基己烷、二胺多元醇、异佛尔酮二胺(IPD)、甲基五亚甲基二胺(MPDM)、双(氨基环己基)甲烷(BACM)和双(3-甲基-4-氨基环己基)甲烷(BMACM)。
作为共聚酰胺的例子,可以提及的是己内酰胺与十二烷基内酰胺的共聚物(PA-6/12),己内酰胺、己二酸与六亚甲基二胺的共聚物(PA-6/6,6),己内酰胺、十二烷基内酰胺、己二酸与六亚甲基二胺的共聚物(PA-6/12/6,6),己内酰胺、十二烷基内酰胺、11-氨基十一(烷)酸、壬二酸与六亚甲基二胺的共聚物(PA-6/6,9/11/12),己内酰胺、十二烷基内酰胺、11-氨基十一(烷)酸、己二酸与六亚甲基二胺的共聚物(PA-6/6,6/11/12)和十二烷基内酰胺、壬二酸与六亚甲基二胺的共聚物(PA-6,9/12)。
理想地,共聚酰胺选自于PA-6/12和PA-6/6,6。
有可能使用聚酰胺共混物。理想地,在20℃以硫酸中的1%溶液测试的聚酰胺的相对粘度介于1.5-5之间。
用具有聚酰胺嵌段和聚醚嵌段的共聚物代替部分聚酰胺(A),即使用包含至少一种上述聚酰胺与至少一种具有聚酰胺嵌段和聚醚嵌段的共聚物的共混物,不会超出本发明的范围。
具有聚酰胺嵌段和聚醚嵌段的共聚物由具有活性端基的聚酰胺嵌段与具有活性端基的聚醚嵌段的共缩聚反应得到,诸如特别是:
1)具有二胺链端基的聚酰胺嵌段与具有二羧酸链端基的聚氧化烯嵌段;
2)具有二羧酸链端基的聚酰胺嵌段与具有二胺链端基的聚氧化烯嵌段,通过称为聚醚二醇的脂族二羟基化α,ω-聚氧化烯嵌段的氰乙基化和氢化而获得;
3)具有二羧酸链端基的聚酰胺嵌段与聚醚二醇,在该特定情况下,所得产物是聚醚酯酰胺。理想地,使用这些共聚物。
具有二羧酸链端基的聚酰胺嵌段例如由如下得到:在链终止二羧酸存在下,α,ω-氨基羧酸、内酰胺、或二羧酸与二胺的缩合反应。
聚醚可例如是聚乙二醇(PEG)、聚丙二醇(PPG)或聚四亚甲基二醇(PTMG)。后者也称为聚四氢呋喃(PTHF)。
聚酰胺嵌段的数均分子量Mn是300-15000,优选600-5000。聚醚嵌段的数均分子量Mn是100-6000,优选200-3000。
具有聚酰胺嵌段和聚醚嵌段的聚合物也可包括无规分布单元。这些聚合物可通过聚醚与聚酰胺嵌段前体的联立反应而制得。
例如,有可能使聚醚二醇、内酰胺(或α,ω-氨基酸)与链终止二酸在少量水存在下反应。得到具有主要为聚醚嵌段和长度变化非常大的聚酰胺嵌段的聚合物,同时各种反应物以无规方式反应,沿着聚合物链无规分布。
无论它们来自于事先制备的聚酰胺和聚醚嵌段的共缩聚反应,还是来自于一步反应,这些具有聚酰胺嵌段和聚醚嵌段的聚合物都具有例如肖氏(Shore)D硬度介于20-75、理想地介于30-70,和在25℃间甲酚中相对于起始浓度为0.8g/100ml时测试的特性粘度介于0.8-2.5。MFIs可以是5-50(235℃,负荷为1kg)。
或是如此使用聚醚二醇嵌段并与具有羧酸端基的聚酰胺嵌段共缩聚,或是将其胺化以便转变成聚醚二胺并与具有羧酸端基的聚酰胺嵌段缩合。也可将它们与聚酰胺前体和链终止剂混合,以便制得具有无规分布单元的聚酰胺嵌段聚醚嵌段聚合物。
具有聚酰胺和聚醚嵌段的聚合物在专利US 4331786、US 4115475、US 4195015、US 4839441、US 4864014、US 4230838和US 4332920中有述。
具有聚酰胺嵌段和聚醚嵌段的共聚物的量与聚酰胺的量之比例理想地介于10/90-60/40(重量)之间。例如可以提及的是下面的共混物:(i)PA-6和(ii)具有PA-6嵌段和PTMG嵌段的共聚物,和下面的共混物:(i)PA-6和(ii)具有PA-12嵌段和PTMG嵌段的共聚物。
理想地,使用PA-6、PA-6,6和PA-6/6,6。
关于聚酰胺(A)/聚烯烃(B)共混物中的聚烯烃(B),其可被或不被官能化,或其可以是至少一种官能化聚烯烃和/或至少一种未官能化聚烯烃的共混物。为了简便起见,官能化聚烯烃在下文中被称为(B1),而未官能化聚烯烃被称为(B2)。
未官能化聚烯烃(B2)通常是α-烯烃或二烯烃诸如乙烯、丙烯、1-丁烯、1-辛烯和丁二烯的均聚物或共聚物。作为例子可以提及的是:
-乙烯均聚物和共聚物,特别是LDPE、HDPE、LLDPE(线性低密度聚乙烯)或VLDPE(极低密度聚乙烯)和茂金属聚乙烯;
-丙烯均聚物和共聚物;
-乙烯/α-烯烃共聚物诸如乙烯/丙烯共聚物;EPRs(乙丙橡胶的缩写);和乙烯/丙烯/二烯共聚物(EPDM);
-苯乙烯/乙烯-丁烯/苯乙烯嵌段共聚物(SEBS)、苯乙烯/丁二烯/苯乙烯嵌段共聚物(SBS)、苯乙烯/异戊二烯/苯乙烯嵌段共聚物(SIS)、苯乙烯/乙烯-丙烯/苯乙烯嵌段共聚物(SEPS);
-乙烯与至少一种选自于下面的物质的共聚物:不饱和羧酸的盐或酯诸如(甲基)丙烯酸烷基酯(例如丙烯酸甲酯)、或饱和羧酸的乙烯基酯诸如乙酸乙烯酯(EVA),共聚用单体的量可能是多达40wt%。
官能化聚烯烃(B1)可以是具有活性单元(官能团)的α-烯烃聚合物;此类活性单元是酸、酸酐或环氧官能团。作为例子可以提及的是接枝了下面物质、或与下面物质共聚或三聚的上述聚烯烃(B2):不饱和环氧化物诸如(甲基)丙烯酸缩水甘油酯,或羧酸或相应的盐或酯诸如(甲基)丙烯酸(这可能被金属诸如锌等完全或部分中和),或羧酸酐诸如马来酸酐。官能化聚烯烃例如是PE/EPR共混物,其重量比可在宽范围内变化,例如40/60-90/10,所述共混物共接枝了酸酐、尤其是马来酸酐,接枝度例如是0.01-5wt%。
官能化聚烯烃(B1)可选自于下面的(共)聚合物,接枝了马来酸酐或甲基丙烯酸缩水甘油酯,其中接枝度例如是0.01-5wt%:
-PE,PP,乙烯与丙烯、丁烯、己烯或辛烯的共聚物且含有例如35-80wt%的乙烯;
-乙烯/α-烯烃共聚物诸如乙烯/丙烯共聚物;EPRs(乙丙橡胶的缩写);和乙烯/丙烯/二烯共聚物(EPDM);
-苯乙烯/乙烯-丁烯/苯乙烯嵌段共聚物(SEBS)、苯乙烯/丁二烯/苯乙烯嵌段共聚物(SBS)、苯乙烯/异戊二烯/苯乙烯嵌段共聚物(SIS)、苯乙烯/乙烯-丙烯/苯乙烯嵌段共聚物(SEPS);
-乙烯/乙酸乙烯酯共聚物(EVA),含有多达40wt%的乙酸乙烯酯;
-乙烯/(甲基)丙烯酸烷基酯共聚物,含有多达40wt%的(甲基)丙烯酸烷基酯;
-乙烯/乙酸乙烯酯(EVA)/(甲基)丙烯酸烷基酯三元共聚物,含有多达40wt%的共聚单体。
官能化聚烯烃(B1)也可选自于主要含有丙烯的乙烯/丙烯共聚物,这些接枝了马来酸酐,然后与单胺化聚酰胺(或聚酰胺低聚物)缩合(产物描述于EP-A-0342066中)。
官能化聚烯烃(B1)也可以是至少下面单元的二元共聚物或三元共聚物:(1)乙烯,(2)(甲基)丙烯酸烷基酯或饱和羧酸的乙烯基酯和(3)酸酐诸如马来酸酐或(甲基)丙烯酸或环氧化物诸如(甲基)丙烯酸缩水甘油酯。
作为该后者类型的官能化聚烯烃的例子,可以提及的是下面的共聚物,其中乙烯优选占至少60wt%且其中三元共聚单体(官能团)例如占共聚物的0.1-10wt%:
-乙烯/(甲基)丙烯酸烷基酯/(甲基)丙烯酸或马来酸酐或甲基丙烯酸缩水甘油酯共聚物;
-乙烯/乙酸乙烯酯/马来酸酐或甲基丙烯酸缩水甘油酯共聚物;
-乙烯/乙酸乙烯酯或(甲基)丙烯酸烷基酯/(甲基)丙烯酸或马来酸酐或甲基丙烯酸缩水甘油酯共聚物。
在上面的共聚物中,(甲基)丙烯酸可与Zn或Li成盐。
(B1)或(B2)中的术语“(甲基)丙烯酸烷基酯”指的是甲基丙烯酸和丙烯酸的C1-C8烷基酯,且可选自于丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸2-乙基己基酯、丙烯酸环己酯、甲基丙烯酸甲酯和甲基丙烯酸乙酯。
而且,上述聚烯烃(B1)也可通过任何合适的方法或试剂(二环氧化物、二酸、过氧化物等)进行交联;术语官能化聚烯烃也包括上述聚烯烃与能够与其反应的二官能活性试剂诸如二酸、二酐、二环氧化物等的共混物,或能够相互反应的至少两种官能化聚烯烃的共混物。
上述共聚物(B1)和(B2)可被共聚合以形成无规或嵌段共聚物,并可具有线性或支化结构。
这些聚烯烃的分子量、MFI指数和密度也可在宽范围内变化,本领域熟练人员会理解。MFI是熔体流动指数的缩写。其根据ASTM 1238标准测试。
理想地,未官能化聚烯烃(B2)选自于丙烯均聚物或共聚物和任意乙烯均聚物或乙烯与高级α-烯烃型共聚单体诸如丁烯、己烯、辛烯或4-甲基-1-戊烯的共聚物。例如可以提及的是高密度PP和PE、中密度PE、线性低密度PE、低密度PE和极低密度PE。这些聚乙烯对于本领域熟练人员来说是已知的,它们可通过“自由基”方法、“Ziegler”-型催化或新近的所谓“茂金属”催化而制得。
理想地,官能化聚烯烃(B1)选自于包含α-烯烃单元和带有极性活性官能团诸如环氧、羧酸或羧酸酐官能团的单元的任意聚合物。作为此类聚合物的例子,可以提及的是乙烯/丙烯酸烷基酯/马来酸酐或乙烯/丙烯酸烷基酯/甲基丙烯酸缩水甘油酯三元共聚物,诸如来自于申请人的LOTADER聚合物,或接枝了马来酸酐的聚烯烃诸如来自于申请人的OREVAC聚合物,以及乙烯/丙烯酸烷基酯/(甲基)丙烯酸三元共聚物。也可以提及的是聚丙烯均聚物,和接枝了羧酸酐、然后与聚酰胺或单胺化聚酰胺低聚物缩合的共聚物。
(A)的MFI和(B1)与(B2)的MFIs可在宽范围内选择;然而,为了促进(B)的分散,建议(A)的MFI应该大于(B)的MFI。
对于少量的(B),例如10-15份,使用未官能化聚烯烃(B2)是足够的。(B)相中(B2)与(B1)的比例取决于(B1)中存在的官能团的量和它们的反应性。理想地,使用(B1)/(B2)重量比的范围是5/35-15/25。也可能仅使用聚烯烃(B1)的共混物以便实现交联。
理想地,含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物具有聚酰胺基质。通常,含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物中聚酰胺的量为至少40wt%、优选40-75wt%是足够的,以便具有聚酰胺基质。这是聚酰胺/聚烯烃共混物的前三个优选实施方案的情况。在第四个优选实施方案中,聚烯烃相被交联,这确保没有相转变并且共混物仍然是聚酰胺基质。
按照本发明的第一个优选实施方案,聚烯烃(B)包含(i)高密度聚乙烯(HDPE)和(ii)聚乙烯(C1)与聚合物(C2)的共混物,其中聚合物(C2)选自于弹性体、极低密度聚乙烯和乙烯共聚物,(C1)+(C2)共混物共接枝了不饱和羧酸或不饱和羧酸酐。
按照本发明的该第一实施方案的一个变化形式,聚烯烃(B)包含(i)高密度聚乙烯(HDPE)、(ii)选自于弹性体、极低密度聚乙烯和乙烯共聚物的聚合物(C2),(C2)接枝了不饱和羧酸或不饱和羧酸酐,和(iii)选自于弹性体、极低密度聚乙烯和乙烯共聚物的聚合物(C′2)。
按照本发明的第二个优选实施方案,聚烯烃(B)包含(i)聚丙烯和(ii)由聚酰胺(C4)与共聚物(C3)的反应得到的聚烯烃,所述共聚物(C3)包含丙烯和被接枝或共聚的不饱和单体X。
按照本发明的第三个优选实施方案,聚烯烃(B)包含(i)EVA、LLDPE、VLDPE或茂金属型的聚乙烯,和(ii)乙烯/(甲基)丙烯酸烷基酯/马来酸酐共聚物。
按照本发明的第四个优选实施方案,聚烯烃包括含有至少50mol%乙烯单元且能够反应以形成交联相的两种官能化聚合物。按照一个变化形式,聚酰胺(A)选自于下面的共混物:(i)聚酰胺和(ii)具有PA-6嵌段和PTMG嵌段的共聚物,和下面的共混物:(i)聚酰胺和(ii)具有PA-12嵌段和PTMG嵌段的共聚物,共聚物的量与聚酰胺的量的重量比是10/90-60/40。
对于第一个实施方案,比例(重量)理想地如下:
60-70%的聚酰胺,
5-15%的(C1)与(C2)的共接枝共混物,
余量是高密度聚乙烯。
对于高密度聚乙烯,其密度理想地是0.940-0.965,且MFI是0.1-5g/10min(190℃/2.16kg)。
聚乙烯(C1)可选自于上述聚乙烯。理想地,(C1)是密度为0.940-0.965的高密度聚乙烯(HDPE)。(C1)的MFI是0.1-3g/10min(190℃/2.16kg)。
共聚物(C2)可例如是乙烯-丙烯弹性体(EPR)或乙烯/丙烯/二烯弹性体(EPDM)。(C2)也可以是或是乙烯均聚物或是乙烯/α-烯烃共聚物的极低密度聚乙烯(VLDPE)。(C2)也可以是乙烯与至少一种选自于下面的物质的共聚物:(i)不饱和羧酸、它们的盐和它们的酯,(ii)饱和羧酸的乙烯基酯,和(iii)不饱和二羧酸、它们的盐、它们的酯、它们的半酯和它们的酐。理想地,(C2)是EPR。
理想地,相对于每40-5份的(C2),使用60-95份的(C1)。
(C1)与(C2)的共混物接枝了不饱和羧酸,即(C1)和(C2)被共接枝。使用该酸的官能化衍生物不会超出本发明的范围。不饱和羧酸的例子是具有2-20个碳原子的那些,诸如丙烯酸、甲基丙烯酸、马来酸、富马酸和衣康酸。这些酸的官能化衍生物包括例如酐、酯衍生物、酰胺衍生物、酰亚胺衍生物和不饱和羧酸的金属盐(诸如碱金属盐)。
具有4-10个碳原子的不饱和二羧酸和它们的官能化衍生物、特别是它们的酐,是特别优选的接枝单体。这些接枝单体包含例如马来酸、富马酸、衣康酸、柠康酸、烯丙基琥珀酸、环己-4-烯-1,2-二羧酸、4-甲基环己-4-烯-1,2-二羧酸、双环[2.2.1]-庚-5-烯-2,3-二羧酸和x-甲基双环[2.2.1]-庚-5-烯-2,3-二羧酸,和马来酸酐、衣康酸酐、柠康酸酐、烯丙基琥珀酸酐、环己-4-烯-1,2-二羧酸酐、4-亚甲基环己-4-烯-1,2-二羧酸酐、双环[2.2.1]-庚-5-烯-2,3-二羧酸酐和x-甲基双环[2.2.1]-庚-5-烯-2,2-二羧酸酐。理想地,使用马来酸酐。
可以使用各种已知方法在(C1)与(C2)的共混物上接枝上接枝单体。例如,这可通过在存在或不存在溶剂且有或没有自由基引发剂的情况下,将聚合物(C1)和(C2)加热到约150℃-约300℃高温来实现。
在以上述方式获得的(C1)与(C2)的接枝改性共混物中,可合适地选择接枝单体的量,但是相对于共接枝的(C1)+(C2)的重量,其优选是0.01-10%,更好地是600ppm-2%。通过FTIR谱分析琥珀酸官能团来测定接枝单体的量。共接枝的(C1)+(C2)的MFI(190℃/2.16kg)是5-30且优选是13-20g/10min。
理想地,共接枝的(C1)+(C2)共混物使得MFI10/MFI2之比大于18.5,MFI10表示在190℃、负载为10kg下的熔体流动指数,MFI2表示负载为2.16kg下的熔体流动指数。理想地,共接枝聚合物(C1)与(C2)的共混物的MFI20小于24。MFI20表示在190℃、负载为21.6kg下的熔体流动指数。
对于第一个实施方案的变化形式,比例(重量)理想地如下:
60-70%的聚酰胺,
5-10%的接枝的(C2),
5-10%的(C′2),
余量是高密度聚乙烯。
理想地,(C2)是EPR或EPDM。理想地,(C′2)是含有70-75wt%的乙烯的EPR。
对于本发明的第二个实施方案,比例(重量)理想地如下:
60-70%的聚酰胺,
20-30%的聚丙烯,
3-10%的由聚酰胺(C4)与共聚物(C3)的反应得到的聚烯烃,所述共聚物(C3)包含丙烯和被接枝或共聚的不饱和单体X。
聚丙烯的MFI(230℃/2.16kg)理想地是小于0.5g/10min,且优选0.1-0.5g/10min。此类物质描述于EP 647681中。
现在描述本发明的该第二个实施方案的接枝产物。首先制备(C3),其或是丙烯与不饱和单体X的共聚物,或是其上接枝了不饱和单体X的聚丙烯。X是能够与丙烯共聚或接枝到聚丙烯上且具有能够与聚酰胺反应的官能团的任何不饱和单体。该官能团可例如是羧酸、二羧酸酐或环氧化物。作为单体X的例子,可以提及的是(甲基)丙烯酸、马来酸酐和不饱和环氧化物诸如(甲基)丙烯酸缩水甘油酯。理想地,使用马来酸酐。对于接枝聚丙烯,X可被接枝到聚丙烯均聚物或共聚物诸如主要由丙烯构成(以mol表示)的乙烯/丙烯共聚物上。理想地,(C3)接枝了X。接枝是本身已知的操作。
(C4)是聚酰胺或聚酰胺低聚物。聚酰胺低聚物描述于EP 342066和FR2291225中。聚酰胺(或低聚物)(C4)是由上述单体的缩合得到的产物。可以使用聚酰胺共混物。理想地使用PA-6、PA-11、PA-12、具有PA-6单元和PA-12单元(PA-6/12)的共聚酰胺,和基于己内酰胺、六亚甲基二胺和己二酸的共聚酰胺(PA-6/6,6)。聚酰胺或低聚物(C4)可具有酸、胺或一元胺端基。为了使聚酰胺具有一元胺端基,需要使用下式的链终止剂:
其中:
R1是氢或含有至多20个碳原子的线性或支化烷基;
R2是具有至多20个碳原子的线性或支化烷基或链烯基、饱和或不饱和环脂基、芳基或上述的结合。链终止剂例如可是月桂胺或油胺。
理想地,(C4)是PA-6、PA-11或PA-12。(C3)+(C4)中(C4)的重量比理想地是0.1-60%。(C3)与(C4)的反应优选在熔融状态下进行。例如有可能在一般为230-250℃的温度下、在挤出机中混合(C3)与(C4)。挤出机中熔体的平均停留时间可以是10秒-3分钟,优选1-2分钟。
对于第三个实施方案,比例(重量)理想地如下:
60-70%的聚酰胺,
5-15%的乙烯/(甲基)丙烯酸烷基酯/马来酸酐共聚物,
余量是EVA、LLDPE、VLDPE或茂金属型聚乙烯;理想地,LLDPE、VLDPE或茂金属型聚乙烯的密度是0.870-0.925,且MFI是0.1-5(190℃/2.16kg)。
理想地,乙烯/(甲基)丙烯酸烷基酯/马来酸酐共聚物含有0.2-10wt%的马来酸酐和至多40wt%、优选5-40wt%的(甲基)丙烯酸烷基酯。它们的MFIs是2-100(190℃/2.16kg)。上面已经描述了(甲基)丙烯酸烷基酯。熔点是80-120℃。这些共聚物可市售。它们通过在可以是200-2500bar的压力下的自由基聚合反应而制得。
对于第四个实施方案,比例(重量)理想地如下:
35-95%的聚酰胺,
65-5%的乙烯/(甲基)丙烯酸烷基酯/马来酸酐共聚物与乙烯/(甲基)丙烯酸烷基酯/(甲基)丙烯酸缩水甘油酯共聚物的共混物。
理想地,乙烯/(甲基)丙烯酸烷基酯/马来酸酐共聚物含有0.2-10wt%的马来酸酐和至多40wt%且优选5-40wt%的(甲基)丙烯酸烷基酯。它们的MFIs是2-100(190℃/2.16kg)。上面已经描述了(甲基)丙烯酸烷基酯。熔点是80-120℃。这些共聚物可市售。它们通过在可以是200-2500bar的压力下的自由基聚合反应而制得。
乙烯/(甲基)丙烯酸烷基酯/甲基丙烯酸缩水甘油酯共聚物可含有至多40wt%且理想地是5-40wt%的(甲基)丙烯酸烷基酯,和至多10wt%且优选0.1-8wt%的不饱和环氧化物。
理想地,(甲基)丙烯酸烷基酯选自于(甲基)丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯和丙烯酸2-乙基己基酯。(甲基)丙烯酸烷基酯的量优选是20-35%。MFI理想地是5-100g/10min(190℃/2.16kg),熔点是60-110℃。该共聚物可通过单体的自由基聚合反应而制得。
有可能加入催化剂以促进环氧与酐官能团之间的反应;在能够促进环氧官能团与酐官能团之间反应的化合物中,特别可以提及的是:
-叔胺,诸如二甲基月桂胺、二甲基硬脂胺、N-丁基吗啉、N,N-二甲基环己胺、苄基二甲胺、吡啶、二甲基氨基-4-吡啶、1-甲基咪唑、四甲基乙基肼、N,N-二甲基哌嗪、N,N,N′,N′-四甲基-1,6-己二胺、具有16-18个碳原子的叔胺的共混物(被称为二甲基牛油脂肪胺);
-叔膦,诸如三苯基膦;
-烷基二硫代氨基甲酸锌;和
-酸。
如果用乙烯/丙烯酸共聚物或乙烯/马来酸酐共聚物代替部分乙烯/(甲基)丙烯酸烷基酯/马来酸酐共聚物,且其中马来酸酐已经被全部或部分水解的话,则不会脱离本发明的范围。这些共聚物也可包含(甲基)丙烯酸烷基酯。此部分可占乙烯/(甲基)丙烯酸烷基酯/马来酸酐共聚物的至多30%。
对于碳纳米管,这些因而是具有直径约5-20纳米(nm)且长度约为直径的100-1000倍的管或中空纤维。
碳具有三种已知的同素异形体,即无定形炭、石墨和金刚石。碳纤维中存在石墨,石墨非常轻且强力。金刚石由于其优越的机械性能和其高导热性而被通常使用。碳纳米管,一种新型的碳的同素异形体,被认为是介乎常规碳纤维与新型碳诸如富勒烯(fullernes)之间的独特的碳体系。它们的长径比大到使得它们就某些性能来说被认为是一维结构。存在两种类型的碳纳米管即单壁和多壁纳米管,其:
直径:在单壁纳米管的情况中是几个纳米,在多壁纳米管的情况中是约10-几十纳米;
长度:几个微米。
如果理想的话,单壁碳纳米管可被定义为自身卷起和闭拢的石墨(graphene)片,于是形成仅由碳原子构成的圆柱体。其末端由两个碳半球形成。
多壁纳米管是单层纳米管的同心体。
可以使用两种方法生产这些纳米管。物理方法是在特定条件下(控制压力,腔室中存在催化剂和特殊气体等)纯化石墨阳极。纯化所需的能量可用各种形式提供:电流、激光、太阳能等等。目前最常用的方法是使用电弧,其在于应用电压以便纯化含有石墨和金属催化剂颗粒的棒。目前该方法生产出相对大量的具有非常高结构性能的材料(因而材料的机械性能、电性能和热性能非常好)。然而,碳和金属杂质存留在碳纳米管的束间。这些杂质可通过提纯方法除去。
化学或柔和方法是在金属分子上分解气态烃。该方法使得有可能获得较大量的纳米管,但是存在的缺陷较高。因此其性能通常比由电弧方法生产的纳米管的性能差。
有可能使用例如由Hyperion Catalysis International生产的纳米管,其描述于“Plastics Additives and Compounding”,9月1日,第3卷,第9版,ISSN 1464-391X(Elsevier)中。
对于聚酰胺/聚烯烃共混物中碳纳米管的量,其可具有任意数值。该量越高,阻挡性和抗静电性越好。理想地,相对于每99.9-90wt%的聚酰胺/聚烯烃共混物,该量相应地是0.1-10wt%。更理想地,相对于每99-93wt%的聚酰胺/聚烯烃共混物,该量相应地是1-7wt%。优选地,相对于每98-94wt%的聚酰胺/聚烯烃共混物,该量相应地是2-6wt%。使用碳纳米管的混合物不会超出本发明的范围。
本发明的组合物可另外含有至少一种选自于下面的添加剂:
-染料;
-颜料;
-增白剂;
-抗氧化剂;
-UV稳定剂。
通过以“直接”方法共混所有组分(A、B、纳米管和任选的添加剂)、或通过向已制得的A/B共混物中加入纳米管和任选的添加剂、还或通过将已含有纳米管的聚酰胺(A)与聚烯烃(B)混合、或通过这些可能的任意组合来制备本发明的组合物。
理想地,可以使用来自于热塑性塑料工业中的标准共混和混合设备诸如挤出机和混合机,例如BussCo-Kneaders。
按照一个特殊实施方案,本发明涉及一多层管,该多层管以其径向方向由外到内包含:
-由选自于PA-11和PA-12的聚酰胺形成的外层(1);
-由结合物形成的层(2);
-由EVOH形成的任选层(3);
-视具体情况而定的粘结层(如果不存在层(3)的话,则该层不存在);
-由具有聚酰胺基质且含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物形成的内层(4);
所述层是连续的且在它们相应的接触表面互相粘合。
对于由PA-11或PA-12制得的外层(1),这些聚酰胺理想地具有数均分子量Mn一般大于或等于5000。它们的比浓对数粘度(在20℃100g间甲酚中相对于0.5g试样进行测试)一般大于0.7。
理想地,该外层的聚酰胺由标准增塑剂诸如N-丁苯磺酰胺(BBSA)增塑且为包含聚酰胺嵌段和聚醚嵌段的共聚物。这些包含聚酰胺嵌段和聚醚嵌段的共聚物在涉及聚酰胺(A)的上述段落中已述。
对于粘结层(2),其因而可定义为提供所述层间良好粘合力的任何物质。结合物理想地选自于共聚酰胺和官能化聚烯烃。
作为基于官能化聚烯烃的结合物的例子,可以提及的是:
-聚乙烯,聚丙烯,乙烯与至少一种α-烯烃的共聚物,这些聚合物的共混物,所有这些聚合物用不饱和羧酸酐诸如马来酸酐接枝,或这些接枝聚合物与这些非接枝聚合物的共混物;
-乙烯与至少一种选自于下面的产物的共聚物:(i)不饱和羧酸、它们的盐、它们的酯,(ii)饱和羧酸的乙烯基酯,(iii)不饱和二羧酸、它们的盐、它们的酯、它们的半酯、它们的酐,和(iv)不饱和环氧化物,这些共聚物有可能用不饱和二羧酸酐诸如马来酸酐或不饱和环氧化物诸如甲基丙烯酸缩水甘油酯接枝。
对于共聚酰胺型结合物,能够用于本发明中的共聚酰胺具有熔点(DIN53736B标准)为60-200℃,它们的相对溶液粘度可以是1.3-2.2(DIN 53727标准;溶剂:间甲酚;浓度:0.5g/100ml;温度:25℃;乌氏(Ubbelohde)粘度计)。它们的熔体流变性优选相当于外层和内层材料的熔体流变性。
共聚酰胺例如衍生自α,ω-氨基羧酸的缩合、内酰胺的缩合或二羧酸与二胺的缩合。
按照第一种类型,共聚酰胺由下面得到:在可例如是一元胺或二胺或一元羧酸或二羧酸的链终止剂的可能存在下,至少两种α,ω-氨基羧酸的缩合,或具有6-12个碳原子的至少两种内酰胺的缩合,或具有不同数目碳原子的内酰胺与氨基羧酸的缩合。在链终止剂中,可以特别提及的是己二酸、壬二酸、硬脂酸和十二烷二胺。此第一种类型的共聚酰胺也可包括作为二胺和二羧酸的残基的单元。
作为二羧酸的例子,可以提及的是己二酸、壬二酸、癸二酸和十二烷二酸。
作为α,ω-氨基羧酸的例子,可以提及的是氨基己酸、氨基十一(烷)酸和氨基十二(烷)酸。
作为内酰胺的例子,可以提及的是己内酰胺和十二烷内酰胺(2-氮杂环十三烷酮)。
按照第二种类型,共聚酰胺由下面得到:至少一种α,ω-氨基羧酸(或内酰胺)、至少一种二胺与至少一种二羧酸的缩合。α,ω-氨基羧酸、内酰胺和二羧酸可以选自于上述的那些。
二胺可以是支化、线性或环状脂族二胺,或者是芳基型二胺。
作为例子可以提及的是,六亚甲基二胺、哌嗪、异佛尔酮二胺(IPD)、甲基五亚甲基二胺(MPDM)、双(氨基环己基)甲烷(BACM)和双(3-甲基-4-氨基环己基)甲烷(BMACM)。
生产共聚酰胺的方法在现有技术中是已知的,这些共聚酰胺可通过例如在高压釜中的缩聚反应生产。
按照第三种类型,共聚酰胺是富含6的6/12共聚酰胺与富含12的6/12共聚酰胺的共混物。关于6/12共聚酰胺的共混物,一个含有6的重量比大于12,另一个含有12的重量比大于6,6/12共聚酰胺由己内酰胺与十二烷内酰胺的缩合反应得到。显然“6”表示来自于己内酰胺的单元,而“12”表示来自于十二烷内酰胺的单元。如果己内酰胺全部或部分地用氨基己酸代替的话,不会超出本发明的范围,同样对于十二烷内酰胺来说,其可以用氨基十二(烷)酸代替。这些共聚酰胺可以包括其他单元,只是要注意6与12的量之比。
理想地,相对于每40wt%-10wt%的12,富含6的共聚酰胺相应地包含60wt%-90wt%的6。
理想地,相对于每40wt%-10wt%的6,富含12的共聚酰胺相应地包含60wt%-90wt%的12。
关于富含6的共聚酰胺和富含12的共聚酰胺的比例,其可以是40/60-60/40(wt/wt)且优选50/50(wt/wt)。
相对于每100份富含6和富含12的共聚酰胺,这些共聚酰胺共混物也可包括至多30wt%的其他(共)聚酰胺或接枝聚烯烃。
这些共聚酰胺的熔点(DIN 53736B标准)是60-200℃,它们的相对溶液粘度可以是1.3-2.2(DIN 53727标准;溶剂:间甲酚;浓度:0.5g/100ml;温度:25℃;Ubbelohde粘度计)。它们的熔体流变性优选相当于相邻层材料的熔体流变性。这些产物使用用于聚酰胺的标准技术来生产。一些方法描述于专利US 4424864、US 4483975、US 47741 39、US 5459230、US5489667、US 5750232和US 5254641中。
如果外层由PA-11制得,则优选的是,介于该PA-11层与EVOH层之间(或介于PA-11层与层(4)之间)的结合物是基于官能化聚烯烃。如果外层由PA-12制得,则优选的是,介于该PA-12层与EVOH层之间(或介于PA-12层与层(4)之间)的结合物是基于共聚酰胺。
对于由EVOH形成的任选层(3),其可由EVOH或由EVOH基共混物构成。EVOH也被称作皂化乙烯/乙酸乙烯酯共聚物。本发明要使用的皂化乙烯/乙酸乙烯酯共聚物是具有乙烯含量为20-70mol%、优选25-70mol%、其乙酸乙烯酯成分的皂化度不小于95mol%的共聚物。在乙烯含量小于20mol%的情况下,高湿度条件下的阻挡性不如需要的那么高,使乙烯含量超过70mol%则导致阻挡性降低。当皂化度或水解度小于95mol%时,会牺牲阻挡性。
应该理解术语“阻挡性”指的是对于气体或液体特别是氧和机动车用汽油的不透过性。
在这些皂化共聚物中,具有熔体流动指数范围是0.5-100g/10min.的那些是特别有用的。理想地,选择MFI(熔体流动指数)在5-30(g/10min.,在230℃/2.16kg下)之间。
应该理解的是,该皂化共聚物可以含有少量的其他共聚单体成分,包括α-烯烃诸如丙烯、异丁烯、α-辛烯、α-十二(碳)烯、α-十八(碳)烯等,不饱和羧酸或它们的盐、部分烷基酯、全烷基酯、腈、酰胺和所述酸的酐,和不饱和磺酸或它们的盐。
关于EVOH基共混物,其中EVOH形成基质,即EVOH占共混物的至少40wt%、优选至少50wt%。共混物的其他成分选自于聚烯烃、聚酰胺和任选的官能化聚合物。
对于层(3)与(4)之间的任选粘结层,其可选自于在层(2)情况中所述的结合物。
关于层(4),上面已有描述。
按照一个变化形式,是用层(4a)和层(5)代替层(4),使得:
●层(4a)由聚酰胺(A1)或具有聚酰胺基质但不含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物所形成;
●层(5)处于管的内面上并且由具有聚酰胺基质且含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物形成;
●处于层(4a)和(5)之间的任选粘结层。
在该变化形式中,层(4a)可以具有与层(4)相同的组成,只是它不含有碳纳米管。
层(4a)也可以由另一种聚酰胺(A1)制得。(A1)可以选自于在聚酰胺(A)/聚烯烃(B)共混物的聚酰胺(A)的叙述中所述的聚酰胺。作为(A1)的例子,可以提及的是PA-6、PA-6,6和PA-6/6,6。
层(4a)也可由与层(4)所不同的聚酰胺/聚烯烃共混物制得。例如,它可由含有EPR(或EPDM)的PA-6制得,EPR(或EPDM)有可能被马来酸酐部分或全部接枝。
关于层(4a)与层(5)之间的任选粘结层,其可选自于在层(2)情况中所述的结合物。
理想地,本发明的管具有外径为6-12mm,总厚度为0.41mm-1.7mm,其包含:
-对于由尼龙-11或尼龙-12制得的外层(1),厚度为300-800μm;
-对于粘结层(2),厚度为10-100μm;
-对于任选的EVOH层(3),厚度为10-200μm;
-对于任选的粘结层,厚度为10-100μm;和
-对于由含有碳纳米管的聚酰胺/聚烯烃共混物形成的层(4),厚度为100-500μm。
按照用层(4a)和层(5)代替层(4)这样的变化形式,层(4a)、层(5)和这些层之间任选的粘结层的厚度总和是100-500μm。
优选地,连接油箱与机动车注射系统的管道具有外径为8mm,厚度为1mm。
这些多层管可以是等径或环形柱体。
通常,这些管可以包括特别是由橡胶制得的保护套,以便使其免受发动机热部位影响。
[实施例]
本发明的含有碳纳米管的聚酰胺/聚烯烃共混物通过在挤出机中混合而制得。然后在150μm厚度的薄膜上测试汽油透过性(在60℃)。
使用下面的物质:
有机合金(Orgalloy)1:这表示聚酰胺/聚烯烃共混物,由下面构成:
25wt%的高密度聚乙烯(HDPE),
10wt%的作为HDPE的聚乙烯(C1)与作为EPR的聚合物(C2)的共混物,(C1)+(C2)共混物用马来酸酐共接枝,
65wt%的PA-6;
有机合金1+2%CNT:含有98wt%的有机合金1和2wt%的碳纳米管的本发明的共混物;
有机合金1+6%CNT:含有94wt%的有机合金1和6wt%的碳纳米管的本发明的共混物;
CNT:由HyperionCatalysis International提供的多壁型且直径为15纳米的碳纳米管。
结果列于表1中。
表1
以g.mm/m2/24h流动的有机合金1 | 以g.mm/m2/24h流动的有机合金1+2%的CNT | 以g.mm/m2/24h流动的有机合金1+6%的CNT | |
甲醇 | 136.2 | 104.0 | 87.3 |
甲苯 | 13.1 | 21.2 | 25.6 |
异辛烷 | 0.343 | 0.857 | 3.048 |
M15 | 149.6 | 126.1 | 116.0 |
6%的CNT的加入导致M15汽油的可透过度下降22%。M15汽油含有15vol%的甲醇、42.5vol%的甲苯和42.5vol%的异辛烷。然而应该注意,该下降主要是由于与有机合金1具有最大亲合力的最轻组分(即甲醇)的可透过度的显著下降,甲苯的可透过度和异辛烷的可透过度随着有机合金1中CNT含量的增加而增加。
也测试表面电阻系数,比较有机合金1与PA-6。结果显示于图1中。
表面电阻系数定义为DC电场强度除以绝缘材料表层中的线性电流密度。实际上,表面电阻系数ρs被取作等于换算成平方面积的表面电阻Rs。
公式:
ρs(ohms)=Rs(ohms)×1(cm)/d(cm)
其中:
l是面对电极的长度;
d是这些电极间的距离。
板上的表面电阻系数:
对于我们的测试元件,l和d要使得:
l:被保护电极的周长;
d:被保护电极与保护电极间的距离;
l/d=53.4
例如,在测试的Rs为106ohms的情况下,得到ρs=106×53.4=53.4·106ohms的数值。
管上的表面电阻系数:
在具有下面尺寸的管的内层上进行测试:
φ:管的直径0.6cm;
d:管的长度10cm。
在测试的Rs为106ohms的情况下,得到ρs=106×(φπ)/d=0.18·106ohms的数值。
生产本发明的管,所述管具有内径0.6cm、厚度为1mm且按照由外到内顺序包含下面材料的层:
PA-12/富含6的6/12共聚酰胺与富含12的6/12共聚酰胺的共混物/EVOH/有机合金1/有机合金+CNT。
然后使用上述方法测试内层的表面电阻系数。
Claims (9)
1.含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物。
2.权利要求1的共混物,其中碳纳米管是具有直径约5-20纳米(nm)且长度为直径的100-1000倍的管或中空纤维。
3.上述权利要求中任一项的共混物,其中相对于每99.9-90wt%的聚酰胺/聚烯烃共混物,纳米管的量相应地是0.1-10wt%。
4.上述权利要求中任一项的共混物,其中相对于每99-93wt%的聚酰胺/聚烯烃共混物,纳米管的量相应地是1-7wt%。
5.上述权利要求中任一项的共混物,其中相对于每98-94wt%的聚酰胺/聚烯烃共混物,纳米管的量相应地是2-6wt%。
6.一种构件,该构件是包含至少一层由上述任一项权利要求的共混物形成的层和视具体情况而定的至少一层另一种材料的构件。
7.权利要求6的构件的用途,用于生产瓶、罐、槽、软管、筒管和壶。
8.多层管,以其径向方向由外到内包含:
·由选自于PA-11和PA-12的聚酰胺形成的外层(1);
·由结合物形成的层(2);
·由EVOH形成的任选层(3);
·视具体情况而定的粘结层,不存在层(3)时该层不存在;
·由权利要求1-5中任一项的具有聚酰胺基质且含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物所形成的内层(4);
·所述层是连续的且在它们相应的接触表面互相粘合。
9.权利要求8的管,其中用层(4a)和层(5)代替层(4),使得:
·层(4a)由聚酰胺(A1)或具有聚酰胺基质但不含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物所形成;
·层(5)处于管的内面上并且由权利要求1-5中任一项的具有聚酰胺基质且含有碳纳米管的聚酰胺(A)/聚烯烃(B)共混物形成;
·处于层(4a)和(5)之间的任选粘结层。
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FR0301933 | 2003-02-18 | ||
FR0301933 | 2003-02-18 |
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US (1) | US7717139B2 (zh) |
EP (1) | EP1449885B1 (zh) |
JP (1) | JP4042857B2 (zh) |
KR (1) | KR100595949B1 (zh) |
CN (1) | CN1263804C (zh) |
ES (1) | ES2437194T3 (zh) |
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- 2004-02-13 ES ES04290391T patent/ES2437194T3/es not_active Expired - Lifetime
- 2004-02-17 CN CNB2004100052248A patent/CN1263804C/zh not_active Expired - Lifetime
- 2004-02-18 KR KR1020040010553A patent/KR100595949B1/ko active IP Right Grant
- 2004-02-18 US US10/780,832 patent/US7717139B2/en not_active Expired - Lifetime
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CN101138896B (zh) * | 2006-09-08 | 2010-05-26 | 清华大学 | 碳纳米管/聚合物复合材料 |
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CN106459578A (zh) * | 2014-05-16 | 2017-02-22 | 东洋纺株式会社 | 结晶性聚酰胺类树脂组合物 |
CN109476839A (zh) * | 2016-07-11 | 2019-03-15 | 阿科玛法国公司 | 由具有高tg的bact/xt共聚酰胺制造的阻隔结构体 |
CN109476839B (zh) * | 2016-07-11 | 2021-11-02 | 阿科玛法国公司 | 由具有高tg的bact/xt共聚酰胺制造的阻隔结构体 |
CN109306177A (zh) * | 2018-12-06 | 2019-02-05 | 深圳宝兴电线电缆制造有限公司 | 手术刀导线 |
CN113121995A (zh) * | 2021-04-19 | 2021-07-16 | 江苏扬农化工集团有限公司 | 一种兼具耐磨和抗静电性能的尼龙复合材料及其制备方法和用途 |
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JP4042857B2 (ja) | 2008-02-06 |
JP2004250707A (ja) | 2004-09-09 |
EP1449885B1 (fr) | 2013-10-02 |
CN1263804C (zh) | 2006-07-12 |
US20050131147A1 (en) | 2005-06-16 |
EP1449885A1 (fr) | 2004-08-25 |
ES2437194T3 (es) | 2014-01-09 |
KR20040074615A (ko) | 2004-08-25 |
US7717139B2 (en) | 2010-05-18 |
KR100595949B1 (ko) | 2006-07-03 |
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