CN1358948A - 以硫化弹性体和含氟聚合物为主要成分的管 - Google Patents
以硫化弹性体和含氟聚合物为主要成分的管 Download PDFInfo
- Publication number
- CN1358948A CN1358948A CN01145063A CN01145063A CN1358948A CN 1358948 A CN1358948 A CN 1358948A CN 01145063 A CN01145063 A CN 01145063A CN 01145063 A CN01145063 A CN 01145063A CN 1358948 A CN1358948 A CN 1358948A
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- Prior art keywords
- block
- fluoropolymer
- layer
- pipe
- internal layer
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
- F16L11/127—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting electrically conducting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract
本发明涉及一种管,沿其径向方向从里到外是:1.)所述的与循环的流体接触的内层,所述的内层包括①含氟聚合物,②任选地导电产品以及③三嵌段ABC共聚物,三嵌段A、B和C彼此按照这种顺序连接,每个嵌段是用两种或多种单体得到的均聚物或共聚物,通过共价键或中间分子将嵌段A与嵌段B连接,嵌段B与嵌段C连接,该中间分子通过共价键与这些嵌段中一个嵌段连接,而通过另外的共价键与另一个嵌段连接,-.嵌段A与含氟聚合物是相容的,-.嵌段B与含氟聚合物是不相容的,与嵌段A也是不相容的,-.嵌段C与含氟聚合物、嵌段A和嵌段B是不相容的,2)任选地一层粘合剂层,3)一层硫化弹性体层。
Description
技术领域
本发明涉及以硫化弹性体和含氟聚合物为主要成分的管,更特别地涉及具有含氟聚合物内层和硫化弹性体外层的管。这些管例如在汽车中是有用的,用于将油箱的汽油送到注油***,用于空调回路,冷却液和输送燃料电池的电池液。
背景技术
在专利EP 683725中描述过相继地由PVDF(聚偏氟乙烯)内层、共挤塑粘合剂和硫化弹性体外层组成的管。它们的优点是具有良好的耐腐蚀性化学液体,是许多流体的阻挡层,特别是汽油和在空调回路中使用的流体。但是,它们在低的温度下可能是很脆的。人们知道,改善PVDF的冲击强度,但又不利于其耐化学性以及阻挡层的性质。
现在发现了,在构成管内层的含氟聚合物中加入聚(苯乙烯)-聚(丁二烯)-聚(甲基丙烯酸甲酯)三嵌段共聚物时,该管有含氟聚合物内层和硫化弹性体外层,这样得到的管其内层保持了含氟聚合物的耐化学性,并且这种管具有非常好的冲击强度。
此外,PVDF层导电有时也是很必要的。溶剂在管PVDF内层上摩擦可能产生静电荷,电荷积累可能导致能引起溶剂燃烧的放电(火花),其结果是灾难性的(***)。因此,使这些部件变成导电也是必要的。
人们知道,在树脂或聚合物材料中加入导体材料和/或半导体材料,例如炭黑、钢纤维、碳纤维、带金、银或镍的金属化微粒(纤维、板、球),可以降低它们的表面电阻率。在这些材料中,因为经济的原因与易于加工性,更特别地使用炭黑。除了它们特别的导电性质外,炭黑还表现例如像滑石、白垩、高岭土一样的填料。因此,本技术领域的技术人员知道,填料比率增加时,聚合物/填料混合物的粘度也增加。同样地,填料比率增加时,填充的聚合物弯曲模量增加,其冲击强度降低。这些已知的可预见现象在由H.S.Katz和J.V.Mileswski编辑的《塑料的填料和增强手册》(Handbook of Fillers andReinforcements for Plastics)-Van Nostrand Reinhold Company-ISBN 0-442-25372-9中解释过,具体参见第2章,第II节“一般填料”和第16章,第VI节“特别的炭黑”。关于炭黑的电性质,AKZONOBEL学会的“Ketjenblack EC-BLACK94/01”技术通报指出,达到炭黑临界比率(称之渗漏阈值)时,配方的电阻率非常剧烈地下降。炭黑比率再增加时,电阻率快速降低,直到达到稳定的水平(平台区域)。对于一定的树脂,因此,可取的是在平台区域操作,在该区域定量误差对化合物电阻率只是很小的影响。
PVDF具有多轴冲击脆性。添加一种能使其PVDF变成导电的试剂,如炭黑,可使它变得更脆。各种不同的改善冲击强度性能的方式往往建议加入柔软的弹性体相,其弹性体相在PVDF基体中可能具有《核-壳》类型的形态。这样结合的主要缺陷是耐化学性严重降低。
现在发现,在构成管内层的含氟聚合物中加入聚(苯乙烯)-聚(丁二烯)-聚(甲基丙烯酸甲酯)三嵌段共聚物和导电产品时,该管有含氟聚合物内层和硫化弹性体外层,制成的管具有抗静电内层,这层还保持含氟聚合物的耐化学性,并且这种管还具有非常好的冲击强度。
发明内容
本发明涉及一种管,沿其径向方向从里到外有:
1)所述的内层,它与循环的流体接触,所述的内层包括①含氟聚合物,②任选地导电产品以及③三嵌段ABC共聚物,三嵌段A、B和C彼此按照这种顺序连接,每个嵌段是用两种或多种单体得到的均聚物或共聚物,通过共价键或中间分子将嵌段A与嵌段B连接,嵌段B与嵌段C连接,该中间分子通过共价键与这些嵌段中一个嵌段连接,而通过另外的共价键与另一个嵌段连接,如:
-嵌段A与含氟聚合物是相容的,
-嵌段B与含氟聚合物是不相容的,与嵌段A也是不相容的,
-嵌段C与含氟聚合物、嵌段A和嵌段B是不相容的,
2)任选地一层粘合剂层,
3)一层硫化弹性体层。
根据本发明第二种方式,内层自身是由两层构成的,一层含有导电产品,另外一层不含有导电产品。有利地,与循环流体接触的这层含有导电产品。
根据本发明第三种方式,把含氟聚合物层放在内层与粘合剂层之间,或内层与硫化弹性体之间,如果没有粘合剂的话。
本发明第二和第三种方式可以同时存在于同一管中。
本发明的管具有许多优点:
·它们耐冷(-40℃)冲击,
·它们可以为抗静电的,
·它们具有非常良好的耐化学品性,因此可以输送腐蚀性流体,
·它们是非常多流体的阻挡层,例如像汽车用汽油,空调的流体,
·它们是特有的,即内层基本上不含有可以迁移的产品,例如低聚物或增塑剂,因此不会出现管中循环的流体引起这些产品堵塞在这种流体回路上的设备的危险。事实上,三嵌段ABC和含氟聚合物构成了稳定的聚合物混合物,任选的导电产品***这种混合物中,而不迁移。
通过共挤塑可以生产这些管,每层以熔融态用挤塑机加入共挤塑头,该共挤塑头产生了形成管的同心物流。这种技术本身是已知的。然后将这种管通到加热炉或加热隧道,以便进行弹性体的硫化作用(交联)。建议在挤塑过程中使用弹性体流仍处于足够低的温度(一般约80-120℃)的共挤塑头,以便在形成管之前没有发生硫化作用,特别是没有造成堵塞挤塑机。还可以采用共挤塑生产不含弹性体层的管,然后再让这种管通过一个所谓的“外壳覆盖”或“曲尺头”设备,使其管覆盖弹性体层。然后,如前面所述,让这种管通过加热炉或加热隧道,以便进行弹性体硫化作用(交联)就足够了。
具体实施方式
关于含氟聚合物,这里是指在其链中有至少一种单体的任何聚合物,该单体选自含有能够打开进行聚合的乙烯基团的化合物,并且含有与这种乙烯基团直接结合的至少一个氟原子,氟烷基或氟烷氧基。
作为单体实例,可以列举氟乙烯;偏氟乙烯(VF2);三氟乙烯(VF3);氯三氟乙烯(CTFE);1,2-二氟乙烯;四氟乙烯(TFE);六氟丙烯(HFP);全氟(烷基乙烯基)醚,例如全氟(甲基乙烯基)醚(PMVE),全氟(乙基乙烯基)醚(PEVE)和全氟(丙基乙烯基)醚(PPVE);全氟(1,3-间二氧杂环戊烯);全氟(2,2-二甲基-1,3-间二氧杂环戊烯)(PDD);式CF2=CFOCF2CF(CF3)OCF2CF2X化合物,式中X是SO2F、CO2H、CH2OH、CH2OCN或CH2OPO3H;式CF2=CFOCF2CF2SO2F化合物;式F(CF2)nCH2OCF=CF2化合物,其中n是1、2、3、4或5;式R1CH2OCF=CF2化合物,其中R1是氢或F(CF2)z,z是1、2、3或4;式R3OCF=CH2化合物,其中R3是F(CF2)z,z是1、2、3或4;全氟丁基乙烯(PFBE);3,3,3-三氟丙烯和2-三氟甲基-3,3,3-三氟-1-丙烯。
含氟聚合物可以是均聚物或共聚物,它也可以含有非氟化单体,例如乙烯。
有利地,含氟聚合物选自:
-偏氟乙烯(VF2)均聚物和共聚物,它们优选含有至少50重量%VF2,共聚物选自氯三氟乙烯(CTFE)、六氟丙烯(HFP)、三氟乙烯(VF3)和四氟乙烯(TFE),
-三氟乙烯(VF3)均聚物和共聚物,
-结合氯三氟乙烯(CTFE)、四氟乙烯(TFE)、六氟丙烯(HFP)和/或乙烯结构单元残基和任选地VF2和/或VF3结构单元的共聚物,任选地三聚物。
优选地,含氟聚合物是聚(偏氟乙烯)(PVDF)均聚物。有利地,PVDF的粘度为100-2000帕.秒,该粘度是用毛细流变仪在剪切梯度100秒-1在230℃下测量的。事实上,这些PVDF非常适合挤塑和注塑。优选地,PVDF的粘度为300-1200帕.秒,该粘度是用毛细流变仪在剪切梯度100秒-1在230℃下测量的。
因此,以商标KYNAR710或720销售的PVDF非常适合于这种配方。
关于导电产品,它是任何的电的导体。作为实例可以列举金属和碳基产品。作为碳基产品实例,可以列举石墨、炭黑、炭纳管和碳纤维。使用多种导电元件没有超出本发明的范围。可以使用的碳基产品在由Chem Tec Publishing出版的《填料手册》,第2版(1999),第62页§2.1.22,第92页§2.1.33和第184页§2.2.2中描述过。
有利地,导电产品选自炭黑:炭黑可以是半-导电的,导电的炭黑,这些炭黑具有低的BET表面。在可使用的炭黑中,MMM炭公司的炭黑是特别令人满意。应特别记住氮吸附表面小于500米2/克的炭黑。有利地,这些炭黑的氮吸附表面小于100米2/克。在这些不同类型中,IENSACO别适合这种应用。
关于ABC三嵌段共聚物,有至少三嵌段A、B和C的嵌段共聚物是这样的共聚物,其嵌段A是通过一个或多个共价单键与嵌段B连接,嵌段B与嵌段C连接。在多个共价键的情况下,嵌段A与嵌段B和/或嵌段B与嵌段C之间可以有用于将这些嵌段彼此连接起来的单个结构单元或结构单元链。在单个结构单元的情况下,它可以来自在三嵌段合成中使用的所谓减速剂单体。在结构单元链的情况下,其链可以是由至少两种不同的单体按照交替顺序或随机顺序排列的单体单元链得到的低聚物。这样一种低聚物可以将嵌段A与嵌段B连接起来,同样的低聚物或不同的低聚物可以将嵌段B与嵌段C连接起来。
ABC共聚物中的嵌段A被认为是与含氟聚合物相容的,如果与这种嵌段相同的聚合物(因此没有B和C顺序)与这种熔融态树脂相容的话。同样地,嵌段A与嵌段B被认为是不相容的,如果与这些嵌段相同的聚合物A和B是不相容的话。一般地,两种聚合物之间相容性应当理解是,一种聚合物溶于另一种呈熔融态的聚合物中的能力,或它们的总混溶性。在相反的情况下,聚合物或嵌段是所谓的不相溶的。
两种聚合物混合物的热焓越低,它们的相容性就越高。在某些情况下,单体之间存在着特别有利的相互作用,这表现为相应的聚合物的混合热焓为负值。在本发明的范围内,可取的是使用混合热焓为负值或零的相容聚合物。
但是,所有聚合物的混合热焓不可能采用通常的方式测量,因此只是可以间接地确定相容性,例如采用扭力式粘度计或振动式粘度计分析测量,或采用差式量热分析确定。对于相容性聚合物,可以检测混合物的2个Tg:两个Tg中至少一个与纯组分的Tg不同,其温度范围是在两个纯组分Tg之间。完全混溶的两种聚合物混合物只有一个Tg。
为证明聚合物的相容性可以使用另外的试验方法,例如测量浊度,测量光散射,红外光测量(L.A.Utracki,《聚合物合金与混合物》(Polymer Alloys andBlends),第64-117页)。
在文献中已汇编了混溶的或相容的聚合物,例如参见J.Brandrup和E.H.Immergut:《聚合物手册》,第3版,Wiley & Son 1979,纽约1989,第VI/348至VI/364页;O.Olabisi,L.M.Robeson和M.T.Shaw:《聚合物相混性》(PolymerMiscibility),Academic Press,纽约1979,第215-276页;L.A.Utracki:《聚合物合金与混合物》,Hanser Verlag,慕尼黑1989。在这些文献中列出的一揽表是作为说明给出的,当然不是穷举的。
有利地,嵌段A选自(烷基)丙烯酸烷基酯均聚物和共聚物,例如甲基丙烯酸甲酯(MAM)和/或丙烯酸甲酯或乙酯和/或由醋酸乙烯酯得到的均聚物和共聚物。有利地,嵌段A是聚(甲基丙烯酸甲酯)(PMMA)。优选地,这种PMMA是间同立构的,采用差热分析测量的玻璃态转化温度Tg(A)是+120℃至+140℃。
有利地,B的Tg低于0℃,优选地低于-40℃
合成弹性体B嵌段使用的单体可以是选自丁二烯、异戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、2-苯基-1,3-丁二烯的二烯。B有利地选自聚(二烯),特别是聚(丁二烯)、聚(异戊二烯)及其无规共聚物,或选自部分或全部氢化的聚(二烯)。在聚丁二烯中,有利地使用Tg最低的聚丁二烯,例如Tg(接近-90℃)低于聚-1,2-丁烯的(接近-0℃)聚-1,4-丁二烯。嵌段B还可以氢化。根据通常的技术进行这种氢化作用。
合成弹性嵌段B使用的单体还可以是(甲基)丙烯酸烷基酯,得到按照丙烯酸酯名称在括号中的下述Tg,:丙烯酸乙酯(-24℃)、丙烯酸丁酯(-54℃)、丙烯酸-2-乙基己酯(-85℃)、丙烯酸羟基乙酯(-15℃)和甲基丙烯酸-2-乙基己酯(-10℃)。有利地使用丙烯酸丁酯。为了保持不相容B和A的条件,这些丙烯酸酯与嵌段A的丙烯酸酯不同。
优选地,嵌段B大部分由聚-1,4-丁二烯组成。
优选地,嵌段C的玻璃态转化温度Tg(C)或熔化温度Tf(C)高于嵌段B的Tg(B)。这种特征赋予这种可能性,对于同样的使用温度Tp,嵌段C处于玻璃态或处于部分结晶态,而嵌段B处于弹性体态。
根据本发明,可能的是选择具有某些确定的Tg(B)的嵌段B的性质,于是在由这种混合物制成的材料或物品的使用温度Tp下,可能的是具有这些嵌段B聚合物的弹性态或柔软态。相反地,嵌段C聚合物的Tg(C)或Tf可能高于Tg(B),它们在相同的使用温度下可能处于相对硬的玻璃态。
如嵌段C与含氟聚合物不相容一样,嵌段A和嵌段B,它们因在材料中生成了所包括的毫微区域结构(nanomaine),并在每个嵌段B的其中一端的区域中起固定物作用,于是它们在材料内形成硬的不连续相。每个嵌段B的另一端与同含氟聚合物具有强亲合性的嵌段A相连。这种强亲合性在嵌段B第二端区域中达到第二个固定作用。
有利地,嵌段C选自苯乙烯或α-甲基苯乙烯均聚物或共聚物。
含有由(烷基)丙烯酸烷基酯衍生得到的序列的三嵌段,具体地可通过阴离子聚合作用进行制备,例如根据在专利申请EP 524 054和EP 749 987中描述的方法制备。
优选地,三嵌段ABC是聚(甲基丙烯酸甲酯-b-丁二烯-b-苯乙烯)。
三嵌段ABC共聚物含有作为其合成副产物的二嵌段B-C共聚物以及任选地C均聚物。三嵌段ABC共聚物还可以含有作为其合成副产物的二嵌段A-B共聚物以及任选地A均聚物。
事实上,根据三嵌段A、B和C的性质,优选地相继让嵌段A与嵌段B,然后与嵌段C连接,或相反地,让嵌段C与嵌段B,然后与嵌段A连接,这样可以合成出三嵌段共聚物。根据定义,嵌段A是与含氟聚合物相容的。三嵌段ABC共聚物还可以含有ABA或CBC类对称直链的或星状的嵌段共聚物。
有利地,合成副产物,即这些A、C均聚物或AB、BC、ABA和CBC嵌段共聚物的总重量是三嵌段ABC量的2倍以下。优选地,这个量是三嵌段ABC量的一倍以下,更好地,0.5倍以下。更确切地,副产物基本上是二嵌段BC,BC的量可以是25-35重量份,而ABC的量相应地为75-65重量份,有利地对于70份ABC,BC的量约30重量份。
三嵌段共聚物的数均分子量(Mn),其中包括合成副产物,是大于或等于20000克.摩尔-1,优选地是50 000-200 000克.摩尔-1。有利地,三嵌段ABC共聚物,其中包括副产物,组成如下:
-20-93,优选地30-70重量份顺序A,
-5-68,优选地10-40重量份顺序B
-2-65,优选地5-40重量份顺序C。
申请人观察到,在三嵌段的情况下,来自合成副产物,例如二嵌段或均聚物,对混合物的机械性能没有不利。
有利地,内层,即含氟聚合物、导电产品和三嵌段ABC共聚物与任选地三嵌段合成副产物的混合物,含有以重量计(总量为100%):
65-97%含氟聚合物,
0-25%导电产品,
3-15%三嵌段ABC共聚物。
关于导电内层,它的重量组成可以是,以总重量100%计:
65-92%,有利地70-85%含氟聚合物,
5-25%,有利地10-20%导电产品,
3-15%,有利地5-10%三嵌段ABC共聚物。
关于粘合剂层,这里是指使得内层与硫化弹性体层之间粘合起来的任何产品。作为实例,可以列举含氟聚合物、PMMA和任选核壳(***核心)类型的丙烯酸弹性体的混合物;PMMA可以包含共聚的(甲基)丙烯酸。这些粘合剂在US5 242 976中描述过。还可以列举通过亚酰胺化改性的,并任选地含有含氟聚合物的以聚(甲基)丙烯酸酯为主要成分的混合物;它们在US 5 939 492、US 6 040025、US5 795 939和EP 726 926中描述过。
关于硫化弹性体层,适合本发明使用的可硫化的合成或天然弹性体是本技术领域的技术人员熟知的,在本发明定义中术语弹性体是指它可以由多种弹性体混合物组成。
这些弹性体或弹性体混合物在100℃下残余变形(D.R.C.)小于50%,一般为5-40%,优选地小于30%。
在这些弹性体中,可以列举天然弹性体,具有高比率顺式双键的聚异戊二烯,以苯二烯/丁二烯共聚物为主要成分的聚合乳液,用镍、钴、钛或钕催化得到的具有高比率顺式双键的聚丁二烯,卤化乙烯/丙烯/二烯三聚物,卤化丁基橡胶,苯乙烯/丁二烯嵌段共聚物,苯乙烯/异戊二烯嵌段共聚物,上述聚合物的卤化产品,丙烯腈/丁二烯共聚物,丙烯酸弹性体,含氟弹性体,氯戊二烯和表氯醇橡胶。
如果本发明的管不含有粘合剂层,建议弹性体选自官能化弹性体,具有丙烯酸酯结构单元的弹性体,卤化弹性体以及表氯醇橡胶。关于官能化弹性体,这种官能有利地是羧酸官能团或羧酸酐官能团。在上面提到的弹性体不含有羧酸或所述酸的酸酐基(大多数弹性体的情况便是如此)的情况下,可以通过以已知方式接枝上述弹性体,或通过弹性体与例如具有像丙烯酸的丙烯酸结构单元的弹性体混合,带有所述的基团。优选地,上述可硫化弹性体含有羧酸基或二羧酸酐基团的重量比率是以所述弹性体计为0.3-10%。
同样地,没有官能又没有丙烯酸酯结构单元的弹性体,它们没有被卤化,也不是表氯醇橡胶,可以与至少一种选自下述弹性体混合:官能化弹性体、具有丙烯酸结构单元的弹性体、卤化弹性体和表氯醇橡胶。
在上述弹性体中,可以选自如下弹性体:羧基化腈弹性体、丙烯酸弹性体、羧基化聚丁二烯、接枝的乙烯/丙烯/二烯三聚物,或这些聚合物与同样的但未接枝的弹性体的混合物,如单个或混合的腈橡胶,聚丁二烯、乙烯/丙烯/二烯三聚物。
适合本发明的硫化***是本技术领域的技术人员熟知的,因此,本发明不限于特定的***类型。
弹性体是以不饱和单体为主要成分(丁二烯、异戊二烯、偏乙烯-降冰片烯……)时,可以列举四类硫化***:
-由与常用促进剂结合的硫构成的硫***,例如二硫代氨基甲酸金属盐(二硫代氨基甲酸二甲酯锌盐、碲盐等),磺酰胺(sulféramide)等。
这些***还可以含有与硬脂酸结合的氧化锌。
-硫的给予体***,其中大多数用于架桥的硫来自含硫的分子,例如前面列举的有机硫化合物。
-酚醛树脂***,该树脂由可能卤化的,与如氯化锡、氧化锌促进剂结合的双官能化甲醛苯酚树脂构成。
-过氧化物***。与氧化锌和硬脂酸结合,可以使用任何自由基给予体(过氧化二枯基等)。
弹性体是丙烯酸(聚丙烯酸丁酯与酸或环氧官能或任何其他反应性官能都可能交联)时,使用以二胺(邻甲苯氨基胍,二苯基胍等)或阻断二胺(六亚甲基二胺氨基甲酸酯等)为主要成分的一般交联剂。
为了某些特定的性质(例如改善机械性能),加入如炭黑、二氧化硅、高岭土、铝、粘土、滑石、白垩等填料,可以使弹性组合物改性。可以用硅烷,聚乙二醇或任何其他偶合分子进行这些填料的表面处理。一般地,每100重量份弹性体,填料的比率为5-100重量份。
另外,使用如由石油得到的矿物油,邻苯二甲酸酯或癸二酸酯增塑剂,如任选羧基化的低分子量聚丁二烯液体聚合物增塑剂,以及本技术领域的技术人员熟知的其他增塑剂,都可以软化这些组合物。
使用的硫化剂的组合是这样一些组合,按照动力学,它们应该能使弹性体完全交联,得到良好的弹性体层和内层或粘合剂层的抗分离性能。
本发明管的外径可以是8毫米至25厘米。内层厚度可以是15-200微米,粘合剂可能厚度是5-100微米。
在本发明第三种方式中,在内层与粘合剂层之间,或内层与硫化弹性体层之间的这层含氟聚合物,如果没有粘合剂时,则选自所描述的用于内层的含氟聚合物。有利地,这是PVDF均聚物或共聚物。
Claims (11)
1、一种管,沿其径向方向从里到外是:
1)所述的与循环的流体接触的内层,所述的内层包括①含氟聚合物,②任选地导电产品以及③三嵌段ABC共聚物,三嵌段A、B和C彼此按照这种顺序连接,每个嵌段是用两种或多种单体得到的均聚物或共聚物,通过共价键或中间分子将嵌段A与嵌段B连接,嵌段B与嵌段C连接,该中间分子通过共价键与这些嵌段中一个嵌段连接,而通过另外的共价键与另一个嵌段连接,
-嵌段A与含氟聚合物是相容的,
-嵌段B与含氟聚合物是不相容的,与嵌段A也是不相容的,
-嵌段C与含氟聚合物、嵌段A和嵌段B是不相容的,
2)任选地一层粘合剂层,
3)一层硫化弹性体层。
2、根据权利要求1所述的管,其中内层含氟聚合物是PVDF均聚物或共聚物。
3、根据权利要求1或2所述的管,其中内层导电产品选自石墨、炭黑、炭纳管和碳纤维。
4、根据权利要求3所述的管,其中导电产品是氮吸附表面小于500米2/克的炭黑。
5、根据权利要求4所述的管,其中表面小于100米2/克。
6、根据上述权利要求中任一权利要求所述的管,其中内层三嵌段ABC是聚(甲基丙烯酸甲酯-b-丁二烯-b-苯乙烯)。
7、根据上述权利要求中任一权利要求所述的管,其中内层三嵌段ABC共聚物的数均分子量(Mn)大于或等于20 000克.摩尔-1,优选地是50 000-200 000克.摩尔-1。
8、根据上述权利要求中任一权利要求所述的管,其中内层中重量比例如下:
65-97%含氟聚合物,
0-25%导电产品,
3-15%三嵌段ABC共聚物。
9、根据权利要求8所述的管,其中内层中重量比例如下:
65-92%含氟聚合物,
5-25%导电产品,
3-15%三嵌段ABC共聚物。
10、根据上述权利要求中任一权利要求所述的管,其中内层本身由两层构成,一层含有导电产品,另一层不含有导电产品。
11、根据上述权利要求中任一权利要求所述的管,其中如果没有粘合剂,在内层与粘合剂层之间,或内层与硫化弹性体层之间提供一层含氟聚合物层。
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US (1) | US20020106470A1 (zh) |
EP (1) | EP1217281A1 (zh) |
JP (1) | JP2002254562A (zh) |
KR (1) | KR100420391B1 (zh) |
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EP1211288A1 (fr) * | 2000-12-01 | 2002-06-05 | Atofina | Composition conductrice à base de polymère fluoré |
DE10152575A1 (de) * | 2001-10-24 | 2003-05-15 | Veritas Ag | Mehrschichtiges Rohr |
EP1493955A4 (en) * | 2002-04-09 | 2009-03-11 | Mitsuboshi Corp Ltd | MULTILAYER TUBE |
WO2004039883A1 (ja) * | 2002-10-29 | 2004-05-13 | Daikin Industries, Ltd. | 含フッ素樹脂組成物、含フッ素成形品、含フッ素層含有積層体及び含フッ素層含有積層体使用方法 |
US20050035334A1 (en) * | 2003-08-01 | 2005-02-17 | Alexander Korzhenko | PTC compositions based on PVDF and their applications for self-regulated heating systems |
EP1505118A1 (en) * | 2003-08-01 | 2005-02-09 | Arkema | PTC compositions based on PVDF and their applications for self-regulated heating systems |
US7360461B2 (en) * | 2004-09-23 | 2008-04-22 | Aircuity, Inc. | Air monitoring system having tubing with an electrically conductive inner surface for transporting air samples |
FR2883879B1 (fr) * | 2005-04-04 | 2007-05-25 | Arkema Sa | Materiaux polymeres contenant des nanotubes de carbone a dispersion amelioree leur procede de preparation |
US9056447B2 (en) * | 2006-07-06 | 2015-06-16 | Arkema Inc. | Flexible multilayer vinylidene fluoride tubes |
EP2938480B1 (en) | 2012-12-28 | 2021-03-31 | AGC Chemicals Americas Inc. | A layered tube for a hose assembly |
US9694528B2 (en) * | 2012-12-28 | 2017-07-04 | Eaton Corporation | Method for forming a layered tube and layer therein |
US9851026B2 (en) * | 2012-12-28 | 2017-12-26 | Eaton Corporation | Layered tube and layer for use in same |
WO2014117860A1 (en) * | 2013-02-01 | 2014-08-07 | Muovitech Ab | Geothermal pipe collector |
CN105658429B (zh) * | 2013-05-10 | 2018-06-12 | Agc 化工美洲公司 | 层状管和用于其中的层 |
WO2015146752A1 (ja) * | 2014-03-25 | 2015-10-01 | 三菱レイヨン株式会社 | 樹脂組成物、及び樹脂組成物からなる成形体 |
HU230824B1 (hu) | 2015-10-21 | 2018-07-30 | Contitech Rubber Industrial Kft. | Vegyszer- és gázálló nagynyomású, nagy átmérőjű, kötött szerkezetű gumi flexibilis vezeték, és eljárás annak előállítására |
WO2017106484A1 (en) | 2015-12-15 | 2017-06-22 | Agc Chemicals Americas Inc. | A layered tube and layer for use in same |
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CN1065480C (zh) * | 1993-12-13 | 2001-05-09 | 埃勒夫阿托化学有限公司 | 包含直接与热塑性塑料结合的硫化弹性体的多层制品 |
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-
2001
- 2001-11-23 EP EP01403010A patent/EP1217281A1/fr not_active Withdrawn
- 2001-12-11 CN CNB011450630A patent/CN1193180C/zh not_active Expired - Fee Related
- 2001-12-11 KR KR10-2001-0078125A patent/KR100420391B1/ko not_active IP Right Cessation
- 2001-12-11 CA CA002364167A patent/CA2364167C/fr not_active Expired - Fee Related
- 2001-12-11 JP JP2001377028A patent/JP2002254562A/ja active Pending
- 2001-12-11 US US10/012,044 patent/US20020106470A1/en not_active Abandoned
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JP2002254562A (ja) | 2002-09-11 |
CA2364167A1 (fr) | 2002-06-11 |
EP1217281A1 (fr) | 2002-06-26 |
CA2364167C (fr) | 2005-03-29 |
KR100420391B1 (ko) | 2004-02-26 |
US20020106470A1 (en) | 2002-08-08 |
CN1193180C (zh) | 2005-03-16 |
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