CN1147447A - 共同挤出具有不同处理温度的两种物料的方法和装置 - Google Patents

共同挤出具有不同处理温度的两种物料的方法和装置 Download PDF

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CN1147447A
CN1147447A CN96108241A CN96108241A CN1147447A CN 1147447 A CN1147447 A CN 1147447A CN 96108241 A CN96108241 A CN 96108241A CN 96108241 A CN96108241 A CN 96108241A CN 1147447 A CN1147447 A CN 1147447A
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materials
heat
polyamide
rubber
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CN1061930C (zh
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G·巴卢
G·科内特
O·丹尼扎特
C·杜松
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Arkema France SA
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Elf Atochem SA
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
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    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
    • B29C48/336—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles the components merging one by one down streams in the die
    • B29C48/3363—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles the components merging one by one down streams in the die using a layered die, e.g. stacked discs
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels

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Abstract

本发明涉及例如在设有至少一个孔的装置中共同挤出至少两种物料的方法，其中两种物料先后或同时经过所述装置。本发明方法尤其可用于共同挤出聚酰胺和有待硫化或含有硫化剂的橡胶或PVC和PVDF。所述装置可包括传热管。

Description

共同挤出具有不同处理温度的两种物料的方法和装置
本发明涉及共同挤出具有极不相同的处理温度的至少两种物料如聚酰胺12(240℃)和基于羧化腈/丁二烯的可硫化组合物(120℃)的方法和装置。
汽车发动机室之中冷却液或空气调节液的柔性管或软管是用硫化橡胶制成的。这些管对于所载的液体和发动机附近可能存在的油和脂均需具有良好的耐热耐压性和良好的化学表现。环保又要求这些管对其载送的流体具有很好的防漏性。因此这些管需具有防漏性好于橡胶的内层，该内层可选自热塑性塑料如聚酰胺，聚酯，聚烯烃或其掺混物。汽车中也用聚酰胺制动回路管，其油箱和发动机间用聚酰胺或聚酰胺加聚1，1-二氟乙烯内层制成的汽油管。这些管完全或部分涂上橡胶以使其与发动机热点隔开并且减少其受热时的蠕变。
聚酰胺等热塑性塑料在200℃以上挤出，而与其添加剂和硫化剂配制的橡胶最高在100-120℃下挤出；否则硫化会在挤出机中开始并且不能进行热塑性材料涂层或包皮。
共同挤出模头或机头用金属制成，因此处于极不相同的温度下的两种材料间的热传导很明显。
按照现有技术，为了制成具有热塑性材料内层和硫化橡胶外层的管，必须用例如挤出机机头制成热塑性管，而芯轴必须放在管中以补偿涂层或包皮期间外层施加的压力，然后再将该管导入称为“直角机头”或“交叉机头”的另一挤出机机头，其中配有添加剂和硫化剂的橡胶对已存在的热塑性管涂层或包皮。这样涂层的管再经过加热隧道或炉而得以硫化。之后再取出芯轴。
可用“直角机头”类挤出机机头给例如电缆包上热塑性材料外皮。电缆在模具中被导向前行，热塑性材料挤出后包在该模具中的电缆上，从而给电缆包皮或涂层。为了获得热塑性材料层和外部弹性层之间良好的结合性，就必须在弹性体和热塑性材料之间加上结合层。
本申请人公司现已发现共同挤出两种具有不同处理或挤出温度的物料如220℃的聚酰胺和120℃或更低温度下硫化的橡胶的新装置。因此可经单一步骤制成具有橡胶涂层或外皮的聚酰胺管，也就是说无需将已挤出的聚酰胺管再导入直角机头。而且，本申请人公司还发现共同挤出这两种材料，即同时制成管的两层这一事实提高了两层之间的结合性，因为两种材料以熔融态汇合，而在现有技术中熔融的第二材料与已固化的第一材料相遇。本发明另一优点是两种物料流在加压下汇合或相遇。
因此，本发明涉及共同挤出具有极不相同的挤出温度的至少两种物料的方法，其中两种物料先后或同时经过设有至少一个孔(orifice)的装置。
共同挤出意指可让至少两种熔融物料经过同一孔而形成其一部分由材料之一制成，另一部分由另一材料制成的制品的任何方法。例如，如果孔是环形并且如果两种材料中每一种都来自挤出机，则可连续制成具有两层并且每一材料形成一层的共同挤出管。也可向预成型和熔合或结合管中吹气以沿着模具壁膨胀而制成空心体如瓶。两种物料共同挤出可连续或间歇进行。例如，如果孔连入吹气模具中，则两种物料可同时或先后挤出。两种物料是这样的，即使其熔融或成为塑性状态以经过孔的温度或温度范围极为不同。
事实上，设有孔的装置在多数情况下是金属组件或部件，因此是良好的导热体。所以说，易于共同挤出在相同温度范围或极为接近的温度范围内熔融的两种物料。但是，如果这些范围极为不同，则热传导会导致这些范围不能保持。本发明还涉及设有至少一个孔并且包括可使两种物料保持在其挤出温度范围内的装置的装置。更具体地讲，本发明涉及热塑性材料。成对的材料例子可举出聚酰胺和配有硫化剂的橡胶。而聚酰胺又可举出PA-6，PA-6，6，PA-11，PA-12，PA-6，4，PA-6，12或聚酰胺和聚烯烃的掺混物。这些聚酰胺及其掺混物在约200-240℃下挤出。配有硫化剂的橡胶例子可举出基于羧化腈-丁二烯(X-NBR)，苯乙烯-丁二烯(SBR)或乙烯-丙烯-二烯(EPDM)的组合物，或任何其他弹性体配方如EP607085中所述配方。这些组合物在约110-120℃下挤出。
其他成对的材料可举出聚烯烃，聚苯乙烯，用不饱和羧酸酐接枝或共聚的聚烯烃，聚碳酸酯，PVDF作为材料之一，而乙烯-丙烯橡胶(EPR)，配有硫化剂的橡胶和聚氯乙烯(PVC)作为另一种材料。
本发明尤其可用于PVC/PVDF材料对。本发明方法适宜于共同挤出其挤出温度相差50-150℃，尤其是80-120℃的两种物料。
设有至少一个孔的装置可为金属组件，这样一来所述孔可为例如长方形的孔，即平模(filière plate)，其中送入两种熔融物料，而且物料之一到达该平模的部分(a)，另一种物料则到达所述平模的部分(b)。该平模的部分(a)和(b)对应于其中以与其最大尺寸平行的直线进行分割。经(a)和(b)到达的物流在一直通道中相互汇合，其中通道长度至少为(a)＋(b)间歇的10倍。
设有至少一个孔的装置也可为例如包括环形孔的金属组件，其中送入两种熔融物料，而且物料之一到达该环的部分(a)，另一种物料则到达所述环的部分(b)。该环的部分(a)和(b)对应于其中以同心环或圆进行分割。经(a)和(b)到达的物流在一环形通道中相互汇合，其中通道长度至少为(a)＋(b)间歇的10倍。
设有至少一个孔并且让两种熔融物料经过的本发明装置中，对于每一种物料，包括至少一个输送段。这些输送段与挤出机或与输送熔融物料的任何装置相连。该装置的孔可向吹气挤出模具或管校准槽的量具供料。本发明所述装置可在其经受很大热或温度梯度的各部分中包括传热管，其目的是避免较热物料热过分地加热不太热的物料。这些管进行冷却操作，也就是说这些管取出热量以避免向不太热的物料传热。这些管也可能是不需要的，如不太热的物料在本发明装置中的停留时间短到足以使物料保持在其挤出温度范围内的情况下就不需要。
这些传热管可使热量以高速长距离传送，而其温度梯度极低。
这些管的操作原理基于液体在毛细管芯中蒸发，冷凝和表面张力泵送。这样可使潜热从一个地方连续传送到另一个地方而又不需要外部能量。
因此，这些毛细管经过本发明包括孔的装置。有利的是，进行蒸发操作传热管足以带走较热物料的热量，从而避免其加热不太热的物料。如果该装置包括将必须更热的物料再加热的传热管，取出该装置中较热物料循环段和不太热物料循环段间传播的热量的管或这些可能性的任何组合，也应属于本发明范围内。常规的油循环和电阻加热系统是不足够的；除了其笨重而外，这些系统还会提高装置中金属体的温度，  而这会干扰将热量取入其他段。
同样，在常规油循环或水加二醇的冷却系统情况下，其能力根据待冷却壁和其温度之间的梯度变化，而这是不够的。如果该装置包括绝热部件和包容该部件并因而限制必须保持高温的各段热损失的部件，则也应属于本发明范围内。事实上，例如制造直径为15或20mm的管的共同挤出装置是很紧凑的并且可包容在0.3m×0.3m×0.3m体积内；热损失很大。必须防止较热材料的热量传向另一物料，但该较热物料又必须保持在其能够被挤出的温度范围内。这同样适用于不太热的物料；其中使该物料必须不超过其挤出温度，但也不低于其挤出温度。
本发明还涉及设有至少一个可使两种物料经过的孔的装置，该装置包括可使两种物料处于极不相同的温度下的传热管。
下图1/2和2/2表明了本发明的两种具体形式。图1/2表明共同挤出管的装置；其中所有部件均由钢制成；该图是沿纵轴的纵向截面图，其中所有部件都沿纵轴呈圆柱状对称形式，但输送段No.2和部件(D)和(E)内的通道例外。No.1是较热物料输送段，而No.2是另一物料输送段。(A)是较热物料挤出模具，而(B)是芯塞，(C)是包含传热管(未示出)的部件，(D)是共同挤出模具的后段，(E)是共同挤出模具的前段，(F)是法兰，(G)是模具，(H)加热元件，(I)是不太热的物料输送导筒，而(J)，(K)和(L)是加热元件。可从部件(E)中清楚地看到两个环形的同心物料输送段。
图2/2是共同挤出片材或薄膜的装置。该装置具有两个垂直的对称面；其中之一代表共同挤出的两片片材或薄膜间的边界及其向装置中的延伸(条件是两片片材或薄膜具有相同的厚度)。XX’代表该对称面的断面或截面，(No.1)代表较热物料输送段，(No.2)代表另一物料输送段，(A)代表下分布段，(B)代表下对称件，(C)代表上对称件，(D)代表上分布段，(E)代表不太热的物料加热装置，(F)代表不太热的物料输送导筒，(G)和(H)代表包含传热管的部件，(I)代表不太热的物料输送导筒和(J)代表不太热的物料加热装置。可从与物料输送段相对的部件(B)和(C)的端部清楚地看到可让两种物料通过的长方形空间(孔)。
图1/2所示装置的芯轴(B)可沿其对称轴钻孔以使电缆或通讯电缆或光学纤维通过。在该图2/2中(A)和/或接近(A)的(B)段可包括改善物流的不同形状的刻蚀槽或沟槽。这同样适用于在部件(B)中输送和分布物料的通道。
如果应用两种以上的物料，则也属于本发明范围内。例如，在1/2所示装置中，如果该第三种物料温度接近不太热的物料温度，则在(E)和(G)之间增加另一部件(D’)和另一部件(E’)就足够了。如果该第三种物料温度接近或等于较热物料温度，则部件(C’)，部件.(D’)和部件(E’)可按顺序设置，也就是说该顺序为(A)，(C)，(D)，(E)，(C’)，(D’)，(E’)和(G)。
本发明可用于下列结构，而不管这些结构是否是管状或薄膜或片状，甚至是注射模塑成型：PVDF/粘结剂/PA/粘结剂/橡胶。
该粘结剂例如为用马来酸酐接枝的聚烯烃；即与PA和PVDF在相同温度下挤出的热塑性材料。
作为例子，可以举出：
PVDF/粘结剂/PA/橡胶
聚酰胺掺混物/橡胶
聚酰胺弹性体/橡胶/PVDF/粘结剂/PVC
或聚甲基丙烯酸甲酯/PVC。
聚酰胺掺混物意指例如聚酰胺和聚烯烃的混合物，其中包括至少一种相容剂。
聚酰胺弹性体意指(i)含有聚酰胺嵌段和聚醚嵌段的共聚物和(ii)任选与聚酰胺混合。
本发明特别适用于共同挤出聚酰胺和待硫化的橡胶或PVC和PVDF。该装置可包括传热管。

Claims (6)

1.在设有至少一个孔的装置中共同挤出至少两种具有极为不同的挤出温度的物料的方法，其中所述物料先后或同时通过该装置。
2.权利要求1的方法，其中两种物料中一种物料选自聚酰胺，聚烯烃，其混合物或聚1，1-二氟乙烯，而另一种物料选自包括硫化剂的橡胶，EPR橡胶或聚氯乙烯。
3.权利要求1或2的方法，其中两种物料挤出温度相差50-150℃，优选80-120℃。
4.权利要求1-3中任一项的方法，其中设有孔的装置包括传热管。
5.设有至少一个可使两种物料在极为不同的温度下通过的孔的装置，其特征在于其中包括传热管，
6.按照权利要求1-4的方法获得的共同挤出物料。
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