CN1263492A - 聚合物的挤制 - Google Patents
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Abstract
本发明提供用于熔融挤制聚合组合物、尤其是导电性聚合物的方法与装置,其中一个齿轮泵3将熔融聚合组合物输送至挤制孔口41。利用聚合物减压装置5避免由于压力变化所致的组合物过度进料,该减压装置以第二个较小齿轮泵5为佳,其是在压力超过选定水平时去除部分熔融组合物。
Description
本发明涉及用于挤制聚合组合物的装置与方法。
聚合组合物经常由熔融挤制成型。于压力下利用输送装置以一连续流方式将该熔融聚合组合物输送至一挤制孔口,强迫该聚合组合物通过该孔口形成一个所需形状的挤制物。在许多实例中,将固态组合物进料至输送装置,在该装置中经由剪切与外部加热的组合熔融该组合物。公知的输送装置包括单螺杆与双螺杆挤制器。不幸的是,因为该输送装置内压力变化之故,尤其是当该组合物的粘度高时,公用的输送装置经常无法以固定速率将该熔融组合物输送至挤制孔口。此现象致使形成的挤制物品质不稳定。众所周知,在介于该输送装置与挤制孔口之间安装齿轮泵(或者已知为熔融泵)可改善此问题。该齿轮泵有助于将实质上固定量的熔融聚合组合物输送至该挤制孔口,随后制造品质经改良的挤制物。然而,该齿轮泵的大小必须正确,而且压力变化必须小到可使该齿轮泵不会缺料或过度进料。
本发明人已发现上述问题于熔融挤制导电性聚合物时尤其严重。本文所使用的“导电性聚合物”一辞是指一种包含聚合组份,且其中分散有粒子状导电性填料,例如碳黑、石墨、一种金属、一种导电性陶瓷或一种金属碳化物或氮化物的组合物。尤其是该导电性聚合物含有高浓度粒子状填料(其可仅为导电性填料或导电性与不导电性填料的混合物)时,即使输送装置与该挤制孔口之间安装有一齿轮泵,挤制期间的压力变化会致使该挤制物的电性质产生不必要的变化。
根据本发明,本发明人发现当齿轮泵与一种输送装置及一种挤制孔口(如上述)并用时,可以藉由使用一种聚合物减压装置得到大幅改善的结果,该装置系于齿轮泵的压力超出选定水平时自该系统去除熔融聚合物,因此确保使该齿轮泵不会过度进料(并且将固定量的熔融聚合组合物连续输送至该挤制孔口)。
本发明尤其适合于挤制导电性聚合物,而且将主要将照这种用途来进行描述。不过,必须了解的是,本发明也可用以挤制其他聚合组合物,而且本文所提供导电性聚合物用的资料通过恰当的改进还能适用于其他聚合组合物(这种改进对于聚合物挤制领域的普通技术人员来说,利用其自身的知识并考虑该资料,是显而易见的)。
在一较佳方面,本发明提供一种制造熔融挤制物件的装置,该物件是由一种聚合组合物、最好是导电性聚合物组成的,该装置包括:
(1)用以在加压下输送熔融聚合组合物的输送装置;
(2)一个通道;
(3)一个齿轮泵;
(4)一个挤制孔口;及
(5)一个聚合物减压装置;
组件(1)、(2)、(3)与(4)之设置方式使得由该输送装置输送的熔融聚合组合物可以连续流方式依序经过该输送装置、该通道、该第一齿轮泵及该挤制孔口;且
该聚合物减压装置与第一齿轮泵联动,因此当第一齿轮泵中的压力超过一选定水平,该聚合物减压装置会去除连续流的熔融聚合组合物,直到第一齿轮泵中的压力低于第二选定水平为止,第二选定水平等于或低于第一选定水平,而且其高到足以去除熔融聚合组合物,但是不会使压力降至造成熔融泵缺料的水平。
如下文所讨论,该聚合物减压装置最好是一齿轮泵,因此当该聚合物减压装置是一种齿轮泵以外的组件时,即使本文中齿轮泵(3)是仅有的齿轮泵,其通常仍称为“第一”齿轮泵。
在第二较佳方面,本发明提供一种制造由熔融聚合组合物组成的物件的方法,该聚合组合物以一种导电性聚合物为佳,该方法包括以下步骤:
(A)在压力下将一种熔融聚合组合物的连续流输送至一齿轮泵;
(B)操作该齿轮泵,使在步骤(A)中被输送至齿轮泵的熔融聚合组合物经由该齿轮泵输送至一挤制孔口,并经由该孔口挤制;及
(C)当该齿轮泵内的压力超过选定水平时,从该连续流去除聚合组合物。
当(a)该熔融聚合组合物具有高粘度(因为此现象容易增加挤制器或其他输送装置中的压力变化);及/或(b)挤制期间该产物受到压力变化负面影响,例如该产物至少一个方面之尺寸极小,或其电性质或其他性质视组合物挤制期间的所受剪切力而定;及/或(c)该挤制器(或其它输送装置)是一种容易产生压力变化的型式时,本发明尤其适用。因此,本发明较佳方法具有下列一或多种特性:
(a)该聚合组合物
(i)包含一种熔点为Tm℃的聚合物;
(ii)剪切速率为50sec-1且温度为Tm的1.5倍下,粘度为2
至15K.Pa.sec,尤其是8至11K.Pa.sec;及
(iii)于温度不高于Tm的1.5倍下挤制。此种组合物可包含例如,至少35%(体积)的一或多种粒子填料,至少40%(体积)的导电性填料为佳,便如碳黑。
(b)(i)该聚合组合物是一种显示PTC行为的导电性聚合物,尤其
是电阻小于10欧姆-厘米的组合物,特别是电阻小于1欧
姆-厘米的组合物。
(b)(ii)将该聚合组合物挤制成厚度小于0.010英寸(0.25毫米),例
如0.005英寸(0.13毫米)或以下的板;或挤制成厚度大于
0.010英寸(0.25毫米)的条状或板状,并压成厚度小于0.010
英寸(0.25毫米),例如0.005英寸(0.13毫米)或以下的板。
(c)该聚合物输送装置是(i)一种往复式单螺杆挤制器,或(ii)一种
长度对直径(l/d)比率相当短的非往复式螺杆挤制器,该比率例
如小于15∶1,例如8∶1至15∶1。
如上述,该聚合物减压装置是一第二齿轮泵为佳,但是其可为任何当压力过大时使该聚合组合物自系统排出,当压力降至所需水平时避免聚合组合物排出的组件。适用的组件包括齿轮泵、减压阀及适用的可关闭孔口。当理起地使用第二齿轮泵作为聚合物减压装置时,其可远小于第一齿轮泵。因此,第一齿轮泵最大容量对于第二齿轮泵最大容量的比率是5∶1至50∶1为佳,例如15∶1至25∶1。第二齿轮泵(或其他聚合物减压装置)的操作由一个控制系统控制为佳,该控制系统连续侦测施加在聚合组合物上的压力,并根据该压力操作第二齿轮泵。该控制系统可以直接侦测第一齿轮泵的压力,或在该系统的可以代表第一齿轮泵压力的其他部分上侦测压力,例如侦测介于输送装置与第一齿轮泵之间的通道的压力。
为使第一齿轮泵输送定量熔融聚合组合物至挤制孔口,该齿轮泵内的压力必须介于较低值Plower与较高值Pupper之间。第一选定水平P1(高于该值时该聚合物减压装置会去除熔融聚合物)必须小于Pupper,以Pupper的0.25至0.9倍为佳。第二选定水平P2(低于该值时,聚合物减压装置不会去除熔融聚合物)是(a)等于或小于P1,以P1的0.4至1.0倍为佳,及(b)大于Plower以Plower的1.2至1.6倍为佳。本发明优点之一是因为该聚合物减压装置确保使挤制器内的压力尖峰不会移转至挤制孔口,所以若第一齿轮泵的压力尖峰低于Pupper时可以进行高速率挤制操作。
本发明尤其适用于熔融挤制电路保护装置所用的导电性聚合物,即PTC组合物,其包含一种结晶聚合物,例如聚乙烯或聚偏二氟乙烯与一种导电性粒子填料,以碳黑为佳,其用量足以将室温电阻降至低水平,例如低于5欧姆-厘米。
适用的导电性聚合组物揭示于美国专利第4,237,441、4,388,607、4,534,889、4,545,926、4,560,498、4,591,700、4,724,417、4,773,024、4,935,156、5,049,850及5,250,228、5,378,407、5,451,919、5,582,770及5,747,147号及国际专利第WO96/29711号。
该导电性聚合物可以用任何适用方式进料至输送装置,包括:
(a)固态例如粒状形式,其是由事先熔融混合处理制备,其中该导电性填料分散于聚合物组份中;或
(b)聚合组合物与导电性填料的干燥掺合物形式,其中该输送装置必须是一种可以熔融混合此等成分,并将其输送至第一齿轮泵的装置;或
(c)导电性填料在聚合物组份中的熔融分散形式,其是于例如内部分批混合器内制备。
例如,本发明可用以改进揭示于国际专利申请案第WO98/05503号及对应的台湾申请案第86110731号的方法。该方法包括以下列方式制造一种导电性聚合物层压板:
(A)将聚合物组份与该导电性填料装填于一混合装置;
(B)于该混合装置内混合该聚合组份与该导电性填料,形成一种熔融混合物;
(C)经由一个模自混合装置输送该熔融混合物;
(D)将该熔融混合物形成一个聚合板;及
(E)在该板的至少一面上贴上金属箔形成一层压板;步骤(A)至(E)可以在单一连续制造中连续进行。
在本发明中,熔融导电性聚合物必须经由该装置以连续流形式通过,但是该方法的期间可长可短。例如,当先在内部分批混合器中制备该导电性聚合物,然后以熔融混合物形式添加至该输送装置时,该批次经处理时该方法可持续数分钟。
现在参考附图,其图示出一单螺杆挤制器1、通道2、第一齿轮泵3、具有喷嘴孔口41的挤制头4与具有出口51的第二齿轮泵5。压力控制系统8侦测通道2与第一齿轮泵3接头的压力,并根据该压力反应控制第二齿轮泵5。由进料斗7将丸粒状的导电性聚合物进料至挤制器1,挤制器1熔融该导电性聚合物,并在压力下以连续流状经由通道2将该导电性聚合物输送至第一齿轮泵3。第一齿轮泵强迫该熔融导电性聚合物通过挤制孔口41。以辊压器6将挤制物压成板状。若控制系统8所观察到的压力超过第一预定水平,该控制系统会启动第二齿轮泵5,使之去除通道2的熔融导电性聚合物,并经由出口51排出。当控制系统8所观察到的压力降至第二选定水平时,其会关闭第二齿轮泵5。
Claims (18)
1.一种制造由导电性聚合物组成的熔融挤制物件的装置,该装置包括:
(1)用以在加压下输送熔融聚合组合物的输送装置;
(2)一个通道;
(3)第一个齿轮泵;
(4)一个挤制孔口;及
(5)一个聚合物减压装置;
组件(1)、(2)、(3)与(4)被设置,以致使藉由输送装置所输送之熔融导电性组合物,以连续流方式依序经过该输送装置、该通道、该第一齿轮泵及该挤制孔口;且
该聚合物减压装置是与第一齿轮泵联动,因此当第一齿轮泵中的压力超过一选定水平,该聚合物减压装置会去除来自其连续流的熔融导电性组合物,直到在第一齿轮泵中的压力降至低于第二选定水平为止。
2.根据权利要求1所述的装置,其特征在于该聚合物减压装置是第二齿轮泵,当其正在操作时会去除通道之熔融导电性聚合物。
3.根据权利要求2所述的装置,其特征在于第一齿轮泵的最大容量对第二齿轮泵的最大容量的比率为5∶1至50∶1。
4.根据权利要求2或3所述的装置,其特征在于该输送装置包括一个单螺杆挤制器或一个双螺杆挤制器。
5.根据权利要求2或3所述的装置,其特征在于该输送装置包括一个往复式单螺杆挤制器。
6.根据权利要求2或3所述的装置,其特征在于该输送装置为一种具有1/d比率为8∶1至15∶1的非往复式螺杆挤制器。
7.根据权利要求3所述的装置,其特征在于该挤制孔口为喷嘴模。
8.根据权利要求3所述的装置,其特征在于包括一个控制系统,该系统连续侦测在第一齿轮泵中施加在导电性聚合物上的压力,并回应该压力操作第二齿轮泵。
9.一种制造由导电性聚合物所组成的物件的方法,此方法包括以下步骤:
(A)在压力下将一种熔融聚合组合物的连续流输送至第一齿轮泵;
(B)操作该齿轮泵,以致使在步骤(A)中被输送至第一齿轮输泵的熔融导电性聚合物,是通过第一齿轮泵输送至挤制孔口,并经由该孔口挤制;及
(C)当该齿轮泵内的压力超过选定水平时,自该连续流去除熔融导电性聚合物。
10.根据权利要求9所述的方法,其特征在于在步骤(C)中,是利用第二齿轮泵去除该熔融导电性聚合物。
11.根据权利要求10所述的方法,其特征在于该导电性聚合物
(i)包含一种具有熔点为Tm℃的聚合物;
(ii)在剪切速度为5sec-1且温度为Tm的1.5倍下,具有粘度为2至15K.Pa.sec;及
(iii)在温度不高于Tm的1.5倍下挤制。
12.根据权利要求11所述的方法,其特征在于该熔融导电性聚合物在剪切速率为50sec-1且温度为Tm的1.5倍下,具有粘度为8至11K.Pa.sec。
13.根据权利要求10至12中任一项所述的方法,其特征在于该导电性聚合物包含至少35%(体积)的至少一种微粒状填料。
14.根据权利要求10至12中任一项所述的方法,其特征在于该导电性聚合物显示PTC行为,而且包含至少40%(体积)的碳黑。
15.根据权利要求10至12中任一项所述的方法,其特征在于该挤制孔口为一喷嘴模,并将该挤制物压延成薄板。
16.根据权利要求10至12中任一项所述的方法,其特征在于该挤制孔口为一具有缝隙至多0.13毫米(0.005英寸)的板模。
17.根据权利要求9所述的方法,其特征在于是权利要求1至8中任一项所述的装置实现的。
18.一种由权利要求9至17中任一项所述的方法制备的导电性聚合物物件。
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US08/891,757 | 1997-07-14 | ||
US08/891,757 US6306323B1 (en) | 1997-07-14 | 1997-07-14 | Extrusion of polymers |
US08/891757 | 1997-07-14 |
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CN1263492A true CN1263492A (zh) | 2000-08-16 |
CN1078524C CN1078524C (zh) | 2002-01-30 |
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US (1) | US6306323B1 (zh) |
EP (1) | EP0996529B1 (zh) |
JP (1) | JP2001510103A (zh) |
CN (1) | CN1078524C (zh) |
AT (1) | ATE233647T1 (zh) |
AU (1) | AU8387598A (zh) |
DE (1) | DE69811898T2 (zh) |
TW (1) | TW442374B (zh) |
WO (1) | WO1999003666A1 (zh) |
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CN104349881A (zh) * | 2012-05-31 | 2015-02-11 | 日东电工株式会社 | 卷筒状片材 |
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- 1998-07-10 CN CN98807071A patent/CN1078524C/zh not_active Expired - Fee Related
- 1998-07-10 AT AT98934325T patent/ATE233647T1/de not_active IP Right Cessation
- 1998-07-10 JP JP2000502929A patent/JP2001510103A/ja active Pending
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CN102917855A (zh) * | 2010-05-28 | 2013-02-06 | 泽宏平 | 混炼挤压装置 |
CN104349881A (zh) * | 2012-05-31 | 2015-02-11 | 日东电工株式会社 | 卷筒状片材 |
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JP2001510103A (ja) | 2001-07-31 |
EP0996529B1 (en) | 2003-03-05 |
CN1078524C (zh) | 2002-01-30 |
DE69811898D1 (de) | 2003-04-10 |
AU8387598A (en) | 1999-02-10 |
US6306323B1 (en) | 2001-10-23 |
TW442374B (en) | 2001-06-23 |
ATE233647T1 (de) | 2003-03-15 |
EP0996529A1 (en) | 2000-05-03 |
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