CN1029316C - 生产微孔塑料的方法 - Google Patents
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Abstract
一种将含发泡剂的塑料物质连续或半连续地生产微孔塑料的方法,包含将原料放在塑料加工机内在一定温度与压力下捏合成撤除压力即发泡的混合料,直接将混合料送到冷却段,在朝向上游的压力分量形成的压力下在冷却段冷却成具高粘度与刚性及近乎平直速度特性的连续坯料,无级地送到降速-保持段,建立朝上游压力分量,直至在上游区内的塑料物质中形成足以防止混合料发泡的压力,将混合料送到加热/膨胀/成型段,在受控条件下发泡至所需密度。
Description
本发明涉及的是用塑料物质连续或半连续地生产微孔塑料的方法,该塑料物质含有发泡剂,并可含有或不含其他加工调节物和添加剂。
由于就体积而言原料的低消耗及高的热绝缘值,用热塑性塑料生产微孔塑料(泡沫塑料)已经迅速地增长起来。
用热塑性树脂生产泡沫塑料有几种公知的方法,例如包括:聚苯乙烯的“珠粒料发泡”(Styropor)法和生产具有低密度和闭孔PVC泡沫的静高压法。“珠粒料发泡”法是一种多步骤方法,生产低密度而物理值较低的聚苯乙烯泡沫。静高压法可生产低密度、闭孔和高质量的PVC泡沫,但是该方法是一种生产成本高、高度人工操作的方法,而且就产品的形状而论,该方法受到很大的限制。
对于完全连续的方法来说,挤出是最常用的方法,它一般比较容易控制而且生产成本低。
目前,在使用塑料加工机械(例如挤出机)连续生产泡沫塑料时通常使用物理发泡剂来形成较低密度的微孔塑料泡沫。对于较高密度的则通常使用化学发泡剂。
最适合形成泡沫的热塑性树脂是:聚苯乙烯(PS),包括聚合产物(HIPS、SB、SAN、ABS)、聚乙烯(LDPE)及共聚物(EVA)、包括聚合掺混物的聚氯乙烯(PVC)、和聚丙烯(PP)。
在熔体粘度在软化的温度范围内缓慢而均匀地下降时,才得到发
泡的有利条件。因此,与结晶的热塑性树脂相比,非晶形热塑性树脂更易于发泡。对于部分结晶的热塑性材料由于在发泡前或在发泡的同时一般是进行化学交联或通过辐射交联的,因此也可以得到一个更有利的作为温度的函数的粘度曲线。
在挤出泡沫塑料的方法中,发泡工艺与塑料的粘度、熔体的拉伸能力、发泡剂的气压、外部压力以及熔体与发泡剂之间的相互作用有关。
由于与未发泡的塑料相比,泡沫塑料对于与塑料加工机械(如挤出机)相连接的模具的壁有较大的摩擦力,所以人们常常希望发泡只发生在塑料混合料已离开模具之后。为此,需要一个这样的条件,即:在含有活性发泡剂的熔体上的外压应当高到足以防止发泡。在目前公知的生产方法中,在塑料熔体离开加工机械的模具后,熔体上的外压便减小,并由于塑料中的气体过饱和而使塑料发泡。
对微孔结构和挤出物的质量有很大影响的另一个参数是材料的温度。在材料的温度太低时,由于熔体的粘度较高,塑料混合物不能完全发泡。因而形成较高的密度。如果材料的温度太高,熔体的粘度则将较低,这样也容易使泡孔破裂而形成较高的密度。
为了生产具有低的、均匀密度的和闭孔的泡沫塑料,必须生产气泡不破裂的挤出物,而这种破裂是在压力减小而形成气泡的成型模具出口处由于流动方向上的速度不同所造成的。同时,还必须在塑料加工机械以及在模具中在塑料熔体上保持一个外压,以防止塑料发泡。
目前上述这两个准则已构成了用自动化方法生产闭孔泡沫塑料厚材的潜力的限制因素,这种厚材的泡沫塑料具有较低的密度并在整个横截面上的密度都是均匀的。由化学发泡剂(例如偶氮二酰胺或碳酸氢钠)所产生的气压远高于通常使用的物理发泡剂(例如KFK气体、CO2或N2)的气压,因此使用化学发泡剂时,这些限制因素更为明
显。
关于由压力减小所引起的对塑料熔体的剪切作用和撕裂气泡的问题,目前是用以下方法来减轻的:限制发泡剂的用量,或者通过在压力建立及膨胀时严格限制塑料熔体层的厚度。对于化学发泡剂,这些方法尤其有效,但是对于使用物理发泡剂,则还有很多限制。
然而,对于比较厚的泡沫塑料产品,常常希望也能用化学发泡剂,这是因为其实际生产方法比使用物理发泡剂简单,并且与使用物理发泡剂相比,一般可以较好地控制终产品的性能。这尤其是由于与物理发泡剂的相比,化学发泡剂产生的气压比较高的结果。
与泡沫的连续生产相联系,尤其是与挤出相联系,各种模具也一同被开发出来了。挤出模具实际上具有两个重要的功能:
1)在模具和挤出机中形成足够的压力;
2)使挤出物成型成所需的形状。
热塑性材料的连续发泡是以两种基本上不同的方法进行的:
1)自由发泡;
2)控制的内向发泡;
自由发泡一般用于比较简单的型材。通常用一个离模具出口不运的定型装置收集发泡挤出物。模具中所需的熔体压力,一般是通过模具的模唇来形成。
在内向发泡过程中,通过模具内的鱼雷芯形成所需的熔体压力,并将定型装置牢固地连接到模具上。该定型装置的内部形状与模具的模口相同。从外部将熔体降温,并通过真空牢固地将熔体保持在定型装置的壁上。同时,模具中的嵌件能使挤出物在定型装置中向内发泡。这种方法用于生产管材、片材和型材。终产品具有密实、光滑的皮层及较低的芯部密度。该方法被称为“塞卢卡”(Celuka)法。
有一些公知的自由发泡和“塞卢卡”法组合的方法,还有一些以
类似于“塞卢卡”法的原理为基础的生产中空型材的方法。
也使用各种不发泡的皮层材料和发泡的芯部材料共挤出的方法。
另一种方法是所谓的“Woodlite”法,该方法在模具中形成压力,并且在发泡状态下对材料的剪切比较小。该方法挤出的发泡绳状物在离开模具出口之后熔焊成为一个整体,但是,在某种程度上由于熔焊在一起的各个次挤出出物熔焊不良,所以造成终挤出制品具有不均匀的结构和低的挠曲强度。
“Armocell”法是一种特别地用于生产发泡管材的方法。通过模具中流道的特别结构,产生足够的压力以防止熔体早期发泡。用一个定型装置将发泡管材保持在离模具不远处。
上述所有模具,都对产品的密度、闭孔的百分率和尺寸造成很大的限制。这种情况主要由于防止早期发泡所需的熔体压力是通过热塑料熔体与模具之间的摩擦而形成的。
本发明的目的是改进现有技术和扩大现有技术的使用范围,同时避免现有技术的不足及其附带的限制。
根据这一目的,本发明涉及在前面的介绍中论述的那种类型的方法,它包含:
a)把原料馈送到塑料加工机械中;
b)在一定的温度和压力条件下,在塑料加工机械中捏合原料,该原料将只靠解除压力来产生发泡的混合料;
c)直接把塑料混合料输送到冷却段;
d)在由朝向上游的压力作用所形成的压力下,在冷却段将该混合料冷却成连续的坯料,该坯料具有高的粘度和刚性,并且有近似平直的速度特性,
e)可有选择地、无级地把坯料输送到降速-保持段,
f)建立朝向上游的压力分量,直到在位于上游区域内的塑料混合
料中的压力足以防止该塑料混合料发泡,
g)把坯料送到加热/膨胀/成形段后,控制该混合料发泡到所需的密度。
在下面将参照附图较为详细地说明本发明,其中附图1和2分别示出实现以上a)至g)的工序的两种可能的设备系统。
将热塑性塑料、发泡剂和其他可选择采用的加工调节物质及添加剂馈入到已知类型的塑料加工机械中,例如馈入到挤出机1中,在那里把它们捏合,捏合是在使混合料的发泡只在解除压力的条件下发生的这样的温度和压力条件下进行。
各种类型的挤出机以及在这些挤出机中采用的混合条件都是已知的,因此在这里将不进行更详细的描述。重要的因素是应避免发泡剂在塑料加工机构中有发泡的机会。
对塑料的捏合是以这样的方法进行,使全部原料达到大致相同的温度,而且是比较迅速地达到这一温度,结果是比较好地控制了来自化学发泡剂的任何可能的放热或吸热交换。
由于通过机械加工过程中迅速加热了全部塑料原料,所以如果使用了化学发泡剂,它也将迅速分解。
在已知的挤塑模具的工艺方法和原理中,为了在模具和挤塑机里得到足够的压力,在挤出机模具的出口处,大量的气泡发生破裂(因为压力是靠剪切作用/摩擦建立的)。为了避免目前存在的这些问题,根据本发明的方法通过以下手段来实现在模具和挤出机中建立足够的压力,以避免塑料的早期发泡。这种手段是:通过对降温后的塑料材料进行降速/保持,使塑料材料形成一个连续的“活塞”,以建立防止发生剪切并造成气泡破裂所需的压力。
下面,参照附图说明本发明。在模具和挤出机中形成必要的压力是这样来完成的:将在挤出模具1出口处处在压力下的塑料坯料经冷
却段连续地降温到使该坯料的刚性高到足以能够使该坯料降速,这种降速是通过例如可以是连续运动的皮带的降速装置3来进行的。塑料的降速按这样的方法来控制,使在塑料混合料中形成的压力高到能防止混合料发泡。来自挤出模具或在挤出机之后的成型装置的塑料材料,必须被保持在高外压之下,而约束壁与塑料坯料之间没有摩擦,或者有很小的摩擦,小到足以使在压力减小后形成的气泡不会破裂。由于在壁和塑料坯料之间不存在摩擦或摩擦极小,所以在这一冷却装置2中的塑料坯料将以在整个坯料内都是一致的速度移动。这意味着在塑料坯料中各层之间在运动方向上不发生剪切,或只发生轻微的剪切。
必须直接连接到模具/成型装置上的冷却装置2,可以直接连接到降速装置3上,或者冷却装置2和降速装置3可以成一个装置。例如,如果塑料的降温是在低温的连续无端钢带之间进行,就可以实现这一目的。通过控制钢带的速度,就可以调节混合料的压力。
在坯料已被降速装置3充分降速并已获得足够的压力之后,在加热段4将塑料材料加热,同时降低压力,使塑料材料发泡。加热可以连续地进行并可直接与冷却装置2的降温和降速装置3的降速相连,例如:通过被加热的无端钢带,或者可以通过把降了温的塑料坯料输送穿过一个用热空气加热的隧道来进行加热。降了温的塑料坯料还可以在例如液体浴中进行加热。
通过加热塑料,将使塑料发泡直到塑料材料中的内膨胀力和塑料材料中的张力之间达到平衡为止。这种加热是通过外加热或借助于均衡塑料材料的内外温度来进行,或者通过外部供热与均衡塑料材料的温度相结合的方法来进行。
在模具/成型装置的出口后面的用于冷却塑料混合料的冷却装置2、降速/保持装置和加热装置可以按几种基本方式构成,其中冷却
装置2中,约束壁和塑料混合料之间只有很小的摩擦或没有摩擦。以下是一些例子:
直接连接到在挤出机后面的模具/成型装置的冷却装置2可以是一个固定冷却器,它的内横截面与模具/成型装置的出口处的内横截面相同或大致相同。在内截面上的壁与塑料混合料之间必须具有最小的摩擦,这可以通过例如将内壁高光泽抛光或镀铬来达到。同时,还可以在冷却装置的内壁与塑料坯料之间施加润滑介质以进一步减小摩擦。冷却可以这样来进行,例如,通过用回火油通过在壁内的槽道来将冷却装置冷却。冷却装置还可以是一组被冷却并被压靠在塑料材料上的无端钢带装置。
在冷却装置2后面的降速装置3可以包含两个或多个辊子,这些辊子压靠在刚性的、降了温的塑料材料上;或者降速装置可以包含一组压靠在塑料材料上的无端钢带装置,通过调节它们的速度就可以调节塑料材料的上游压力。
在降速/保持装置后面的加热装置4可以一个其压力可以调节的、充灌热的液体的腔室。加热装置还可以是一组被加热的无端带装置。还可以在一个固定加热装置中进行塑料的加热,该装置的内截面与在降速装置出口后面的塑料坯料的截面相同或大致相同。在固定加热装置的内壁与塑料坯料之间的摩擦必须是很小的或是没有摩擦。还可以在塑料挤出物能在其中自由运动的加热腔室中进行加热。
在足够高的压力下加热塑料混合料使之不会在该加热装置内发泡,往往会是有利的。因为发泡时塑料材料的热绝缘值显著地提高了,因而对塑料材料的加热可能要快得多。
加热装置的内壁与塑料坯料之间的摩擦应该是极小的,这是因为如果不是这样就会对在挤出模具和挤出机上游的塑料混合料的最佳压力控制带来困难。此外,如果加热装置与塑料之间的摩擦是极小的或
是没有摩擦,对发泡的控制就容易得多。
当塑料挤出物是在压力下进行加热,则在全部挤出物都已达到要求的温度后降低外压,此时,塑料材料便膨胀,直到内膨胀力与塑料中的张力之间达到平衡为止。
在没有外压的情况(如在加热腔室中)下加热塑料挤出物时,塑料材料将在加热的同时发泡。
在本说明书中具体地描述了使用一台或多台塑料挤出机的方法,但是,任何满足对加工程序和温度/压力条件要求的连续或半连续塑料加工机械都可以使用。
塑料混合物及加工条件的说明及举例
如前所述,在开发塑料混合物的配方或制法中,必须要考虑到要使用的加工机械并估计想要的终产品的性质。本方法使用PVC来进行开发,使用如下的机械作为塑料加工机械。
塑料混合物各种组份在常规的热/冷、立式/立式塑料混合机中进行共混/混合。使用双螺杆挤出机(110mm切粒装置)作为PVC混合物的均化机/胶化机。使用一个单螺杆挤出机(90mm)作为化学发泡剂分解的塑料加工机。
使用过各种模具/成型装置,包括生产直径大约50mm园形型材的模具在内。使用一个固定装置作为冷却装置,在把一种液体润滑剂加到冷却装置的内壁与塑料坯料之间的同时,也对冷却装置的壁进行了冷却。采用了无端带装置来作为降速/保持装置。在具有加热壁的固定装置中进行塑料坯料的加热。
在研制工作中,还使用了一种冷却/降速与加热装置,它是由无端钢带形式的连续壁形成的、构成一个整体的装置。
以下是已使用过的一些塑料混合物(都是以PVC热塑性塑料为基础)的例子:
例1
PVC(M型,K值大约为60) 100
石油蜡(Pe-Wax) 0.8
硬脂酸钙 0.4
三碱价硫酸铅 10
二碱价硬脂酸铅 2
偶氮二碳酰胺 1
碳酸氢钠 15
聚甲基丙烯酸甲酯(PMMA) 12
邻苯二甲酸二辛酯(DOP) 16
例2
PVC(M型,K值大约为60) 100
石油蜡 0.2
月桂酸钙 0.3
三碱价硫酸铅 10
二碱价硬脂酸铅 1
偶氮二碳酰胺 1
碳酸氢钠 25
聚甲基丙烯酸甲酯(PMMA) 15
邻苯二甲酸二辛酯(DOP) 25
用例1的配方生产的PVC泡沫的密度约为0.1(大约为100Kg/m3)
用例2的配方生产的PVC泡沫的密度约为0.07(大约为70Kg/m3)
上述塑料混合物中的各种组分在热/冷、立式/立式高速混合机中混合到温度约为120℃。
冷却后,将该混合物送到一个由双螺杆挤出机构成的切粒装置中。在该切粒装置的出口处的塑料物质的温度约为130℃。然后将粒
料送到一个伸展到约40D的、单螺杆的90mm挤出机中。
紧贴在料斗后的挤出机中的压力被升至约1200巴,在该机的出口处,压力被降低到大约250巴。紧贴在料斗后的混合料的温度被升到大约210℃,在该机的出口处,混合料的温度被降低到大约165℃。在由冷却装置、降速装置和加热装置组成的发泡装置的出口处,坯料的温度大约为120℃。
在特殊情况下,最好是使泡沫塑料交联。可以通过使用辐射、过氧化物、酰胺、硅烷或异氰酸酯来进行这种交联。由于塑料有在塑料加工机械中进行交联的危险,所以最好在塑料加工机械的较后加工步骤中加入交联组分,或者紧接在塑料加工机械后面一个单独的混合装置中加入交联组分。
Claims (1)
1、用塑料混合料连续或半连续地生产微孔塑料材料的方法,该塑料混合物含有发泡剂,可有选择地含有其他加工调节物和添加剂,该方法包含:
a)把原料馈送到塑料加工机械中;
b)在一定的温度和压力条件下,在塑料加工机械中捏合原料,该原料将只靠解除压力来产生发泡的混合料;
c)直接将塑料混合料输送到冷却段;
其特征在于该方法还包含:
d)在由指向上游的压力作用所形成的压力下,在冷却段将该混合料冷却成连续的坯料,该坯料具有高的粘度和刚性,并且有近似平直的速度特性,
e)可有选择地、无级地把坯料输送到降速-保持段,
f)建立指向上游的压力分量,直到在位于上游区域内的塑料混合料中的压力足以防止该塑料混合料发泡,
g)把坯料输送到加热/膨胀/成型段后,控制该混合料发泡到所需的密度。
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JPS527022A (en) * | 1975-07-05 | 1977-01-19 | Ichirou Kikuchi | Improved typed earthquake proof self gas stop device |
US4187066A (en) * | 1977-10-07 | 1980-02-05 | H & S Industries, Inc. | Apparatus for the preparation of display blocks of urea formaldehyde foam |
JPS5645928A (en) * | 1979-09-21 | 1981-04-25 | Teijin Ltd | Production of polyester extruded expanded article |
DE3016926C2 (de) * | 1980-05-02 | 1982-08-12 | Heggenstaller, Anton, 8891 Unterbernbach | Vorrichtung zum Aushärten stranggepreßter Körper |
US4344710A (en) * | 1980-06-10 | 1982-08-17 | Mobil Oil Corporation | Polymer foam extrusion system |
US4456571A (en) * | 1982-12-13 | 1984-06-26 | Mobil Oil Corporation | Process and apparatus for forming a composite foamed polymeric sheet structure having comparatively high density skin layers and a comparatively low density core layer |
US4657715A (en) * | 1984-12-31 | 1987-04-14 | Mobil Oil Corporation | Process for preparing smooth skinned extruded foams with water-organic blowing agent |
US4773448A (en) * | 1987-02-26 | 1988-09-27 | Francis Norman L | Freeze-resistant plastic pipe and method for its manufacture |
US4789513A (en) * | 1987-06-05 | 1988-12-06 | P.C.E. Corp. | Coextrusion apparatus and process |
US4960549A (en) * | 1988-05-23 | 1990-10-02 | Amoco Corporation | Process for preparing polyamide-imide foam |
US5116881A (en) * | 1990-03-14 | 1992-05-26 | James River Corporation Of Virginia | Polypropylene foam sheets |
-
1989
- 1989-11-17 NO NO89894583A patent/NO894583L/no unknown
-
1990
- 1990-07-16 BR BR909007538A patent/BR9007538A/pt unknown
- 1990-07-16 DK DK170990A patent/DK170990A/da not_active Application Discontinuation
- 1990-07-16 IE IE258590A patent/IE902585A1/en not_active Application Discontinuation
- 1990-07-16 WO PCT/NO1990/000118 patent/WO1991001212A1/en active IP Right Grant
- 1990-07-16 FI FI903586A patent/FI903586A0/fi not_active IP Right Cessation
- 1990-07-16 JP JP2510542A patent/JPH05500779A/ja active Pending
- 1990-07-16 AU AU60512/90A patent/AU642894B2/en not_active Ceased
- 1990-07-16 DE DE69016659T patent/DE69016659T2/de not_active Expired - Fee Related
- 1990-07-16 EP EP90911316A patent/EP0483230B1/en not_active Expired - Lifetime
- 1990-07-16 AT AT90911316T patent/ATE117937T1/de not_active IP Right Cessation
- 1990-07-16 ES ES90911316T patent/ES2067751T3/es not_active Expired - Lifetime
- 1990-07-16 US US07/820,860 patent/US5277852A/en not_active Expired - Fee Related
- 1990-07-16 AR AR90317377A patent/AR244734A1/es active
- 1990-07-16 KR KR1019920700105A patent/KR920703314A/ko not_active Application Discontinuation
- 1990-07-16 CA CA002064199A patent/CA2064199A1/en not_active Abandoned
- 1990-07-17 SE SE9002455A patent/SE505638C2/sv not_active IP Right Cessation
- 1990-07-17 PL PL90286085A patent/PL165163B1/pl unknown
- 1990-07-17 CN CN90107076A patent/CN1029316C/zh not_active Expired - Fee Related
-
1992
- 1992-01-16 RU SU925010963A patent/RU2033925C1/ru active
Also Published As
Publication number | Publication date |
---|---|
DE69016659T2 (de) | 1995-09-07 |
AR244734A1 (es) | 1993-11-30 |
IE902585A1 (en) | 1991-02-27 |
WO1991001212A1 (en) | 1991-02-07 |
DK170990D0 (da) | 1990-07-16 |
SE505638C2 (sv) | 1997-09-22 |
DK170990A (da) | 1991-01-18 |
AU6051290A (en) | 1991-02-22 |
SE9002455L (sv) | 1991-01-18 |
PL286085A1 (en) | 1991-04-08 |
EP0483230A1 (en) | 1992-05-06 |
ATE117937T1 (de) | 1995-02-15 |
BR9007538A (pt) | 1992-06-23 |
CA2064199A1 (en) | 1991-01-18 |
KR920703314A (ko) | 1992-12-17 |
ES2067751T3 (es) | 1995-04-01 |
RU2033925C1 (ru) | 1995-04-30 |
DE69016659D1 (de) | 1995-03-16 |
AU642894B2 (en) | 1993-11-04 |
US5277852A (en) | 1994-01-11 |
NO894583L (no) | 1991-01-18 |
SE9002455D0 (sv) | 1990-07-17 |
PL165163B1 (pl) | 1994-11-30 |
NO894583D0 (no) | 1989-11-17 |
FI903586A0 (fi) | 1990-07-16 |
CN1052489A (zh) | 1991-06-26 |
JPH05500779A (ja) | 1993-02-18 |
EP0483230B1 (en) | 1995-02-01 |
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