CN1052489A - 生产微孔塑料的方法 - Google Patents
生产微孔塑料的方法 Download PDFInfo
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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/发泡/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,该塑性物质含有发泡剂,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已知的方法,例如包括:聚苯乙烯(Styropor)的“珠粒发泡”法和生产具有低密度和闭孔PVC泡沫的静高压法。“珠粒发泡”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(例如挤塑机)连续生产泡沫塑料时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)及共聚产物(EVA)、包括聚合掺混物的聚氯乙烯(PVC)和聚丙烯(PP)。
由于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比较有利的作为温度函数的粘度曲线。
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化合物已离开模具之后。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高到能足以防止发泡为止。在目前已知的生产方法中,塑料熔体在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。当材料的温度太低时,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和模具中的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型材潜力的限制因素,这种型材的泡沫塑料具有较低的密度,并且贯穿整个横截面的密度都是均匀的。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,这些限制更为明显。
关于由压力减小所引起的剪切塑料熔体和撕裂气泡的问题,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,往往也希望能用化学发泡剂,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。这尤其是与物理发泡剂的气压相比,化学发泡剂产生的气压比较高的结果。
与泡沫的连续生产一起,尤其是与挤出一起,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)使挤出物成型为想要的形状。
热塑性材料的连续发泡基本是以两种不同的方法进行的:
1)自由发泡;
2)控制的向内发泡;
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远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。
在向内发泡过程中,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。从外部将熔体冷却,并通过真空确实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。
有一些已知的自由发泡法和“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。
也使用各种未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被焊接成为一个整体,但是,在某种程度上由于焊接在一起的不同次级挤出物的焊接不良,所以造成终挤出制品的结构不均匀和低的挠曲强度。
“Armocell”法是一种特别地用于生产发泡软管的方法。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。这种情况主要是由于根据热塑料熔体与模具之间的摩擦而形成必要的熔体压力以防止早期发泡所造成的。
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加的限制。
根据这一目的本发明是关于在前面的介绍中论述的一种类型的方法,它包含:
a)把原料加到塑料加工机械中,
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化合物,
c)直接把塑料化合物输送到冷却段。
d)在由指向上游的压力作用形成的压力下,在冷却段将该化合物冷却为连续的坯料,该坯料具有高的粘度和刚性,并且有近似平直的速度分布图,
e)不是必须的,无级地把坯料输送到减速-保持段,
f)产生指向上游的压力作用,直到在上游固定区域内的塑料化合物中的压力足以防止该塑料化合物发泡,
g)把坯料送到加热/膨胀/成形段后,控制该化合物以发泡到想要的密度。
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表示进行以上a)到g)的工序的两种可能的设备系统。
将热塑性塑料,发泡剂和其他不是必须的加工调节物及添加剂加入到本身型号已知的塑料加工机械中,例如加入到挤出机1中,在那里把它们捏合,捏合是在这样的温度和压力条件下进行的,以致于化合物的发泡将只发生在解除压力时。
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械中有发泡的机会。
对塑料的捏合是以这样的方法进行的,以致使全部原料达到大致相同的温度,而且事实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。
因为经机械加工迅速加热了全部塑料原料,所以如果使用了化学发泡剂,它也将迅速达到分解。
在已知的挤塑模具方法和原理中,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:为了产生必要的压力,对冷却后以致形成连续“活塞”状的塑料进行减速/保持,以防止发生剪切并造成气泡破裂。
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:在连续加工中,在挤出模具1的出口压力下,将冷却段2的塑料坯料冷却到使该坯料的刚性高到足以能将该坯料减速,这种减速是通过减速装置3进行的,例如,该装置可以是连续的可移动的带子。以这样的方法来控制塑料的减速,能使塑料化合物中形成的压力高到能防止化合物发泡。来自挤出机之后的挤出模具或成型装置的塑料,必须被保持在高外压之下,使约束壁与塑料坯料之间没有磨擦,或者有非常小的摩擦,因此在压力减小后形成的气泡不会破裂。因为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,塑料坯料将以贯穿整个坯料都相同的速度移动。因此在该装置中,在运动方向上塑料坯料中各层之间不存在剪切或只有轻微的剪切。
必须直接连接到模具/成型装置上的冷却装置2,可以被直接连接到减速装置3上,或者冷却装置2和减速装置3可以是一个整体。例如,如果塑料的冷却是在具有低温的连续无接头钢带之间进行,就可以实现这一目的。通过控制钢带的速度,就可以调节化合物的压力。
在坯料已被减速装置3充分减速并已获得足够的压力之后,在加热段4将塑料加热,同时压力被减少,使塑料发泡。加热可以连续地进行并且直接与冷却装置2和减速装置3的操作相连接,例如:通过热的无接头钢带,或者可以通过把冷的塑料坯料输送穿过一个用热空气加热的通道来进行加热。冷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中的内发泡力和塑料中的张力之间达到平衡为止。这种过程是通过使用外加热或借助于平衡塑料内外的温度来进行,或者通过外部供热和平衡塑料温度相结合的方法进行的。
在模具/成型装置的出口后面的塑料化合物冷却装置2、减速/保持装置和加热装置可以几种基本方式构成,其中冷却装置2中,约束壁和塑料化合物之间几乎没有或没有摩擦。以下是一些例子:
直接与挤出机后面的模具/成型装置连接的冷却装置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。内断面的壁在壁和塑料化合物之间应形成最小限度的摩擦,这可以通过例如内壁的高光泽磨光或镀铬来达到。同时,还可以在冷却装置的内壁和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,通过用壁的通道中的回火油将冷却装置骤冷。冷却装置还可以是一个无接头钢带装置,它被骤冷并被压在塑料上。
在冷却装置2后面的减速装置3可以由两个或多个辊子组成,这些辊子压在刚性的、已冷却的塑料上;或者减速装置可以由一个无接头钢带装置构成,钢带是压在塑料上的,通过调节减速装置的速度,可以调节塑料的上游压力。
在减速/保持装置后面的加热装置可以是一个充满热的液体的腔,在那里可以调节压力。加热装置还可以是一个被加热的无接头带。还可以在一个固定加热装置中进行塑料的加热,该装置的内截面与减速装置出口后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和塑料坯料之间的摩擦应该很小或没有。还可以在塑料挤出物能在其中自由运动的加热腔中进行加热。
在足够高的压力下加热塑料化合物,以致在该加热装置中塑料化合物将不发泡,这往往可能是有利的。因为发泡时塑料的热绝缘值惊人地增加了,所以对塑料的加热可能要快得多。
加热装置的内壁和塑料坯料之间的摩擦应该是最小的,这是因为不然的话会对挤出模具和挤出机上游的塑料混合物的压力最佳控制带来困难。此外,如果加热装置和塑料之间的摩擦力极小或没有,对发泡的控制就容易得多。
当塑料挤出物是在压力下加热的,则在全部挤出物都已达到要求的温度后减小外压,此时,塑料便膨胀,直到内发泡力与塑料中的张力之间达到平衡为止。
在没有外压的情况(如在加热腔中)下加热塑料挤出物时,塑料将在加热的同时发泡。
在本说明书中详细地描述了使用一台或多台塑料挤出机的方法,但是,任何满足对加工程度和温度/压力条件需要的连续或半连续塑料加工机械都可以使用。
塑料组合物及加工条件的说明及举例
如前所述,在设计塑料组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。本方法被开发为使用PVC,使用如下的机械作为塑料加工机械:
在普通的热/冷、立式/立式塑料混合机中,将塑料组合物的各种组份共混/混合。作为用于PVC混合物的均化机械/胶化机械,使用双螺杆挤出机(110mm切粒装置)。作为与化学发泡剂分解有关的塑料加工机械,使用单螺杆挤出机(90mm)。
已经使用了包括生产直径大约50mm园形型材的模具在内的各种模具/成型装置。作为冷却装置使用固定冷却装置,在该装置中壁被冷却,同时在冷却装置的内壁和塑料坯料之间加液体润滑剂。作为减速/保持装置,采用了无接头带装置。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/减速及加热装置,它是由呈环形的钢带状连续壁而制成的一个整体。
以下是已使用过的一些塑料组合物(都是基于PVC热塑性塑料)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)。
在热/冷、立式/立式高速混合机中,将上述塑料组合物中的各种组分混合到温度约为120℃。
冷却后,将该混合物加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温度约为130℃。然后将粒料加到一个增大到约40D的90mm单螺杆挤出机中。
在料斗后的挤出机中的压力立即被升至约1200巴,在该机的出口处,压力被减小到大约250巴。在料斗后的化合物的温度立即被升到大约210℃,在该机的出口处,化合物温度被减小到大约165℃。在由冷却装置、减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。因为塑料有在塑料加工机械中交联的危险,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,或者在塑料加工机械后面一个单独的混合装置中立即加入交联组分。
Claims (1)
1、用塑料化合物连续或半连续地生产微孔塑料的方法,该塑料化合物含有发泡剂,可含有或不含其他加工调节物和添加剂,该方法包含:
a)把原料加到塑料加工机械中;
其特征在于该方法进一步包含:
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化合物,
c)直接将塑料化合物输送到冷却段,
d)在由指向上游的压力作用所形成的压力下,在冷却段将该化合物冷却为连续的坯料,该坯料具有高的粘度和刚性,并且有近似平直的速度分布图,
e)不是必须的,无级地把坯料输送到减速-保持段,
f)建立指向上游的压力作用,直到在上游设定区域内的塑料化合物中的压力足以防止该塑料化合物发泡,
g)把坯料输送到加热/发泡/成型段后,控制该化合物发泡到想要的密度。
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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 FI FI903586A patent/FI903586A0/fi not_active IP Right Cessation
- 1990-07-16 AT AT90911316T patent/ATE117937T1/de not_active IP Right Cessation
- 1990-07-16 WO PCT/NO1990/000118 patent/WO1991001212A1/en active IP Right Grant
- 1990-07-16 KR KR1019920700105A patent/KR920703314A/ko not_active Application Discontinuation
- 1990-07-16 AU AU60512/90A patent/AU642894B2/en not_active Ceased
- 1990-07-16 IE IE258590A patent/IE902585A1/en not_active Application Discontinuation
- 1990-07-16 AR AR90317377A patent/AR244734A1/es active
- 1990-07-16 US US07/820,860 patent/US5277852A/en not_active Expired - Fee Related
- 1990-07-16 JP JP2510542A patent/JPH05500779A/ja active Pending
- 1990-07-16 CA CA002064199A patent/CA2064199A1/en not_active Abandoned
- 1990-07-16 BR BR909007538A patent/BR9007538A/pt unknown
- 1990-07-16 DK DK170990A patent/DK170990A/da not_active Application Discontinuation
- 1990-07-16 ES ES90911316T patent/ES2067751T3/es not_active Expired - Lifetime
- 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
- 1990-07-17 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 |
---|---|
CN1029316C (zh) | 1995-07-12 |
CA2064199A1 (en) | 1991-01-18 |
EP0483230A1 (en) | 1992-05-06 |
DK170990A (da) | 1991-01-18 |
FI903586A0 (fi) | 1990-07-16 |
US5277852A (en) | 1994-01-11 |
PL165163B1 (pl) | 1994-11-30 |
DK170990D0 (da) | 1990-07-16 |
NO894583L (no) | 1991-01-18 |
RU2033925C1 (ru) | 1995-04-30 |
PL286085A1 (en) | 1991-04-08 |
DE69016659D1 (de) | 1995-03-16 |
DE69016659T2 (de) | 1995-09-07 |
ATE117937T1 (de) | 1995-02-15 |
ES2067751T3 (es) | 1995-04-01 |
AU642894B2 (en) | 1993-11-04 |
JPH05500779A (ja) | 1993-02-18 |
BR9007538A (pt) | 1992-06-23 |
SE505638C2 (sv) | 1997-09-22 |
EP0483230B1 (en) | 1995-02-01 |
AU6051290A (en) | 1991-02-22 |
KR920703314A (ko) | 1992-12-17 |
SE9002455D0 (sv) | 1990-07-17 |
SE9002455L (sv) | 1991-01-18 |
WO1991001212A1 (en) | 1991-02-07 |
NO894583D0 (no) | 1989-11-17 |
AR244734A1 (es) | 1993-11-30 |
IE902585A1 (en) | 1991-02-27 |
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