CN1231338C - 制备粒状聚烯烃的方法 - Google Patents

制备粒状聚烯烃的方法 Download PDF

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CN1231338C
CN1231338C CNB998142425A CN99814242A CN1231338C CN 1231338 C CN1231338 C CN 1231338C CN B998142425 A CNB998142425 A CN B998142425A CN 99814242 A CN99814242 A CN 99814242A CN 1231338 C CN1231338 C CN 1231338C
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rotational moulding
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K·克努德森
A·M·法特尼斯
M·杜伊
O·豪尔
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Abstract

本发明提供一种制备滚塑微粒组合物的方法，该方法包括：制备聚烯烃和任选至少一种添加剂的混合物；通过模头的模孔挤出熔融态的该混合物；将通过该模孔挤出的混合物造粒而形成粒度分布D(v，0.5)为0.1-1mm，D(v，0.9)-D(v，0.1)与D(v，0.5)的比值不超过1的微粒；将该微粒干燥到残余的含水量不超过1%wt；而且如果需要的话，将该微粒包装。

Description

制备粒状聚烯烃的方法
本发明涉及制备用于滚塑的粒状聚烯烃的方法。
滚塑是一种成形方法，其中聚合物颗粒，模塑粉末，被装填到置于烘箱中并且旋转的模具中，从而使聚合物熔化并且涂覆模具的内表面。为了保证成形的产品是无缺陷的，模塑粉末必须具有较小的粒度，并且优选粒度和组成是均匀的。通常，粒度约300μm。其中，如通常那样，成形粉末必须含有着色剂或其他的添加剂，例如稳定剂，模塑粉末通常是通过研磨由稳定的反应器级粉末挤出的聚合物颗粒而制备的，颗粒的尺寸例如通常为3-6mm，研磨成适合滚塑的粒度，通常着色剂和或其他的添加剂与聚合物颗粒一起被添加或混合到磨碎的成形粉末中。除了昂贵之外，研磨过程嘈杂且灰尘多，因此，通常研磨操作意味着工人的环境恶劣。
使用挤出机有可能混合聚合物和添加剂，并挤出含有聚合物或添加剂的颗粒。然而由于所得成形制品的表面覆盖有小孔“针孔”时，还没有发现该颗粒被接受用来进行滚塑。
我们已经发现，挤出的微粒可以应用于滚塑中，如果他们的含水量被降低到小于0.1％wt(103ppm)，或者更优选小于200ppm。在这种情况下，可以避免传统方法的制备用于滚塑的成形粉末的昂贵和工人不喜欢的研磨步骤。而且，与研磨过的粉末相比微粒更容易处理，并且使用常规输送系统更容易输送，例如，由于干流动性。而且，具有较高的堆积密度，微粒在输送体积方面和滚塑方法本身方面都是有益的。
因此，一方面本发明提供了一种滚塑组合物，该组合物包括粒状的烯烃聚合物，具有的粒度分布D(v，0.5)为0.1-1mm，优选0.2-0.9mm，特别是0.3-0.8mm，D(v，0.9)-D(v，0.1)与D(v，0.5)的比值不超过1，优选不超过0.8，例如0.45-0.70，含水量小于0.1％wt，优选小于200ppm，更优选小于150ppm，特别是小于100ppm，例如10-200ppm，特别是30-140ppm。
通过混合、造粒和干燥加工可以制造这些非常干燥的微粒，并且这形成了本发明的另一方面。
从该方面看出，本发明提供了一种制备滚塑微粒组合物的方法，该方法包括：
制备聚烯烃和任选但优选至少一种添加剂的混合物，添加剂例如是一种或多种选自着色剂、稳定剂(例如热稳定剂或辐射稳定剂)、抗氧剂、UV吸收剂、抗静电剂、润滑剂和填料(例如有机填料)；
从模头中的模孔挤出熔融态的该混合物；
将通过该模孔挤出的该混合物造粒，而形成粒度分布D(v，0.5)为0.1-1mm，优选0.2-0.9mm等，D(v，0.9)-D(v，0.1)与D(v，0.5)的比值不超过1，优选不超过0.8的微粒；
将该微粒干燥到残余水的含量不超过1％wt，优选小于0.1％wt，更优选小于200ppm等；
如果需要的话，包装该微粒，例如，在随后用收缩性外涂层涂覆的水密性容器或微孔容器。
通过造粒法，在所得的滚塑颗粒中非常均匀地分布混合物中被造粒的任何添加剂(例如稳定剂(例如热或辐射稳定剂例如UV-稳定剂，特别是HALS(受阻胺光稳定剂))，着色剂，抗静电剂，抗氧剂(例如酚醛和亚磷酸盐抗氧剂)，润滑剂等)。这导致在颗粒内和颗粒之间产生了高均匀度。由于滚塑法本身不包括挤出步骤，所以这对于滚塑是非常重要的，因为滚塑本身并不能够使添加剂分布变得均匀。
通常使用的添加剂例如抗氧剂，润滑剂，UV吸收剂的数量为约100-5000ppm，例如500-2500ppm，相对于总的聚合物重量。
本发明的方法可以连续方式进行有益的操作，虽然干燥加工可以间歇方式进行，间歇干燥通过根据由连续操作的造粒机得来的微粒的分批投料进行。在这种情况下，该方法的操作度(该方法运行时间的百分比)至少为95％。对于任何工业化生产的满负荷的聚合物成形组合物制备方法，至少95％的操作度是理想的。
从另一个方面看出，本发明提供了本发明的或由本发明方法制备的微粒组合物在滚塑中的应用。从另一个方面看出，本发明还提供了一种滚塑方法，其中颗粒聚合物组合物被转换而制备成形制品，特征在于：使用本发明的或由本发明方法制备的微粒组合物作为该组合物。
滚塑是成熟的技术(例如见SE-A-9203167)，而且本发明的微粒可以在传统滚塑设备中使用。
对于本发明的方法，初始原料通常是粒状和非粒状的无水聚烯烃(例如，C2-10 1-烯烃的均聚物或共聚物，更优选是乙烯或丙烯、特别是乙烯的均聚物或共聚物)，任选反应器级聚合物或熔融聚合物。一般聚烯烃是通过聚合法制备的，由齐格勒-纳塔、或基于铬的或金属茂或单点催化剂催化。该聚烯烃可以具有窄的或宽的分子量分布；但窄分子量分布是优选的，例如小于4。最好聚烯烃的MFR2.16在2-10的范围内，特别是3-6。密度为950-920kg/m3的PE是特别优选的。
一般，初始原料的温度在室温和30℃之间是特别优选的。
优选使用的任何着色剂都以母炼胶的形式，即，以与聚合物、通常是与初始原料相同或相似的聚合物混合的形式。在这点上，适合使用LDPE。着色剂可以是无机或有机材料，正如通常应用于成形的聚烯烃产品中的。炭黑是特别优选的。
通过确保组分以所需比例均匀混合的控制系统，将初始原料、着色剂和任何其他所需的添加剂例如辐射稳定剂、抗氧剂、抗静电剂等加入到挤出机、混合器或熔体泵中。通常，初始原料占所得混合物的至少60％wt，更优选至少80％wt，且该混合物含有至少85％wt、优选至少90％wt的聚烯烃。因此例如使用两个减量进料器将99-80％wt颗粒状的HDPE和1-20％wt的在LDPE中含有40％wt炭黑的母炼胶喂入挤出机中。
根据混合和聚合物是否已被熔融的需要，使用混合器、挤出机或熔体泵来混合组分，并且建立必要的压力来保证通过模孔的适当流动。通常混合包括由一个或多个贮料槽在控制的流动条件下喂入添加剂(例如，如果需要的话，使用适当的控制阀和泵)。将添加剂和聚合物加入到混合器/均化器中而产生对于挤出机的均匀的进料流。如果需要的话，可以将添加剂与一定比例的聚合物混合而产生添加剂母炼胶，并且其可以与剩余的聚合物一起被加入到挤出机中。这可以包括通过副挤出机将母炼胶喂入到聚合物中。对于所有的混合物在挤出模头的压力例如可以达到550巴；但是通常是在100和300巴之间。当混合物到达模板时的混合物的温度将根据使用的特定聚合物而定，但应该足够的高而使聚合物通过模头，并且为了降低或避免聚合物降解应该保持尽可能的低。
口模板应该是适于经受挤出熔融聚合物所需的压力的形式，模孔的直径应该使微粒形成所需的尺寸。通常模孔直径在0.05-1.0mm的范围内，更优选在0.1-0.8mm，更优选0.2-0.4mm。对于工业生产的大量操作，口模板适合包括多个这样的模孔，例如1000-50000个，并且适于挤出至少0.25吨/小时，更优选至少为1吨/小时。
适合的造粒机是水下造粒机，在冷却熔体使其快速固化的水的存在下，通过使切割机旋转横切口模板的下游面而操作。造粒机运行时的速度根据口模板的尺寸和模孔的数量而选择，而得到所需的颗粒尺寸和形状。根据本发明的方法，为了制备微粒，需要使用比用于制备较大颗粒所需的更多的造粒机水，因此离开造粒机的组合物通常具有非常高的水含量，例如95-99％wt，更普遍的是97-98％wt。
优选将该含水组合物筛分以除去块料，然后进行粗除水操作，例如通过经过预浓缩机的旁路，组合物成切线进入锥形筛的顶部处，并且水通过足够小的防止了微粒从其通过的开口(例如0.15×2mm)流出。通过在筛的基底处的输送管将微粒除去。最好是这可以将含水量降低到50-80％wt。除去的水可以循环到造粒机中。
该含水的微粒组合物还可以进行第二次除水操作以降低含水量，例如降低到1-10％wt。这一般可以通过使用离心器，例如推进离心器来实现。除去的水又循环到造粒机中。可以选择离心器旋转速度和停留时间来得到所需的脱水度，并且根据微粒尺寸、离心器尺寸和离心器的负荷而定。通常需要的克力为300-800g，停留时间是分钟级，例如＜4分钟。
以这种方式，可以很大程度地降低含水量，而不使用在加热基础上操作的干燥器。
可以通过一个或多个再干燥步骤实现将所得的部分干燥的组合物的含水量降低到滚塑所需的值，例如通过使用流化床干燥器，其中加热了的气体(例如空气)经过微粒的流化床，或通过使用闪蒸干燥器。
使用流化床干燥器，进气口温度约95℃，出气口温度约75℃，所需的停留时间通常又是分钟级的，例如7-13分钟。
由卡尔·费歇尔法可以测量颗粒的含水量。例如，1g的样品在烘箱中被加热到180℃；汽化的水进入到KF溶液中；滴定并计算水含量，以ppm计。
在将微粒干燥到所需的程度之后，最好是将它们筛选以除去粗料，以及(如果需要的话)细粒组分。
例如，然后通过常规的气力输送机系统可以输送干燥和筛选的微粒，包装并保存。在最后的干燥步骤之后，例如在运送、保存和包装过程中，优选微粒保持在干燥条件之下，以防止水分含量增加到不希望的程度。而且，优选，在该步骤中使用的管道应该如此选择和配置：以避免微粒的静电荷和由其导致的缺点，例如在同一设备上随后输送产品时的交叉污染。
从另一个方面看出，本发明提供了用于制备滚塑聚烯烃颗粒的装置，该装置包括：
(i)混合器，用于提供聚烯烃和至少一种添加剂的混合物；
(ii)挤出机和造粒机，用于将该混合物挤出和造粒；
(iii)离心器，用于将该混合物脱水；和
(iv)流化床干燥器，用于将该脱水的混合物干燥，例如到含水量不超过1％重量，优选不超过0.1％重量，特别优选不超过200ppm，等。
在该装置中，优选配置的挤出机和造粒机用于产生粒度分布为D(v，0.5)为0.1-1mm，且D(v，0.9)-D(v，0.1)与D(v，0.5)的比值不超过1的颗粒。而且，过量的水优选在离心分离之前被排出粒状的混合物，例如在如上所述的预浓缩机中。
由于根据本发明的微粒很干燥，所以可以得到由其制备的滚塑产品，而没有导致机械性能差和不令人满意外观的表面点蚀和不规则度。
比较使用这种滚塑颗粒制造的滚塑产品可以看出，当颗粒的含水量降低时，可见“针孔”(产品表面上使用光显微镜可见的和至少100μm直径的孔)的数量降低了，因此在含水量低于约150ppm(wt.)时，用光显微镜便观察不到针孔。在270和160ppm之间时，用光显微镜可见的针孔数量下降了约34倍。在80ppm时，在195mm×195mm的测试表面上观察不到针孔。例如使用光显微镜，通过计算滚塑产品表面(例如10cm2-50cm2)上的直径为100μm或更高的针孔数量可以很容易地确定针孔表面密度。因此从另一个方面可以看出，本发明提供了一种滚塑的聚合物(例如聚烯烃)制件，在其表面上的针孔密度小于10/cm2，优选小于5/cm2，更优选小于1/cm2。
如上所述，与磨成粉末的相应聚合物相比，本发明的颗粒具有改进的干流性和堆积密度。因此，例如，对于一种聚合物，根据本发明的颗粒具有的干流性和堆积密度(根据ASTM-D 1895-89)值为14s/100g和476kg/m3，与粉末状聚合物的值22s/100g和360kg/m3相比。
下面将参照如下非限定性实施例和附图来描述本发明的实施方案，其中：
图1所示为本发明方法的一个实施方案的工艺步骤的流程图；
图2-4是例如本发明组合物的粒度分布曲线；和
图5和6是两个滚塑产品的表面光显微镜照片。
参照图1，从贮料筒仓将聚合物加入到挤出机加料槽1中，从贮料槽2将炭黑母炼胶加入到挤出机加料槽3中。从加料槽1，经过标准的减量进料器6聚合物被加入到挤出机5中。从槽3将母炼胶加入到减量进料器4中，然后加到挤出机5。如果需要的话，可以混入其他的添加剂，例如以母炼胶的形式，任选与炭黑母炼胶一起或从单独的并联进料器(未示出)加入。挤出机5可以是标准挤出机，从Werner&Pfleiderer(例如ZSK70MC)、Berstorff或者Kobe Steel(例如Hyperktx 59 xht)可买到。在挤出机5中，将聚合物和母炼胶混合，形成熔体，并通过齿轮泵穿过口模板进入造粒机8，其被加入来自水槽9的造粒机水。适合的口模板可从BKG或Gala买到。
由造粒机制造的含有含水微粒的产物经过除块器15进入预浓缩机10中，如上所述。适合的预浓缩机可从Krauss-Mafei买到(例如EC800)。分离出的水又回到槽9中，和浓缩的含水微粒组合物进入推式离心器11中。适合的离心器可从Krauss-Mafei买到(例如SZ32)。被离心器除去的水又回到槽9中，并且被离心分离的微粒经过流化床干燥器12。适合的流化床干燥器可从Buhler(例如OTWG160)或NiroA/S(例如Vibro-Fluidizer)买到。经干燥器12干燥过的微粒通过筛13被筛选，并通过气力输送机14被输送，保存和/包装。
实施例1
将94重量份的HDPE(Borecene ME8168(MFR2＝6，密度＝934g/L，并且含有抗氧剂、UV稳定剂和润滑剂，在约每千几份(重量)的水平上)，来自Borealis)和6重量份的炭黑母炼胶(含有60％wt的LDPE和40％wt的炭黑)的混合物在约250℃熔融挤出并造粒，经过具有0.4mm孔的模板，模板被加热到约290℃。将所得颗粒的样品干燥到残余含水量在60-200ppm之间。
粒度分布如图2所示，是使用Malvern Instruments粒度分析器测量的。粒度分布为：D(v，0.9)为797μm，D(v，0.1)为462μm，D(v，0.5)642μm，即(D(v，0.9)-D(v，0.1μm)/D(v，0.5))＝0.52。
类似地又制备两个微粒的样品，在第一种情况下，使用0.3mm孔径的口模板；在第二种情况下，使用Borecene ME8166(MFR2＝3，密度＝940g/L)代替ME8168，并使用0.3mm孔径的口模板。粒径分布分别示于图3和4，为D(v，0.9)为701μm，D(v，0.1)为410μm，D(v，0.5)510μm，即(D(v，0.9)-D(v，0.1)/D(v，0.5))＝0.57和D(v，0.9)为740μm，D(v，0.1)为410μm，D(v，0.5)523μm，即(D(v，0.9)-D(v，0.1)/D(v，0.5)＝0.63)。
实施例2
针孔密度
将以与实施例1的那些相似的方法制备的微粒，进行再水合作用而使含水量为80-7000ppm(重量)。由卡尔·费歇尔法(对于较低的含水量)和重量分析法(对于较高的含水量)测量含水量。
在烘箱温度为270℃时，使用Rotospeed E-60滚塑装置使用不同的样品制备立方体的箱子。在每一种情况下，将箱子的相同的面切开并洗涤。将带有8个14mm×18mm窗口的面板放置在切口和洗涤过的面上，并且使用带有环形照明器的Wild photo macroscopeM420，将每一窗口都进行数码照相并传送到计算机上。进行成像来确定直径大于100μm的表面针孔的数量。图5和6所示为使用270ppm wt和160ppm wt的含水量的微粒制备的表面的图像。可以看出，在160ppmwt的含水量处，基本上观察不到针孔。

Claims (18)

1.一种滚塑组合物，包括粒状的乙烯或丙烯的均聚物或共聚物，其粒度分布D(v，0.5)为0.1-1mm，D(v，0.9)-D(v，0.1)与D(v，0.5)的比值不超过1，并且含水量小于0.1％wt。
2.如权利要求1所述的组合物，具有的(D(v，0.9)-D(v，0.1))/D(v，0.5)的比值至多0.8。
3.如权利要求1和2任一所述的组合物，具有的含水量小于200ppm重量。
4.如权利要求1和2任一所述的组合物，具有的含水量小于150ppm重量。
5.如权利要求1和2任一所述的组合物，具有的含水量小于100ppm重量。
6.如权利要求1-5任一所述的组合物，包括至少一种添加剂。
7.如权利要求1-6任一所述的组合物，包括至少一种选自如下着色剂，稳定剂，抗氧剂，UV吸收剂，抗静电剂，润滑剂和填料的添加剂。
8.如权利要求6或7所述的组合物，其中该至少一种添加剂在该粒状聚合物的颗粒中均匀分布。
9.一种制备滚塑微粒组合物的方法，该方法包括：
制备乙烯或丙烯的均聚物或共聚物和任选至少一种添加剂的混合物；
通过模孔将熔融态的该混合物挤出；
将挤出该模孔的混合物造粒，形成D(v，0.5)为0.1-1mm、D(v，0.9)-D(v，0.1μm)与D(v，0.5)的比值不超过1的微粒；和
将该微粒干燥到残余含水量小于0.1％wt。
10.如权利要求9所述的方法，其中将该微粒包装。
11.如权利要求9所述的方法，其中该混合物被造粒形成[D(v，0.9)-D(v，0.1μm)]/D(v，0.5)至多0.8的微粒。
12.如权利要求9和11任一所述的方法，其中将该微粒干燥到残余含水量小于0.1％wt。
13.如权利要求9和11任一所述的方法，其中将该微粒干燥到残余含水量至多150ppm重量。
14.如权利要求9-13任一所述的方法，其中该混合物包括至少一种选自着色剂，稳定剂，抗氧剂，UV吸收剂，抗静电剂，润滑剂和填料的添加剂。
15.权利要求1-8中任一项或权利要求9-14中任一项的方法制造的微粒组合物在滚塑中的应用。
16.一种滚塑方法，其中将颗粒状的聚合物组合物加工成模塑产品，其特征在于：使用权利要求1-8中的任一项的或权利要求9-14任一项的方法制备的微粒组合物作为所述组合物。
17.一种用于制备滚塑聚烯烃粒料的装置，该装置包括：
(i)混合器，用于提供乙烯或丙烯的均聚物或共聚物和至少一种添加剂的混合物；
(ii)挤出机和造粒机，用于将该混合物挤出和造粒；
(iii)离心器，用于将该混合物脱水；和
(iv)流化床干燥器，用于将该脱水的混合物干燥。
18.如权利要求17所述的装置，还包括预浓缩机，用于在混合物经过所述离心器前将来自所述挤出机和造粒机的混合物脱水。
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