CN101519522A - 用于热塑性多孔材料的聚合物掺合物 - Google Patents
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Abstract
本发明涉及用于热塑性多孔材料的聚合物掺合物,具体涉及包含聚酯掺合物的耐高温、坚硬但有弹性且低密度的多孔泡沫材料,所述掺合物由约80至约98重量%的高粘度聚对苯二甲酸乙二醇酯(I.V.=1.0-1.9dl/g)和约2至约20,优选至约5重量%的平均MW高于4000g/mol的聚碳酸酯构成。
Description
技术领域
本发明描述了通过处理聚合物掺合物获得的发泡的热塑性多孔产物。这种泡沫材料具有比包含纯的均聚或共聚树脂的多孔材料好得多的机械性能。
背景技术
制造低密度PET泡沫产品的发泡过程目前主要是采用连续挤出生产线(由作为主挤出机的具有相对较小螺旋直径的双螺杆挤出机和作为冷却挤出机的具有较大螺旋直径的单挤出机构成)或双螺杆挤出机并在PET纯树脂中加入物理发泡剂(CO2、N2或HFC等)和成核剂(例如,滑石)实现的。该过程可采用不同成型工具加工。尽管PET原料的粘度较高(I.V.基本大于1.2dl/g),但一方面,其机械性能不令人满意:通过挤出方法测得,用这种方法制造的以及在市场上购得的PET泡沫的抗压强度为,例如,在密度分别为100-110和150-160kg/m3时不高于1.3和2.0MPa。另一方面,当密度分别为100-110和150-160kg/m3时,在抗压强度为1.3和2.0MPa时的断裂剪切延伸大于2.5%。在许多应用中,如建筑、建造快艇或制造风力涡轮机,低密度PET泡沫的机械值越高则能保证最终应用有更好的性能、更加安全和更长使用期。然而,坚固泡沫的市场还有待开发。另一方面,当PCT泡沫具有低密度(低于200kg/m3)时实现细且均匀的孔结构就更加困难。绝缘应用中更需要低密度PET泡沫,因此它能提供更好的绝热性。
造成相对较差产品特性和较差孔结构的主要原因是PET对制造过程中的热降解或热氧化降解敏感。这种降解到只最终泡沫产品的MW和特性进一步降低。由于挤出生产线的较高剪切应力,高分子量PET树脂由于高剪切在制造时被降解。另一方面,无法令人满意的机械值主要是由于PET泡沫产品中央的较大孔结构造成的。在过去公开的所有专利[1-10]或报道[11]中,通过制造纯聚合物的方法或迄今所述的标准挤出方法无法制造机械性能优于上述产品的大尺寸发泡PET挤出物(厚度大于40mm,宽度大于100mm)。低密度PET泡沫(密度低于200kg/m3)的挤出制造过程不是一个简单的过程,在工业生产上尤其如此。
发明内容
本发明的总目的是通过掺合PET树脂及改进挤出生产线来提高所述PET泡沫产品的机械值。
泡沫挤出聚酯树脂以制造坚硬的低密度多孔结构是一种经济的方法。通过使用物理发泡剂制造的低密度多孔聚酯材料显示出轻核材料的许多特性:尤其是刚度、强度、耐高温、尺寸稳定性和可循环使用。
提高材料性能的一个最经济的方法是用聚合物掺合物代替纯聚合物。通过加入第二种热塑性材料将聚合物掺合起来能改善一种聚合物的特性。聚合物掺合物被定义为两种或多种聚合物的混合物。根据[12,13],术语“聚合物掺合物”是指包含至少2wt%第二种聚合物的体系。低于该水平时,第二相则被认为是添加剂。通常,掺合聚合物能补偿给定的主要材料的特定缺点。PET/PC掺合物是一种紧密的材料,据报道它具有较好的耐热性[14]。
在本发明中,将均聚和共聚的聚酯PET与PC(1-20wt%)掺合在一起。PET/PC掺合物被加入双螺杆挤出机并与CO2或易燃气体以及发泡成低密度PET泡沫板(ρ<200kg/m3,根据ISO 845测得)的核混合在一起。发现在本发明中,将PC加入PET树脂首先能提高挤出机内的融化压力。这有可能对气体溶解度和扩散产生正面影响。此外,熔融物强度得到提高并能更好地控制成核作用和生长机制。由于较高的应***化效应和更好地控制了开放/闭合孔的含量,PET/PC掺合物的泡沫结构较之作为原材料的PET纯树脂更加均匀。加工PET/PC掺合物更重要的结果是大幅度提高了硬度(ρ分别为100-110和150-160kg/m3时的抗压强度>1.55和2.2,根据ISO 844在挤出后测得)。此外,弹性从低于2.5%提高到大于3.5%(剪切断裂伸长率,根据ISO 1922测得)。基于25℃时对PET泡沫样品的测量(根据DIN EN 12667),这种泡沫产品(泡沫密度=100-200kg/m3)的导热性为0.028-0.038W/m.K。
如果活性(reactive)挤出充气的PET/PC掺合物,还能发现挤出机内融化压力和应***化的提高。此时,PET大多为低粘度树脂(PET细粉或瓶装PET的I.V.皆≤0.8,根据ASTM 4603),并处理相同的PC级别。通过活性挤出发泡的PET/PC掺合物体系的泡沫产品因此比任何一种纯的PET树脂更优秀。
已知在挤出机出口处横截面上的融化温度是不均匀的。冷却挤出机如动态混合器或静态混合器通常用于补偿熔融物在横截面上的温度均匀性。在进一步的研究中,双螺杆挤出机、熔融物冷却器如热交换机和静态混合器的组合提供了比上述设备更加均匀的熔融物体系。大孔可被减小,而机械性能(例如压缩和剪切强度)得到进一步改善。
在所有上述工艺中,物理发泡剂可用于发泡(通常指“气体”)并通常是二氧化碳(CO2)、氮气(N2)、醇、酮、甲基酰胺、氢氟碳(例如HFC-152a或HFC-134a)或烃(如正己烷、异戊烷、环戊烷和正庚烷)、或上述气体的气体混合物。所述核通常是滑石,但也可使用其他类型的核。
除了成核剂和发泡剂,还可在配料中采用阻燃剂如卤化的、成焦的(charforming)或防水(如含有磷的)化合物和UV稳定剂。
具体实施方式
PET/PC泡沫挤出物的实施例
给出以下实施例来阐述而非限制本发明。
对比例1
该例采用的挤出机是BC180,一种BC泡沫公司(BC Foam)生产的共旋双螺杆挤出机,Dmax=180mm,长度=28D。该双螺杆挤出机与静态混合器以及由物块转接器和多孔平板构成的挤出成型模具相连。在该挤出机中加入500kg/h聚对苯二甲酸乙二醇酯(PET)(一种MG制造的PET均聚物Cobitech 0,I.V.=1.25dl/g(根据ASTM 4603))并在滑石核和物理发泡剂CO2或易燃气体(FG)的帮助下发泡成PET板。熔融物体系在流经Sulzer混合器时被均质并冷却至大约240℃。挤出机的RMP被设定为14(1/min),PET通过量为500kg/h。通过推离速度为1.5-2.0m/min的校准器推出泡沫挤出物。
挤出参数如下所列:
表01:加工参数
参数 | 试验1 | 试验2 |
PET流速(kg/h) | 500 | 500 |
核百分比(%) | 0.2-1.0 | 0.2-1.0 |
气体类型 | CO2 | 易燃气体 |
气体含量(wt%) | 0.5-0.8 | 1.5-1.7 |
融化温度Tm(℃) | 240 | 237 |
融化压力pd(巴) | 45 | 48 |
RPM(1/min) | 14 | 14 |
牵引速度(m/min) | 2.0 | 2.0 |
在物块转接器处测量融化温度和压力。
可制得泡沫产品,但板材(630×45mm)中间有许多大孔(大于1mm)。在泡沫挤出样品的挤出方向上测量抗压强度。在垂直于挤出方向的样品表面进行剪切以便进行剪切试验。泡沫PET板的机械性能列于表2:
表2:PET泡沫的特性
参数 | 试验1 | 试验2 |
PET泡沫密度(kg/m3) | 156 | 114 |
孔结构 | 大孔可见 | 大孔可见 |
抗压强度(MPa) | 1.24 | 0.73 |
剪切强度(MPa) | 1.0 | 0.55 |
对比例2
重复对比例1的泡沫挤出过程,不同之处在于采用MG制造的共聚PETCobitech 2,I.V.=1.25dl/g(根据ASTM 4603)。加工参数也略有不同:
表3:加工参数s
参数 | 试验1 | 试验2 |
PET通过量(kg/h) | 400 | 430 |
核百分比(wt%) | 0.2-0.7 | 0.2-1.2 |
发泡剂类型 | CO2 | 易燃气体 |
气体含量(wt%) | 0.5-0.9 | 1.5-1.8 |
融化温度Tm(℃) | 239 | 240 |
融化压力pd(巴) | 60 | 60 |
RPM(1/min) | 12 | 12 |
牵引速度(m/min) | 2.8 | 3.8 |
由于牵引速度较快,挤出后PET泡沫板的厚度小于30mm。PET泡沫板的强度类似于用PET Cobitech 0制造的泡沫:
表4:PET泡沫的特性
参数 | 试验1 | 试验2 |
PET泡沫密度(kg/m3) | 147 | 112 |
孔结构 | 大孔可见 | 大孔可见 |
抗压强度(MPa) | 1.37 | 0.71 |
实施例1
重复对比例1的泡沫挤出过程,不同之处在于将PC(陶氏化学(DowChemicals)的PC CalibreTM 603-3:一种支化聚碳酸酯树脂并配有UV稳定剂)加入均聚PET Cobitech 0。采用与低密度泡沫相同的易燃气体作为物理发泡剂。将PET/PC掺合物加入双螺杆挤出机。PET/PC掺合物中含2.7-6.0wt%PC使挤出机内的压力提高约80巴。将总通过量降至380kg/h以降低挤出生产线的融化压力并保持物块转接器内熔融物的压力为65巴:
通过处理PET/PC聚合物掺合物不仅能更好地控制孔生长还能使挤出物更加膨胀。泡沫挤出板的大小为630×55mm。孔结构更加均匀且大孔被显著减少。发泡的PET/PC板的性能得到提升:
表5:PET/PC泡沫的特性
参数 | Value |
泡沫密度(kg/m3) | 110 |
孔结构 | 更加均匀 |
抗压强度(MPa) | >1.55 |
剪切强度(MPa) | 0.85 |
剪切断裂伸长率 | >3.5% |
25℃的导热性(W/m.K) | 0.030 |
实施例2
将50kg/h MG制造的均聚PET Cobitech 0与2.5-6.0wt%上述级别的PC混合并加入LMP制造的双螺杆共旋挤出机LMP 90,挤出机与包含热交换机和静态混合器的冷却/混合单元相连,然后连接多孔平板。螺杆的直径为90mm,长度/直径比为30D。CO2被用作发泡剂,核为0.4-0.8wt%滑石。
与纯PET树脂Cobitech 0相比,PET/PC掺合物的融化压力较高,获得的泡沫材料的密度为150kg/m3,具有闭合的孔结构。孔结构也能得到改善。在挤出方向测得发泡的PET/PC样品的的抗压强度为2.4MPa。
实施例3
在实施例2的挤出生产线上进行活性挤出,不同之处在于此时采用Sulzer混合器。在该试验中,加工的是含或不含同级别PC作为第二组分的55kg/h PETCobitech 0,但使用Clariant的环氧基增链剂CESA Chain-ExtenderNCA0025531,增链剂应在适当位置使用以稳定甚至提高挤出过程中聚酯熔融物的I.V.。挤出的泡沫板的厚度超过50mm。
配方、加工参数和加工行为总结在下表中:
表6:加工参数和加工行为
参数 | PET纯树脂 | PET/PC掺合物 |
PET树脂 | Cobitech 0 | Cobitech 0 |
PC含量(wt%) | 0 | 2.0 |
滑石核(wt%) | 0.2-0.5 | 0.2-0.5 |
增链剂(wt%) | 0.5 | 0.5 |
CO2发泡剂(wt%) | 0.73 | 0.73 |
泡沫密度(kg/m3) | 154 | 147 |
挤出机出口的融化压力(巴) | 113 | 180 |
模头的融化压力(巴) | 43 | 67 |
如表7所证实,当用双螺杆挤出机加工PET/PC掺合物时挤出机出口以及多孔模具上的融化压力有很大差异。在配方中加入PC使压力提高证实能提高熔融物的强度和更好地控制孔生长。在这种活性泡沫挤出中使用PET/PC掺合物预计能得到更加均匀的泡沫、较好的发泡能力和较好的韧性/强度。
文献
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Claims (9)
1.一种耐高温、坚硬但有弹性且低密度的多孔泡沫材料,其形式为挤出的片材或板材,密度低于200kg/m3,导热性为0.028-0.038W/m.K,包含由以下物质构成的PET/PC掺合物:
a)约80至约98重量%的高粘度PET(I.V.=1.0-1.9dl/g),以及
b)约2至约20,优选至约5重量%的平均MW高于4000g/mol的PC,其中施加了物理发泡剂。
2.一种泡沫材料,其包含PC含量最至多40wt%的PET/PC掺合物,其中,PET的I.V.为1.0-1.9dl/g,且PC的平均MW高于4000g/mol。
3.一种在增链剂或接枝剂如每分子含有2个或更多酸酐或环氧基团的化合物的帮助下将聚酯或聚酯/PC掺合物发泡获得的活性挤出泡沫材料,其中,所述聚酯的I.V.为0.2-1.5dl/g,且PC的平均MW高于4000g/mol。
4.一种从权利要求1、2或3所述的泡沫材料获得的多孔制品。
5.如权利要求1、2或3所述的泡沫材料,其特征在于,其密度为40-200kg/m3。
6.如权利要求1、2或3所述的泡沫材料,其特征在于,其抗压强度大于1.3MPa。
7.如权利要求1、2或3所述的泡沫材料,其特征在于,其剪切强度大于0.80MPa。
8.如权利要求1、2或3所述的泡沫材料,其特征在于,其剪切断裂伸长率为3.5-30%。
9.一种制造如上述权利要求中任一项所述的泡沫材料的挤出方法,该方法包括以下步骤:
a.将聚合物和添加剂加入挤出机中融化成熔融物体系;
b.在挤出机内注入发泡剂并与熔融的聚合物体系混合;
c.通过热交换器冷却并进一步均质化,然后在静态混合器内冷却并进一步均质化;
d.通过线料模头或扁平模头挤出熔融的混合物;
e.在形状和尺寸固定或可调的校准器的帮助下使挤出物成型;以及
f.在校准后空气冷却所述挤出物。
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