CN110914036B - 从烯烃聚合物中去除挥发性组分的方法和获得的制品 - Google Patents
从烯烃聚合物中去除挥发性组分的方法和获得的制品 Download PDFInfo
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Abstract
本发明涉及一种从烯烃聚合物中去除挥发性组分的方法,所述方法在包含至少一个真空脱气区的挤出机中进行,所述方法包括以下步骤:(a)将烯烃聚合物的料流引入挤出机;(b)将挤出机中的烯烃聚合物在高于烯烃聚合物的熔融温度但低于烯烃聚合物的分解温度的温度下挤出,从而产生挥发性组分的量减少的烯烃聚合物熔体,其中所述方法在挤出机中具有如等式(1)限定的在800至4000范围内的停留时间分布宽度(σ2),其中:σ2是停留时间分布宽度,τ是平均停留时间,t是烯烃聚合物的流体元在挤出机中度过的停留时间间隔,E(t)是停留时间分布函数,并且其中所述方法任选包括步骤(c),在所述步骤(c)中使所述烯烃聚合物的熔体通过模头区到达造粒机以将所获得的烯烃聚合物造粒。
Description
本发明涉及从烯烃聚合物中去除挥发性组分的方法,所述方法在挤出机中进行。本发明还涉及通过所述方法生产的烯烃聚合物。本发明还涉及包含通过所述方法生产的烯烃聚合物的制品以及所述烯烃聚合物在生产制品中的用途。
烯烃聚合物中夹带或溶解有挥发性组分。这些挥发性组分通常使用闪蒸分离器、利用惰性气体(例如氮气)的吹扫塔或利用水蒸汽的蒸汽干燥器从烯烃聚合物中清除。从烯烃聚合物材料中去除挥发性组分的其他方法是在包含其中施加真空压力的真空脱气区的挤出机中进行的。这种方法的例子见于现有技术中,例如,同向旋转双螺杆挤出机(Co-rotating twin screw extruders),K.Kohlgrüber,181-201页,2008。
然而,已知的挥发性组分减少方法仍具有针对特定目的的不足。例如在含有重单体、例如己烯或1-辛烯的低密度和低熔体流动速率的烯烃聚合物(例如,低密度C2C6或C2C8塑性体和弹性体)中。根据VDA277测量,这些烯烃聚合物通常存在例如超过400ppm的挥发性组分量。
低密度烯烃聚合物的各种应用要求极低的挥发性组分浓度,例如低于100ppm(VOC,VDA277),在塑性体和弹性体的情况下,通常需要挥发性组分浓度低于65ppm。
这通常是个问题,因为与较轻的共聚单体、例如丁烯相比,己烯和1-辛烯更难以去除,导致需要后处理。
因此,仍然需要一种从烯烃聚合物中去除挥发性组分的方法,从而适合于去除挥发性有机化合物,例如1-辛烯和己烯。
发明内容
现在,通过提供一种从烯烃聚合物中去除挥发性组分的方法,已经克服了上述缺点,所述方法在包含至少一个真空脱气区的挤出机中进行,所述方法包括以下步骤:
(a)将烯烃聚合物的料流引入所述挤出机;
(b)在高于所述烯烃聚合物的熔融温度但低于所述烯烃聚合物的分解温度的温度下将所述挤出机中的烯烃聚合物挤出,从而产生挥发性组分的量减少的烯烃聚合物熔体,
其中所述方法在挤出机中具有如等式1限定的在800至4000范围内的停留时间分布宽度(σ2),
其中:
σ2是停留时间分布宽度,
τ是平均停留时间,
t是烯烃聚合物的流体元在挤出机中度过的停留时间间隔,
E(t)是停留时间分布函数,
并且其中所述方法任选包括步骤(c),在所述步骤(c)中使所述烯烃聚合物的熔体通过模头区到达造粒机以将所获得的烯烃聚合物造粒。
意外地发现,拓宽所述挤出机中的停留时间分布是实现有效去除所述烯烃聚合物中挥发性组分的关键,即,大的停留时间分布宽度(σ2)对于有效减少所述烯烃聚合物中的挥发性组分至关重要。
具体实施方式
本发明提供了一种从烯烃聚合物中去除挥发性组分的方法,所述方法在包含至少一个真空脱气区的挤出机中进行,所述方法包括以下步骤:
(a)将烯烃聚合物的料流引入所述挤出机;
(b)在高于所述烯烃聚合物的熔融温度但低于所述烯烃聚合物的分解温度的温度下将所述挤出机中的烯烃聚合物挤出,从而产生挥发性组分的量减少的烯烃聚合物熔体,
其中所述方法在所述挤出机中具有如等式1限定的在800至4000范围内的停留时间分布宽度(σ2),
其中:
σ2是停留时间分布宽度,
τ是平均停留时间,
t是烯烃聚合物的流体元在挤出机中度过的停留时间间隔,
E(t)是停留时间分布函数,
并且其中所述方法任选包括步骤(c),在所述步骤(c)中使所述烯烃聚合物的熔体通过模头区到达造粒机以将所获得的烯烃聚合物造粒。
烯烃聚合物
用于本发明的方法中的烯烃聚合物可以是任何的丙烯均聚物、乙烯均聚物、丙烯与选自乙烯和具有4至10个碳原子的α-烯烃的一种或多种共聚单体的共聚物、乙烯与选自具有3至10个碳原子的α-烯烃的一种或多种共聚单体的共聚物及其混合物。
上述共聚物的具体类型是塑性体和弹性体。诸如本文所用的塑性体和弹性体是结合了弹性体和塑料的性质的烯烃聚合物,即它具有橡胶样性质和塑料的可加工性。塑性体和弹性体的例子是乙烯和1-辛烯的共聚物,例如Borealis以商标QueoTM出售的。塑性体和弹性体的其他例子是以EngageTM、AffinityTM、VersifyTM、InfuseTM、ExactTM、VistamaxxTM、TafmerTM、FortifyTM和LuceneTM的名称出售的那些。
用于本发明的方法中的烯烃聚合物的MFR2通常为0.1至100g/10min,优选0.5至90g/10min,更优选0.5至80g/10min。对于基于乙烯的聚合物,熔体流动速率MFR2根据ISO1133在2.16kg的负荷和190℃的温度下测量。对于基于丙烯的聚合物,熔体流动速率MFR2根据ISO 1133在2.16kg的负荷和230℃的温度下测量。
当用于本发明的方法中的烯烃聚合物是塑性体或弹性体时,它的MFR2通常为0.1至100g/10min,优选0.5至90g/10min,更优选0.5至80g/10min。对于基于乙烯的塑性体和弹性体,熔体流动速率MFR2根据ISO 1133在2.16kg的负荷和190℃的温度下测量。对于基于丙烯的塑性体和弹性体,熔体流动速率MFR2根据ISO 1133在2.16kg的负荷和230℃的温度下测量。
当用于本发明的方法中的烯烃聚合物是塑性体或弹性体时,其肖氏(Shore)A机械硬度值根据ISO 868测量通常超过50,优选超过55。
当用于本发明的方法中的烯烃聚合物是塑性体或弹性体时,其肖氏D机械硬度值根据ISO 868测量通常低于45,优选低于43。
当用于本发明的方法中的烯烃聚合物是塑性体或弹性体时,其密度通常在855至910kg/m3、优选860至905kg/m3的范围内。
所述烯烃聚合物可以是粒子或团粒的形式。所述烯烃聚合物的粒子特性对于本发明的方法不是关键的。
所述烯烃聚合物通常在聚合过程例如淤浆聚合过程、气相聚合过程或溶液聚合过程中产生,其中至少一种烯烃在烯烃聚合催化剂的存在下聚合。通常,从所述聚合过程中回收所述烯烃聚合物,并对其进行减压和吹扫步骤以从所述烯烃聚合物中去除残留的烃,然后将其引入本发明方法的挤出机中。
本发明方法的挤出机
本发明的从烯烃聚合物中去除挥发性组分的方法在挤出机中进行。挤出机可以是本领域已知的任何挤出机。因此挤出机可以是单螺杆挤出机;双螺杆挤出机,例如同向旋转双螺杆挤出机或异向旋转双螺杆挤出机;或多螺杆挤出机,例如环形挤出机。优选挤出机是单螺杆挤出机或双螺杆挤出机。特别优选的挤出机是同向旋转双螺杆挤出机。这些挤出机是本领域中公知的,并且例如由Coperion、Japan Steel Works、Krauss Maffei Berstorff或Leisteritz供应。
所述挤出机通常包含进料区、熔融区、混合区和任选的模头区。所述挤出机还包含至少一个真空脱气区和任选的至少一个剥离区。
所述挤出机的长度与直径比L/D通常至多60:1,优选至多40:1。如本领域所公知的,同向旋转双螺杆挤出机通常具有比异向旋转双螺杆挤出机更大的L/D。
所述挤出机也可具有一个或多个用于将其它组分例如添加剂进料至挤出机中的进料口。这样的附加进料口的位置取决于通过所述口添加的材料的类型。
方法
进料区
根据本发明方法的步骤(a),将烯烃聚合物的料流通过进料区引入所述挤出机。
进料区将烯烃聚合物引入熔融区。
熔融区
烯烃聚合物从进料区传到熔融区。在熔融区中,烯烃聚合物熔融。固体烯烃聚合物粒子通过旋转螺杆引起的拉动力传送。然后,通过摩擦热的消散使温度沿着螺杆的长度增加,并增加到高于烯烃聚合物的熔融温度但低于烯烃聚合物的分解温度的水平。由此固体烯烃聚合物粒子开始熔融。
优选将熔融区中的螺杆设计成使得所述熔融区中的螺槽被完全填充。从而使所述固体粒子在熔融区中形成紧密的床。当螺槽中有足够的压力产生并且螺槽被完全填充时,会发生这种情况。通常,熔融区中的螺杆包含传送元件,没有显著的倒流。
混合区
在熔融区之后,烯烃聚合物熔体传到混合区。混合区中的螺杆通常包含一个或多个混合段,所述混合段包含提供一定程度的倒流的螺杆元件。在混合区中,将烯烃聚合物熔体混合以获得均匀混合物。
真空脱气区
所述挤出机还包含至少一个真空脱气区,用于从烯烃聚合物熔体中去除挥发性组分。所述挥发性组分可包括挥发性有机化合物,例如烃、残余单体、低聚物、添加剂、增塑剂和/或降解产物。所述至少一个真空脱气区沿挤出机置于下游。合适地,所述至少一个真空脱气区可以位于熔融区的下游端或混合区内。可以使用多于一个真空脱气区。如果在挤出机中存在大量气态材料,则这样的布置是有利的。
特别是如果存在多个真空脱气区,那么最上游的真空脱气区在熔融区之后而随后的真空脱气区在混合区中和/或在混合区之后,有时是有利的。
在真空脱气区中,施加真空压力。真空脱气区中的真空压力通常在50至600毫巴的范围内,优选在100至500毫巴的范围内,更优选在150至350毫巴的范围内。
剥离区
所述挤出机可具有至少一个剥离区,在其中将剥离剂,例如水、蒸汽或氮气,适当地引入到挤出机中,以帮助从烯烃聚合物熔体中去除挥发性组分。在本发明的方法中,水是优选的剥离剂。
所述剥离剂,当使用时,通常被引入所述至少一个真空脱气区的上游,或当有多个真空脱气区时,被引入最下游的真空脱气区的上游。
相对于挤出机中烯烃聚合物的总通量,引入挤出机中的剥离剂的流量通常为0.5至1.5%,优选0.5至1.0%。
在本发明的方法中使用剥离区的优点在于,引入到挤出机中的剥离剂降低了烯烃聚合物熔体和挥发性组分混合物的分压,从而增强了真空脱气区中挥发性组分的去除。
本发明的方法任选包括步骤(c),在所述步骤(c)中使烯烃聚合物的熔体通过模头区到达造粒机,以将所获得的烯烃聚合物造粒。
模头区
模头区通常包含模头板,其通常是具有多个孔的厚金属圆盘。所述孔平行于螺杆轴。当烯烃聚合物熔体通过模头时,它通常被冷却并造粒。
造粒机
造粒机通常是拉条造粒机或水下造粒机。
在本发明的方法中,在高于烯烃聚合物的熔融温度但低于烯烃聚合物的分解温度的温度下挤出烯烃聚合物。合适地,在比烯烃聚合物的熔融温度高至少30℃的温度下挤出烯烃聚合物,优选在比烯烃聚合物的熔融温度高至少40℃的温度下挤出烯烃聚合物,更优选在比烯烃聚合物的熔融温度高至少50℃的温度下挤出烯烃聚合物,但所述温度低于烯烃聚合物的分解温度。
在本发明的方法中,挤出机的螺杆速度通常在180至450rpm的范围内,优选在200至400rpm的范围内。
在本发明的方法中,在挤出机中的平均停留时间(τ)通常在100至220秒的范围内,优选在100至200秒的范围内。
本发明的方法在挤出机中具有如等式1限定的在800至4000范围内的停留时间分布宽度(σ2),
其中:
σ2是停留时间分布宽度,
τ是平均停留时间,
t是烯烃聚合物的流体元在挤出机中度过的停留时间间隔,
E(t)是停留时间分布函数。
优选地,本发明的方法在挤出机中的停留时间分布宽度(σ2)在850至3800的范围内,更优选在900至3500的范围内。
大的停留时间分布宽度对于有效减少烯烃聚合物中的挥发性有机化合物至关重要。大的停留时间分布宽度允许烯烃聚合物沿挤出机更好地混合,并通过使挤出机中烯烃聚合物的全部料流重新取向而增加挤出机中的表面积。
在本发明的方法中,可以将其他组分例如添加剂引入挤出机中。添加剂的例子包括但不限于,稳定剂例如抗氧化剂(例如位阻酚、亚磷酸酯/亚膦酸酯、含硫抗氧化剂,烷基自由基清除剂、芳族胺、受阻胺稳定剂或其掺合物)、金属钝化剂(例如MD 1024)或UV稳定剂(例如受阻胺光稳定剂)。
通常,在本发明的方法期间引入挤出机中的添加剂的总量不多于5.0重量%,优选不多于1.0重量%,更优选不多于0.8重量%。所述添加剂的量相对于引入挤出机中的烯烃聚合物料流的总量。
通常将添加剂在进料区引入挤出机中。
本发明还提供了通过本发明的方法产生的烯烃聚合物。
通过本发明的方法产生的所得烯烃聚合物,根据VDA277测量,通常挥发性有机化合物含量(VOC)小于65ppm,优选小于60ppm,更优选小于50ppm。
本发明还提供了包含本发明的烯烃聚合物的制品。包含本发明的烯烃聚合物的合适的制品是例如模塑制品,例如注塑或吹塑制品,汽车制品,例如保险杠和汽车内部零件。
最后,本发明涉及本发明的烯烃聚合物在生产制品中的用途。
实施例
除非另外定义,否则术语和测定方法的以下定义适用于上面的本发明一般描述以及下面的实施例。
I.测量方法
a)熔体流动速率
熔体流动速率(MFR)根据ISO 1133测定并以g/10min指示。MFR是聚合物的流动性的指示,因此是可加工性的指示。熔体流动速率越高,聚合物的粘度越低。对于基于乙烯的聚合物、基于乙烯的塑性体和基于乙烯的弹性体,根据ISO 1133在2.16kg的负荷和190℃的温度下测量熔体流动速率MFR2。对于基于丙烯的聚合物、基于丙烯的塑性体和基于丙烯的弹性体,根据ISO 1133在2.16kg的负荷和230℃的温度下测量熔体流动速率MFR2。
b)挥发性有机化合物(VOC)VDA277.
烯烃聚合物的总排放根据VDA 277:1995,使用气相色谱仪和顶空方法,通过使用顶空提取来测定。设备是Agilent气相色谱仪,具有长30米和内径0.25毫米x 1.0微米(膜厚度1μm)的WCOT毛细管柱(蜡型)。使用以氢气作为燃料气体的火焰电离检测器。GC设置如下:50℃下等温3分钟,以12K/min加热至200℃,在200℃下等温4分钟,进样温度:200℃,检测温度:250℃,载气氦,流动模式分流比1:20,载气流速1ml/min。在以丙酮作为校准标准的气相色谱分析和火焰电离检测之后,基于由排放物质提供的所有值的总和来测量排放潜力。在测量之前将进样(团粒,约2g)在120℃下调理5小时后,进行顶空分析(20ml顶空小瓶)。单位是每克样品的微克碳,相应地是ppm。
c)停留时间分布宽度(σ2)的计算
通过使用Sciences Computers Consultants Inc.提供的名为的用于挤出机的软件来计算停留时间分布宽度(σ2)。该计算主要基于挤出机中给定的生产速率(kg/h)和挤出机中的螺杆速度(rpm)进行。所述计算假定沿螺杆轮廓分布有一定数量的具有自己的局部分布时间的虚拟局部反应器来计算。软件算出使用以下等式1来计算停留时间分布宽度(σ2)所需的t、τ和E(t)dt的值:
其中:
σ2是停留时间分布宽度,
τ是平均停留时间,
t是烯烃聚合物的流体元在挤出机中度过的停留时间间隔,
E(t)是停留时间分布函数。
d)密度
根据ISO 1183D和ISO1872-2测量密度用于样品制备。
e)肖氏A和肖氏D机械硬度
根据ISO 868在80x10x4 B型试样上测量肖氏A和肖氏D机械硬度。对于基于乙烯的聚合物,试样根据EN ISO 1872-2进行模制;对于基于丙烯的聚合物,试样根据EN ISO1873-2进行模制。对于基于丙烯的塑性体、基于丙烯的弹性体、基于乙烯的塑性体和基于乙烯的弹性体,根据ISO 20753制备B型80x10x4 mm的注塑试样。
II.发明例和比较例
用于下面的发明例和比较例中的烯烃聚合物是由Borealis制造并以Queo 6800LA的名称分销的乙烯-1-辛烯共聚物(P1)。该乙烯-1-辛烯共聚物(P1)的MFR2为0.5(ISO1133/190℃/2.16kg)、密度为868kg/m3、肖氏A机械硬度为74、肖氏D机械硬度为22和熔融温度为47℃。
所有发明例和比较例均在螺杆直径为18mm和L/D比为40:1的Coperion ZSK 18型同向旋转双螺杆挤出机中进行。所述挤出机在挤出机的混合区内包含两个真空脱气区,在其中连续施加300毫巴的真空压力。对于每个发明例和比较例,将乙烯-1-辛烯共聚物(P1)的料流引入挤出机中,并在230℃的温度下挤出。.挤出后,将所得的乙烯-1-辛烯共聚物熔体在拉条造粒机中的水浴中于15℃的水温下将拉条固化后进行造粒。
所述方法如上所述使用乙烯-1-辛烯共聚物(P1)在不同的停留时间分布宽度(σ2)下进行。表1中可以看到每个发明例和比较例的过程条件以及所得的挥发性有机化合物值(VDA277)。
表1:发明例(IE)和比较例(CE)
IE1 | CE1 | IE2 | CE2 | IE1* | IE2* | |
螺杆速度(rpm) | 200 | 200 | 400 | 400 | 200 | 400 |
挤出机中的平均停留时间(τ) | 186 | 91 | 103 | 65 | 186 | 103 |
挤出机中的生产速率(kg/h) | 1.7 | 4.5 | 3.0 | 5.0 | 1.7 | 3.0 |
停留时间分布宽度(σ<sup>2</sup>) | 3215 | 555 | 1020 | 365 | 3215 | 1020 |
VDA277(ppm) | 30 | 76 | 58 | 84 | 15 | 23 |
*所述方法还包括一个剥离区的发明例,其中将水作为剥离剂引入挤出机。相对于挤出机中烯烃聚合物的总通量,水的流量为1.0%。
从表1中可以看出,在IE1和IE2中,具有较大的停留时间分布宽度(σ2)的本发明方法导致所得的乙烯-1-辛烯共聚物中挥发性有机化合物(VOC,VDA277)的降低更大。
从表1中可以看出,在IE1*和IE2*中,在本发明的方法中使用水作为剥离剂的剥离区的存在进一步改善了所得的乙烯-1-辛烯共聚物中挥发性有机化合物(VOC,VDA277)的降低。
Claims (14)
1.一种从烯烃聚合物中去除挥发性组分的方法,所述方法在包含至少一个真空脱气区的挤出机中进行,所述方法包括以下步骤:
(a)将烯烃聚合物的料流引入所述挤出机中,其中所述烯烃聚合物是乙烯与选自具有3至10个碳原子的α-烯烃的一种或多种共聚单体的共聚物;
(b)在高于所述烯烃聚合物的熔融温度但低于所述烯烃聚合物的分解温度的温度下将所述挤出机中的烯烃聚合物挤出,从而产生挥发性组分的量减少的烯烃聚合物熔体,
其中所述方法在所述挤出机中具有如等式1限定的在800至4000范围内的停留时间分布宽度(σ2),
其中:
σ2是停留时间分布宽度,
τ是平均停留时间,
t是烯烃聚合物的流体元在所述挤出机中度过的停留时间间隔,
E(t)是停留时间分布函数,
并且其中所述方法任选包括步骤(c),在所述步骤(c)中使所述烯烃聚合物的熔体通过模头区到达造粒机以将所获得的烯烃聚合物造粒。
2.权利要求1的方法,其中所述挤出机的螺杆速度在180rpm至450rpm的范围内。
3.权利要求1的方法,其中在所述挤出机中的平均停留时间(τ)在100秒至220秒的范围内。
4.权利要求1的方法,其中所述乙烯与选自具有3至10个碳原子的α-烯烃的一种或多种共聚单体的共聚物是塑性体或弹性体或其混合物。
5.权利要求4的方法,其中所述塑性体或弹性体是乙烯和1-辛烯的共聚物或乙烯和己烯的共聚物。
6.权利要求1至5任一项的方法,其中所述挤出机还包含至少一个剥离区。
7.权利要求1至5任一项的方法,其中所述挤出机是单螺杆挤出机或双螺杆挤出机。
8.权利要求1至5任一项的方法,其中根据VDA277测量,所得烯烃聚合物的挥发性有机化合物含量(VOC)小于65ppm。
9.权利要求1至5任一项的方法,其中在比所述烯烃聚合物的熔融温度高至少40℃但低于所述烯烃聚合物的分解温度的温度下挤出所述烯烃聚合物。
10.由权利要求1至9任一项的方法产生的烯烃聚合物,根据VDA277测量,所述烯烃聚合物的挥发性有机化合物含量(VOC)小于65ppm,其中所述烯烃聚合物是乙烯与选自具有3至10个碳原子的α-烯烃的一种或多种共聚单体的共聚物。
11.权利要求10的烯烃聚合物,其中所述乙烯与选自具有3至10个碳原子的α-烯烃的一种或多种共聚单体的共聚物是塑性体或弹性体或其混合物。
12.权利要求11的烯烃聚合物,其中所述塑性体或弹性体是乙烯和1-辛烯的共聚物或乙烯和己烯的共聚物。
13.一种制品,其包含权利要求10至12任一项的烯烃聚合物。
14.权利要求10至12任一项的烯烃聚合物用于生产制品的用途。
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PCT/EP2018/063781 WO2018219805A1 (en) | 2017-05-29 | 2018-05-25 | Process for removing volatile components from an olefin polymer and article obtained |
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CA3082038C (en) | 2018-01-17 | 2022-04-19 | Borealis Ag | Process for obtaining low volatile plastomers |
EP3913030A4 (en) * | 2019-02-26 | 2022-03-16 | Moresco Corporation | METHOD OF MAKING A HOTMELT ADHESIVE AND HOTMELT ADHESIVE |
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CN104487466A (zh) * | 2012-07-02 | 2015-04-01 | 米其林集团总公司 | 用于连续合成二烯弹性体的方法 |
CN107848222A (zh) * | 2015-02-04 | 2018-03-27 | 博里利斯股份公司 | 在挤出机中制备改性烯烃聚合物的方法 |
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NL8203281A (nl) * | 1982-08-21 | 1984-03-16 | Stamicarbon | Inrichting en werkwijze voor het winnen van polymeer uit een oplossing. |
US5062713A (en) * | 1989-09-06 | 1991-11-05 | The Dow Company | Method for determining the residence time distribution of a polymer extruder |
WO1991016189A1 (en) | 1990-04-12 | 1991-10-31 | Exxon Chemical Patents Inc. | Polymer grafting process, apparatus and products obtained therewith |
JP4414408B2 (ja) | 2006-03-28 | 2010-02-10 | 株式会社日本製鋼所 | スクリュ式押出機の脱揮シミュレーション装置、およびスクリュ式押出機の脱揮シミュレーションプログラム |
WO2016017429A1 (ja) * | 2014-08-01 | 2016-02-04 | 株式会社片山化学工業研究所 | 樹脂ペレットの製造方法 |
KR101637104B1 (ko) | 2014-12-31 | 2016-07-06 | 한국신발피혁연구원 | 발포비드용 올레핀계 폴리머의 개질방법 및 개질된 올레핀계 조성물을 이용한 발포비드용 조성물 |
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US20210095058A1 (en) | 2021-04-01 |
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WO2018219805A1 (en) | 2018-12-06 |
CA3065652A1 (en) | 2018-12-06 |
EP3630447A1 (en) | 2020-04-08 |
BR112019021169A2 (pt) | 2020-04-28 |
EP3630447B1 (en) | 2022-09-14 |
CA3065652C (en) | 2022-01-18 |
CN110914036A (zh) | 2020-03-24 |
BR112019021169B1 (pt) | 2023-05-09 |
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