CN1225867A - 由高熔体强度聚丙烯材料制备有良好低温韧性的泡沫制品的方法 - Google Patents
由高熔体强度聚丙烯材料制备有良好低温韧性的泡沫制品的方法 Download PDFInfo
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Abstract
一种用下述方法制得的泡沫制品:(1)辐照丙烯聚合物材料,所述材料选自:(a)丙烯、乙烯和1-丁烯的三元共聚物,(b)聚烯烃组合物,包含(i)约31%至39%丙烯和乙烯的共聚物,(ii)约58%至72%丙烯、乙烯和1-丁烯的三元共聚物,(c)聚烯烃组合物,包含(i)约30%至65%丙烯和1-丁烯的共聚物,(ii)约35%至70%丙烯和乙烯的共聚物,(2)在物理发泡剂和泡核剂的存在下,使经辐照的丙烯聚合物材料挤压通过口模,由此形成泡沫制品,其密度比丙烯聚合物材料初始密度小至少10倍。该泡沫制品与普通的丙烯聚合物材料相比,其柔性和低温韧性均提高。
Description
本发明涉及由高熔体强度丙烯聚合物材料制备泡沫制品的方法。
具有较高柔性和低温韧性的能发泡的聚合物对于下述应用都是理想的:(1)用于高操作温度环境的软管隔热,(2)重要的具有柔软感的汽车内部部件,如用于仪器面板和/或门板的热塑性烯烃外层/泡沫系统,以及车内顶部衬里和车尾行李箱衬里,在其中泡沫和毡层被层压和热成形形成复合物结构,(3)需要具有冲击缓冲性能的挤出溶条应用,如汽车减能器(外部保险杠、内部柱状缓冲层和侧面冲击面板)、敏感电子器件的包装和漂浮器件。
目前低密度聚乙烯树脂在软管隔热体市场上占优势,但它们缺乏工业应用和汽车隔热体应用中所需的热稳定性。
丙烯类聚合物由于具有高的熔点和化学惰性,因而是引人注目的。通过辐照普通的丙烯聚合物制得的具有高熔体强度的丙烯聚合物材料已用于制造泡沫制品。例如,在美国专利4,916,198中揭示了使用辐照过的高熔体强度的丙烯聚合物材料,通过用发泡剂使熔融的聚合物发泡制造泡沫制品。在美国专利5,414,027中揭示了在氯氟烃发泡剂和成核剂的存在下,通过将经辐照的高熔体强度的聚烯烃组合物挤压通过口模而制得泡沫体。在美国专利5,324,753和5,338,764中揭示了通过使由经辐照的高熔体强度的丙烯聚合物材料制得的预发泡珠粒经烧结热成形而制造发泡丙烯聚合物制品的方法。
然而,通过这些方法制得的发泡辐照丙烯聚合物材料的性能(尤其是韧性)在-20℃的温度下是不能令人满意的。
用一种方法制得泡沫制品,所述方法包括:
(1)辐照丙烯聚合物材料,所述材料选自:
(a)丙烯、乙烯和1-丁烯的三元共聚物,含有约85%至96%丙烯、约1.5%至5%乙烯和2.5%至10%1-丁烯,其中与丙烯共聚的单体总含量约为4.0%至15.0%;
(b)聚烯烃组合物,包含(ⅰ)约31%至39%丙烯和乙烯的共聚物,其中乙烯含量约为1.5%至10%,(ⅱ)约58%至72%丙烯、乙烯和1-丁烯的三元共聚物,其中丙烯含量约为85%至96%,乙烯含量约为1.5%至6%,1-丁烯含量约为2.5%至12%,其中与丙烯共聚的单体总含量约为4.0%至18.0%;
(c)聚烯烃组合物,包含(ⅰ)约30%至65%丙烯和1-丁烯的共聚物,其中丙烯含量约为80%至98%,(ⅱ)约35%至70%丙烯和乙烯的共聚物,其中乙烯含量约为2%至10%,
(2)在物理发泡剂和泡核剂(cell nuleating agent)的存在下,使经辐照的丙烯聚合物材料挤压通过口模,由此形成泡沫制品,其密度比丙烯聚合物材料初始密度小至少10倍。
所述泡沫制品与辐照的不含丁烯共聚单体的丙烯聚合物材料相比,它具有更高的低温韧性。
图1为乙烯/丙烯/1-丁烯三元共聚物(C2C3C4)、乙烯/丙烯共聚物和丙烯/1-丁烯共聚物的共混物(OPC2)和乙烯/丙烯共聚物和乙烯/丙烯/1-丁烯三元共聚物的共混物(OPC3)的熔体张力(cN)与辐射剂量(Mrad)的关系曲线。
图2为C2C3C4三元共聚物、OPC2和OPC3的泡沫密度(单位为每立方英尺磅(pcf))与辐射剂量(Mrad)的关系曲线。
图3为23℃和-20℃时0.068英寸泡沫板的冲击能(ft.lb/in)图,表示该板的韧性。试验用的泡沫板是由经辐照的丙烯均聚物、经辐照的含3.3%乙烯的乙烯/丙烯共聚物(C2C3)、OPC2和OPC3制成的。
本发明方法的第一步是辐照丙烯聚合物材料,所述丙烯聚合物材料选自(a)丙烯、乙烯和1-丁烯的三元共聚物,(b)含有以下组分的聚烯烃组合物:(ⅰ)丙烯和乙烯的共聚物,(ⅱ)丙烯、乙烯和1-丁烯的三元共聚物,以及(c)含有以下组分的聚烯烃组合物:(ⅰ)丙烯和1-丁烯的共聚物,(ⅱ)丙烯和乙烯的共聚物。
丙烯、乙烯和1-丁烯的三元共聚物含有约85%至96%(较好约为90%至95%)丙烯;约1.5%至5.0%(较好约为2%至3%)乙烯和约2.5%至10%(较好约为4%至6%)1-丁烯,其中与丙烯共聚的单体总含量约为4.0%至15.0%。
聚烯烃组合物(b)含有(ⅰ)约31%至39%(较好约为33%至37%)丙烯和乙烯的共聚物,其中乙烯含量约为1.5%至10%(较好约为2%至6%),(ⅱ)约58%至72%(较好约为61%至69%)丙烯、乙烯和1-丁烯的三元共聚物,其中丙烯含量约为85%至96%(较好约为90%至95%),乙烯含量约为1.5%至6%(较好约为2%至4%),1-丁烯含量约为2.5%至12%(较好约为6%至10%),其中与丙烯共聚的单体总含量约为4.0%至18.0%。
聚烯烃组合物(c)含有(ⅰ)约30%至65%(较好约为35%至65%,更好约为45%至65%)丙烯和1-丁烯的共聚物,其中丙烯含量约为80%至98%(较好约为85%至95%),(ⅱ)约35%至70%(较好约为35%至65%,更好约为35%至55%)丙烯和乙烯的共聚物,其中乙烯含量约为2%至10%(较好约为7%至9%)。
上述丙烯聚合物材料可根据美国专利5,296,548和5,486,419中所揭示的聚合方法并使用催化剂制备,上述专利文献在此引作参考。所述三元共聚物和烯烃聚合物组合物通常在有规立构齐格勒-纳塔催化剂的存在下通过单体的序列聚合而制备。这些催化剂含有作为主要成分的固态催化剂组分,所述固态催化剂组分包含具有至少一个钛-卤键的钛化合物和电子给体化合物,这两种化合物均负载在活性卤化镁上。另外,也可以用单级反应器制备所述三元共聚物,通过物理共混各组分制备烯烃聚合物组合物。
为了使泡沫产品具有所需的低温韧性,重要的是使本发明的丙烯聚合物材料含有1-丁烯作为共聚单体。现已发现,本发明的材料的熔体强度和发泡性随辐射剂量的增加而提高,而在本发明的方法中通常采用的电子束剂量下,含乙烯而不含1-丁烯作为共聚单体的丙烯聚合物显示出交联的倾向。熔体强度随含1-丁烯的聚合物所接受的能量的增加而提高的量通常表示链支化,且可据此粗略预测发泡性。本发明的含丁烯聚合物还显示出比经辐照的不含1-丁烯共聚单体的丙烯聚合物材料更好的低温韧性。
本发明的辐照丙烯聚合物材料的方法包括(1)在活性氧浓度确定并保持在小于约15%(体积)环境中用高能电离辐射以每分钟约1至1×104兆拉德的剂量率辐照丙烯聚合物材料,辐照时间为足以使大量丙烯聚合物发生断链而又不足以导致所述材料凝胶化,(2)将所述经辐照的材料在所述环境中最多保持一小时,(3)在所述环境中处理所述经辐照的材料,使所述经辐照的材料中存在的所有自由基基本上失活。所述经辐照的聚合物在200℃时的熔体张力通常为10cN或更大。当表面吸收剂量约为4.5至6兆拉德时通常能得到具有所需多孔性结构的泡沫制品,剂量大小取决于所用的原料。乙烯含量越低,所用剂量越高。
在美国专利4,916,198和5,414,027中详细叙述了辐照方法,这些方法在此引作参考。
在本发明方法的第二步中,在物理发泡剂和泡核剂的存在下,将经辐照的丙烯聚合物材料挤压通过口模。得到具有均匀的多孔性结构且不存在不规则空隙的低密度发泡制品。
为了制备发泡制品,可使用市售的挤出机,包括单螺杆挤出机。较好的是将发泡剂从将固态聚合物加入挤出机处的下游处注入挤出机内的熔融的聚合物中,由于两个加料处之间存在的距离,使聚合物达到熔融均质的形态。在挤出机中加入发泡剂的部分的温度最好为190℃至250℃。在挤出机的出口处装有一口模,此处的温度保持在足以获得聚合物泡沫的温度,较好为119℃至125℃。
适宜的发泡剂包括戊烷、正丁烷、异丁烷、正戊烷、异戊烷、HCHC-22(CHF2Cl)、HCFC-142b(CF2ClCH3)、HFC-152a(CHF2CH3)、HCFC-123(CHCl2CF3)、HCFC-123a(CHFClCF2Cl)、HCFC-124(CHFClCF3)、HFC-134a(CH2FCF3)、HFC-143a(CH3CF3)、CFC-11(CFCl3)、CFC-12(CF2Cl2)、CFC-113(CFCl2CF2Cl)、CFC-114(CF2ClCF2Cl)、CFC-115(CF2ClCF3)、CH3Cl、CH2Cl2、CO2、N2和O2。加入聚合物中的发泡剂的量约为1%至30%,较好约为2%至15%,以聚合物的重量计。
在挤压之前或挤压过程中加入一种或多种泡核剂的量约为0.1%至1.0%(重量)活性成分,以聚合物的重量计。优选的浓度取决于所述成核剂是化学类成核剂还是物理类成核剂、成核剂的效率、口模的结构(design)、操作时的压力和所选用的发泡剂。化学类成核剂的优选浓度通常约为0.2%(重量)活性成分,而物理类成核剂的优选浓度通常约为0.4%(重量)。适宜的物理成核剂是微细的颗粒形状,粒度小于10微米,包括滑石、胶态二氧化硅、碳酸钙和炭黑。适宜的化学类成核剂包括碳酸氢钠或其与柠檬酸的混合物以及偶氮衍生物,如偶氮二酰胺。
在挤压之前或挤压过程中可加入可能需要的其它添加剂、染料或涂料。
制得的泡沫制品的密度比丙烯聚合物材料的初始密度小至少10倍,且在-20℃的低温下显示出提高的韧性,较好的是在-20℃韧性大于1ft.lb/in。
在下面的实施例中,熔体张力值是用2001型Gottfert Rheotens熔体张力测试仪测得的。熔融聚合物线料的拉伸强度是在特定的拉伸速度下测定的,单位为cN(厘牛顿)。在200℃使待测聚合物挤压通过带有长22毫米、直径1毫米的毛细孔的模头。然后排出的线料用牵引轮(traction pulleys)系统以0.012cm/sec2的恒定加速度拉伸,测定直至断裂点的张力。该仪器记录随拉伸而变化的线料的张力值(阻力,单位cN)。最大张力值对应于熔体强度。
根据ASTM D-1238在230℃、2.16Kg的条件下测定聚合物的熔体流动速率。
根据ASTM D4272-90用装有落镖的测试仪测定泡沫板的韧性。
通过在135℃将2.5克聚合物溶于250毫升邻二甲苯中,在恒温浴中冷却至25℃,并通过快速滤纸过滤,测定可溶于二甲苯部分的百分数。将一份滤液的等分试样蒸干,对残余物称重,计算可溶部分的重量百分数。
在本说明书中,除非另有说明,否则所有的份数和百分数都是按重量计。
实施例1
本实施例显示了当增加电子束辐照原料聚合物的剂量时,对于熔体流动速率、熔体张力、结晶温度和第二加热温度的影响。第二加热温度是聚合物的真实熔点,而且表示晶体成核。
乙烯/丙烯无规共聚物(C2C3)含有4.7%乙烯。烯烃聚合物组合物(OPC)1含有35%丙烯均聚物、58.1%在室温下可溶于二甲苯的乙烯/丙烯共聚物和6.9%在室温下不溶于二甲苯的乙烯/丙烯共聚物,可从Montell USA Inc.购得。乙烯/丙烯/1-丁烯三元共聚物(C2C3C4)含有2.5%乙烯、92.3%丙烯和4.7%1-丁烯,可从Montell USA Inc.购得。OPC2是48%丙烯/1-丁烯共聚物(C3C4,其中16%为1-丁烯)和52%乙烯/丙烯共聚物(其中4.0%为乙烯)的共混物,可从Montell USA Inc.购得。OPC3是35%乙烯/丙烯共聚物(其中3.3%为乙烯)和65%乙烯/丙烯/1-丁烯三元共聚物(其中3.3%为乙烯、10%为1-丁烯、86.7%为丙烯)的共混物,可从Montell USA Inc.购得。所述聚合物辐照之前的性能列于表1中。
表1
聚合物 | MFR(dg/min) | 熔体张力@200℃(cN) | 结晶温度(℃) | 第二加热温度(℃) |
C2C3 | 4 | 4 | 91.9 | 139 |
OPC1(PP+C2C3) | 0.75 | 8 | 105 | 167 |
C2C3C4 | 5 | 2 | 84 | 133 |
OPC2(C2C3+C3C4) | 7 | 1.6 | 83 | 134 |
OPC3(C2C3+C2C3C4) | 5.4 | 2 | 81 | 134 |
在纯氮气的气氛中,将各种聚合物粒料通过传输带经过由一台2Mev范德格拉夫静电加速器产生的束流强度为80微安的电子束。调节传输带的速度使聚合物粒料表面的吸收剂量达到表2中的值。辐照之后聚合物的性能列于表2中。
表2
聚合物 | 电子束剂量(Mrad) | 粒料MFR(dg/min) | 熔体张力@200℃(cN) | 结晶温度(℃) | 第二加热温度(℃) |
C2C3 | 1.5;3;4.5 | 9.3;6.3;5.3 | 10;4;7 | l10;111;111 | 145;144;144 |
OPC1(PP+C2C3) | 1.5;3;6;9 | 0.2;0.2;0.5;0.7 | 8;15;9;5 | 117;118;118;118 | 161;161;160;157 |
C2C3C4 | 1.5;3;5 | 11;11;10 | 3;6;6 | 100;101;101 | 136;136;136 |
OPC2(C2C3+C3C4) | 3;6 | 9;7 | 5;16 | 97;101 | 135;137 |
OPC3(C2C3+C2C3C4) | 1.5;3;4.5;6 | 9;9;10;8 | 5;3;13;19 | 90;93;101;101 | 133;135;138;137 |
表2中的数据表明随着含1-丁烯共聚单体的聚合物中吸收剂量的增加其熔体张力明显增大。该值通常表示链支化的程度,且可据此粗略预测发泡性。
实施例2
本实施例表示实施例1中所述的经辐照的聚合物经过热塑性发泡同时保持连续的多孔性结构的能力。具有令人满意的发泡性的聚合物形成一种低密度的连续多孔性固体。“低密度”是指与初始固态聚合物相比,密度减小至少10倍(每立方英尺小于6磅)。如果聚合物标为“不能发泡”,则指其形成了塌陷的不规则的孔隙结构。
用于发泡性试验的配方由经辐照的聚合物、0.2%(重量)用于控制泡孔尺寸的Hydrocerol CF-20泡核剂以及至少6%(体积)发泡剂组成。Hydrocerol CF-20泡孔尺寸控制剂是封装在聚乙烯载体树脂中的碳酸氢钠和柠檬酸的混合物,可从Bohringer Ingelheim购得。在实验室泡沫生产线上制得泡沫产品,所述泡沫生产线包括2英寸直径(D)16L/D反向旋转双螺杆挤出机接至3/4英寸直径10∶1L/DKenex静态混合器,而该混合物则接至5/32英寸直径棒材模头,用于制备1英寸直径泡沫棒材,或接至1英寸直径可调节缝隙的环形口模,用于制备泡沫板。
使用11%(重量)CFC 114作为发泡剂用于经辐照的C2C3无规共聚物、OPC1和C2C3C4三元共聚物。该配方中还含有0.2%(重量)Vertol 360滑石,其平均粒径为3-7微米,可从Cypress Industries购得。由这些聚合物制得直径为一英寸的泡沫棒材。发泡性试验结果列于表3中。
表3
聚合物 | 密度减小 | 说明 |
C2C3 | 1.5Mrad=12倍3Mrad=18倍 | ·3Mrad给出最微细泡孔结构·4.5Mrad-不能发泡,4.4%不溶 |
OPC1(PP+C2C3) | 在任何试验剂量下均不能发泡 | 19%不溶 |
C2C3C4 | 1.5Mrad=5倍3Mrad=10倍4.5Mrad=14倍 | 4.5Mrad给出最微细泡孔结构 |
经辐照的C2C3无规共聚物和含C2C3共聚物作为其组分之一的OPC1在电子束能量的存在下显示出交联的倾向。C2C3共聚物在3Mrad能发泡,而在6Mrad不能发泡,这表明对于该共聚物存在一定的能量范围(energy window)。OPC1在任何试验剂量下都不能发泡。经辐照的C2C3C4三元共聚物的熔体张力和发泡性随电子束剂量的增加而提高(参见图1和2)。
异丁烷用作OPC2和OPC3的发泡剂,并由这些聚合物制得泡沫板。该配方中也含有0.4%(重量)Vertal 360滑石作为泡孔尺寸控制剂。将7%(重量)异丁烷发泡剂注入熔体中,使该溶液冷却,通过环形口模成型,同时使溶液的温度保持在246-255°F 。在直径为3.5英寸的冷却模芯上使得到的泡沫管取向和稳定,单缝纵切(single slit)形成板材。该泡沫板宽11英寸,厚0.068英寸,将其卷绕在滚筒上,在对该板材表征之前使其稳定五天。发泡性试验结果列于表4中。
表4
聚合物 | 密度减小 | 说明 |
OPC2(C2C3+C3C4) | 1.5Mrad=4倍3Mrad=6倍4.5Mrad=11倍6Mrad=13倍 | 4.5Mrad和6Mrad给出最微细泡孔结构 |
OPC3(C2C3+C2C3C4) | 3Mrad=4倍6Mrad=15倍 | 6Mrad给出最佳结果 |
OPC2和OPC3的熔体张力和发泡性随电子束剂量的增加而提高(参见图1和2)。虽然C2C3C4三元共聚物和OPC2和OPC3具有不同的分子结构,但它们在主链上都具有C4。这些数据以及熔体张力升高的趋势都表明C4作为共聚单体而存在促进支化。
实施例3
本实施例显示了含有与不含有1-丁烯共聚单体的聚合物之间韧性的差别。
根据落镖试验测定实施例2中制得的泡沫板的韧性。使用由经辐照的丙烯均聚物(PP)制得的泡沫板(熔体流动速率为3g/10min,购自Montell USA Inc.)和由经辐照的含3.3%乙烯的乙烯/丙烯共聚物(C2C3,购自Montell USA Inc.)进行比较。结果如图3所示。含1-丁烯共聚单体的聚合物的低温性能优于经辐照的丙烯均聚物和乙烯/丙烯共聚物。认为20℃时大于1ft.lb/in的值是可接受的。该值越高,该材料的低温韧性越好。
在阅读了上述内容之后,本发明的其它特点、优点和实施方案对于本领域的技术人员将是很显然的。因此,虽然对本发明的具体实施方案作了很详细的叙述,但仍可以在不脱离本发明的说明书和权利要求书的精神和范围的情况下,对这些实施方案进行变化和改进。
Claims (2)
1.一种制备泡沫制品的方法,包括:
(1)辐照丙烯聚合物材料,所述材料选自:
(a)丙烯、乙烯和1-丁烯的三元共聚物,含有约85%至96%丙烯、约1.5%至5%乙烯和2.5%至10%1-丁烯,其中与丙烯共聚的单体总含量约为4.0%至15.0%;
(b)聚烯烃组合物,包含(ⅰ)约31%至39%丙烯和乙烯的共聚物,其中乙烯含量约为1.5%至10%,(ⅱ)约58%至72%丙烯、乙烯和1-丁烯的三元共聚物,其中丙烯含量约为85%至96%,乙烯含量约为1.5%至6%,1-丁烯含量约为2.5%至12%,其中与丙烯共聚的单体总含量约为4.0%至18.0%;
(c)聚烯烃组合物,包含(ⅰ)约30%至65%丙烯和1-丁烯的共聚物,其中丙烯含量约为80%至98%,(ⅱ)约35%至70%丙烯和乙烯的共聚物,其中乙烯含量约为2%至10%。
(2)在物理发泡剂和泡核剂的存在下,使经辐照的丙烯聚合物材料挤压通过口模,由此形成泡沫制品,其密度比丙烯聚合物材料初始密度小至少10倍。
2.如权利要求1所述的方法,其特征在于所述丙烯聚合物材料是经电子束辐照的,剂量约为4.5至6Mrad。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101177496B (zh) * | 2006-11-10 | 2012-11-14 | 良澔科技企业股份有限公司 | 连续制备聚烯烃橡胶发泡材料的方法及其制得的成品 |
CN103589070A (zh) * | 2013-11-27 | 2014-02-19 | 天津市普立泰高分子科技有限公司 | 物理发泡聚丙烯电缆料及其制备方法 |
CN112352012A (zh) * | 2018-06-14 | 2021-02-09 | 利安德巴塞尔先进聚合物公司 | 可发泡聚烯烃组合物及其方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE277733T1 (de) * | 2000-06-23 | 2004-10-15 | 3M Innovative Properties Co | Schaumstoff und verfahren zur herstellung |
EP1170306A1 (en) * | 2000-07-05 | 2002-01-09 | ATOFINA Research | Production of polypropylene having improved properties |
US20030211310A1 (en) | 2001-06-21 | 2003-11-13 | Haas Christopher K. | Foam and method of making |
CN100480321C (zh) * | 2003-08-12 | 2009-04-22 | 巴赛尔聚烯烃意大利有限公司 | 辐照过的丁烯-1聚合物组合物 |
BRPI0417945A (pt) * | 2003-12-24 | 2007-04-17 | Petroquimica Cuyo S A I C | composições de resina de camada de selamento |
JP2005298769A (ja) * | 2004-04-16 | 2005-10-27 | Kaneka Corp | ポリプロピレン系樹脂予備発泡粒子、及び型内発泡成形体 |
JP2006003816A (ja) * | 2004-06-21 | 2006-01-05 | Sharp Corp | 画像形成装置及びこれに用いられる濃度補正データ生成方法 |
DE102009028200A1 (de) | 2009-08-04 | 2011-02-17 | Evonik Degussa Gmbh | Verwendung von Polyolefinen zur Herstellung von Schäumen |
WO2016082212A1 (en) * | 2014-11-28 | 2016-06-02 | Dow Global Technologies Llc | Process for foaming polyolefin compositions using fluororesin/citrate mixture as nucleating agent |
EP3331940B1 (en) * | 2015-08-06 | 2019-05-29 | Basell Poliolefine Italia S.r.l. | Composition comprising propylene-ethylene-1-butene terpolymers |
US11725086B2 (en) | 2018-03-05 | 2023-08-15 | Berry Global, Inc. | Shrink films and methods for making the same |
Family Cites Families (11)
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DE3688258T3 (de) * | 1985-01-31 | 2001-02-22 | Montell North America Inc | Polypropylen mit freier Langkettenverzweigung, Verfahren zur Herstellung und Verwendung davon. |
ZA86528B (en) * | 1985-01-31 | 1986-09-24 | Himont Inc | Polypropylene with free-end long chain branching,process for making it,and use thereof |
US5047446A (en) * | 1988-07-22 | 1991-09-10 | Himont Incorporated | Thermal treatment of irradiated propylene polymer material |
IT1243430B (it) * | 1990-09-28 | 1994-06-10 | Himont Inc | Composizioni di polimeri cristallini del propilene aventi bassa temperatura |
JP2887379B2 (ja) * | 1991-10-09 | 1999-04-26 | 住友化学工業株式会社 | 硬質熱可塑性樹脂組成物およびその射出成形体 |
CZ5693A3 (en) * | 1992-01-23 | 1993-10-13 | Himont Inc | Elastic yarn of polypropylene polymer and articles made therefrom |
IT1255364B (it) * | 1992-09-15 | 1995-10-31 | Himont Inc | Processo per la preparazione di manufatti in polipropilene espanso mediante produzione di granuli pre-espansi e termoformatura per sinterizzazione degli stessi |
US5414027A (en) * | 1993-07-15 | 1995-05-09 | Himont Incorporated | High melt strength, propylene polymer, process for making it, and use thereof |
JPH08176395A (ja) * | 1994-10-27 | 1996-07-09 | Showa Denko Kk | 樹脂組成物 |
JP2907749B2 (ja) * | 1995-03-24 | 1999-06-21 | 積水化成品工業株式会社 | 改質ポリプロピレン系樹脂発泡体の製法、成形品の製法、並びにそれら製法から得られた発泡体及び成形品 |
KR0162284B1 (ko) * | 1996-02-16 | 1999-01-15 | 하태준 | 충격강도 및 내열성이 우수한 폴리프로필렌계 수지 조성물 |
-
1998
- 1998-01-09 US US09/004,831 patent/US6060533A/en not_active Expired - Lifetime
-
1999
- 1999-01-06 KR KR1019990000100A patent/KR100580802B1/ko not_active IP Right Cessation
- 1999-01-07 EP EP99100173A patent/EP0928805B1/en not_active Expired - Lifetime
- 1999-01-07 ES ES99100173T patent/ES2227910T3/es not_active Expired - Lifetime
- 1999-01-07 DE DE69922060T patent/DE69922060T2/de not_active Expired - Lifetime
- 1999-01-07 AT AT99100173T patent/ATE283308T1/de not_active IP Right Cessation
- 1999-01-08 CA CA002258169A patent/CA2258169C/en not_active Expired - Fee Related
- 1999-01-08 CN CN99100932A patent/CN1102941C/zh not_active Expired - Fee Related
- 1999-01-08 TW TW088100254A patent/TW477801B/zh active
- 1999-01-11 JP JP11004168A patent/JPH11246716A/ja active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101177496B (zh) * | 2006-11-10 | 2012-11-14 | 良澔科技企业股份有限公司 | 连续制备聚烯烃橡胶发泡材料的方法及其制得的成品 |
CN103589070A (zh) * | 2013-11-27 | 2014-02-19 | 天津市普立泰高分子科技有限公司 | 物理发泡聚丙烯电缆料及其制备方法 |
CN103589070B (zh) * | 2013-11-27 | 2016-01-20 | 天津市普立泰高分子科技有限公司 | 物理发泡聚丙烯电缆料及其制备方法 |
CN112352012A (zh) * | 2018-06-14 | 2021-02-09 | 利安德巴塞尔先进聚合物公司 | 可发泡聚烯烃组合物及其方法 |
Also Published As
Publication number | Publication date |
---|---|
TW477801B (en) | 2002-03-01 |
ES2227910T3 (es) | 2005-04-01 |
ATE283308T1 (de) | 2004-12-15 |
US6060533A (en) | 2000-05-09 |
JPH11246716A (ja) | 1999-09-14 |
EP0928805B1 (en) | 2004-11-24 |
EP0928805A3 (en) | 2000-08-09 |
CA2258169A1 (en) | 1999-07-09 |
DE69922060T2 (de) | 2005-11-10 |
KR100580802B1 (ko) | 2006-05-23 |
CN1102941C (zh) | 2003-03-12 |
EP0928805A2 (en) | 1999-07-14 |
KR19990067741A (ko) | 1999-08-25 |
DE69922060D1 (de) | 2004-12-30 |
CA2258169C (en) | 2003-12-16 |
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