CN1798804B - 具有改善的流动性能的抗冲改性剂组合物 - Google Patents
具有改善的流动性能的抗冲改性剂组合物 Download PDFInfo
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- CN1798804B CN1798804B CN2004800097054A CN200480009705A CN1798804B CN 1798804 B CN1798804 B CN 1798804B CN 2004800097054 A CN2004800097054 A CN 2004800097054A CN 200480009705 A CN200480009705 A CN 200480009705A CN 1798804 B CN1798804 B CN 1798804B
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Abstract
本发明涉及氯化聚烯烃和弹性乙烯共聚物的固体颗粒物理共混物会产生出带有抗结块特性的共混产物，其优于按照基于重量比例线性内插法定义的任一共混成份。这种共混组合物可以用作聚氯乙稀组合物的抗冲改性剂。
Description
发明领域
本发明涉及具有改善的整体流动性能的弹性乙烯共聚物和氯化聚烯烃的物理共混物。
技术背景
氯化聚烯烃一直被广泛用作聚氯乙稀(PVC)组合物的抗冲改性剂，以形成不易于在冲击中遭到损坏的组合物。例如在美国专利3,006,889和3,209,055中，揭示了宽范围的氯化和氯磺化聚乙烯与聚氯乙稀共混的使用。例如乙烯/α-烯烃共聚物的弹性乙烯共聚物也已经被用作抗冲改性剂。例如，在美国专利5,925,703中，Betso等人记载了使用直链乙烯/α-烯烃来改善填充热塑性组合物的冲击性能，包括聚氯乙稀。近来，人们指出了含有氯化聚乙烯和弹性乙烯共聚物的混合物的抗冲改性剂。例如，美国申请专利2003005040，2003014442和2003015368记载了改善抗冲击性的聚氯乙稀组合物，其含有随机分布的氯化聚乙烯和聚烯烃弹性体的抗冲改性剂共混物。在美国专利6,124,406中，Cinader等人也记载了块状氯化聚乙烯能够用来兼容聚烯烃弹性体和聚氯乙稀，以得到具有改善的抗冲击性的聚氯乙稀组合物。
典型地，上述申请中所使用的氯化聚合物和聚烯烃弹性体为颗粒固体。使用这些原料需要考虑固体加工方面的问题，例如这些微粒固体的封装、运输、储藏和拆封。当作为单独组分进行处理时，氯化聚烯烃和聚烯烃弹性体都显示出各不相同程度的颗粒团聚(agglomeration)，也就是所知道的结块、聚集、或粘结。这种团聚产品是不合乎要求的。延长仓库储藏或运输时间，尤其是在温暖气候的月份里，将加重产品的聚集问题。在Factors Affecting AntiblockPerformance of Ethylene Vinyl Acetate Copolymers，Journal of PlasticFilm ant sheeting，Vol.11，pp326-337(1995).中，Botros注意到在使颗粒受到的压力变大的夏季高温和大装载量下，处理粘性的乙烯醋酸乙烯 酯颗粒问题的材料就变得更苛刻。
正如格里菲思在1991年VCH出版的Cake Formation in ParticulateSystems中指出的，“任何厂家生产粉状固体......如果那些产品在到达客户的基地、工厂或工地时，粘结和结块到不能立即使用的程度时，不能认为他们的产品为优质产品。”团聚固体可以引起一些问题，例如中断进度、残品或返修品而令客户恼怒。
许多机理能够潜在地引起颗粒团聚或粘结。格里菲思把粘结机理分为四大种类—电的、化学的、机械的和塑性流动。导致粘结的电特性包括来自晶体结构的静位觉和电相互作用。例如水化和结晶化的化学特性也能引起粘结。颗粒缠结可以引起机械粘结。当无定形或弱晶体物质在遭受压力或升温下融合时，会产生塑性流动粘结。在最苛刻的条件下，颗粒可以流到一起并形成一个单独的块。
格里菲思指出加入流动调节剂或抗粘结剂能够阻止颗粒团聚。其中一类抗粘结剂可以从有机物中获得，例如胺、醇、酸或盐。这些物质在颗粒周围形成阻挡层并显示出表面活性或润滑作用。另一个关于有机抗粘结剂的例子在日本授权的专利No.90049207中揭示出来，其中聚氧化乙烯表面活性剂可用来阻挡氯磺化聚乙烯片的结块。
在颗粒周围形成物理阻挡层的细粉状固体也可以用作抗粘结剂。例子包括热解法二氧化硅、粘土、滑石、碳酸镁和聚乙烯粉末。在欧洲授权的专利No.100434中，Bohm等人混入如碳黑或细分酚醛树脂的抗粘结剂，来阻挡未硫化橡胶颗粒如烯烃和氯化弹性体的团聚。在欧洲申请专利410914中，McCoskey等人用含有非粘性物质的冷却液接触聚合物熔体，随后再用第二种非粘性物质接触塑料颗粒，来从常规的粘性塑料中产生可流动的颗粒。McCoskey通过在球形水滴和聚合物成品中加入聚乙烯粉末，来改善丙烯聚合物的粘结特性。在美国专利3,258,841中，平均颗粒尺寸小于10微米的聚乙烯粉末也被用作醋酸乙烯酯颗粒的抗粘结剂。
例如有机分散剂和固体添加剂的结合物的抗结块剂已经在氯化聚乙烯的加工过程中用来阻止团聚。例如，在美国专利4,562,224中，Busch等人指出了生产氯化聚乙烯的方法，其中在氯化过程中聚-N-乙烯基吡咯烷酮和二氧化硅存在于分散剂中。在PCT申请WO 01/12716， McMichael等人指出了热处理乙烯共聚物颗粒的方法，并应用滑石抗粘结剂和硅氧烷粘合剂来产生基本上自由流动的颗粒。
发明内容
本发明涉及一种颗粒的物理共混物，包括：第一组分，其中所述第一组分是氯化聚乙烯，且所述第一组分为粉末状、微粒形式或球粒形式；和第二组分，其中所述第二组分是弹性乙烯共聚物且所述第二组分为粉末状、微粒形式或球粒形式；其中所述共混物具有比第一组分或第二组分的自由屈服强度小的自由屈服强度。
令人惊讶地，我们发现氯化聚烯烃和弹性乙烯共聚物的固体颗粒物理共混物会产生出带有抗结块特性的共混产物，其优于按照基于重量比例线性内插法定义的任一共混成份。这种共混组合物可以用作聚氯乙稀组合物的抗冲改性剂。
发明的详细描述
本发明中的共混物包括氯化聚烯烃和弹性乙烯共聚物。另外，氯化聚烯烃的结合物或弹性乙烯共聚物的结合物可以用来调整整体混和的流变性。
本发明中组合物的氯化聚烯烃组份选自：a)氯化聚乙烯均聚物或b)氯化共聚物，其由含有共聚单元i)烯烃和ii)可共聚单体的聚烯烃来制备。氯化烯烃聚合物可以任意地包括氯磺化基团。也就是说，聚合物链将含有侧链氯化基团和氯磺化基团。这种聚合物被认为是氯磺化烯烃聚合物。
具有代表性的氯化烯烃聚合物包括a)乙烯的氯化和氯磺化均聚物和b)乙烯的氯化和氯磺化共聚物以及至少一种选自以下的含烯不饱和单体：C3-C10α单烯烃；C3-C20一元羧酸的C1-C12烷基酯；不饱和C3-C20 的一元或二元羧酸；不饱和C4-C8二元羧酸的酸酐；或饱和C2-C18羧酸的醋酸乙烯酯。氯化和氯磺化接枝共聚物也包括在内。合适的聚合物的特例包括氯化聚乙烯；氯磺化聚乙烯；氯化乙烯基醋酸乙烯酯共聚物；氯磺化乙烯基醋酸乙烯酯共聚物；氯化丙烯酸乙烯酯共聚物；氯磺化丙烯酸乙烯酯共聚物；氯化甲基丙烯酸乙烯酯共聚物；氯磺化甲 基丙烯酸乙烯酯共聚物；氯化乙烯基甲基丙烯酸酯共聚物；氯化甲基乙烯基甲基丙烯酸酯共聚物；氯化乙烯基正丁基甲基丙烯酸酯共聚物；氯化乙烯基甲基丙烯酸缩水甘油酯共聚物；乙烯和马来酸酐的氯化接枝共聚物；乙烯和丙稀、丁烯、3-甲基-1-戊烯或辛烯的氯化共聚物与乙烯和丙稀、丁烯、3-甲基-1-戊烯或辛烯的氯磺化共聚物。这些共聚 体可以为二聚体、三聚体或多聚体。优选的氯化烯烃聚合物为氯化聚乙烯和乙烯基醋酸乙烯酯的氯化共聚物。
可以从带有支链的或无支链的聚烯烃树脂中制得本发明中适用于抗冲击组合物的氯化烯烃聚合物和氯磺化烯烃聚合物。可以通过自由基反应、齐格勒—纳塔催化或金属茂催化体系催化制得聚烯烃树脂主剂(base resin)，例如在美国专利5,272,236和5,278,272中所述。氯化或氯磺化树脂主剂可以在悬浮液、溶液、固相或流动相中发生。在美国专利3,454,544和4,767,823以及其引用的参考文献中描述并记载了自由基悬浮液氯化反应。这个反应包括用于后面氯化的细分乙烯聚合物的水悬浮液的制备。在美国专利4,591,621中揭示了自由基溶液氯化反应的例子。聚合物也可以在熔体或流动相中进行氯化，如美国专利4,767,823中所述。氯磺化反应一般在溶液中进行，但是悬浮液和非溶剂反应也是为人们所知道的。氯磺化烯烃聚合物的制备在美国专利2,586,363、3,296,222、3,299,014和5,242,987中有所描述。
弹性乙烯共聚物，例如乙烯/α-烯烃共聚物是乙烯和至少一种C3-C8α-烯烃(优选脂肪族的α-烯烃)共聚单体的共聚物，并且任意地，和多烯烃共聚单体如共轭二烯烃、非共轭二烯烃、三烯烃等的共聚物。C3-C8α-烯烃的例子包括丙稀、1-丁烯、4-甲基-1-戊烯、1-己烯和1-辛烯。α-烯烃也可以含有环状结构如环己烷或环戊烷，得到α-烯烃例如3-环己基-1-丙稀(烯丙基-环己烷)和乙烯基-环己烷。尽管α-烯烃不是经典条件，但为本发明的目的，例如降冰片烯和相关烯烃的特定环烯烃作为α-烯烃并可以替代上述的某些或全部α-烯烃。同样地，苯乙烯及其相关烯烃(例如α-甲基苯乙烯等)作为本发明中的α-烯烃。
多烯烃是分子链中含有多于四个碳原子和至少两个双键和/或三键的不饱和脂肪族或脂环族化合物，例如共轭和非共轭二烯烃和三烯烃。非共轭二烯烃的例子包括脂肪族二烯烃例如1，4-戊二烯，1，4-己二烯，1，5-己二烯，2-甲基-1，5-己二烯，1，6-庚二烯，6-甲基-1，5-庚二烯，1，6-辛二烯，1，7-辛二烯，7-甲基-1，6-辛二烯，1，13-十四二烯，1，19-二十二烯等等；环二烯例如1，4-环己二烯，双环[2.2.1]庚-2，5-二烯，5-亚乙基-2-降冰片烯，5-亚甲基-2-降冰片烯，5-乙烯基-2-降冰片烯，双环[2.2.2]辛-2，5-二烯，4-乙烯基环己-1-烯，双环[2.2.2]辛-2，6-二烯，1，7，7-三甲基 双环-[2.2.1]庚-2，5-二烯，双环戊二烯，甲基四氢化茚，5-烯丙基双环[2.2.1]庚-2-烯，1，5-环辛二烯等等；芳香族二烯例如1，4-二烯丙基苯，4-烯丙基-1H-茚；和三烯例如2，3-二异丙烯基二烯-5-降冰片烯，2-亚乙基-3-亚异丙基-5-降冰片烯，2-丙稀基-2，5-降冰片烯，1，3，7-辛三烯，1，4，9-癸三烯等等；以及5-亚乙基-2-降冰片烯，5-乙烯基-2-降冰片烯和7-甲基-1，6-辛二烯为优选的非共轭二烯。
共轭二烯的例子包括丁二烯，异戊二烯，2，3-二甲基丁二烯-1，3，1，2-二甲基丁二烯-1，3，1，4-二甲基丁二烯-1，3，1-乙基丁二烯-1，3，2-苯基丁二烯-1，3，己二烯-1，3，4-甲基戊二烯-1，3，1，3-戊二烯(CH3CH＝CH-CH＝CH2；通常命名为戊间二烯)，3-甲基-1，3-戊二烯，2，4-二甲基-1，3-戊二烯，3-乙基-1，3-戊二烯等等；1，3-戊二烯为优选的共轭二烯。
三烯的例子包括1，3，5-己三烯，2-甲基-1，3，5-己三烯，1，3，6-庚三烯，1，3，6-环庚三烯，5-甲基-1，3，6-庚三烯，5-甲基-1，4，6-庚三烯，1，3，5-辛三烯，1，3，7-辛三烯，1，5，7-辛三烯，1，4，6-辛三烯，5-甲基-1，5，7-辛三烯，6-甲基-1，5，7-辛三烯，7-甲基-1，5，7-辛三烯，1，4，9-癸三烯和1，5，9-环癸三烯。
示例性二元共聚物包括乙烯/丙稀，乙烯/丁稀，乙烯/1-辛稀，乙烯/5-亚乙基-2-降冰片稀，乙烯/5-乙基-2-降冰片稀，乙烯/1，7-辛二稀，乙烯/7-甲基-1，6-辛二稀，乙烯/苯乙烯和乙烯/1，3，5-己三稀。示例性三元共聚物包括乙烯/丙稀/1-辛烯，乙烯/丁稀/1-辛烯，乙烯/丙稀/5-亚乙基-2-降冰片烯，乙烯/丁稀/5-亚乙基-2-降冰片烯，乙烯/丁稀/苯乙烯，乙烯/1-辛稀/5-亚乙基-2-降冰片烯，乙烯/丙稀/1，3-戊二烯，乙烯/丙稀/7-甲基-1，6-辛二烯，乙烯/丁稀/7-甲基-1，6-辛二烯，乙烯/1-辛稀/1，3-戊二烯和乙烯/丙稀/1，3，5-己三烯。示例性四元共聚物包括乙烯/丙稀/1-辛稀/二稀(例如ENB)，乙烯/丁稀/1-辛稀/二稀和乙烯/丙稀/混合二烯，例如乙烯/丙稀/5-亚乙基-2-降冰片烯/戊间二烯。另外，混合组份可以包括微量例如0.05～0.5重量百分比的长链支链增强子(enhancer)，例如2，5-降冰片二烯(aka双环[2.2.1]庚-2，5-二烯)，二丙烯基苯，1，7-辛二烯(H2C＝CH(CH2)4CH＝CH2)和1，9-癸二烯(H2C＝CH(CH2)6CH＝CH2)。
可以利用已知技术中的所有常规烯烃聚合技术来生产本发明的弹 性乙烯共聚组份。例如，聚合反应可以在公知的齐格勒—纳塔技术或Kaminsky-Sinn型聚合反应条件下完成。本发明的弹性乙烯共聚物组份可以用单-或双-环戊二烯基、茚基或芴基过渡金属催化剂(优选第四族)、抑制几何构型催化剂或金属茂催化剂制备。在美国专利5,565,521中描述并记载了金属茂催化剂和使用这些催化剂的聚合反应。如果需要，可以使用悬浮液、溶液、浆、气相、固态粉末聚合反应或其它反应条件。如果需要，也可以使用载体例如二氧化硅、矾土或聚合物(例如聚四氟乙烯或聚烯烃)。
惰性液体用作适当的聚合溶剂，例子包括直链和支链烃类如异丁烷、丁烷、戊烷、正己烷、庚烷、辛烷和其混合物；环状或脂环状烃类如环己烷、环庚烷、甲基环己烷和其混合物；全氟烃类例如全氟C4-10 烷烃；以及芳香族和烯丙基取代的芳香族化合物例如苯、甲苯、二甲苯和乙苯。适当的溶剂还包括可以作为单体或共聚单体的液体烯烃，其包括丁二烯、环戊烯、1-己烯、4-乙烯基环己烯、乙烯基环己烷、3-甲基-1-戊烯、4-甲基-1-戊烯、1，4-己二烯、1-辛烯、1-癸烯、苯乙烯、二乙基苯、丙烯基苯和乙烯基甲苯(包括所有单独的异构体或在混合物中)。上述溶剂的混合物也适用。如果需要，常规气态烯烃可以通过加压转变为液体并在此使用。
本发明的氯化聚烯烃和弹性乙烯共聚物以粉碎固体粒子形式存在，其大小分布范围从粉末到碎片。典型定义粉末为颗粒平均尺寸小于2000微米的粉碎固体粒子。球粒为普通的粉碎固体粒子，但不是唯一的，在挤出和造粒过程中形成，其颗粒的典型平均尺寸大于2毫米，典型的是2～4毫米。典型微粒的颗粒平均尺寸小于标准化球粒但大于一般商品化模具性能所能达到的尺寸。微粒的颗粒平均尺寸分布范围从300微米到2毫米。微粒一般呈现为半球状。颗粒平均尺寸大于2毫米的碎片大于非球粒状粉碎固体粒子的尺寸。
可以通过已知的方法制备本发明的粉碎固体粒子。例如Knight在掌握微粒：Mastering Micropellets：A Processing Primer，PlasticsTechnology，pp55-57(1995)中记载了制备微粒的方法。例如已经报道的微粒化产品的例子包括聚丙烯、聚乙烯、聚苯乙烯、聚氯乙稀和聚碳酸酯。Cockbain等人在PCT申请WO 00/35646中记载了运用旋转式模 具体系生产微粒。Cockbain使用一个单螺旋戴维斯标准挤出机来抽吸聚烯烃弹性体，使其通过一个装备了孔洞直径为0.020″的Gala造粒体系。
可以通过任何已知的固体混合或共混的方法制备本发明的粉碎固体粒子共混物。例如在Chapman和Hall的“Mixing of Powder”Handbook of Powder Science and Technology-Second Edition，pp568-585(1997)中，Kaye注意到使用转鼓混合机来作为可以生成块状混合物的低剪切方法。混合技术领域的人员可以使用变化的混合技术，例如Kaye描述的高剪切设备，来潜在地改善混合分布的均匀性。
通过挤压试样，然后测量其自由屈服强度来确定实施例中粉碎固体粒子相对减轻的流动性。这种普通的方法由Williams等人发明，见 The Direct Measurement of the Failure Function of a Cohesive Powder，Powder Technology，Vol.4，pp328-337(1970-1971)。Griend等人在BulkFlow of Ethylene-Vinyl Acetate Copolymers，Adhesives Age，pp14-24(1998)中记载了在模仿实际操作温度和压力条件下，使用挤压单元来测量被挤压的乙烯基醋酸乙烯酯的自由屈服强度。选择实施例的测试负荷来模仿示例性储藏个例的综合应力。
实施例
表1和表2对实施例中所使用的氯化烯烃聚合物和弹性乙烯共聚物进行了描述。
表1 
| 外形 | 粉末 | 粉末 | 粉末 | 粉末 | 粉末 | 粉末 | 粉末 |
1含氯的标称重量百分率通过Schoniger分析来测定。
2高密度聚乙烯的总残留结晶度(卡路里/克)通过差式扫描量热法来测定。
3熔融粘度(泊)在145秒-1，190℃条件下通过毛细管流变学测定。
4总的抗结块为成品中的滑石(测量含灰量)，硬脂酸钙(红外分析方法测量)，或碳酸钙(红外分析方法测量)的重量百分率总和。
表2 
1聚合物密度(克/立方厘米)依照ASTM D-792测量。
2聚合物I2熔融指数(克/10分钟)在120℃条件下依照ASTMD-1238测量。
本发明的共混组合物是在塑料加工设备DTC0513型搅拌机装配的5加仑桶中用滚筒混合10.0-11.11bs.原料15-20分钟制备而成。
通过特殊的结块测试来测定抗聚集特性。按照以下过程来进行这种特殊的结块测试来测量在预定时间内对已知应力水平和温度下的颗粒块的强度。使用一个用软管把两部分连接到一起的直径为2″的圆筒。圆筒的内表面涂渍了硬脂酸钙。用喷雾器去掉过量的硬脂酸钙灰。典型地，将60-150克共混组合物样品注入圆筒。在安放固体的装填过程中轻拍圆筒侧壁。将一个2″特氟纶
圆片放置在圆筒中固体的顶端以防止其粘住装载重量器。在模仿相对苛刻的运输和储藏条件下设定负荷、温度和持续时间。在预定的时间间隔里，在圆片上放置了装载重量器并且将圆筒放置在37℃烘箱中。使用6lb.负荷来模仿275lbf/ft2 的压力和4.25lb.负荷来模仿195lbf/ft2的压力。然后去掉负荷，将圆筒 放在室温(20℃)下冷却至少12小时。然后从圆筒中移出共混样品。用克斯特朗测量自由屈服强度。在接近90天的不同时间间隔中，重复这个过程来测量自由屈服强度。
可以通过这个方程来定义重量比例的线性内插法：
B＝∑Wfb
其中B＝所设计共混物的自由屈服强度(UYS)，Wf＝共混物各组份的重量分数，b＝各相应组份所测量的UYS。在混合测量的UYS小于任意单个组份UYS的情况下，测量的共混物UYS一定小于所设计的重量比例的UYS。
对比实施例1
对样品100％CPE-1、100％CPE-2、和100％POE-1进行结块实验过程。在37℃和195lbf/ft2压力下操作测试。原始结果显示于图1中(屈服强度比时间)。样品显示出变化的自由屈服强度，其屈服强度明显随时间提高，这表明随时间结块的倾向增大。
图1
实施例1
POE-1和CPE以10.0wt％CPE-2和10.0wt％CPE-1的浓度混合。在37℃和195lbf/ft2压力条件下操作结块实验。带有对比实施例1的原 始结果的结果显示于图2中。本发明的例子证明自由屈服强度随时间大大降低，并因此相对于含有对照原样的单个组份来说，抗结块性能有所改善。
图2
对比实施例2
对样品100％CPE-3和100％POE-2进行结块实验过程。在37℃和195lbf/ft2压力下操作测试。原始结果显示于图3中(屈服强度比时间)。样品显示出变化的自由屈服强度，屈服强度随时间明显提高，这表明随时间结块的倾向增大。
图3
实施例2
POE-2和CPE以10.0wt％CPE-3的浓度混合。在37℃和195lbf/ft2 压力条件下操作结块实验。带有对比实施例2的最原始结果的结果显示于图4中。本发明的例子证明自由屈服强度随时间大大降低，并因此相对于含有对照原样的单个组份来说，抗结块性能有所改善。
图4
对比实施例3
对样品100％CPE-1和100％POE-3进行结块实验过程。在37℃和195lbf/ft2压力下操作测试。原始结果显示于图5中(屈服强度比时间)。样品显示出变化的自由屈服强度，屈服强度随时间明显提高，这表明随时间结块的倾向增大。
图5
实施例3
POE-3和CPE以10.0wt％CPE-1的浓度混合。在37℃和195lbf/ft2 压力条件下操作结块实验。带有对比实施例3的最原始结果的结果显示于图6中。本发明的例子证明自由屈服强度随扩展时间大大降低，并因此相对于含有对照原样的单个组份来说，抗结块性能有所改善。
图6
对比实施例4
对样品100％CPE-2和100％POE-4进行结块实验过程。在37℃和195lbf/ft2压力下操作测试。原始结果显示于图7中(屈服强度比时间)。样品显示出变化的自由屈服强度，屈服强度随时间明显提高，这表明随时间结块的倾向增大。
图7
实施例4
POE-4和CPE以10.0wt％CPE-2的浓度混合。在37℃和195lbf/ft2 压力条件下操作结块实验。带有对比实施例4的最原始结果的结果显示于图8中。本发明的例子证明自由屈服强度随扩展时间段降低较大，并因此相对于含有对照原样的单个组份来说，抗结块性能有所改善。事实上，共混原料的结块特性太低而不能测量。
图8
对比实施例5
对样品100％CPE-4、100％CPE-5、100％CPE-6、和100％POE1进行结块实验过程。在37℃和195lbf/ft2压力下操作测试。原始结果显示于图9中(自由屈服强度比时间)。结果显示出变化的自由屈服强度，屈服强度随时间明显提高，这表明随时间结块的倾向增大。
图9
实施例5
POE-1和CPE以10wt％CPE-4、10wt％CPE-5和10wt％CPE-6的浓度混合。在37℃和195lbf/ft2压力条件下操作结块实验。带有对比实施例5的原始样品的结果显示于图10中。本发明的例子证明自由屈服强度随扩展时间大大降低，并因此相对于含有对照原样的单个组份抗来说，结块性能有所改善。
图10
实施例6
将变化水平的CPE-2和POE-1共混来测定氯化聚乙烯浓度对共混结块特性的影响。7天中，共混实验条件设置为37℃和195lbf/ft2压力。结果表明浓度为大于零并小于90％的CPE的自由屈服强度降低，在接近5wt％CPE时为最适宜值。结果见图11所述。
图11
实施例7
对100％CPE-7、100％POE-3和混合了10wt％CPE-7的POE-3进行结块实验过程。在22天中，在37℃和195lbf/ft2压力条件下操作实验。测量的自由屈服强度显示于图12中。对于10wt％CPE-7(USY＝138lbf/ft2)和90wt％POE-3(USY＝193lbf/ft2)的共混组合物，单个组份基于重量比例内插法所设计的共混自由屈服强度为187lbf/ft2。结果显示加入CPE-7所改善的共混物的结块性能会超过基于重量线性内插法所希望得到的。
图12
实施例8
为了证明使用共混组合物的潜能，生产出50wt％CPE-2和50wt％CPE-5的共混物。对50∶50 CPE-2∶CPE-5混合物、100％POE-3和混合了10wt％[50∶50 CPE-2∶CPE-5]的POE-3共混物进行结块实验过程。在22天中，在37℃和195lbf/ft2压力条件下操作实验。测量的自由屈服强度显示于图13中。结果显示出也可以使用多种组份的共混物来改善整体共混物的结块性能。
图13
Claims (6)
1.一种颗粒的物理共混物，包括：
第一组分，其中所述第一组分是氯化聚烯烃；
第二组分，其中所述第二组分是弹性乙烯共聚物；和
抗结块剂；
其中所述共混物包括0.3到90重量％的第一组分，以共混物的总重量计，其中所述共混物具有比第一组分或第二组分的自由屈服强度小的自由屈服强度。
2.根据权利要求1所述的共混物，其中所述共混物包括1-60重量％第一组分，以共混物的总重量计。
3.根据权利要求1所述的共混物，其中所述弹性乙烯共聚物为乙烯/α-烯烃共聚物。
4.根据权利要求1所述的共混物，其中所述氯化聚烯烃为氯化聚乙烯。
5.根据权利要求1所述的共混物，其中所述第一组分为粉末状。
6.根据权利要求1所述的共混物，其中所述第二组分为微粒形式。
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US45487603P | 2003-03-14 | 2003-03-14 | |
| US60/454,876 | 2003-03-14 | ||
| US10/795,103 US7199191B2 (en) | 2003-03-14 | 2004-03-05 | Impact modifier compositions with improved flowability |
| US10/795,103 | 2004-03-05 | ||
| PCT/US2004/007729 WO2004083300A1 (en) | 2003-03-14 | 2004-03-12 | Impact modifier compositions with improved flowability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1798804A CN1798804A (zh) | 2006-07-05 |
| CN1798804B true CN1798804B (zh) | 2011-05-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2004800097054A Expired - Fee Related CN1798804B (zh) | 2003-03-14 | 2004-03-12 | 具有改善的流动性能的抗冲改性剂组合物 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US7199191B2 (zh) |
| EP (1) | EP1603972B1 (zh) |
| KR (1) | KR101113519B1 (zh) |
| CN (1) | CN1798804B (zh) |
| AT (1) | ATE408645T1 (zh) |
| CA (1) | CA2519078A1 (zh) |
| DE (1) | DE602004016635D1 (zh) |
| PL (1) | PL1603972T3 (zh) |
| WO (1) | WO2004083300A1 (zh) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006083279A2 (en) * | 2004-09-13 | 2006-08-10 | Velcon Filters, Inc. | Filter dehydrator |
| US20080207831A1 (en) * | 2007-02-28 | 2008-08-28 | Stewart Carl Feinberg | Composition comprising polyvinyl chloride and halogenated polyethylene or core-shell resin |
| WO2009035877A1 (en) * | 2007-09-14 | 2009-03-19 | Dow Global Technologies Inc. | A coat polymeric particulate, and a process for coating a polymeric particulate |
| US20090143535A1 (en) | 2007-11-29 | 2009-06-04 | Dow Global Technologies Inc. | Impact modifier composition, an impact resistant composition, method of producing the same, and articles made therefrom |
| WO2013016398A1 (en) * | 2011-07-28 | 2013-01-31 | Dow Global Technologies Llc | Polymeric blend formulations suitable for synthetic leather applications |
| EP2970601B1 (en) | 2013-03-15 | 2021-10-20 | Dow Global Technologies LLC | Epdm packaging system and process |
| CN104829936B (zh) * | 2013-04-22 | 2017-01-25 | 江苏亨通电力电缆有限公司 | 高伸长率阻燃型电缆料的制造工艺 |
| EP3684864B9 (en) | 2017-09-18 | 2022-04-20 | Dow Global Technologies LLC | Compositions containing coated polymer particles and tpo compositions formed from the same |
| KR102597958B1 (ko) | 2017-12-29 | 2023-11-06 | 다우 글로벌 테크놀로지스 엘엘씨 | 폴리올레핀 아크릴 입자 |
| WO2019133196A1 (en) | 2017-12-29 | 2019-07-04 | Dow Global Technologies Llc | Method for modifying polycarbonate |
| CN111727205B (zh) | 2017-12-29 | 2023-02-21 | 陶氏环球技术有限责任公司 | 制备聚烯烃-丙烯酸粒子的方法 |
| CN109181158A (zh) * | 2018-08-27 | 2019-01-11 | 四川亮力新材料科技有限公司 | 一种高分子抗冲改性剂及其制备方法和应用 |
| CN113105685B (zh) * | 2021-04-16 | 2022-12-06 | 潍坊亚星化学股份有限公司 | 氯化聚乙烯共混改性高密度聚乙烯材料及其制备方法 |
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| US5834558A (en) * | 1994-05-17 | 1998-11-10 | Cheil Industries, Inc. | Weather resistant theromplastic resin composition |
| US5925703A (en) * | 1992-09-15 | 1999-07-20 | The Dow Chemical Company | Impact modification of filled thermoplastics |
| US6124406A (en) * | 1998-03-31 | 2000-09-26 | The B. F. Goodrich Company | Blocky chlorinated polyolefins, process for making and use as impact modifier compatibilizer for PVC or CPVC |
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| GB1219352A (en) * | 1968-04-19 | 1971-01-13 | Ici Ltd | Compositions containing vinyl chloride polymers |
| US3634385A (en) | 1969-05-16 | 1972-01-11 | Dow Chemical Co | Method of deagglomerating polymer particles |
| JPS5025936B2 (zh) * | 1971-10-04 | 1975-08-27 | ||
| DE2913855A1 (de) | 1979-04-06 | 1980-10-23 | Hoechst Ag | Rieselfaehiges, pulverfoermiges chlorpolyaethylen |
| JPS5767604A (en) * | 1980-10-16 | 1982-04-24 | Mitsui Petrochem Ind Ltd | Chorinated rubber |
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2004
- 2004-03-05 US US10/795,103 patent/US7199191B2/en not_active Expired - Fee Related
- 2004-03-12 CA CA002519078A patent/CA2519078A1/en not_active Abandoned
- 2004-03-12 KR KR1020057017210A patent/KR101113519B1/ko not_active IP Right Cessation
- 2004-03-12 CN CN2004800097054A patent/CN1798804B/zh not_active Expired - Fee Related
- 2004-03-12 DE DE602004016635T patent/DE602004016635D1/de not_active Expired - Lifetime
- 2004-03-12 AT AT04720464T patent/ATE408645T1/de not_active IP Right Cessation
- 2004-03-12 WO PCT/US2004/007729 patent/WO2004083300A1/en active Application Filing
- 2004-03-12 EP EP04720464A patent/EP1603972B1/en not_active Expired - Lifetime
- 2004-03-12 PL PL04720464T patent/PL1603972T3/pl unknown
Patent Citations (3)
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| US5925703A (en) * | 1992-09-15 | 1999-07-20 | The Dow Chemical Company | Impact modification of filled thermoplastics |
| US5834558A (en) * | 1994-05-17 | 1998-11-10 | Cheil Industries, Inc. | Weather resistant theromplastic resin composition |
| US6124406A (en) * | 1998-03-31 | 2000-09-26 | The B. F. Goodrich Company | Blocky chlorinated polyolefins, process for making and use as impact modifier compatibilizer for PVC or CPVC |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004083300A1 (en) | 2004-09-30 |
| US7199191B2 (en) | 2007-04-03 |
| CN1798804A (zh) | 2006-07-05 |
| KR101113519B1 (ko) | 2012-02-29 |
| EP1603972B1 (en) | 2008-09-17 |
| ATE408645T1 (de) | 2008-10-15 |
| PL1603972T3 (pl) | 2009-03-31 |
| EP1603972A1 (en) | 2005-12-14 |
| CA2519078A1 (en) | 2004-09-30 |
| DE602004016635D1 (de) | 2008-10-30 |
| US20040236023A1 (en) | 2004-11-25 |
| KR20050117562A (ko) | 2005-12-14 |
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