CN112011142A - 模塑组合物和由其制成的发泡制品 - Google Patents

模塑组合物和由其制成的发泡制品 Download PDF

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CN112011142A
CN112011142A CN202010477297.6A CN202010477297A CN112011142A CN 112011142 A CN112011142 A CN 112011142A CN 202010477297 A CN202010477297 A CN 202010477297A CN 112011142 A CN112011142 A CN 112011142A
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foamed article
styrene
block
foamed
diene
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CN112011142B (zh
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M·格雷格尔
K·怀特
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Kraton Polymers Research BV
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Kraton Polymers Research BV
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Abstract

公开了通过组合物的泡沫注塑或泡沫挤出而形成的发泡制品。所述组合物基本上由以下物质组成：100phr的至少两种不同的氢化苯乙烯类嵌段共聚物(HSBC)，即，第一HSBC和第二HSBC，其具有至少1.2:1的分子量比的不同分子量，且其重量比为5:95‑95:5；10‑55phr的聚丙烯，其熔体流动速率为至少2g/10min；和任选地，至多55phr的增塑剂，其选自烃基油、脂肪酸、甘油三酯油、及其混合物。其中所述组合物具有2‑50g/10min的熔体流动速率，60‑90的肖氏A硬度，至少0.010N的熔体强度(F)和至少10的熔体强度(V)。

Description

模塑组合物和由其制成的发泡制品
技术领域
本公开涉及一种模塑组合物，其制备方法以及由其制成的制品。
背景技术
汽车内部部件通常具有缓冲的、触感柔软的美学特征。由于对轻型设计的汽车的需求稳定增长，因此包含聚合物泡沫的模塑组合物在此类汽车部件的制造中起着重要的作用。“缓冲”特征可以通过包含具有变化厚度的柔性聚合物泡沫或弹性体垫以及是相对较硬的材料的“软皮”材料的组合物来赋予。这样的汽车部件可以在芯背式注塑(core backinjection molding)工艺中生产，从而在同一工艺中生产多层。
需要用于通过芯背式注塑工艺生产诸如汽车内部部件之类的制品的改进的模塑组合物，其具有高密度降低以及诸如易加工性和所需硬度之类的性能。
发明概述
一方面，本发明涉及一种发泡制品，其由基本上由以下物质组成的组合物制成：100phr的至少两种不同的氢化苯乙烯类嵌段共聚物(HSBC)，即，第一HSBC和第二HSBC，其具有至少1.2:1的分子量比的不同分子量，且其重量比为5:95-95:5；10-55phr的聚丙烯，其熔体流动速率为至少2g/10min，根据ASTM D1238-82在230℃和5kg下测定；和任选地，至多55phr的增塑剂，其选自烃基油、脂肪酸、甘油三酯油、及其混合物；其中所述组合物具有：根据ASTM D1238-04在230℃和2.16kg下测定的2-50g/10min的熔体流动速率，根据ISO 868在15秒和23℃下测定的60-90的肖氏A硬度，至少0.010N的熔体强度(F)，和至少10的熔体强度(V)。所述发泡制品通过泡沫注塑或泡沫挤出形成，且相对于由未发泡的组合物形成的制品，其密度降低了至少10％。所述发泡制品具有完全包裹发泡内芯的非发泡表层。
附图说明
图1是由实施例9的配方获得的发泡样品的横截面的光学显微镜图像。
发明内容
本说明书中使用了以下术语，它们具有以下含义。
“phr”是指每100份苯乙烯类嵌段共聚物(SBC)的份数。
“分子量”是指以g/mol计的聚合物嵌段或嵌段共聚物的苯乙烯当量分子量。分子量可以通过凝胶渗透色谱法(GPC)使用聚苯乙烯校准标准物进行测量，例如根据ASTM5296-19进行。色谱仪使用市售的聚苯乙烯分子量标准物进行校准。使用如此校准的GPC测量的聚合物的分子量是苯乙烯当量分子量。当已知聚合物的苯乙烯含量和二烯链段的乙烯基含量时，苯乙烯当量分子量可以转化为真实分子量。检测仪可以是紫外和折射率检测仪的组合。在此表示的分子量是在GPC迹线的峰处测量的，转换为真实分子量，通常称为“峰值分子量”，表示为Mp。如上所述，除非换算成真实的分子量，否则分子量是指苯乙烯当量峰值分子量。
嵌段共聚物的“聚苯乙烯含量”或PSC是指嵌段共聚物中聚合的苯乙烯的wt％，其通过将所有聚苯乙烯嵌段的分子量之和除以嵌段共聚物的总分子量来计算。可以使用任何合适的方法来确定PSC，例如质子核磁共振(NMR)。
模塑组合物中组分的“熔体流动速率”或“MFR”可以根据ISO1133-1在230℃的温度和2.16kg的负载条件下测量。熔体流动速率还可以根据ASTM D1238-04在230℃的温度和2.16kg的负载条件下测量。
“肖氏A硬度”是基于锥形压头的穿透深度的弹性或软塑料材料的耐压痕性的量度，且可以根据ISO-868进行测量。
“熔体强度”是指聚合物熔体对聚合物组合物的拉伸或延伸粘度的抵抗力，这可以通过Goettfert Rheotens设备确定，在该设备中，熔融挤出物或纤维束在离开向下的挤出孔口时被牵拉经过两个动力辊之间。随着所述辊的速度增加，在所述纤维束中会产生张力，这由Rheotens设备测量。延伸和然后使挤出物断裂所需的力定义为熔体强度，最大牵引速度或熔体强度(V)作为熔体“伸长率”的相对度量，最大力或熔体强度(F)作为以牛顿(N)为单位测量的熔体强度的相对值。除非另有说明，否则熔体强度是在230℃下测量的。
“A/B”是指在二烯聚合物嵌段中具有受控分布的单烯基芳烃单元的聚合物嵌段。例如，B/S是指在丁二烯嵌段中具有受控分布的苯乙烯的聚合物嵌段。
本公开内容涉及一种具有泡沫内层和(更)致密的软表层的“发泡”制品。所述制品由包含至少两种苯乙烯类嵌段共聚物组分、高熔体流动的聚丙烯和任选的增塑剂和添加剂的模塑组合物形成。
苯乙烯类嵌段共聚物(SBC)组分：所述模塑组合物包含两种或更多种分子量不同的氢化的苯乙烯类嵌段共聚物(HSBC)。适合使用的不同HSBC独立地包括但不限于选择性氢化的苯乙烯-二烯嵌段共聚物，选择性氢化的苯乙烯-二烯-苯乙烯三嵌段共聚物，选择性氢化的苯乙烯-二烯二嵌段共聚物，苯乙烯-二烯-苯乙烯三嵌段共聚物的选择性氢化的树脂，选择性氢化的苯乙烯-二烯无规共聚物，选择性氢化的苯乙烯-二烯无规共聚物，选择性氢化的受控分布的苯乙烯-二烯/苯乙烯类嵌段共聚物，选择性氢化的受控分布的苯乙烯-二烯/苯乙烯-苯乙烯嵌段共聚物，及其组合。二烯可以是任何共轭二烯，例如丁二烯，异戊二烯，2,3-二甲基-1,3-丁二烯，氯丁二烯和间戊二烯，或其任何组合。
在某些实施方案中，在氢化之前，所述HSBC组合物包含表示为式A-B的苯乙烯二嵌段共聚物(SBC)，式A-B-A的线性三嵌段共聚物(其中每个A嵌段可以具有不同或相同的峰值分子量或者相同或不同的单烯基芳烃含量)，和/或式(A-B)nX的多臂偶联的嵌段共聚物。在这些方面，A是单烯基芳烃嵌段，B是共轭二烯嵌段，n为1-6的整数，X是偶联剂的残基。当使用式(A-B)nX的多臂偶联的嵌段共聚物时，n为2-4。
在某些实施方案中，SBC是受控分布的苯乙烯嵌段共聚物，其可以是式A-B的苯乙烯二嵌段共聚物，式A-B-A的线性三嵌段共聚物和/或式(A-B)nX的多臂偶联的嵌段共聚物，其中A、B、X和n的类型和数值如前文所公开的。
在一个实施方案中，所述HSBC组合物包含氢化的苯乙烯嵌段共聚物(HSBC)，其在氢化之前是一种或多种包括下述的SBC：式A-B的苯乙烯二嵌段共聚物，式A-B-A的线性三嵌段共聚物和/或式(A-B)nX的多臂偶联的嵌段共聚物，其中A、B、X和n的类型和数值如前文所公开的。在一个实施方案中，HSBC是苯乙烯-异戊二烯-苯乙烯三嵌段共聚物的氢化树脂，苯乙烯-丁二烯-苯乙烯三嵌段共聚物的氢化树脂，或其中聚合的共轭二烯的特定部分(例如丁二烯)被选择性氢化的树脂。在一个实施方案中，HSBC包含的B嵌段，其中B嵌段中的氢分子已经加入到大于92mol％或大于95mol％或大于98mol％的其中的碳-碳双键上。在另一个实施方案中，HSBC是具有B嵌段的部分饱和的氢化苯乙烯嵌段共聚物，其中的B嵌段中氢分子已经加入到20-92mol％或25-85mol％或30-80mol％的其中的碳-碳双键上。
单烯基芳烃嵌段(A嵌段)包括苯乙烯、邻甲基苯乙烯、对甲基苯乙烯、对叔丁基苯乙烯、2,4-二甲基苯乙烯、α-甲基苯乙烯、乙烯基萘、乙烯基甲苯、乙烯基二甲苯或其混合物中的任何一种。在某些实施方案中，单烯基芳烃嵌段包含基本上纯的单烯基芳烃单体。在一些实施方案中，苯乙烯是A嵌段中的主要组分，具有较小比例(小于10wt％)的结构上相关的乙烯基芳族单体，例如邻甲基苯乙烯、对甲基苯乙烯、对叔丁基苯乙烯、2,4-二甲基苯乙烯、α-甲基苯乙烯、乙烯基萘、乙烯基甲苯、乙烯基二甲苯或其组合。在一些实施方案中，每个单烯基芳烃嵌段(例如A嵌段)的峰值分子量为5,000-12,000g/mol，或5,000-11,000g/mol，或5,000-10,500g/mol。
在某些实施方案中，每个A嵌段的单烯基芳烃含量为10-60wt％，或15-50wt％，基于SBC的总重量。在其中SBC具有式A-B-A的方面，所有A嵌段的结合的单烯基芳烃含量为10-60wt％，或15-50wt％，基于直链三嵌段共聚物的总重量。在一些实施方案中，共轭二烯嵌段(B嵌段)包含任何合适的共轭二烯，例如，具有4-10个碳原子的共轭二烯，由丁二烯单体或异戊二烯单体形成的共轭二烯，所述丁二烯单体或异戊二烯单体是基本上纯的单体或包含少量(最多10wt％)结构相关的共轭二烯，例如2,3-二甲基-1,3-丁二烯、1,3-戊二烯和1,3-己二烯。
在某些实施方案中，HSBC是具有结构S-B-S或(S-B)2X的嵌段共聚物的线性、选择性氢化的形式，其中B代表共轭二烯嵌段或受控分布的共轭二烯/苯乙烯嵌段，其峰值分子量为50,000-290,000g/mol，或70,000-150,000g/mol，或80,000-130,000g/mol，或小于150,000g/mol。
在某些实施方案中，HSBC是具有结构S-EB/S-S或(S-EB/S)nX的选择性氢化的共聚物，其中X是偶联剂残基且n为1-6。选择性氢化的共聚物在中间嵌段(即EB/S)中具有受控分布的苯乙烯，总的聚苯乙烯含量为约58％，总分子量为约250kg/mol，在230℃/2.16kg下熔体流动速率为<1g/10min。
在某些实施方案中，HSBC是具有结构S-EB/S-S或(S-EB/S)nX的选择性氢化的共聚物，其中X是偶联剂残基且n为1-6。选择性氢化的共聚物在中间嵌段中具有受控分布的苯乙烯，总的聚苯乙烯含量为约35％，总分子量为约125kg/mol，在230℃/2.16kg下的熔体流动速率为约40。
在某些实施方案中，HSBC是具有结构S-EB-S或(S-E-B)nX的选择性氢化的共聚物，其中X是偶联剂残基，n为1-6。选择性氢化的共聚物的总聚苯乙烯含量为约13％，总分子量为约150kg/mol，在230℃/2.16kg下的熔体流动速率为约9g/10min，如美国专利No.6177521所公开的，其通过引用方式并入本文。
在某些实施方案中，HSBC是具有式S-EB-S或(S-E-B)nX的选择性氢化的共聚物，其中X是偶联剂残基，n为1-6。选择性氢化的共聚物的总聚苯乙烯含量为约20％，总分子量为约67kg/mol，在230℃/2.16kg下的熔体流动速率为>100g/10min，或100-500g/10min。
在某些实施方案中，所述选择性氢化的嵌段共聚物或选择性氢化的受控分布的嵌段共聚物的总聚苯乙烯含量(PSC)为10-65wt％,或10-50wt％,或12-45wt％。
在丁二烯为共轭二烯单体的实施方案中，共轭二烯嵌段(例如B嵌段)的乙烯基含量为10-95mol％，或15-85mol％，或35-80mol％。在异戊二烯为共轭二烯单体的实施方案中，B嵌段的乙烯基含量为5-95mol％，或5-85mol％，或5-80mol％。
在某些实施方案中，HSBC是具有式S-EP-S、(S-EP)nX、S-EEP-S、(S-EEP)nX、S-EB-S、(S-EB)nX、S-EB/S-S或(S-EB/S)nX的选择性氢化的苯乙烯-二烯嵌段共聚物，其中S是聚苯乙烯嵌段，EB是氢化的聚丁二烯嵌段，EP是氢化的聚异戊二烯嵌段，EEP是氢化的丁二烯和异戊二烯的聚合物嵌段，n为1-6,X为偶联剂残基。在氢化之前，选择性氢化的苯乙烯-二烯嵌段共聚物是具有乙烯基含量为10-95mol％的聚丁二烯嵌段的苯乙烯类嵌段共聚物。选择性氢化的苯乙烯-二烯嵌段共聚物的总PSC为10-65wt％。
在某些实施方案中，在氢化之前，选择性氢化的苯乙烯-二烯嵌段共聚物是包括下述的苯乙烯类嵌段共聚物：式A-B或A-B/A的二嵌段共聚物，式A-B-A或A-B/A-A的直链三嵌段共聚物，或式(A-B)nX或(A-B/A)nX的多臂偶联的嵌段共聚物，其中A是单烯基芳烃聚合物嵌段，B是共轭二烯聚合物嵌段，和B/A表示在共轭二烯聚合物嵌段中具有受控分布的单烯基芳烃的聚合物嵌段，n为1-6，X为偶联剂残基。选择性氢化的苯乙烯-二烯嵌段共聚物具有至少92mol％的聚合丁二烯单元被氢化。
在某些实施方案中，选择性氢化的嵌段共聚物或选择性氢化的控制分布的嵌段共聚物具有根据ASTM D 1238在230℃和2.16kg质量下测定的0.01-50g/10min或者0.1-45g/10min或者0.5-40g/10min的熔体流动速率。
所述两种不同的HSBC成分的存在量为100phr，其中第一HSBC和第二HSBC的重量比为5:95-95:5，或10:90-90:10，或20:80-80:20，或30:70-70:30。在另一个实施方案中，所述至少两种不同的HSBC组分的分子量比为至少1.2:1，或至少1.3:1，或至少1.5:1，或至少1.7:1或至少2.0:1。
聚丙烯组分：在某些实施方案中，聚丙烯组分选自：(i)丙烯的均聚物，(ii)丙烯和选自乙烯和C4-C10α-烯烃的烯烃的无规共聚物，或(ii)丙烯与两个选自乙烯和C4-C10α-烯烃的α-烯烃的无规三元共聚物。C4-C10α-烯烃包括直链和支链C4-C10α-烯烃，例如1-丁烯，1-戊烯，4-甲基-戊烯-1，3-甲基-1-丁烯，1-己烯，3-4-二甲基-1-丁烯，1-庚烯，3-甲基-1-己烯，1-辛烯等。
在某些实施方案中，聚丙烯组分是丙烯的均聚物。在其他实施方案中，聚丙烯组分是多相丙烯共聚物(HECO)。所述共聚物包含具有三种具有不同的熔体流动速率的不同聚丙烯馏分的聚丙烯基质，其中HECO的熔体流动速率MFR(230℃，2.16kg,根据ISO 1133测量)等于或大于20.0g/10min。
在某些实施方案中，聚丙烯组分具有通过ASTM D1238-82(230℃/5kg)测定的高于2g/10min或至少2.1g/10min或至少2.2g/10min的MFR。
在某些实施方案中，基于100phr的HSBC组分的总量，聚丙烯组分的存在量为10-55phr，或小于50phr，或至少20phr，或30-45phr。
增塑剂组分：所述模塑组合物任选地包含选自脂族烃基油、脂肪酸、甘油三酯油及其混合物的分散助剂或增塑剂。实例包括脂肪油(动物或植物脂肪酸甘油三酸酯的混合物)、矿物油和硅油。
在某些实施方案中，所述油选自矿物油、石蜡油、富含石蜡的油及其混合物。在一些实施方案中，所述油是基于GTL的加工油(或费-托油)。在某些实施方案中，所述油是合成油。在某些实施方案中，所述油包括柴油、生物柴油和羧酸酯，例如油酸2-乙基己酯。
增塑剂的存在量为0-55phr，或少于50phr，或至少20phr，或30-45phr，基于100phr的总HSBC组分。
其他聚合物成分：在某些实施方案中，所述模塑组合物任选地包含选自下述的其他聚合物组分：热塑性聚氨酯、热塑性共聚酯、工程热塑性树脂(聚酰胺、聚酯、聚苯醚)、聚芳基醚、聚芳基砜、缩醛树脂、腈类阻隔树脂、聚甲基丙烯酸甲酯、环烯烃共聚物、香豆酮-茚树脂、聚茚树脂，聚甲基茚树脂、聚苯乙烯树脂、乙烯基甲苯-α甲基苯乙烯树脂、α-甲基苯乙烯树脂和聚苯醚(特别是聚(2,6-二甲基-1,4-亚苯基醚))、其共聚物、及其混合物。
添加剂：在某些实施方案中，所述模塑组合物还包含一种或多种选自下述的添加剂：成核剂、澄清剂、脱模剂、抗氧化剂、稳定剂(例如热稳定剂、可见光稳定剂、紫外光稳定剂)、着色剂、阻燃剂、润滑剂(例如硬脂酸钙)、增效剂、脱模剂、流动增强剂、抗静电剂、玻璃填料、不同于玻璃填料的填料(例如滑石粉)、耐刮擦添加剂/表面改性剂(例如硅氧烷、可以是长链支化低密度聚乙烯的低密度聚乙烯)、或包含上述至少一种的组合。
表面改性剂的实例包括超高分子量聚二烷基硅氧烷，例如聚二甲基硅氧烷，与二氧化硅结合的超高分子量聚二烷基硅氧烷，聚烯烃硅氧烷，及其组合。
添加剂的存在量为1-30phr，或小于25phr，或至少3phr，或5-25phr，基于100phr的总SBC组分。
发泡剂：在某些实施方案中，发泡剂(即推进剂)与泡沫注塑(FIM)工艺一起使用。发泡剂不是所述模塑组合物的一部分，而是作为在FIM工艺中的成分以1-5重量％的量添加，基于所述模塑组合物的总重量。
发泡剂可以是化学发泡剂、物理发泡剂和/或微球中的任何一种。物理发泡剂的实例包括但不限于氮气，二氧化碳，水,有机发泡剂，例如脂族烃，例如丙烷，丁烷，戊烷和环己烷；卤代烃，例如氯二氟甲烷，二氟甲烷，三氟甲烷，三氯氟甲烷，二氯甲烷，二氯氟甲烷，二氯二氟甲烷等。化学发泡剂的实例包括碳酸氢钠，碳酸氢铵，氯化铵，碳酸铵等，它们是热分解型的发泡剂。可热膨胀的微球发泡剂通常具有热塑性树脂的外壳和包含在其中的膨胀剂。
模塑组合物的性能：所述模塑组合物的特征在于熔体流动速率(根据ASTM D1238-04在230℃和2.16kg下测定)为2-50g/10min，或至少5g/10min，或15-40g/10min，或至少20g/10min，或少于60g/10min。
在某些实施方案中，所述组合物的根据ISO 868测定的肖氏A硬度(15秒，23℃)为60-90，或在70-90，或至少65。
在某些实施方案中，所述模塑组合物的熔体强度(F)或最大力为至少0.010N，或至少0.015N，或至少0.02N，或至少0.03N。在某些实施方案中，所述模塑组合物的在230℃下测定的熔体强度(V)或最大脱模速度为至少10，或至少15，或至少20，或至少25，或至少30。
形成制品的方法：可以根据本领域已知的方法，通过组合各个组分并共混以形成共混物，将共混物挤出以形成粒料(随后将其用于形成制品)，来加工所述模塑组合物，其中所述粒料随后将用于形成制品，例如在模塑或挤出工艺(例如泡沫注塑FIM工艺或型材挤出工艺)中的注塑软表层制品。
在某些实施方案中，泡沫注塑方法是通过所谓的芯背式注塑方法，其中将模塑组合物注塑到在注塑设备的金属模具中形成的空腔空间中，和立即或在经过预定的时间后，将可动模具或者设置在所述可动模具中的可动芯以预定速率缩回至预定位置以扩大模腔空间，从而实现发泡。由于金属模具的温度通常比注射期间的热塑性弹性体组合物的温度低得多，因此在注射发泡产品的表面上形成与空腔表面接触的具有几乎不发泡的致密的表层。在某些实施方案中，发泡产品还可以与由树脂等制成的基体的表面接触一体形成。可以通过将基体预先放置在模腔空间中并将组合物注射到基体的表面来形成层压制品。
所述组合物可用于低压工艺或高压工艺中。在具有相对较低的模腔压力的低压工艺中，模具模腔填充有80-95％的聚合物气体熔体。当模具中的压力下降时，熔体会膨胀并以5-20％的发泡度填充模具的剩余体积。在高压工艺中(也称为“精密模具打开”或“呼吸模具技术”)，模腔完全充满了聚合物熔体，然后立即打开了几毫米。通过这样模腔的打开，压力下降并且熔体能够发泡。通过夹紧单元的拉回进行所述打开。
在某些实施方案中，可以通过泡沫挤出形成发泡制品。在泡沫挤出中，将组合物与合适的发泡剂混合以形成混合物。用混合物的熔体填充挤出机机筒，并且将混合物挤出通过型材模头，从而通过压力和/或温度的降低来产生发泡的结构体。然后将发泡制品切成所需的尺寸。
应用：所述模塑组合物可用于生产多种轻型车辆应用，尤其是门板、仪表板和控制台等，它们具有带发泡芯和紧密的非发泡表层的整体泡沫结构体。在某些实施方案中，所述组合物用于制备鞋底组件、包装/填充材料。在某些实施方案中，所述组合物用于制造密封件、垫片和合成软木塞。
发泡制品：通过注塑所述组合物而制成的发泡制品的特征在于具有优化的密度降低、改进的表面质量、均匀的内部气孔和最小厚度的非发泡表层，例如0.1-1.5mm或小于2.5mm或小于3mm厚的致密表层，或者至少0.1mm或至少1mm或至少3mm或至少4mm或0.1-20mm厚的发泡内芯。
通过挤出所述组合物而形成的发泡制品的特征在于具有优化的密度降低、改善的表面质量、均匀的内部气孔和最小厚度的非发泡表层，例如0.1-3mm或小于2mm厚的致密表层，至少0.1mm、至少1mm、至少3mm、至少4mm或0.1-20mm厚的发泡内芯。
在某些实施方案中，非发泡表层完全包裹制品的发泡内芯。
在某些实施方案中，所述制品是特征在于密度降低5-40％、或至少30％、或至少15％、或至少20％的模塑制品。通过比较发泡后的密度和发泡前的密度(即，固体致密聚合物的密度)来给出密度降低。
实施例
通过举例的方式给出实施例。
实施例中使用的主要组分如下。
HSBC7是具有结构(S-EB)nX的中分子量氢化的苯乙烯嵌段共聚物，其聚苯乙烯含量为13％，分子量为145kg/mol，氢化前的中间嵌段(EB)乙烯基含量为44％。
HSBC8是结构(S-EB)nX的低分子量苯乙烯嵌段共聚物，其聚苯乙烯含量为20％，分子量为67kg/mol，氢化前的中间嵌段(EB)乙烯基含量为77％。
HSBC5是具有结构S-EB/S-S的高分子量苯乙烯嵌段共聚物，其聚苯乙烯含量为58％，分子量为245kg/mol，氢化前的中间嵌段(S/EB)乙烯基含量为38％。
HSBC1是具有结构(S-EB/S)nX的中分子量的苯乙烯嵌段共聚物，其聚苯乙烯含量为34％，分子量为125kg/mol，氢化前的中间嵌段(S/EB)乙烯基含量为77％。
HSBC3是具有结构(S-EB)nX的低分子量苯乙烯嵌段共聚物，其聚苯乙烯含量为30％，分子量为57kg/mol，氢化前的中间嵌段(EB)乙烯基含量为38％。
PP125是长链支化聚丙烯树脂，其熔体流动速率(230℃/2.16kg)为2.4g/10min，拉伸强度为40MPa，屈服伸长率为6％。
PP140是另一种长链支化聚丙烯树脂，其熔体流动速率(230℃/2.16kg)为2.1g/10min，拉伸强度为40MPa，屈服伸长率为6％。
PP2030是均聚丙烯树脂，其熔体流动速率(230℃/2.16kg)为2.5g/10min。
PP185是另一种均聚丙烯，其熔体流动速率(230℃/2.16kg)为2.2g/10min。
PP348是聚丙烯无规共聚物树脂，其熔体流动速率(230℃/2.16kg)为11g/10min，抗张强度为29MPa，屈服伸长率为13％。
实施例1-20:将下表中以重量百分比表示的各组分混合并挤出以形成粒料，随后将其用于在芯背式注塑工艺中形成发泡制品。
测量模塑组合物的性能，并将其示于表1和2中。对于熔体强度测量，在挤出机下方使用四轮设备进行Rheotens试验，纺丝长度为100mm，挤出机的生产量为0.5kg/h。通过用酒精冷却来运行设备。根据测量的数据，计算出数值曲线，并应用Wagner的伸长粘度模型。
对于发泡制品，使用具有三区挤出机的注射泡沫成型机，其测试板为90x 90x2mm。模具温度从40-220℃不等(T模具为40℃，T区域1为220℃，T区域2为190℃，T区域3为180℃)。注射速度为90％，注射时间为0.58秒。背压为23巴，背压时间为4秒。发泡剂包括物理发泡剂(0.8％CO2)和化学发泡剂2.0％Hydrocerol CF40E。生产的发泡制品的表层厚度为约2mm，致密表层/发泡内芯的厚度比为1.0-2.0。使用静水平衡来确定发泡前和发泡后的标准密度降低。
结果示于表1-2。图1是由实施例9配方获得的发泡样品的横截面的光学显微镜图像。
表1
Figure BDA0002516253080000131
表2
Figure BDA0002516253080000141

Claims (15)

1.一种发泡制品，其由基本上由以下物质组成的模塑组合物制成：
100phr的至少两种不同的氢化苯乙烯类嵌段共聚物(HSBC)，即，第一HSBC和第二HSBC，其具有至少1.2:1的分子量比的不同分子量，且其重量比为5:95-95:5；
10-55phr的聚丙烯，其熔体流动速率为至少2g/10min，根据ASTM D1238-82在230℃和5kg下测定；和
任选地，至多55phr的增塑剂，其选自烃基油、脂肪酸、甘油三酯油、及其混合物；
其中所述模塑组合物具有：根据ASTM D1238-04在230℃和2.16kg下测定的2-50g/10min的熔体流动速率，根据ISO 868在15秒和23℃下测定的60-90的肖氏A硬度，至少0.010N的熔体强度(F)，和至少10的熔体强度(V)；
其中所述发泡制品通过泡沫注塑或泡沫挤出形成；
其中相对于由未发泡的模塑组合物形成的制品，所述发泡制品的密度降低了至少10％；和
其中所述发泡制品具有完全包裹发泡内芯的非发泡表层。
2.根据权利要求1所述的发泡制品，其中所述非发泡表层的厚度为0.1-5mm。
3.根据权利要求1所述的发泡制品，其中所述发泡内芯的厚度为0.1-20mm。
4.根据权利要求1-3任一项所述的发泡制品，其中所述模塑组合物还包含一种或多种选自下述的其他聚合物成分：热塑性聚氨酯、热塑性共聚酯、工程热塑性树脂(聚酰胺、聚酯、聚苯醚)、聚芳基醚、聚芳基砜、缩醛树脂、聚酰胺、腈阻隔树脂、聚甲基丙烯酸甲酯、环烯烃共聚物、香豆酮-茚树脂、聚茚树脂、聚甲基茚树脂、聚苯乙烯树脂、乙烯基甲苯-α-甲基苯乙烯树脂、α-甲基苯乙烯树脂、聚苯醚、聚(2,6-二甲基-1,4-亚苯基醚)、其共聚物、及其混合物。
5.根据权利要求1-3任一项所述的发泡制品，其中所述组合物还包含1-30phr的添加剂，基于100phr的所述至少两种不同的氢化苯乙烯类嵌段共聚物。
6.根据权利要求1-3任一项所述的发泡制品，其中所述第一HSBC和第二HSBC独立地选自选择性氢化的苯乙烯-二烯嵌段共聚物、选择性氢化的苯乙烯-二烯-苯乙烯三嵌段共聚物、选择性氢化的苯乙烯-二烯二嵌段共聚物、苯乙烯-二烯-苯乙烯三嵌段共聚物的选择性氢化的树脂、选择性氢化的苯乙烯-二烯无规共聚物、选择性氢化的苯乙烯-二烯无规共聚物、选择性氢化的受控分布的苯乙烯-二烯/苯乙烯类嵌段共聚物、选择性氢化的受控分布的苯乙烯-二烯/苯乙烯-苯乙烯类嵌段共聚物、及其组合。
7.根据权利要求6所述的发泡制品，其中在氢化之前，所述选择性氢化的苯乙烯-二烯嵌段共聚物是包括式A-B或A-B/A的二嵌段共聚物、式A-B-A或A-B/A-A的线性三嵌段共聚物、或者式(A-B)nX或(A-B/A)nX的多臂偶联的嵌段共聚物的苯乙烯类嵌段共聚物，其中A是单烯基芳烃聚合物嵌段，B是共轭二烯聚合物嵌段，且B/A表示在共轭二烯聚合物嵌段中具有受控分布的单烯基芳烃的聚合物嵌段，n为1-6，X为偶联剂残基。
8.根据权利要求6所述的发泡制品，其中所述第一HSBC和第二HSBC独立地选自具有式S-EP-S、(S-EP)nX、S-EEP-S、(S-EEP)nX、S-EB-S、(S-EB)nX、S-EB/S-S或(S-EB/S)nX的氢化的苯乙烯-二烯嵌段共聚物，其中S是聚苯乙烯嵌段，EB是氢化的聚丁二烯嵌段，EP是氢化的聚异戊二烯嵌段，EEP是丁二烯和异戊二烯的氢化的聚合物嵌段，n为1-6，X是偶联剂残基。
9.根据权利要求7所述的发泡制品，其中在氢化之前，所述选择性氢化的苯乙烯-二烯嵌段共聚物是具有乙烯基含量为10-95mol％的聚丁二烯嵌段的苯乙烯类嵌段共聚物。
10.根据权利要求7所述的发泡制品，其中所述选择性氢化的苯乙烯-二烯嵌段共聚物的总聚苯乙烯含量为10-65wt％。
11.根据权利要求7所述的发泡制品，其中在所述选择性氢化的苯乙烯-二烯嵌段共聚物中至少92mol％的聚合丁二烯单元被氢化。
12.根据权利要求1-3任一项所述的发泡制品，其中所述模塑组合物进一步包含1-5wt％的发泡剂，基于所述模塑组合物的总重量。
13.根据权利要求1-3任一项所述的发泡制品，其中所述发泡制品选自：选自门板、仪表板和控制台的轻型车辆类型的应用，鞋底组件，包装和填充材料。
14.根据权利要求1-3任一项所述的发泡制品，其中所述制品通过包括下述步骤的注塑工艺制成：
a)将所述模塑组合物与合适的发泡剂混合，以形成混合物；
b)采用注塑工艺，将所述混合物的熔体填充到模腔中；
c)通过降低压力和/或升高温度，使所述混合物在模腔中发泡；和
d)从所述模腔中取出发泡制品。
15.根据权利要求1-3任一项所述的发泡制品，其中所述制品通过包括下述步骤的挤塑工艺制成：
a)将所述模塑组合物与合适的发泡剂混合，以形成混合物；
b)用所述混合物的熔体填充挤出机筒；
c)将所述混合物挤出通过型材模头，并降低压力和/或温度，以产生发泡制品；和
d)将所述发泡制品切割成所需的长度。
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