CN111278907A - 具有增加的熔体强度的聚烯烃聚合物 - Google Patents
具有增加的熔体强度的聚烯烃聚合物 Download PDFInfo
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- CN111278907A CN111278907A CN201880069118.6A CN201880069118A CN111278907A CN 111278907 A CN111278907 A CN 111278907A CN 201880069118 A CN201880069118 A CN 201880069118A CN 111278907 A CN111278907 A CN 111278907A
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- polymer composition
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- melt strength
- polypropylene
- sorbitol
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明公开了一种具有增加的熔体强度的聚合物组合物。所述聚合物组合物包含与至少一种熔体强度改性剂组合的至少一种聚丙烯聚合物。所述熔体强度改性剂可以包含足以改变所述聚合物的熔体强度特性和性质的量的山梨醇衍生物。所述聚合物组合物可以用在热成型工艺中并产生聚合物泡沫。所述熔体强度改性剂可以增加所述聚合物的熔体强度,而不必在所述聚丙烯聚合物中引起支化。
Description
相关申请
本申请基于提交日期为2017年10月27日的美国临时专利申请序列号62/578,162并要求其优先权,该临时专利申请的全文以引用方式并入本文。
背景技术
聚烯烃聚合物用于多种且不同的应用。聚烯烃聚合物(诸如聚丙烯)是具有良好的耐化学性、良好的耐热性和良好的抗疲劳性的半结晶聚合物。聚丙烯也相对坚韧,并具有出色的热塑性性质,从而允许将聚合物制成多种且不同的形状。
在一些特定的应用中,诸如热成型和发泡工艺,通常需要高熔体强度。例如,为了使组合物热成型为所需的形状或为了形成泡沫孔,需要高熔体强度。例如,在热成型工艺期间,将聚合物加热到特定温度以上,并且然后成型为所需的物体。当形成具有复杂形状的物体时,当形成厚规格的大型部件时,需要高熔体强度以便维持形状稳定性以及在成型工艺期间的拉伸性。例如,聚合物应该能够在上述工艺期间保持足够的结构完整性,并且直到制品固化为止。
相似地,在热发泡工艺期间也需要高熔体强度。没有足够的熔体强度,薄的泡孔壁可能塌陷或以其他方式形成物理性质不如所需的泡沫。
过去,已经使用各种方法和技术以便增加聚丙烯聚合物的熔体强度。例如,一种增加熔体强度的方法是在聚丙烯聚合物上产生长支链。具有长支链的聚丙烯聚合物可以使用反应器内方法和反应器后方法产生。对于反应器内方法,需要特殊的催化剂以便引起大分子单体聚合。反应器内工艺不仅过于昂贵,而且产生低产率。
用于产生长支链聚丙烯聚合物的反应器后方法包括将聚合物暴露于电子束或伽玛辐射。高能辐射引起断链和聚合物自由基,它们最终在低/零氧环境下重组形成长支链。然而,不幸的是,暴露于电子束会产生辐射后降解。此外,辐射仍然需要进一步加工聚合物,因此导致成本增加。
在助剂或多官能单体存在下,聚丙烯的后反应也是在聚丙烯中产生长支链的一种选择。然而,类似于辐射方法,成本和低生产率已经限制了进一步商业化。
增加聚丙烯熔体强度的另一种方式是加宽分子量分布。但是,与具有长支链的聚丙烯相比,通过这种方法实现的熔体强度有限。
鉴于上述情况,需要一种无需在聚合物内产生长支链而增加聚丙烯聚合物的熔体强度的方法。还需要具有增加的熔体强度的聚丙烯聚合物组合物,该组合物可在热成型工艺和发泡工艺期间使用。
发明内容
一般来讲,本公开涉及包含具有增强的熔体强度的基于丙烯的聚合物的聚合物组合物。根据本公开,熔体强度改性剂与聚丙烯聚合物以足以增加聚合物的熔体强度的量组合。例如,将熔体强度改性剂以足以使聚合物在聚合物处于熔融状态时在较高温度下保持凝胶状网络的量与聚合物共混。凝胶状网络增加弹性并显著增加熔体强度。
例如,在一个实施方案中,本公开涉及具有增加的熔体强度的聚合物组合物。该聚合物组合物包含含有至少60摩尔%的丙烯的聚丙烯聚合物。聚丙烯聚合物例如可以包含聚丙烯均聚物、聚丙烯共聚物或它们的混合物。
根据本公开,聚合物组合物还包含存在于聚合物组合物中的熔体强度改性剂,当该聚合物组合物处于熔融状态时,该熔体强度改性剂足以使聚合物组合物形成渗透网络。如本文所用,渗透网络是遍及聚合物基体的物理固体状三维网络。该网络可以经由共价或物理结合的分子结构形成。在一个实施方案中,聚合物网络仅在单一聚合物内形成并且可以包括缠结的聚合物链。
在一个实施方案中,熔体强度改性剂存在于聚合物组合物中,使得聚合物组合物具有大于约180℃、诸如大于约185℃的粘弹性转变温度。
本公开的聚合物组合物还可以具有各种物理性质。例如,聚合物组合物可以具有大于约0.4的应变硬化指数。
在一个实施方案中,除了具有大于约0.4的应变硬化指数之外,聚合物组合物还可以具有大于约50、诸如大于约60、诸如大于约70、诸如大于约80的剪切致稀因子。剪切致稀因子通常小于约300。此外,聚合物组合物可具有大于约0.2的弹性指数。
在一个实施方案中,熔体强度改性剂可包含亚苄基山梨醇衍生物。熔体强度改性剂的示例例如包括1,3:2,4-双(3,4-二甲基二亚苄基)山梨醇、1,2,3-三脱氧-4,6:5,7-双-O-[(4-丙基苯基)亚甲基]壬醇、1,3:2,4-双(对硝基亚苄基)山梨醇、(1,3-2,4-二亚苄基山梨醇)、1,3-2,4-双(对甲氧基亚苄基)山梨醇、1,3:2,4-双(间甲氧基亚苄基)山梨醇、1,3:2,4-双(对氯亚苄基)山梨醇、1,3:2,4-双(对甲基亚苄基)山梨醇或其混合物。在一个实施方案中,熔体强度改性剂可以以通常大于约0.6重量%的量、诸如以大于约0.8重量%的量、诸如以大于约1重量%的量、诸如以大于约1.2重量%的量、诸如以大于约1.4重量%的量、诸如以大于约1.6重量%的量、诸如以大于约1.8重量%的量、诸如以大于约2重量%的量存在于聚合物组合物中。熔体强度改性剂通常以小于约10重量%的量、诸如以小于约5重量%的量、诸如以小于约4重量%的量存在于聚合物组合物中。
特别有利的是,本公开的聚合物组合物可以具有上述熔体强度性质,而不必使用具有长支链的聚丙烯聚合物。就这一点而言,在一个实施方案中,可以将线性聚丙烯聚合物用于形成组合物。
在一个实施方案中,可以将聚合物组合物配制为形成聚丙烯泡沫。例如,聚合物组合物可以包含成核剂和发泡剂。发泡剂可包括例如氮气、二氧化碳、异丁烷、环戊烷、空气、氯甲烷、氯乙烷、戊烷、异戊烷、全氟甲烷、氯三氟甲烷、二氯二氟甲烷、三氯氟甲烷、全氟乙烷、1-氯-1,1-二氟乙烷、氯五氟乙烷、二氯四氟乙烷、三氯三氟乙烷、全氟丙烷、氯七氟丙烷、二氯六氟丙烷、全氟丁烷、氯九氟丁烷、全氟环丁烷、偶氮二甲酰胺(ADCA)、偶氮二异丁腈、苯磺酰肼、4,4-苯酚磺酰氨基脲(4,4-oxybenzene sulfonylsemicarbazide)、对甲苯磺酰基氨基脲、偶氮二甲酸钡、N,N′二甲基-N,N′-二亚硝基对苯二甲酰胺、三肼基三嗪、N,N-二亚硝基五亚甲基、柠檬酸衍生物、四胺、5-苯基四唑、亚肼基二甲酰胺(hydrazodicarbonamide)、对甲苯磺酰肼或其混合物。
就这一点而言,本公开还涉及用于形成聚丙烯泡沫的方法。该方法包括以下步骤:将如上所述的包含熔体强度改性剂的聚丙烯组合物组合,并将聚合物组合物与发泡剂和成核剂组合。将聚合物组合物加热至足以使发泡剂引起形成泡沫孔的熔融状态。
例如,在一个实施方案中,可以将基于丙烯的聚合物组合物加热至熔融条件。可以将发泡剂掺入组合物中,以便在熔融状态下形成气态材料在聚合物组合物中的分散体。然后使熔融聚合物组合物产生发泡结构。可以将发泡结构模制成所需的形状而不塌陷泡沫结构。例如,发泡制品可以是一次性饮用杯。
本公开还涉及用于热成型聚丙烯聚合物的方法。该方法包括将聚丙烯聚合物与如上所述的熔体强度改性剂共混。将聚合物组合物加热至足以在热成型工艺期间将聚合物形成制品的熔融状态。例如,聚合物制品可以包括食品包装中使用的制品、诸如饮用杯的一次性制品、诸如冰箱内衬的大型电器的部件、诸如休闲车面板的汽车部件等。
本公开还涉及一种用于增加聚丙烯聚合物的熔体强度的方法。该方法包括将聚丙烯聚合物与如上所述的熔体强度改性剂共混的步骤。
下面更详细地讨论本公开的其他特征和方面。
附图说明
在说明书的其余部分中(包括参考附图),更具体地阐述本公开的完整且能够实现的公开内容,在附图中:
图1是在以下实施例中获得的一些结果的图形表示。
在本说明书和附图中重复使用参考字符旨在表示本发明的相同或类似的特征或元件。
具体实施方式
本领域的普通技术人员将理解,本讨论仅是对示例性实施方案的描述,而无意于限制本公开的较宽方面。
一般来讲,本公开涉及包含具有增加的熔体强度的聚烯烃聚合物(诸如聚丙烯聚合物)的聚合物组合物。本公开还涉及用于形成聚合物制品(包括由聚合物组合物制成的泡沫制品)的各种方法和工艺。
在一个实施方案中,本公开的聚合物组合物包含与熔体强度改性剂组合的一种或多种聚丙烯聚合物。将熔体强度改性剂以足以在升高的温度下,诸如在聚合物组合物处于熔融状态的温度下,增加聚合物组合物的弹性的量添加到聚合物组合物中。例如,在一个实施方案中,熔体强度改性剂可以包含在较高温度下保持凝胶状网络的胶凝剂。熔体强度改性剂也可以不足以增加聚合物组合物的粘度的量添加,其量使熔融聚合物不适合模塑应用。通过在升高的温度下增加聚合物组合物的弹性,聚合物组合物的熔体强度显著增加,从而允许将聚合物组合物热成型为所有不同的形状,并且还允许聚合物组合物形成具有闭孔的泡沫。
在一个实施方案中,熔体强度改性剂以足以产生如上所述的渗透网络的量存在于聚合物组合物中。
在一个实施方案中,熔体强度改性剂可以包含山梨醇衍生物。过去,特定的山梨醇衍生物已与聚烯烃聚合物组合,以便用作成核剂或用作澄清剂。在这些应用中,以相对少的量添加山梨醇衍生物。然而,根据本公开,将山梨醇衍生物以足以改变和增加熔体强度的量加入到聚合物中,使得聚合物组合物在升高的温度下具有在热成型模塑工艺期间和/或发泡工艺期间发现特别适合的性质的特定组合。实际上,在一些实施方案中,实际上可能不利地影响所得聚合物的清晰度。
为了限定根据本公开制成的聚合物组合物,对与聚合物的熔体强度有关的聚合物组合物进行了各种不同的测试。以下是各种测试的描述:
剪切致稀因子(STF)
剪切致稀因子是低剪切和高剪切时聚合物组合物的粘度之比。使用先进的流变扩展系统(ARES-G2)以及独立的电机和传感器进行流变测量。聚合物组合物的复数粘度通过在190℃下从350至0.1的频率扫描来测量。应变振幅为2%,已证实在线性粘弹性区域内。粒料形式的聚合物可以被压缩成直径为25毫米且厚度为2毫米的圆盘。应用Carreau-Yasuda模型以拟合零剪切粘度。剪切致稀因子(STF)根据以下公式定义为零剪切粘度与G*=100kPa时的粘度之比:
STF=η0/ηG*=100kPa
多分散性指数
使用公式PDI=〖10〗^5/Gx计算PDI,其中Gx是G’和G”的交叉模量,因此Gx=G’=G”。G’和G”是通过上述频率扫描获得的储能模量和损耗模量。
粘弹性转变温度
粘弹性转变温度是当相对于温度绘制粘度时发生粘度跳跃的温度。使用ARES-G2系统通过温度扫描来测量粘度转变温度。粘度在lrad/s的频率(250℃至150℃)下通过3℃/min从170℃至250℃测量。粘度对温度的一阶导数曲线的峰值温度被视为转变温度。
应变硬化指数
应变硬化指数是组合物的拉伸粘度的量度。拉伸粘度使用ARES-G2系统中的拉伸粘度夹具(EVF)进行测量。可以呈粒料形式的聚合物组合物可以被压缩成尺寸为18mm×10mm×0.7mm的片。应用1s-1的拉伸速率。样品在190℃下等温5分钟,然后在145/155/160℃下测量拉伸粘度。应变硬化指数定义为以10为底的对数在1和3的Hencky应变下的粘度之间的弦斜率。根据以下公式计算应变硬化指数:
SHI=log(ηE(ε=1))-log(ηE(ε=3))/log(3)-log(1)
弹性指数
使用结合有电机和传感器的流变系统AR-G2获得蠕变和恢复测量值。在300秒的蠕变时间内施加50Pa的恒定应力。消除应力使样品恢复600秒。600秒时的恢复顺应性定义为平衡顺应性。弹性指数计算如下:
本公开的聚合物组合物可以由上述性质和特性中的一种或多种来定义。
聚合物组合物通常可具有大于约50、诸如大于约55、诸如大于约60、诸如大于约65、诸如大于约70、诸如大于约75、诸如大于约80、诸如大于约85、诸如大于约90、诸如大于约95、诸如大于约100的剪切致稀因子。剪切致稀因子通常小于约500,诸如小于约400,诸如小于约300,诸如小于约200,诸如小于约100。
聚合物组合物的应变硬化指数通常大于约0.4,诸如大于约0.8,诸如大于约1,诸如大于约1.2,诸如大于约1.4,诸如大于约1.6,诸如大于约1.8,诸如大于约2。应变硬化指数通常小于约5,诸如小于约4,诸如小于约3。
基于组合物的蠕变特性的聚合物组合物的弹性指数通常大于约0.2,诸如大于约0.4,诸如大于约0.6,并且通常小于约0.8,诸如小于约0.7。
聚合物组合物的粘弹性转变温度通常大于约180℃、诸如大于约190℃、诸如大于约200℃、诸如大于约210℃。粘弹性转变温度通常小于约240℃、诸如小于约230℃、诸如小于约220℃。
如上所述,本公开的聚合物组合物通常包含与一种或多种熔体强度改性剂组合的一种或多种聚丙烯聚合物。可以在本公开中使用的基于丙烯的聚合物包括例如丙烯均聚物。另选地,基于丙烯的聚合物可以是丙烯共聚物。此类丙烯共聚物可以是丙烯无规共聚物。另选地,此类丙烯共聚物可以是异相丙烯聚合物。
在一个实施方案中,例如,本公开的聚合物组合物包含聚丙烯均聚物。聚丙烯均聚物可以以大于约40重量%的量、诸如以大于约50重量%的量、诸如以大于约60重量%的量、诸如以大于约70重量%的量、诸如以大于约80重量%的量、诸如以大于约90重量%的量存在于聚合物组合物中。
在一个实施方案中,聚合物组合物可以包含与丙烯-α-烯烃共聚物组合的聚丙烯均聚物,或者可以仅包含丙烯-α-烯烃共聚物。丙烯-α-烯烃共聚物包含衍生自丙烯和一种或多种α-烯烃共聚单体的单元。用于制造丙烯/α-烯烃共聚物的示例性共聚单体是C2和C4至C10α-烯烃;例如C2、C4、C6和C8α-烯烃。
在又一个实施方案中,聚合物组合物可以包含异相丙烯聚合物组合物。异相丙烯聚合物可例如包含基体相和至少一个分散相。异相丙烯聚合物的基体相可以例如包含丙烯聚合物,诸如丙烯均聚物或基于丙烯的共聚物。基体相可以例如包含丙烯均聚物。基于丙烯的共聚物可以例如是丙烯与α-烯烃共聚单体的共聚物。
异相丙烯共聚物的分散相可以例如包含乙烯-丙烯弹性体。相对于乙烯-丙烯弹性体的总重量,乙烯-丙烯弹性体可以例如包含≥10.0重量%且≤65.0重量%,另选地≥20.0重量%且≤50.0重量%的衍生自乙烯的聚合单元。相对于异相丙烯共聚物的总重量,分散相可以例如≥5.0重量%且≤40.0重量%、另选地≥15.0重量%且≤35.0重量%的量存在。
可以经由本领域已知的用于生产基于丙烯的聚合物的任何工艺来生产基于丙烯的聚合物。此类工艺可以例如包括气相聚合工艺、淤浆相聚合工艺和溶液聚合工艺中的一种或多种。此类工艺可以例如是催化聚合工艺。此类催化聚合工艺可以例如在齐格勒-纳塔型催化剂、单中心型催化剂诸如茂金属型催化剂或基于丙烯的聚合物的生产领域中已知的任何其他类型的催化剂中的一种或多种存在下进行。此类工艺可以例如涉及单个聚合阶段或另选地多个聚合阶段。涉及多个聚合阶段的此类工艺例如可以涉及串联的多个聚合阶段。此类多个聚合阶段可以在单个聚合反应器中或在多个聚合反应器中进行。此类多阶段聚合工艺可以例如包括一个或多个气相聚合反应器、一个或多个淤浆相聚合反应器和/或一个或多个溶液聚合反应器,或存在任何顺序的此类反应器的任何组合。
如上所述,根据本公开,将一种或多种聚丙烯聚合物与熔体强度改性剂组合。熔体强度改性剂例如可以包含以足以增加熔体强度的量添加到聚合物组合物中的山梨醇衍生物。一般来讲,根据本公开可以使用能够增加熔体强度的任何合适的山梨醇衍生物。在一个实施方案中,例如,山梨醇衍生物可以包括二亚苄基山梨醇衍生物或山梨醇乙酸酯。
可以根据本公开使用的山梨醇衍生物的示例包括1,3:2,4-双(3,4-二-甲基二亚苄基)山梨醇、1,2,3-三脱氧-4,6:5,7-双-O-[(4-丙基苯基)亚甲基]壬醇、1,3:2,4-双(对硝基亚苄基)山梨醇、(1,3:2,4-二亚苄基山梨醇)、1,3:2,4-双(对甲氧基亚苄基)山梨醇、1,3:2,4-双(间甲氧基亚苄基)山梨醇、1,3:2,4-双(对氯亚苄基)山梨醇、1,3:2,4-双(对甲基亚苄基)山梨醇、1,3:(4-亚甲苯基)-2,4-(2-亚噻吩基)-D-山梨醇、1,3-(对甲硫基亚苄基)-2,4-(对亚甲苯基)-D-山梨醇、1,3-(对正丁基亚苄基)-2,4-(对亚甲苯基)-D-山梨醇、1,3:2,4-二(2-亚萘基)-D-山梨醇或其混合物。
在一个实施方案中,山梨醇衍生物可以包括二取代的二亚苄基山梨醇衍生物,其具有在山梨醇链的第一碳(C-1位)上取代的烯丙基基团或正丙基基团。山梨醇化合物可以由式I表示:
其中R1和R2独立地选自由CH3CH2CH2-(即正丙基)和CH3CH2CH2O-(即正丙氧基)构成的组;并且
其中R3独立选自由-CH2CH2CH3(正丙基)和-CH2-CH=CH2(烯丙基)构成的组。
在一个实施方案中,提供了式I的化合物,其中R3为正丙基基团(-CH2CH2CH3)。在另选的实施方案中,R3是烯丙基基团(-CH2CH=CH2)。
在一个实施方案中,R1和R2是正丙基。在另选的实施方案中,R1和R2是正丙氧基。
在另一个实施方案中,R1和R2是相同的;即,式I的化合物是对称的。在另一个实施方案中,R1和R2是不同的;即,式I的化合物是不对称的。
在另一个实施方案中,R3是烯丙基,并且R1和R2独立地选自由正丙基和正丙氧基构成的组。
在另一个实施方案中,R3是正丙基,并且R1和R2独立地选自由正丙基和正丙氧基构成的组。
根据一个实施方案,式I的化合物如下:
根据另一个实施方案,式I的化合物如下:
根据另一个实施方案,式I的化合物如下:
根据另一个实施方案,式I的化合物如下:
一种或多种熔体强度改性剂以足以达到所需的熔体强度的量存在于聚合物组合物中,熔体强度可根据剪切致稀因子、粘度转变温度、应变硬化指数、弹性指数或其混合形式来测量。一般来讲,一种或多种熔体强度改性剂以大于约0.6重量%的量、诸如以大于约0.8重量%的量、诸如以大于约1重量%的量、诸如以大于约1.2重量%的量、诸如以大于约1.4重量%的量、诸如以大于约1.6重量%的量、诸如以大于约1.8重量%的量、诸如以大于约2重量%的量、诸如以大于约2.2重量%的量、诸如以大于约2.4重量%的量、诸如以大于约2.6重量%的量存在于聚合物组合物中。一种或多种熔体强度改性剂通常以小于约10重量%的量、诸如以小于约8重量%的量、诸如以小于约6重量%的量、诸如以小于约4重量%的量、诸如以小于约3.5重量%的量、诸如以小于约3重量%的量存在于聚合物组合物中。
除了熔体强度改性剂之外,聚合物组合物还可以包含各种其他添加剂和成分。例如,抗氧化剂可以包括酚类和磷类抗氧化剂,可以包括这些抗氧化剂以增强产品的加工和最终使用稳定性。例如,季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、三(2,4-二叔丁基苯基)亚磷酸酯、催化剂中和剂诸如金属硬脂酸盐(诸如硬脂酸钙)、水滑石、乳酸钙和金属氧化物以及它们的组合可以被包含在组合物中。此外,组合物可以包含加工助剂、颜料、紫外线吸收剂、阻燃剂和润滑剂。
通过增加聚丙烯聚合物的熔体强度,本公开的聚合物组合物非常适合需要高熔体强度的应用,诸如在热成型工艺中和在泡沫形成工艺期间。
例如,在挤出-热成型工艺期间,将熔体强度改性剂与一种或多种聚丙烯聚合物共混并加热至熔融状态。例如,可以将熔体强度改性剂与聚丙烯聚合物配混,或者可以在将聚合物加热之后将熔体强度改性剂添加到聚丙烯聚合物中。一旦处于熔融状态,就可以将聚合物组合物形成任何合适的制品。
因此,本公开的聚合物组合物特别适合于形成此类制品。可以根据本公开制成的聚合物制品包括例如食品包装中使用的制品、诸如饮用杯的一次性制品、诸如冰箱内衬的大型电器的部件、诸如休闲车面板的汽车部件等。
除了通过热成型来形成聚合物制品之外,本公开的组合物还非常适合于产生泡沫结构。泡沫结构可以使用任何合适的方法来制成。在一个实施方案中,例如,将聚合物组合物加热至熔融状态。熔体强度改性剂可以直接与一种或多种聚丙烯聚合物预配混,或者可以与丙烯聚合物同时添加到挤出机中。类似地,也可以将设计成引起泡沫形成的一种或多种发泡剂和/或成核剂添加到聚合物组合物中。例如,发泡剂可以分散在熔融聚合物组合物中以最终形成泡沫孔。然后可以将包含泡沫孔的聚合物组合物模制成所需的形状,以便形成泡沫制品。例如,泡沫制品可以是一次性饮用杯。
如上所述,除了发泡剂之外,还可以添加成核剂。成核剂可以包括例如滑石、碳酸钙、酰胺诸如脂肪酸酰胺,例如硬脂酰胺。
例如,在一个实施方案中,本公开的聚合物组合物在熔体加工步骤中被加热至熔融状态。例如,在一个实施方案中,熔体加工步骤可以在挤出机中进行。发泡剂包含在聚合物组合物内或与熔融状态的聚合物组合。发泡剂可以包括能够引起泡孔形成的任何合适的发泡剂。发泡剂例如可以是化学发泡剂或物理发泡剂。
添加到聚合物组合物中的发泡剂的量可以取决于各种因素,包括所形成的泡沫的类型和所使用的发泡剂的类型。一般来讲,发泡剂以大于约0.1重量%的量,诸如以大于约0.5重量%的量,诸如以大于约1重量%的量,诸如以大于约2重量%的量,诸如以大于约5重量%的量添加。通常将发泡剂以小于约15重量%的量、诸如以小于约10重量%的量、诸如以小于约8重量%的量、诸如以小于约6重量%的量、诸如以小于约4重量%的量添加到聚合物组合物中。
可以采用的发泡剂(也称为起泡剂或膨胀剂)包括气态材料、挥发性液体和分解成气体和其他副产物的化学试剂。代表性的发泡剂包括但不限于氮气、二氧化碳、异丁烷、环戊烷、空气、氯甲烷、氯乙烷、戊烷、异戊烷、全氟甲烷、氯三氟甲烷、二氯二氟甲烷、三氯氟甲烷、全氟乙烷、1-氯-1,1-二氟乙烷、氯五氟乙烷、二氯四氟乙烷、三氯三氟乙烷、全氟丙烷、氯七氟丙烷、二氯六氟丙烷、全氟丁烷、氯九氟丁烷、全氟环丁烷、偶氮二甲酰胺(ADCA)、偶氮二异丁腈、苯磺酰肼、4,4-苯酚磺酰氨基脲、对甲苯磺酰基氨基脲、偶氮二甲酸钡、N,N′二甲基-N,N′-二亚硝基对苯二甲酰胺、三肼基三嗪、N,N-二亚硝基五亚甲基、柠檬酸衍生物、四胺、5-苯基四唑、亚肼基二甲酰胺、对甲苯磺酰肼或其混合物。发泡剂可以单独使用或与一种或多种其他发泡剂组合使用。
在一个实施方案中,一旦组合发泡剂并加热聚合物组合物,就可以将熔融聚合物组合物挤出并形成所需的形状。
特别有利的是,本公开的聚合物组合物可以热成型为任何合适的形状或形成泡沫结构,而不必使用具有长支链的聚丙烯聚合物。例如,在本公开中使用的聚丙烯聚合物可以是线性的并且可以具有相对低的支化量,诸如<0.001LCB/1000C。
参考以下实施例可以更好地理解本公开。
实施例
配制了各种不同的聚合物组合物并测试了熔体强度。
样品3、4和5
将具有限定的MFR、二甲苯可溶物重量百分比(重量)和多分散性指数的聚丙烯均聚物与0.8重量%、1重量%和2重量%的熔体强度改性剂和另外的抗氧化剂和酸清除剂预混,并在双螺杆挤出机中配混以形成粒料。
样品1和2对比
将按照相同的方法混合的用于制备样品3、4和5的聚丙烯均聚物粉末用于制备样品3、4和5,不同之处在于不使用熔体强度改性剂。
样品6是均聚物,其包含的长支链的水平约为0.2LCB/1000C,并且不含有熔体强度改性剂。
根据ASTM-D 1238测试方法在230℃下用2.16kg的砝码测量熔体流动速率(MFR)。
按照ASTM-D5492测量二甲苯可溶物。
特别是,制备了以下样品:
表1
样品 | MFR | XS | PDI | 规格 |
1 | 2.3 | 6.8 | 5.8 | |
2 | 2.3 | 2.6 | 3.9 | |
3 | 2.4 | 6.7 | 5.8 | 1重量%山梨醇衍生物 |
4 | 2.5 | 6.7 | 5.8 | 2重量%山梨醇衍生物 |
5 | 2.4 | 2.6 | 3.9 | 0.8重量%山梨醇衍生物 |
6 | 1.9 | 3.6 | - | ~0.2LCB/1000C |
然后根据以上定义的测试法测试上述配方。首先,测试了聚合物组合物的剪切致稀因子(STF)。获得了以下结果:
表2
样品 | 零剪切粘度 | SHI | V-E转变温度 | STF | 弹性指数 |
CE1 | 43033 | 0.39 | 无转变 | 86 | 0.11 |
CE2 | 25518 | 0.31 | 无转变 | 35 | 0.05 |
3 | 2E9 | 1.27 | 230 | 4.7E4 | 0.55 |
4 | 1.2E6 | 1.47 | - | 264 | 0.33 |
5 | 1.8E7 | 1.31 | 220 | 1683 | 0.47 |
CE6 | 3.3E6 | 3.0 | 无转变 | 3.8E4 | 0.50 |
参考图1,示出了所测试的样品的振荡流变学。
在不脱离本发明的精神和范围的情况下,本领域的普通技术人员可以对本发明进行这些和其他修改和变化,本发明的精神和范围在所附权利要求中更具体地阐述。此外,应当理解,各个实施方案的方面可以整体或部分地互换。另外,本领域的普通技术人员将理解,前述描述仅是示例性的,并且无意限制在此所附权利要求中进一步描述的本发明。
Claims (24)
1.一种具有增加的熔体强度的聚合物组合物,所述聚合物组合物包含:
与熔体强度改性剂共混的聚丙烯聚合物,所述熔体强度改性剂以足以在所述聚合物组合物被加热至熔融状态时形成渗透网络的量存在于所述聚合物组合物中。
2.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物包含至少90重量%的聚丙烯聚合物。
3.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物具有至少180℃的粘弹性转变温度。
4.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物具有大于0.4的应变硬化指数、大于100的剪切致稀因子和大于0.2的弹性指数。
5.根据权利要求1所述的聚合物组合物,其中所述聚丙烯聚合物包括聚丙烯均聚物。
6.根据权利要求1所述的聚合物组合物,其中所述聚丙烯聚合物包括聚丙烯共聚物。
7.根据权利要求1所述的聚合物组合物,其中所述熔体强度改性剂包括亚苄基山梨醇衍生物。
8.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物具有大于约0.9的应变硬化指数。
9.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物具有大于约120的剪切致稀因子。
10.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物具有约190℃至约230℃的粘度转变温度。
11.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物具有大于约0.4的弹性指数。
12.根据权利要求1所述的聚合物组合物,其中所述熔体强度改性剂包括1,3:2,4-双(3,4-二甲基二亚苄基)山梨醇、1,2,3-三脱氧-4,6:5,7-双-O-[(4-丙基苯基)亚甲基]壬醇、1,3:2,4-双(对硝基亚苄基)山梨醇、(1,3-2,4-二亚苄基山梨醇)、1,3-2,4-双(对甲氧基亚苄基)山梨醇、1,3:2,4-双(间甲氧基亚苄基)山梨醇、1,3:2,4-双(对氯亚苄基)山梨醇、1,3:2,4-双(对甲基亚苄基)山梨醇或其混合物。
13.根据权利要求1所述的聚合物组合物,其中所述熔体强度改性剂以约0.6重量%至约10重量%的量存在于所述聚合物组合物中。
14.根据权利要求1所述的聚合物组合物,其中所述聚丙烯聚合物具有小于约0.001的支化指数。
15.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物除了包含所述熔体强度改性剂之外,还包含引起形成泡沫的成核剂。
16.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物包含发泡剂。
17.根据权利要求16所述的聚合物组合物,其中所述发泡剂包括氮气、二氧化碳、异丁烷、环戊烷、空气、氯甲烷、氯乙烷、戊烷、异戊烷、全氟甲烷、氯三氟甲烷、二氯二氟甲烷、三氯氟甲烷、全氟乙烷、1-氯-1,1-二氟乙烷、氯五氟乙烷、二氯四氟乙烷、三氯三氟乙烷、全氟丙烷、氯七氟丙烷、二氯六氟丙烷、全氟丁烷、氯九氟丁烷、全氟环丁烷、偶氮二甲酰胺(ADCA)、偶氮二异丁腈、苯磺酰肼、4,4-苯酚磺酰基氨基脲、对甲苯磺酰基氨基脲、偶氮二甲酸钡、N,N'-二甲基-N,N'-二亚硝基对苯二甲酰胺、三肼基三嗪、N,N-二亚硝基五亚甲基、柠檬酸衍生物、四胺、5-苯基四唑、亚肼基二甲酰胺、对甲苯磺酰肼或其混合物。
18.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物具有大于约0.9的应变硬化指数、大于约50的剪切致稀因子,具有约180℃至约230℃的粘度转变温度,并具有大于约0.2的弹性指数。
19.一种制品,所述制品由根据权利要求1所述的聚合物组合物制成。
20.一种用于形成聚丙烯泡沫的方法,所述方法包括:
将根据权利要求1所述的聚合物组合物与发泡剂和成核剂组合;以及
将所述聚丙烯组合物加热至足以使所述发泡剂引起形成泡沫孔的熔融状态。
21.根据权利要求20所述的方法,其中所述发泡剂包括氮气、二氧化碳、异丁烷、环戊烷、空气、氯甲烷、氯乙烷、戊烷、异戊烷、全氟甲烷、氯三氟甲烷、二氯二氟甲烷、三氯氟甲烷、全氟乙烷、1-氯-1,1-二氟乙烷、氯五氟乙烷、二氯四氟乙烷、三氯三氟乙烷、全氟丙烷、氯七氟丙烷、二氯六氟丙烷、全氟丁烷、氯九氟丁烷、全氟环丁烷、偶氮二甲酰胺(ADCA)、偶氮二异丁腈、苯磺酰肼、4,4-苯酚磺酰基氨基脲、对甲苯磺酰基氨基脲、偶氮二甲酸钡、N,N'-二甲基-N,N'-二亚硝基对苯二甲酰胺、三肼基三嗪、N,N-二亚硝基五亚甲基、柠檬酸衍生物、四胺、5-苯基四唑、亚肼基二甲酰胺、对甲苯磺酰肼或其混合物。
22.根据权利要求20所述的方法,其中在与所述发泡剂组合之前将所述聚丙烯组合物加热至熔融状态。
23.一种用于热成型聚丙烯聚合物组合物的方法,所述方法包括:
将根据权利要求1所述的聚合物组合物加热至熔融状态;以及
将经加热的聚合物组合物形成模塑制品。
24.一种用于增加聚丙烯聚合物的熔体强度的方法,所述方法包括:
将聚丙烯聚合物与熔体强度改性剂共混以形成聚合物组合物,所述熔体强度改性剂以足以使所述聚合物组合物具有大于约0.4的应变硬化指数和大于约100的剪切致稀因子、大于0.2的弹性指数和大于180℃的粘弹性转变温度的量存在于所述聚合物组合物中。
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- 2018-10-26 US US16/754,794 patent/US20210189085A1/en not_active Abandoned
- 2018-10-26 EP EP18870794.7A patent/EP3700974A4/en active Pending
- 2018-10-26 CA CA3079517A patent/CA3079517A1/en active Pending
- 2018-10-26 JP JP2020523713A patent/JP2021501237A/ja active Pending
- 2018-10-26 KR KR1020207010946A patent/KR20200068669A/ko not_active Application Discontinuation
- 2018-10-26 CN CN201880069118.6A patent/CN111278907A/zh active Pending
- 2018-10-26 WO PCT/US2018/057644 patent/WO2019084360A1/en unknown
- 2018-10-26 US US16/171,437 patent/US20190127552A1/en not_active Abandoned
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CN116218085A (zh) * | 2023-01-03 | 2023-06-06 | 万华化学(宁波)有限公司 | 一种发泡用高熔体强度聚丙烯材料及其制备方法 |
CN116218085B (zh) * | 2023-01-03 | 2024-05-03 | 万华化学(宁波)有限公司 | 一种发泡用高熔体强度聚丙烯材料及其制备方法 |
Also Published As
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WO2019084360A1 (en) | 2019-05-02 |
US20190127552A1 (en) | 2019-05-02 |
RU2020117287A (ru) | 2021-11-29 |
RU2020117287A3 (zh) | 2022-01-27 |
KR20200068669A (ko) | 2020-06-15 |
US20210189085A1 (en) | 2021-06-24 |
EP3700974A1 (en) | 2020-09-02 |
JP2021501237A (ja) | 2021-01-14 |
EP3700974A4 (en) | 2021-09-29 |
CA3079517A1 (en) | 2019-05-02 |
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