CN1646632A - 聚合物改性沥青组合物 - Google Patents

聚合物改性沥青组合物 Download PDF

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CN1646632A
CN1646632A CNA038075040A CN03807504A CN1646632A CN 1646632 A CN1646632 A CN 1646632A CN A038075040 A CNA038075040 A CN A038075040A CN 03807504 A CN03807504 A CN 03807504A CN 1646632 A CN1646632 A CN 1646632A
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D·L·小汉德林
C·L·威利斯
K·E·史蒂芬司
R·Q·克鲁茨
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Abstract

本发明是具有改进相稳定性，热老化和粘度特性的聚合物改性沥青组合物。沥青组合物是包括沥青和0.5－25％新颖阴离子嵌段共聚物的共混物，其中嵌段之一是在共聚物嵌段中具有单体特定排列的共轭二烯烃和单烯基芳烃的受控分布共聚物。本发明的组合物用于铺路、油毡纸、防水隔膜、粘合剂、涂抹沥青、地毯衬垫和管涂料应用。

Description

聚合物改性沥青组合物
发明领域
本发明涉及具有改进的相稳定性、热老化和粘度特性的聚合物改性沥青组合物。特别地，本发明涉及含有一种新颖阴离子嵌段共聚物的组合，其中嵌段之一是在共聚物嵌段中具有单体特定排列的共轭二烯烃和单烯基芳烃的受控分布共聚物。
发明背景
天然或石油衍生的沥青是许多应用的有用材料。然而，沥青自身通常不能满足应用如铺路、油毡纸或防水隔膜的性能要求。因此，已经开发方案，从而将聚合物加入到沥青中以增加性能如低温柔韧性和高温软化点。低温或高温性能的改进导致实际使用的温度范围增加。在一些聚合物改性沥青组合物中，聚合物特别有效和同时发生这些性能增加。除使用温度范围的改进以外，可以达到抗疲劳性耐热断裂和凹陷性能的改进。
在聚合物改性沥青组合物领域中有特别功用的是阴离子乙烯基芳族-共轭二烯烃嵌段共聚物。U.S.专利4129541教导了使用星形苯乙烯-丁二烯嵌段共聚物以改进沥青的低温柔韧性和耐应力开裂性，用于冷温度涂敷应用。
然而，聚合物与沥青组分的有限相容性经常导致不稳定的共混物和因此导致可变和/或较差的性能。
已经采取各种方案以改进阴离子嵌段共聚物与沥青的相容性。在U.S.专利4145322中公开的技术教导了与阴离子嵌段共聚物结合使用硫交联剂。交联的组合物显示优异的高温和低温特性。重要地，阴离子三嵌段共聚物的加入将沥青的固有特征从粘性改变成粘弹性。
硫交联方案的进一步改进教导于U.S.专利5773496，其中阴离子嵌段和星形、或多臂共聚物的结合用于与沥青的共混物。由于二嵌段共聚物的相对高数量，由硫的交联是必须的以达到性能改进，特别地是力延性的改进。在U.S.专利6429241中，教导了达到改进性能的方案，从而由采用共聚物和交联剂增量加入的方法，达到阴离子三嵌段共聚物/沥青共混物硫交联的相对高数量。
尽管导致性能改进，交联以稳定阴离子嵌段共聚物/沥青共混物的方案，仍具有要求额外材料(即交联剂)和引入这些试剂的额外工艺步骤的缺点。当不合适地使用交联剂时，此方法具有导致不合格产物或高度胶凝化产物的进一步缺点。硫交联的进一步不希望的特征是加工期间硫化氢的产生，它呈现环境和健康危险。
通过稳定聚合物改性沥青组合物的形成达到改进性能组的另一种方案是使用增容剂。U.S.专利5331028教导使用缩水甘油化乙烯共聚物作为SBS/沥青共混物的增容剂。在此技术中，官能化乙烯共聚物与沥青反应以形成更易于接收阴离子嵌段共聚物共混的沥青组分。
可用作嵌段共聚物-沥青增容剂的其它官能化聚合物如环氧化聚二烯烃已经教导于U.S.专利5451619和极性聚合物如官能化聚乙烯教导于U.S.专利6100317。
引入增容聚合物以稳定阴离子嵌段共聚物-沥青共混物导致显著的性能改进。然而，此方案要求加入通常昂贵的第三组分。此外，由于生产增容剂所要求的步骤或用于共混入沥青组合物中所要求的那些，共混物的制备方法可能一般是复杂的。
借此在它的初始制造期间改性阴离子嵌段共聚物组合物或结构的更简单方案从工艺和成本观察来看是有吸收力的。U.S.专利4530652和U.S.专利5854335教导了阴离子嵌段共聚物的丁二烯橡胶嵌段改性以达到增强的相容性和性能。特别地，改性橡胶中间嵌段以增加聚合期间丁二烯的1，2-加成。由此方案达到的增加相容性导致在热老化之后增加的性能保持，增加的柔韧性和改进的耐高温流动性能。
现在已经发现含有受控分布橡胶嵌段的阴离子嵌段共聚物具有与沥青的优异相容性，该受控分布橡胶嵌段包括烯基芳烃和共轭二烯烃单体单元。这样的嵌段共聚物及其制备方法描述于以上提及的在先未决、通常拥有的专利申请系列号60/335210。此外，这样组合物的性能特性对于如下各种应用是有吸收力的：铺路、油毡纸、防水隔膜、沥青粘合剂、涂抹沥青、地毯衬垫、消音材料和涂料。
发明概述
本发明是一种沥青组合物，该组合物包括：
(I)75％-99.5％沥青；和
(II)0.5wt％-25wt％含有至少一个A嵌段和至少一个B嵌段的嵌段共聚，其中：
(a)每个A嵌段独立地是单烯基芳烃均聚物嵌段和每个B嵌段独立地是至少一种共轭二烯烃和至少一种单烯基芳烃的受控分布共聚物嵌段；
(b)每个A嵌段的数均分子量为3,000-60,000和每个B嵌段的数均分子量为30,000-300,000；
(c)每个B嵌段包括邻近A嵌段、富含共轭二烯烃单元的末端区域和一个或多个不邻近A嵌段、富含单烯基芳烃单元的区域；
(d)嵌段共聚物中单烯基芳烃的总数量是20-80wt％；和
(e)每个B嵌段中单烯基芳烃的重量百分比是10-75％。
本发明的嵌段共聚物可以是不饱和的或由于氢化反应是选择性、部分或完全饱和的。本发明的优点是具有改进热老化特性和宽使用温度的增加相容性的沥青组合物。此组合物的具体应用是铺路配制剂、油毡纸、防水隔膜、沥青粘合剂、涂抹沥青、管涂料和地毯衬垫。
本发明的详细描述
本发明提供包括新颖阴离子嵌段共聚物的沥青组合物。新颖阴离子嵌段共聚物来自烯基芳烃和二烯烃的共聚，该烯基芳烃和二烯烃作为单烯基芳烃/共轭二烯烃嵌段共聚物的一部分。令人惊奇地，(1)单体加入的独特控制和(2)乙醚或其它改性剂作为溶剂组分(它以下称为“分布剂”)的使用的结合导致两种单体(在此称为“受控分布”聚合，即导致“受控分布”结构的聚合)的某些特性分布，和也导致在聚合物嵌段中某些单烯基芳烃富集区域和某些共轭二烯烃富集区域的存在。对于在此的目的，“受控分布”定义为表示具有如下属性的分子结构：(1)邻近单烯基芳烃均聚物(“A”)嵌段的末端区域，该区域富含共轭二烯烃单元；(2)一个或多个不邻近A嵌段的区域，该区域富含单烯基芳烃单元；和(3)具有相对低嵌段度的总体结构。对于在此的目的，“富含”定义为大于平均数量，优选大于平均数量5％。此受控分布(“B”)嵌段的相对低嵌段度可以由该受控分布嵌段中间体的单一(“Tg”)的存在表现出，当使用差示扫描量热法(“DSC”)(热)方法或通过机械方法分析时，该单一Tg在单独的任一单体的Tg之间，或如通过质子核磁共振(“H-NMR”)方法表现出。也可以在B嵌段聚合期间适于聚苯乙烯基锂端基检测的波长范围内，从UV-可见吸光度的测量推断嵌段度的可能性。此数值的急剧和显著增加表示聚苯乙烯基锂链端的显著增加。在此方法中，这仅在共轭二烯烃浓度下降到保持受控分布聚合所需的临界水平以下才发生。在此点存在的任何苯乙烯单体以嵌段的形式加入。由本领域技术人员使用质子NMR测量的术语“苯乙烯嵌段度”定义为在聚合物链上含有两个S最近邻接部分的聚合物中S单元的比例。在使用H-1 NMR测量两个试验数量之后测量苯乙烯嵌段如下：
首先，通过在7.5-6.2ppm的H-1 NMR光谱中积分总苯乙烯芳族信号和将此数量除以5以解释每个苯乙烯芳族环上的5个芳族氢，测定苯乙烯单元(即当成比例时抵消的任意仪器单元)的总数目。
其次，通过从6.88和6.80之间的信号最小值到6.2ppm的H-1 NMR光谱中积分芳族信号部分和将此数量除以2以解释每个嵌段苯乙烯芳族环上的2个邻位氢，测定嵌段苯乙烯单元。此信号对那些苯乙烯单元的环上两个邻位氢的指定报导于F.A.Bovey，大分子的高分辩率NMR(Academic Press，纽约和伦敦，1972)，第6章，该苯乙烯单元含有两个苯乙烯最近邻接部分。
苯乙烯嵌段度简单地是嵌段苯乙烯对总苯乙烯单元的百分比：
嵌段％＝100乘(嵌段苯乙烯单元/总苯乙烯单元)
这样表达的聚合物-Bd-S-(S)n-S-Bd-聚合物，其中n大于零，定义为嵌段苯乙烯。例如，如果在以上例子中n等于8，则嵌段度指数是80％。优选嵌段度指数小于40。对于苯乙烯含量为10wt％-40wt％的一些聚合物，优选嵌段度指数小于10。
在此使用的“热塑性嵌段共聚物”定义为含有如下嵌段的嵌段共聚物：至少一种或多种单烯基芳烃，如苯乙烯的第一嵌段(A嵌段)及二烯烃和单烯基芳烃受控分布共聚物的第二嵌段(B嵌段)。制备此热塑性嵌段共聚物的方法是通过对于嵌段聚合一般已知的任何方法。本发明包括作为实施方案的热塑性共聚物组合物，它们可以是二嵌段共聚物、三嵌段共聚物、四嵌段共聚物或多嵌段共聚物组合物。在二嵌段共聚物组合物的情况下，一个嵌段是烯基芳烃基均聚物嵌段和与其聚合的是二烯烃和烯基芳烃受控分布共聚物的第二嵌段。在三嵌段共聚物组合物的情况下，它包括作为端嵌段的玻璃性烯基芳烃基均聚物和作为中间嵌段的二烯烃和烯基芳烃受控分布共聚物。在制备三嵌段共聚物组合物的情况下，受控分布二烯烃/烯基芳烃共聚物可以在此指定为“B”和烯基芳烃基均聚物指定为“A”。A-B-A三嵌段共聚物组合物可以由顺序聚合或偶合制备。在顺序溶液聚合技术中，首先将单烯基芳烃引入以生产相对硬的芳族嵌段，随后引入受控分布二烯烃/烯基芳烃混合物以形成中间嵌段，和然后随后引入单烯基芳烃以形成末端嵌段。除线性A-B-A构型以外，可以构造嵌段以形成星形(支化)聚合物(A-B)nX，或可以在混合物中结合两种类型的结构。一些A-B二嵌段聚合物可以存在，但优选至少约70wt％嵌段共聚物是A-B-A或星形的(或另外支化的以每个分子含有2个或更多末端树脂性嵌段)以赋予强度。
受控分布结构在控制所得热塑性弹性体的强度和Tg中非常重要。在受控分布结构中，苯乙烯嵌段度低和这保证实质上没有两种单体的相分离。这与如下的共聚物形成对照：其中单体实际保持为具有单独“微相”并从而具有单独和不同的Tg。由于在受控分布共聚物中仅存在一个Tg，所得共聚物的热性能是可预测的和事实上是预先确定的。
本发明热塑性弹性体二嵌段、三嵌段、多嵌段和星形嵌段共聚物的重要特征是A和B嵌段的单独Tg，该共聚物包括一个或多个受控分布二烯烃/烯基芳烃共聚物嵌段(B嵌段)和一个或多个单烯基芳烃嵌段(A嵌段)。烯基芳烃A嵌段的Tg高于受控分布共聚物B嵌段的Tg。受控分布嵌段的Tg优选是至少-60℃，更优选-40～+30℃，和更优选-40～+10℃。烯基芳烃A嵌段的更高Tg优选+80～+110℃，更优选+80～+105℃。
当这样的受控分布结构用作二嵌段、三嵌段或多嵌段共聚物中的一个嵌段时，通过适当构成的受控分布共聚物区域的存在变为可能的相对更高Tg倾向于改进流动和加工性能。此外，可能的是尽管共轭二烯烃橡胶嵌段中单烯基芳烃的引入导致阴离子嵌段的升高芳族含量，同时保持此嵌段的橡胶性特征。当制备与高度芳族材料如沥青的共混物时，此升高的芳族含量是特别有用的。在此状况下，升高的芳族含量提供共混物的增强相容性，从而允许新结合和/或改进的表现性能。也可达到阴离子嵌段共聚物自身以及与其它材料的共混物的某些其它性能的改进。
在本发明的优选实施方案中，主题受控分布共聚物嵌段含有两个不同的区域：在嵌段端部的共轭二烯烃富集区域和靠近嵌段中间或中心的单烯基芳烃富集区域。希望的是单烯基芳烃/共轭二烯烃受控分布共聚物嵌段，其中单烯基芳烃单元的比例逐渐增加到靠近嵌段中间或中心的最大值。此结构是显著的和不同于现有技术中讨论的渐变和/或无规结构。
如上所讨论的那样，受控分布聚合物嵌段含有邻近A嵌段的二烯烃富集区域和不邻近A嵌段、和典型地靠近B嵌段中心的芳烃富集区域。典型地邻近A嵌段的区域包括嵌段的前15-25％和包括二烯烃富集区域，及剩余部分被认为富集芳烃。术语“二烯烃富集”表示与芳烃富集区域相比，区域具有可测量地高的二烯烃对芳烃比例。表达此的另一种方式是单烯基芳烃单元的比例沿聚合物链逐渐增加到靠近嵌段中间或中心的最大值(如果我们描述ABA结构)和然后逐渐降低直到聚合物嵌段完全聚合。对于受控分布嵌段B，单烯基芳烃的重量百分比是10-75％。
用于制备本发明新颖共聚物的聚合条件典型地相似于一般用于阴离子聚合的那些。用于受控分布嵌段合成的具体聚合过程是一种方法，其中(1)独特地控制单体加入和(2)采用分布剂。可以使用一个双反应器或单一反应器聚合方案制备受控分布嵌段共聚物。本领域技术人员理解的是精确的聚合条件依赖于采用哪个方案。
受控分布嵌段共聚物的烯基芳烃单体可以选自苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、乙烯基萘、和对丁基苯乙烯或其混合物。在这些物质中，苯乙烯是最优选的和可购自各个制造商和相对便宜。在此使用的共轭二烯烃是1，3-丁二烯和取代丁二烯如异戊二烯、戊间二烯、2，3-二甲基-2，3-丁二烯、和1-苯基-1，3-丁二烯、或其混合物。在这些物质中，最优选是1，3-丁二烯。在此使用的和在权利要求中使用的“丁二烯”具体地表示“1，3-丁二烯”。
对于受控分布或B嵌段，对于选择性氢化聚合物，每个B嵌段中单烯基芳烃的重量百分比是10-75wt％，优选25-50wt％。
也重要的是控制各个嵌段的分子量。对于AB二嵌段，所需的嵌段重量对于单烯基芳烃A嵌段为3,000-60,000，和对于受控分布共轭二烯烃/单烯基芳烃B嵌段为30,000-300,000。优选的范围对于A嵌段为5000-45,000和对于B嵌段为50,000-250,000。对于三嵌段，它可以是顺序ABA或偶合(AB)2X嵌段共聚物，A嵌段应当是3,000-60,000，优选5000-45,000，而对于顺序嵌段的B嵌段应当是30,000-300,000，和对于偶合聚合物的B嵌段(两个)为该数量的一半。三嵌段共聚物的总平均分子量应当为40,000-400,000，和对于星形共聚物为60,000-600,000。对于四嵌段共聚物ABAB，末端B嵌段的嵌段尺寸应当是2,000-40,000，和其它嵌段可以类似于顺序三嵌段的尺寸。这些分子量最精确地由光散射测量测定。
本发明的另一个重要方面是控制受控分布共聚物嵌段中共轭二烯烃的微结构或乙烯基含量。术语“乙烯基含量”表示通过1，2-加成(在丁二烯的情况下-在异戊二烯的情况下它是3，4-加成)聚合共轭二烯烃。尽管纯“乙烯基”仅在1，3-丁二烯的1，2-加聚情况下形成，异戊二烯3，4-加聚(和对于其它共轭二烯烃的相似加成)对嵌段共聚物最终性能的影响相似。术语“乙烯基”表示聚合物链上侧乙烯基的存在。当指丁二烯作为共轭二烯烃应用时，优选共聚物嵌段中20-80mol％的缩合丁二烯单元具有由质子NMR分析测定的1，2乙烯基构型。对于选择性氢化的嵌段共聚物，优选地30-70mol％的缩合丁二烯单元应当具有1，2构型。对于不饱和嵌段共聚物，优选地20-40mol％的缩合丁二烯单元应当具有1，2乙烯基构型。这有效地通过改变分布剂的相对数量而控制。聚合期间使用的分布剂典型地是非螯合性醚诸如乙醚或邻二甲氧基苯。如理解的那样，分布剂起两个目的-它产生单烯基芳烃和共轭二烯烃的受控分布，和也控制共轭二烯烃的微结构。分布剂对锂的合适比例公开和教导于US Pat.Re27145，它的公开内容引入作为参考。
星形(支化)聚合物的制备要求称为“偶合”的聚合后步骤。在以上星形通式中，n是2-30，优选2-15的整数，和X是偶合剂的剩余部分或残基。各种偶合剂是本领域已知的和包括例如二卤代烷烃、卤化硅、硅氧烷、多官能环氧化物、二氧化硅化合物、一元醇与羧酸的酯、和环氧化油。星型聚合物采用多烯基偶合剂制备，如例如在U.S.专利号3985830、4391949、和4444953，加拿大专利号716645中公开的那样。合适的多烯基偶合剂包括二乙烯基苯，和优选间二乙烯基苯。优选是四烷氧基硅烷如四乙氧基硅烷(TEOS)，脂族二酯如己二酸二甲酯和己二酸二乙酯，和二缩水甘油基芳族环氧化合物如衍生自双酚A和环氧氯丙烷反应的二缩水甘油醚。
可用于进一步改性聚合物构型和因此改进它们性能的另外可能的聚合后处理包括封端和链终止。封端剂，如环氧乙烷、二氧化碳、或其混合物用于向链末端加入官能团，其中它们然后可用作进一步性能改进反应的反应部位。相反，链终止简单地阻止进一步的聚合和因此阻止分子量生长超过所需的点。或者，活性共聚物可简单地氢化以失活金属部位。
应当注意到，在本发明的仍然另一个实施方案中，可以通过仍然另一个聚合后处理，通过嵌段共聚物氢化达到其组合物的另外性能改进。优选的氢化是最终嵌段共聚物二烯烃部分的选择性氢化。或者可以氢化B嵌段和A嵌段两者，或可以仅氢化一部分B嵌段。氢化一般改进最终聚合物的热稳定性，紫外光稳定性，氧化稳定性，和由此的耐侯性。本发明的主要优点在于分布剂，如非螯合单醚，它在初始聚合工艺期间存在，不干扰或另外“毒害”氢化催化剂，和因此避免任何附加脱除步骤的需要。
可以通过本领域已知的任何几种氢化或选择性氢化方法进行氢化。例如，使用方法如在例如如下文献中教导的那些完成这样的氢化：U.S.专利3595942、3634549、3670054、3700633、和Re.27145，该文献的公开内容在此引入作为参考。
氢化可以在一定的条件下进行使得减少至少90％的共轭二烯烃双键，和减少0-10％的芳烃双键。优选的范围是减少至少95％的共轭二烯烃双键，和更优选减少至少98％的共轭二烯烃双键。或者，可以氢化聚合物使得芳族不饱和度也减少超过上述10％水平。这样的完全氢化作用通常在较高温度取得。在该情况下，共轭二烯烃和芳烃两者的双键可以减少90％或更多。
另外，可以采用许多方式官能化本发明的嵌段共聚物。一种方式是采用含有一个或多个官能团或它们的衍生物，如羧酸基团和它们的盐、酸酐、酯、酰亚胺基团、酰胺基团、和酰氯的不饱和单体处理。要接枝到嵌段共聚物上的优选单体是马来酸酐、马来酸、富马酸、和它们的衍生物。官能化这样的嵌段共聚物的进一步描述可以发现于Gergen等人，U.S.Pat.No.4578429和发现于U.S.Pat.No.5506299。在另一种方式中，可以通过接枝含硅或硼化合物到聚合物上官能化本发明的选择性氢化嵌段共聚物，如在U.S.Pat.No.4882384中教导的那样。在仍然另一种方式中，可以将本发明的嵌段共聚物与烷氧基硅烷化合物接触，以形成硅烷改性的嵌段共聚物。在仍然另一种方式中，可以通过接枝至少一个环氧乙烷分子到聚合物上，如在U.S.Pat.No.4898914中教导的那样，或通过聚合物与二氧化碳反应，如在U.S.Pat.No.4970265中教导的那样官能化本发明的嵌段共聚物。仍然进一步地，可以金属化本发明的嵌段共聚物，如在U.S.Pat.No.5206300和5276101中教导的那样，其中将聚合物与烷基碱金属，如烷基锂接触。和仍然进一步地，可以通过接枝磺酸类基团到聚合物上官能化本发明的嵌段共聚物，如在U.S.5516831中教导的那样。在此段落中提及的所有专利引入本申请作为参考。
在根据本发明的沥青组合物中存在的沥青组分，也称为沥青，可以是天然沥青或衍生自矿物油。同样由裂化工艺和煤焦油获得的石油沥青可以用作沥青组分以及各种沥青材料的共混物。合适组分的例子包括蒸馏或“直馏沥青”、沉淀沥青，如丙烷沥青、吹制沥青，如催化吹制沥青或“Multiphalt”、及其混合物。其它合适的沥青组分包括一种或多种这些沥青与填充剂(稀释剂)如石油提取物，如芳族提取物、馏出物或残余物，或与油的混合物。合适的沥青组分(“直链沥青”或“加过稀释剂的沥青”)是在25℃下针入度为50-300dmm(“分毫米”或根据ASTMD-5的“单位”)的那些。在其中产物的柔韧性，粘性或粘合力具有高度重要性的应用中，特别使用25℃下针入度大于300dmm的加过稀释剂的沥青。本发明的聚合物可用于从硬质沥青到半液体沥青的宽范围。
聚合物改性剂在沥青组合物中的存在量合适地为0.5-25wt％。聚合物含量的下范围对于应用，如铺路是特别感兴趣的，它要求沥青特征从粘性向粘弹性的变化。性能的此变化一般随0.5％-8％的聚合物含量而发生。在到25％的更高聚合物含量下，可以达到柔韧性和弹性强度的显著增加。这对于油毡纸、粘合剂和防水隔膜应用是特别感兴趣的。
沥青组合物也可非必要地包含其它成分，如设想的最终用途要求的那些。因此可以包括填料，例如滑石、聚集体、碳酸钙和炭黑，或可以引入包括树脂、油、稳定剂或阻燃剂的其它组分。这样的填料和其它组分的含量可以为从0到多至90wt％。当然，如果有利的话，其它聚合物改性剂也可以包括在本发明的沥青组合物中。
与改进耐老化性结合的本发明聚合物-沥青共混物的有用低温和高温性能，使得这样的共混物在如下用途中具有显著的益处：其中将共混物曝露于外部气侯条件，如用于盖屋顶应用，例如作为油毡纸的组分。有用低的高温粘度不仅仅意味着聚合物-沥青共混物可以更容易地加工，而且也意味着它们能够在达到最大可允许加工粘度之前引入更大数量的填料，和因此在其中通常使用填料的那些应用中导致更便宜的产物。
本发明中固有的粘弹性特征能够实现作为热混合铺路水泥的应用。在热混合铺路水泥中，将沥青组合物与相对大数量聚集体混合。聚集体一般由沙子，岩石和细粒组成。沥青组合物一般构成总热混合铺路水泥的1-20wt％。
本发明的受控分布嵌段共聚物特别用于沥青粘合剂应用。沥青粘合剂应用包括3-20wt％聚合物，5-50wt％填料(如石灰石、碳酸钙、炭黑)和轻质的低粘度沥青组分。沥青粘合剂用于要求防潮性的室外应用，和一般具有良好的流动和高粘性与对其它沥青基材料和一般对建筑材料的特别良好粘合。
涂抹沥青是实施方案的一种特别有用的应用，其中受控分布嵌段共聚物由氢化饱和。由于饱和的受控分布嵌段共聚物特别耐热氧化降解，它们比涂抹沥青中的不饱和聚合物更稳定，该涂抹沥青被加热到高温，保持在高温下，和在高温下施涂。涂抹沥青一般包括5-15wt％沥青和85-95wt％聚合物。涂抹沥青的聚合物改性一般导致异常的粘性，在宽温度范围内稳定的软化点和异常的粘合强度，弹性恢复和拉伸伸长率。
其中本发明沥青组合物可能有用的其它应用是消声和振动衰减应用、密封剂或涂料应用、和管涂料和地毯衬垫。
实施例
用于这些实施例共混物的沥青材料在表1中表征。在这些实施例中与沥青共混的聚合物在表2中表征。表1中列出的本发明聚合物和对比聚合物两者由苯乙烯A嵌段组成。在本发明聚合物的情况下，B嵌段是由丁二烯和苯乙烯组成的受控分布共聚物嵌段。在对比聚合物的情况下，B嵌段仅由丁二烯组成。没有一种表1的聚合物是选择性氢化的。
根据如下过程制备展示本发明的聚合物改性沥青配制剂。采用Silverson L4R高剪切混合机制备沥青和聚合物的共混物。将沥青加热到150-180℃和随后在几分钟时间内加入聚合物。在混合时，温度增加到170-200℃，它由从混合机的机械能输入引起。在此温度下的共混持续到获得均匀的共混物。由共混物稠度的目测观察监测共混物的均匀性。在混合45-90分钟之后达到均匀性。
在表3中显示具有相对低聚合物含量的配制剂1-12。在表4中显示具有相对高聚合物含量的配制剂13-19。
根据ASTM D-5测量净沥青和聚合物改性沥青的针入度。根据ASTMD-36测量净沥青和聚合物改性沥青的环球软化点。根据ASTM D-5892测量静态贮存稳定性。
                                     表1
沥青ID 描述，公称 通用相容性 相对粘度 针入度(dmm) 环球软化点(℃)
沥青I  AC-30级沥青 相容 高 46  138
沥青II  AC-5级沥青 相容 低 111  125
沥青III  PG 64-22级沥青 中度不相容 高 56  131
PG＝性能等级
                                         表2
聚合物ID 类型 PSC(％) MW A嵌段 MW B嵌段 B嵌段中的％S 1，2-丁二烯 NMR嵌段度 计算的B嵌段度 CE(％)
聚合物29 星形 66  21.4  113  53  19  66  40  82
聚合物30 星形 49  21.2  114  28  19  74  37  81
对比A 星形 30  21.0  98  0  8  NA  NA  84
聚合物16 线性 42  15.5  116  28  23.5  56  12  ＞90
聚合物17 线性 63  15.6  100  50  24.6  45  11  ＞90
聚合物18 线性 40  11.7  101  25  22.8  59  22  70
对比B 线性 31  16.1  72  0  8  NA  NA  84
NA＝不可应用，中间嵌段整个由丁二烯单体组成。
MW B嵌段＝受控分布共聚物嵌段的总分子量。
B嵌段中的％S＝由缩合苯乙烯单体组成的B嵌段的重量百分比。
CE＝偶合效率
                                    表3
                                     配制剂
组分  1  2  3  4  5  6  7  8  9  10  11  12
聚合物29  3  3
聚合物30  3  3
聚合物16  3
聚合物17  3
聚合物18  3
对比A  3  3
对比B  3
沥青I  100  97  97  97  97  97  97  97
沥青II  100  97  97  97
数字表示所示组分的重量百分比。
                     表4
               配制剂
组分 13  14  15  16  17  18  19
聚合物29  12
聚合物30  12
聚合物16  12
聚合物17  12
聚合物18  12
对比A  12
对比B  12
沥青I
沥青II  88  88  88  88  88  88  88
数字表示所示组分的重量百分比。
实施例1.
对配制剂14-19测量平均针入度和环球软化点并分别显示于表5和6。将配制剂在密闭容器中在70℃下老化指示的时间。在老化样品的顶部和底部区段上进行针入度和环球软化点两个测量。表中报告的测量值表示这些测量的平均值。采用沥青II制备所有这些配制剂。未改性沥青II在25℃下的针入度是111。未改性沥青II的环球软化点是125°F。由降低的针入度数值证明针入度的改进。由增加的数值证明环球软化点的改进。表5和6的数值显示由受控分布嵌段共聚物的引入，针入度和环球软化点两者相对于未改性沥青得到改进。
                             表5
                      在25℃下的针入度(dmm)
                           配制剂
老化天数     14     15     16     17     18     19
    0     44     49     43     49     55     49
    28     23     26     17     25     30     28
    42     22     19     41     24     26     25
    63     29     45     55     47     36     50
表5的数据显示在63天热老化时间内保持针入度的改进。表6的数据显示在63天热老化时间内保持如由环球软化点证明的高温性能的改进。在热老化期间的改进保持说明聚合物与沥青的良好相容性。
                                           表6
                                     环球软化点(°F)
                                 配制剂
  老化天数     13     14     15     16     17     18     19
    0     256     221     242     240     236     221     197
    28     246     224     236     223     224     206     198
    42     246     212     236     220     232     208     196
    63     210     230     244     241     228     216     195
实施例2
使用ASTM D-5892的静态贮存稳定性方法评价配制剂的相容性。配制剂在管中在163.5℃下老化48小时。然后将它们骤冷到-6.7℃下4小时。然后将管状样品切成三分之一和测量顶部和底部三分之一的环球软化点。在试验的热老化部分期间，聚合物改性的沥青倾向于分离成聚合物富集顶部层和沥青富集底部层。这发生的程度依赖于聚合物与沥青的相容性。当聚合物与沥青非常相容时，在顶部和底部层之间的性能差异小。在表7中列出在顶部和底部层环球软化点之间的差异。
                                     表7
                          在升高的热老化之后的环球软化点
配制剂ID     沥青     聚合物 聚合物含量，(％)          环球软化点，(°F)
    顶部     底部     差异
    7     III     对比A     3     208     139     69
    4     III     聚合物30     3     153     140     13
    3     III     聚合物29     3     143     135     8
    8     I     对比A     3     208     143     66
    6     I     聚合物30     3     158     142     17
    5     I     聚合物29     3     145     138     7
    9     I     对比B     3     190     143     48
    10     I     聚合物16     3     193     144     50
    12     I     聚合物18     3     172     146     27
    11     I     聚合物17     3     162     145     17
    16     II     对比B     3     236     169     68
    17     II     聚合物16     3     228     216     12
    19     II     聚合物18     3     196     188     8
    18     II     聚合物17     3     200     168     33
表7的数据显示对于包含对比聚合物的配制剂，存在顶部和底部测量值之间的相对大差异。对比聚合物不含有受控分布中间嵌段。在对比聚合物的橡胶嵌段中没有分散苯乙烯单体单元。采用含有受控分布嵌段的聚合物，根据本发明的相容性改进由顶部和底部测量值之间的较小差异证明。
实施例3(预示的)
为制备沥青粘合剂，将55重量份AC-3级沥青加热到150℃。使用表2中列出的本发明的任何一种未氢化聚合物。或者，可以使用表2中聚合物的氢化类似物。高剪切Silverson L4R混合机用于分散10重量份聚合物，同时在5分钟时间内将它加入到热沥青中。混合持续60分钟和在混合期间将温度保持在180℃。中断高剪切混合。将沥青-聚合物混合物保持在180℃下和将35重量份细粉碎的石灰石在低剪切混合条件下加入。低剪切混合持续直到石灰石均匀分散。一旦混合完成，使混合物冷却到室温。
根据ASTM D1970和ASTM D6135测试沥青粘合剂的性能。本发明沥青粘合剂的伸长率大于10％，柔韧性温度低于-29℃，在4.4℃下对胶合板的粘合力大于0.92kfg/30.5cm试样宽度，和水汽渗透率小于5.7ng/Pa.S.M2。
实施例4(预示的)
为制备涂抹沥青，将92重量份AC-10级沥青加热到180℃。在高剪切条件下使用Silverson L4R混合机，将8重量份星形或线性的氢化的受控分布嵌段共聚物加入到热沥青中。在5分钟时间内加入聚合物。将混合物混合和保持在200℃下60分钟。停止混合和使涂抹沥青配制剂冷却。
根据ASTM D 6152测试涂抹沥青的性能。本发明涂抹沥青的软化点为85-116℃，在热老化之后软化点变化为5℃或更小，在25℃下针入度为20-60dmm和在热老化之后针入度降低不大于5个单位或针入度增加不大于12个单位，在25℃下拉伸伸长率为750％和弹性恢复为80％。

Claims (10)

1.一种沥青组合物，包括：
(I)75％-99.5％沥青；和
(II)0.5wt％-25wt％含有至少一个A嵌段和至少一个B嵌段的嵌段共聚物，其中：
(a)每个A嵌段独立地是单烯基芳烃均聚物嵌段和每个B嵌段独立地是至少一种共轭二烯烃和至少一种单烯基芳烃的受控分布共聚物嵌段；
(b)每个A嵌段的数均分子量为3,000-60,000和每个B嵌段的数均分子量为30,000-300,000；
(c)每个B嵌段包括邻近A嵌段、富含共轭二烯烃单元的末端区域和一个或多个不邻近A嵌段、富含单烯基芳烃单元的区域；
(d)嵌段共聚物中单烯基芳烃的总数量是20-80wt％；和
(e)每个B嵌段中单烯基芳烃的重量百分比是10-75％。
权利要求1的沥青组合物，其中该单烯基芳烃是苯乙烯和该共轭二烯烃选自异戊二烯和丁二烯。
2.根据权利要求1的沥青组合物，其中该共轭二烯烃是丁二烯，和其中嵌段B中20-80mol％的缩合丁二烯单元具有1，2-构型。
3.根据权利要求1的沥青组合物，其中嵌段B的苯乙烯嵌段度指数小于40mol％，该苯乙烯嵌段度指数定义为在聚合物链上含有两个苯乙烯邻接部分的嵌段B中苯乙烯单元的比例。
4.根据权利要求1-4任意一项的沥青组合物，其中嵌段共聚物具有通用构型(A-B)n、(A-B-A)n、(A-B)nX或(A-B-A)nX及其混合，其中X是偶合剂残基和n是1-30的整数。
5.根据权利要求1-5任意一项的沥青组合物，其中嵌段共聚物是选择性、部分或完全氢化的。
6.根据权利要求1-6任意一项的沥青组合物，其中嵌段共聚物是0.5-8wt％。
7.根据权利要求1-6任意一项的沥青组合物，其中嵌段共聚物是8wt％-25wt％。
8.根据权利要求1-8任意一项的沥青组合物，其中沥青在25℃下的针入度为40-120dmm。
9.根据权利要求1-8任意一项的沥青组合物，其中沥青的环球软化点是110-150℃。
10.铺路配制剂、油毡纸、防水隔膜、粘合剂、管涂料、地毯衬垫、或涂抹沥青，包括权利要求1-10任意一项的沥青组合物。
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CN102190957A (zh) * 2011-03-21 2011-09-21 武汉理工大学 一种镁铝基层状双氢氧化物耐老化弹性体改性沥青涂盖料及其制备方法
CN102190957B (zh) * 2011-03-21 2013-04-24 武汉理工大学 一种镁铝基层状双氢氧化物耐老化弹性体改性沥青涂盖料及其制备方法
CN104428366A (zh) * 2013-07-05 2015-03-18 Lg化学株式会社 具有改善的混合性能的沥青改性剂和含该沥青改性剂的沥青组合物
CN104428366B (zh) * 2013-07-05 2017-09-19 Lg化学株式会社 具有改善的混合性能的沥青改性剂和含该沥青改性剂的沥青组合物
CN105899562A (zh) * 2014-01-17 2016-08-24 旭化成株式会社 聚合物和沥青组合物
CN105899562B (zh) * 2014-01-17 2019-05-28 旭化成株式会社 聚合物和沥青组合物
CN106398618A (zh) * 2016-08-27 2017-02-15 安徽天瞳智能科技有限公司 一种高密度树脂胶粘剂
CN115948121A (zh) * 2023-01-05 2023-04-11 江苏凯伦建材股份有限公司 一种基于单环氧封端二嵌段共聚物的改性沥青涂料及其制备方法和应用
CN115948121B (zh) * 2023-01-05 2023-10-20 江苏凯伦建材股份有限公司 一种基于单环氧封端二嵌段共聚物的改性沥青涂料及其制备方法和应用

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