CN103975004A - 高压缩强度挤塑san泡沫 - Google Patents

高压缩强度挤塑san泡沫 Download PDF

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CN103975004A
CN103975004A CN201280059636.2A CN201280059636A CN103975004A CN 103975004 A CN103975004 A CN 103975004A CN 201280059636 A CN201280059636 A CN 201280059636A CN 103975004 A CN103975004 A CN 103975004A
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polymer composition
weight
foaming
polymeric foam
foam
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R·E·史密斯
S·A·多纳蒂
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Dow Global Technologies LLC
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Abstract

利用可发泡聚合物组合物制备挤塑聚合泡沫，所述可发泡聚合物组合物包含具有苯乙烯-丙烯腈共聚物的聚合物组合物、只具有1,1,1,2-四氟乙烷(74-78重量％)、二氧化碳(13-16重量％)和水(7-9重量％)的发泡剂组合物，其中所述浓度相对于总发泡剂重量，和基于可发泡聚合物组合物重量小于0.5重量％的填充剂，通过利用发泡温度为120-125摄氏度的挤出发泡方法产生聚合泡沫，所述聚合泡沫的密度为29-37千克/立方米并且以千帕斯卡计的垂直压缩强度量值超过比以千克/立方米计的泡沫密度的量值与25.9的乘积减520。

Description

高压缩强度挤塑SAN泡沫
技术领域
本发明涉及制备具有高压缩强度的挤塑聚合泡沫的方法。
背景技术
聚合泡沫以许多不同的方式用于建筑业，包括承重应用例如在公路结构中、屋面应用和地质技术应用。用于承重应用的聚合泡沫比用作例如垂直空腔绝缘的聚合泡沫需要更高的压缩强度。提高聚合泡沫压缩强度性质的一种方法是通过增加聚合泡沫的密度。增加泡沫密度增加了孔之间的棱或孔壁中的聚合物量并从而提高压缩强度。然而，在理想的高压缩强度的应用中，高绝热性质经常是所希望的。泡沫密度增加到超过每立方米大约48千克易于造成泡沫的绝热性质降低，这是不期望的。泡沫中聚合物的增加也增加了由此产生的聚合物泡沫超过较低密度泡沫的成本。因此，通过增加泡沫密度来获得较高的压缩强度不是所期望的。
美国专利4,840,976(‘976)公开了利用包含氯乙烷的发泡剂制造的高压缩强度泡沫。氯化发泡剂由于环境顾虑已经变成不期望的发泡剂。
美国专利5,006566(‘566)公开了利用包含80-100％二氧化碳的发泡剂的高压缩强度泡沫。二氧化碳是在制备聚合泡沫中用起来具有挑战性的发泡剂，因此在发泡剂中希望最小化二氧化碳的量。
找到制备聚合泡沫的方法，所述泡沫的密度低于48千克/立方米、尤其低于40千克/立方米并且甚至更期望37千克/立方米或更低，并且垂直压缩强度超过在这样的密度下以其它方式可达到的垂直压缩强度，同时避免使用氯化发泡剂并通过使用基于总发泡剂重量二氧化碳小于20重量％的发泡剂组合物，这将是承重聚合泡沫领域的进步。特别地，希望获得这样的泡沫，它具有275千帕斯卡或更高的垂直压缩强度和37千克/立方米或更低的密度。
发明内容
本发明通过确定制备聚合泡沫的方法，提供了聚合泡沫领域的进步，所述泡沫的密度低于48千克/立方米、尤其低于40千克/立方米并且甚至更期望37千克/立方米或更低，并且垂直压缩强度超过在这样的密度下以其它方式可达到的垂直压缩强度，同时避免使用氯化发泡剂并通过使用基于总发泡剂重量小于20重量％二氧化碳的发泡剂组合物。本发明的方法可以制备这样的泡沫，它具有275千帕斯卡或更高、甚至350千帕斯卡或更高的垂直压缩强度和同时37千克/立方米或更低的密度。
令人惊讶地，本发明起因于以下发现：特定聚合物组合物结合特定发泡剂组合物和特定发泡温度产生了具有垂直压缩强度和密度的理想组合的挤塑聚合泡沫。
在第一个方面，本发明是制备挤塑聚合泡沫的方法，所述方法包括以下步骤：(a)在混合温度和混合压力下在挤出机中提供包含聚合物组合物和发泡剂组合物的可发泡聚合物组合物；(b)将所述可发泡聚合物组合物冷却到低于所述混合温度的发泡温度；和(c)将所述可发泡聚合物组合物在发泡温度下通过挤出模头驱出到发泡压力下的环境中，所述发泡压力低于所述混合压力并且足够低以允许所述可发泡聚合物组合物膨胀成聚合泡沫；其中所述方法特征在于包含烯基芳族聚合物的聚合物组合物，所述烯基芳族聚合物的至少一种是苯乙烯-丙烯腈共聚物，并且所述发泡剂组合物由74-78重量％的1,1,1,2-四氟乙烷、13-16重量％二氧化碳和7-9重量％水组成，其中重量％基于总发泡剂组合物重量，所述可发泡聚合物组合物基于可发泡聚合物组合物重量包含小于0.5重量％的填充剂，所述发泡温度在120-125摄氏度的范围内，并且由此产生的聚合泡沫通过ASTMD1622测定的密度为29千克/立方米或更高且37千克/立方米或更低，以及通过ASTM D1621测定的以千帕斯卡计的垂直压缩强度，其量值超过25.9和以千克/立方米计的泡沫密度的量值的乘积减520。
本发明的方法可用于制备具有高压缩强度的挤塑聚合泡沫。
具体实施方式
当试验方法编号没有指明日期时，所述试验方法是指本文件的优先权日为止最新近的试验方法。参考试验方法包括参考试验协会和试验方法编号二者。本文中采用以下试验方法缩写和标识符：ASTM是指美国试验和材料协会(American Society for Testing and Materials)；EN是指欧洲标准(European Norm)；DIN是指德国标准协会(DeutschesInstitute fur Normung)；和ISO是指国际标准组织(InternationalOrganization for Standards)。
“多个”是指两个或更多个。“和/或”是指“和，或者作为替代”。所有的范围包括端点在内，除非另外指出。
本方法是挤塑泡沫方法。挤塑泡沫方法需要在混合温度和混合压力下的挤出机中提供包含聚合物组合物和发泡剂组合物的可发泡聚合物组合物；将所述可发泡聚合物组合物冷却到低于所述混合温度的发泡温度，并然后将所述可发泡聚合物组合物在发泡温度下通过挤出模头驱出并进入发泡压力下的环境中。所述发泡压力低于所述混合压力并且足够低从而允许所述可发泡聚合物组合物膨胀成聚合泡沫。
所述挤塑方法可以是挤出发泡领域中任何已知的，只要满足本文中阐述的条件即可。例如，所述挤出发泡方法可以使用常规的双挤出机串联系统，每个挤出机具有单个螺杆。可替换地，所述挤出发泡方法可以是双挤出机串联系统，其中第一挤出机是双螺杆的而第二挤出机具有单螺杆。恰当冷却的单螺杆挤出机也可以适合用于本发明中。
本发明的聚合物组合物由所述可发泡聚合物组合物中的所有聚合物组成并且特征为包含烯基芳族聚合物，所述烯基芳族聚合物的至少一种是苯乙烯-丙烯腈(SAN)共聚物。所述可发泡聚合物组合物可以包含除烯基芳族聚合物以外的聚合物或只由烯基芳族聚合物组成。理想地，所述聚合物组合物相对于总的聚合物组合物重量具有超过50重量％(wt％)、优选75wt％或更多、还更优选85wt％或更多、并且仍更优选90wt％或更多的烯基芳族聚合物。相对于总的聚合物组合物重量，所述聚合物组合物可以具有95wt％或更多、98wt％或更多并且甚至100wt％烯基芳族聚合物。所述烯基芳族聚合物理想地选自SAN共聚物和聚苯乙烯均聚物。最优选地，所述烯基芳族聚合物是SAN共聚物。理想地，所述聚合物组合物具有热塑性聚合物的连续相，其优选是至少90wt％热塑性聚合物并可以完全是热塑性聚合物。
在本发明的一种实施方式中，所述聚合物组合物由烯基芳族聚合物以及相对于总的聚合物组合物重量最多5wt％、优选最多1wt％、甚至更优选最多0.5wt％聚乙烯(理想地是线性低密度聚乙烯)组成。聚乙烯经常有利地作为添加剂的载体树脂存在并且有时作为孔尺寸控制剂存在。
相对于聚合物组合物的总重量，共聚丙烯腈(AN)理想地以10wt％或更高，优选13wt％或更高，并且同时理想地20wt％或更低，优选17wt％或更低的浓度存在。最理想地，所述共聚AN相对于所述聚合物组合物的总重量以14-16wt％并最优选15wt％的浓度存在。在这方面，所述聚合物组合物可以包含具有不同量的共聚AN的SAN共聚物，和/或SAN共聚物与不含共聚AN的聚合物的共混物，然而基于总聚合物组合物重量，共聚AN总量理想地落在这些范围内。例如，所述聚合物组合物可以由等量的包含12wt％共聚AN的SAN共聚物和包含16wt％共聚AN的SAN共聚物组成，以形成共聚AN浓度为14wt％的聚合物组合物。所述聚合物组合物中共聚AN的总量，与任何一种共聚物中的相比，是重要的。如果AN的浓度超过所述SAN共聚物重量的20wt％，所述聚合物组合物变得难以发泡。如果AN的浓度小于10wt％，本发明的发泡剂组合物的溶解性变得如此低，使它难以达到期望的泡沫密度并且均一的孔结构变得难以实现。利用傅立叶变换红外(FTIR)光谱学，按照Sargent等在Styrene-Acrylonitrile Copolymers，Applied Spectroscopy，45，10，pp.1726-1732(1991)中的教导测量相对FTIR峰值吸收强度，来测定AN相对于聚合物组合物总重量的浓度。
另外，理想地，相对于总的SAN共聚物重量，所述聚合物组合物中的SAN共聚物具有的共聚AN浓度为5wt％或更高、优选10wt％或更高并更优选13wt％或更高，并且同时25wt％或更低、优选20wt％或更低并且还更优选17wt％或更低。还更理想地，所述SAN共聚物相对于总的SAN共聚物重量具有14-16wt％并且最期望15wt％的共聚AN浓度。具有在这些浓度范围中的共聚AN的SAN共聚物提供了向总的聚合物组合物提供AN并且在挤出发泡管线中仍然保持容易加工这两种益处。当共聚AN的量超过共聚物重量的25wt％时，所述共聚物变得难以在挤出发泡过程中加工。利用如上所述的FTIR光谱学测定SAN共聚物中AN的浓度。
除了这些优选的共聚AN水平之外，还期望所述SAN共聚物的重均分子量(Mw)为115,000克/摩尔(g/mol)或更高，优选125,000g/mol或更高，并且还更优选128,000g/mol或更高，并同时为180,000g/mol或更低，优选150,000g/mol或更低，还更优选140,000或更低，仍更优选132,000或更低。最理想地，所述SAN共聚物的Mw为130,000g/mol加或减1000g/mol。如果Mw低于115,000g/mol，所述可发泡聚合物组合物难以膨胀成所期望的泡沫厚度。如果Mw超过180,000g/mol，则所述可发泡聚合物组合物的粘度变得如此高，使其难以制备优质的泡沫。根据ASTM D5296-11测定SAN共聚物的Mw。
所述SAN共聚物的特征还可在于多分散指数(Mw/Mn)，这是所述共聚物的Mw与数均分子量(Mn)的比率。理想地，所述SAN共聚物的Mw/Mn为2.0或更高，优选2.1或更高，还更优选2.2或更高，并且同时为2.9或更低，优选2.7或更低，还更优选2.5或更低。最理想地，所述SAN共聚物的Mw/Mn为大约2.35。根据ASTM D5296-11测定SAN共聚物的Mn。
本发明的发泡剂组合物由三种发泡剂的组合构成：1,1,1,2-四氟乙烷(HFC-134a)，二氧化碳和水。HFC-134a的量是总发泡剂组合物重量的74wt％或更多，优选75wt％或更多，并可以是76wt％或更多，而同时是78wt％或更低，优选77wt％或更低。二氧化碳的浓度是总发泡剂组合物重量的13wt％或更高，优选14wt％或更高，并同时是16wt％或更低，且可以是15wt％或更低。水的浓度是总发泡剂组合物重量的7wt％或更高并且9wt％或更低。HFC-134a、二氧化碳和水的总和占总发泡剂组合物的100wt％。
除了所述聚合物组合物和发泡剂组合物之外，所述可发泡聚合物组合物还可以包含其他添加剂。例如，所述可发泡聚合物组合物可以包含以下任何一种或超过一种的任何组合：阻燃剂(例如，溴化聚合物和含磷化合物)，抗氧化添加剂(例如，主要和辅助抗氧化剂及其掺合物)，成核剂(例如滑石、硅酸镁和碳酸钙)，挤出助剂(例如硬脂酸锌和硬脂酸钡)，红外衰减剂(例如石墨和炭黑)，和着色剂。其他添加剂的总量相对于总聚合物组合物重量理想地小于2wt％。此外，基于总聚合物组合物重量，不溶于所述聚合物组合物的SAN共聚物中的其他添加剂的总量是0.5wt％或更低。所述可发泡聚合物组合物可以不含上述其他添加剂的任何一种或多于一种。例如，可发泡聚合物组合物可以不含红外衰减剂。
至于如何将所述可发泡聚合物组合物提供到挤出机中，没有已知的限制。作为一个说明性的例子，所述聚合物组合物可以进给到挤出机中并加热到足以软化所述聚合物组合物的温度。通常，所述聚合物组合物加热到足以熔融所述聚合物组合物的热塑性聚合物。根据这个说明性的例子，发泡剂组合物在它处于软化状态时添加到聚合物组合物，并混合到所述聚合物组合物中形成可发泡聚合物组合物。其他添加剂可以与聚合物组合物一起或在聚合物组合物已经熔融之后添加，但是通常与所述聚合物组合物一起添加。
可发泡聚合物组合物的温度起初在混合温度和混合压力下。混合温度高得足以软化所述聚合物组合物，通常是超过所述聚合物组合物中热塑性聚合物的熔融温度的温度。例如，混合温度通常是175摄氏度(℃)或更高，优选190℃或更高，并同时通常是225℃或更低，优选210℃或更低。混合压力足够高，从而阻止发泡剂组合物膨胀。混合压力通常是35兆帕(MPa)或更低并同时10MPa或更高。
所述可发泡聚合物组合物然后从混合温度冷却到低于所述混合温度的发泡温度。发泡温度理想地120℃或更高，优选121℃或更高，并同时理想地125℃或更低，优选124℃或更低。同时，可发泡聚合物组合物的压力仍然足够高，从而阻止发泡剂膨胀。
所述可发泡聚合物组合物然后在发泡温度下通过挤出模头驱出到发泡压力下的环境中。发泡压力低于混合压力并且足够低从而允许发泡剂膨胀。通常，膨胀压力是110千帕斯卡或更低。随着所述发泡剂组合物膨胀，它将所述聚合物组合物膨胀成为聚合泡沫。
令人惊讶的是，所述聚合物组合物膨胀成具有特别理想的低密度和高垂直压缩强度组合的聚合泡沫。分析聚合泡沫的性质揭示，制备聚合泡沫是特别具有挑战性的，而按照以上阐述的聚合物组合物和发泡剂限制，其在密度和垂直压缩强度之间具有下面阐明的关系：
垂直压缩强度(千帕斯卡)>[25.9(密度(kg/m3))–520]
其中“>”是指“大于”或“超过”。就是说，以千帕斯卡计的垂直压缩强度的量值超过25.9和以千克/立方米计的泡沫密度量值的乘积减520。供本文中参考，[25(密度(kg/m3))–520]的值称作聚合泡沫的“垂直压缩强度指数”或“VCS指数”。
虽然如此，本发明的方法能够制备挤塑苯乙烯聚合物泡沫，其中以千帕斯卡计的垂直压缩强度的量值超过25.9乘以以千克/立方米计的密度的量值减去520。特别有意义的是，本发明的方法能够制备这种密度为48kg/m3或更低、40kg/m3或更低并且甚至37kg/m3或更低的泡沫。同时，根据ASTM D1621，垂直压缩强度可以是275千帕斯卡或更高，甚至350千帕斯卡或更高。
本发明制备的聚合物泡沫是“挤塑”聚合泡沫。挤塑聚合泡沫的特征在于没有延伸整个泡沫结构和包围(封闭)泡沫内部的孔群的聚合物膜网络表皮，而这是膨胀珠泡沫中明显的。
实施例
利用单螺杆挤出机供给回转式搅拌机，来制备以下比较例和实施例。进给挤出机100重量份的包含50wt％的SAN A(相对于SAN重量为15wt％AN，Mw＝144k和Mw/Mn＝2.4)和50wt％的SAN B(相对于SAN重量为15wt％AN，Mw＝116k和Mw/Mn＝2.3)的聚合物组合物、0.8重量份六溴环十二烷、0.11重量份IrganoxTMB2150品牌抗氧化剂(Irganox是Ciba Specialty Chemicals Corporation的商标)、0.11重量份环氧甲酚酚醛清漆(ECN1280，来自Huntsman Araldite)、0.15重量份滑石、0.3重量份硬脂酸钡、0.3重量份DOWLEXTM2247品牌的线性低密度聚乙烯(DOWLEX是The Dow Chemical Company的商标)、和0.025重量份蓝色染料。所述聚合物组合物加热到175℃-235℃范围内的混合温度。
在回转式搅拌机中同时在所述混合温度和15兆帕的混合压力下，向所述聚合物组合物添加发泡剂组合物，制备可发泡聚合物组合物。发泡剂的组成和浓度在表1和表2中。
所述可发泡聚合物组合物冷却到121-124℃的发泡温度，并通过具有53厘米宽度和可变模隙间距的可调节狭缝挤出模头驱出所述可发泡聚合物组合物进入大气压(101千帕斯卡)和大气温度(25℃)，并让所述可发泡聚合物组合物膨胀成聚合泡沫。所述可发泡聚合物组合物以1800千克/小时的速率通过挤出模头挤出。
利用如表1报告的发泡剂组合物和发泡温度制备实施例1-4。由此产生的泡沫性质也在表1中报告。
表1
实施例1-4说明，根据本发明的方法制备的泡沫产生了令人惊讶地具有超过泡沫的VCS指数的垂直压缩强度的泡沫。特别地，实施例1-3同时具有至少350千帕斯卡的垂直压缩强度和35千克/立方米或更低的密度。
利用如表2中报告的发泡剂组合物和发泡温度制备比较例A-D。由此产生的泡沫性质也在表2中报告。
表2
比较例A-D说明当不按照本发明的发泡剂组合物时密度和垂直压缩强度发生了什么。与实施例1-4相比，由此产生的泡沫不能达到大于所述泡沫的VCS指数的垂直压缩强度。

Claims (6)

1.制备挤塑聚合泡沫的方法，所述方法包括以下步骤：
a.在混合温度和混合压力下在挤出机中提供包含聚合物组合物和发泡剂组合物的可发泡聚合物组合物；
b.将所述可发泡聚合物组合物冷却到低于所述混合温度的发泡温度；和
c.将所述可发泡聚合物组合物在发泡温度下通过挤出模头驱出到发泡压力下的环境中，所述发泡压力低于所述混合压力并且足够低以允许所述可发泡聚合物组合物膨胀成聚合泡沫；
其中所述方法的特征在于所述聚合物组合物包含烯基芳族聚合物，所述烯基芳族聚合物的至少一种是苯乙烯-丙烯腈共聚物，并且所述发泡剂组合物由74-78重量％的1,1,1,2-四氟乙烷、13-16重量％二氧化碳和7-9重量％水组成，其中重量％基于总发泡剂组合物重量，所述可发泡聚合物组合物基于可发泡聚合物组合物重量包含小于0.5重量％的填充剂，所述发泡温度在120-125摄氏度的范围内，并且由此产生的聚合泡沫通过ASTM D1622测定的密度为29千克/立方米或更高且37千克/立方米或更低以及通过ASTM D1621测定的以千帕斯卡计的垂直压缩强度量值超过25.9和以千克/立方米计的泡沫密度量值的乘积减520。
2.权利要求1的方法，其中允许所述可发泡聚合物组合物膨胀成聚合泡沫，所述聚合泡沫通过ASTM D1621测定的垂直压缩强度为至少275千帕斯卡。
3.权利要求1或权利要求2任一项的方法，其中允许所述可发泡聚合物组合物膨胀成聚合泡沫，所述聚合泡沫通过ASTM D1621测定的垂直压缩强度为至少350千帕斯卡和通过ASTM D1622测定的密度在29千克/立方米或更高且35千克/立方米或更低的范围内。
4.权利要求1-3任一项的方法，其中所述烯基芳族聚合物由苯乙烯-丙烯腈共聚物组成。
5.权利要求1-4任一项的方法，其中共聚丙烯腈基于总烯基芳族聚合物重量以15重量％的浓度存在。
6.权利要求1-5任一项的方法，其中所述烯基芳族聚合物由苯乙烯-丙烯腈共聚物组成并且共聚丙烯腈基于总苯乙烯聚合物重量以15重量％的浓度存在。
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