CN1249102C - 抗应力开裂性能提高的单乙烯基芳族聚合物 - Google Patents
抗应力开裂性能提高的单乙烯基芳族聚合物 Download PDFInfo
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Abstract
本发明揭示了一种提高耐冲击的弹性体改性单乙烯基芳族化合物的抗环境应力开裂性能和所要求的其他性能的方法，该方法采用包含过缩酮和过氧碳酸酯的组合的聚合引发剂。
Description
本发明涉及使用单乙烯基芳族化合物的聚合物的热塑性组合物，它用橡胶改性以提高冲击强度，尤其适合制造要求抗环境应力开裂性能(ESCR)增高的制品。更确切地说，本发明揭示了高抗冲聚苯乙烯(HIPS)，它尤其可有利地用于在正常情况下会发生环境应力开裂的食品容器。
众所周知，单乙烯基芳族化合物例如苯乙烯、α-甲基苯乙烯和环上取代的苯乙烯的橡胶增强的聚合物可用于多种用途。更确切地说，橡胶增强的苯乙烯聚合物中含有交联橡胶的分散粒子例如聚丁二烯，橡胶的分散粒子分散于整个苯乙烯聚合物基质内，该聚合物可以用于多种用途，包括冰箱衬里、包装、家具、家用器具和玩具。这些橡胶增强聚合物的惯用术语是“高抗冲聚苯乙烯”或“HIPS”。HIPS的物理性能和力学性能依赖于许多因素，包括交联橡胶粒子的粒度。HIPS材料的一个最适宜的特性是这种材料能够抵抗由例如与食品和食用油接触这样的因素所导致的降解或损坏。另外，这些制品必须保持的其他性能包括弯曲强度和拉伸强度。
抗应力开裂性或抗环境应力开裂性能(ESCR)在用于食品容器的热塑性共聚物中尤其重要。这些聚合物容器内装的食品在正常情况下不会降解制成容器的类型的聚合物材料，但是当热塑性聚合物由挤出的片材热成形时，残留应力就残留在成型的制品内。在制品要正常地完全耐受的物质的作用下，这些应力会将聚合物胀裂。这些由用橡胶改性以提高冲击强度的苯乙烯聚合物制成的制品，与在有机食品例如脂肪和油中存在的常见物质接触时，很容易应力开裂。同样，这些制品与有机发泡剂例如含有氟和氯的卤代烃接触时，也会应力开裂。这些聚合物通常存在于家用器具例如冰箱衬里，由于泡沫材料中使用发泡剂，当冰箱内的空腔被聚氨酯泡沫材料填充时，聚合物就会开裂。
过去，是用复杂的工序防止环境应力开裂，它通常包括多层聚合物结构，其中聚合物的中间保护层放置于聚苯乙烯层与发泡剂或脂肪食品材料之间。这种用来隔离苯乙烯与这些物质的一层材料是已知的ABS即丙烯腈-丁二烯-苯乙烯三元共聚物。提高耐冲击性能高的单乙烯基芳族聚合物的抗应力开裂性的其他尝试，是提高混入聚合物内的橡胶量。不幸的是，橡胶量较高，会降低最终材料的拉伸和弯曲强度。其他的解决方法包括严格控制工艺条件，保持对聚苯乙烯基质内的交联橡胶粒子粒度的严格控制。一个揭示该技术的专利是转让给本发明的受让人的美国专利4,777,210,1988年10月11日授权，其中揭示了制造高抗冲聚苯乙烯并提供改变粒度的可靠和可重复的方法的连续流程。在该专利方法中，利用预转化反应器将苯乙烯、橡胶(例如聚丁二烯)和过氧化物催化剂的溶液转化成高抗环境应力开裂性的高抗冲聚苯乙烯材料。
1979年3月13日授予Mittnacht等的美国专利4,144,204揭示了另一种改善抗应力开裂性能的尝试，其中用橡胶改性单乙烯基芳族化合物以提高ESCR，而且聚合之前对溶解于单体内的橡胶量进行选择，使耐冲击聚合物内的软组分(凝胶相)含量至少为28％(重量)，优选38％(重量)或更多，以耐冲击聚合物重量为基准。发现软组分含量的上限约为50-60％(重量)、优选30-40％(重量)是有利的。
用来提高HIPS中的ESCR的第三种常规方法，在英国专利说明书1,362,399中有揭示，其中具有不饱和碳链的液态烃调聚物以0.2-5份/100份的量加入到HIPS材料中。在Websters大词典中，调聚物定义为涉及一个分子(例如醇、缩醛或氯仿)的碎片加成到聚合的烯烃链末端的化学反应的产物。在英国专利中，使用的调聚物的数均分子量为1000-6000。由于交联，利用低分子量聚丁二烯制造ESCR-HIPS的实验尝试已经成功，这说明该专利方法采用的丁二烯是与聚苯乙烯复合或混合，而不是在聚合反应期间加入的。
在英国专利№GB2,153,370A中能够发现改善HIPS材料的抗应力开裂性的另一种尝试，其中用规定分子量至少300,000、粘度高于或等于140厘泊的高分子量橡胶材料制备HIPS材料，所制成的HIPS含有7-10％(重量)橡胶、而且聚合是在α-甲基苯乙烯二聚物，或选自正月桂基硫醇、叔月桂基硫醇、二苯基1，3丁二烯或其各种不同的混合物的物质存在下进行的。该方法也可以在等于总成分的至少7％(重量)的环己烷和乙苯存在下进行。另外，添加剂包括硬脂酸的三酸单甘油酯和聚乙烯蜡也是必需的。
另一方面，除了改善ESCR，使用添加剂也有其他原因。授予Dempsey等的专利№3,506,740揭示了使用低分子量聚烯烃作为耐冲击聚苯乙烯组合物的内润滑剂。所列出的实施例包括分子量为800-1600(由蒸汽压的渗透压测试法测得)的聚丙烯和聚丁烯。
也发现所用聚合引发剂的量和类型能够影响聚合物材料的最终性能例如它们的分子量。例如美国专利5,266,603揭示了采用过缩酮(perketal)和/或单过氧碳酸酯引发剂制备低苯残留量的可发泡的球状聚苯乙烯。
授予Sosa等的美国专利4,861,827揭示了采用下述自由基引发剂制备高抗冲聚苯乙烯的苯乙烯聚合工艺，所述引发剂在聚合过程中分解，仅形成能够留在循环物流中并不会进一步抑制聚合的非酸性分解副产物。这些自由基引发剂的例子包括偶氮和过氧化物。
美国专利5,559,162揭示了制备过氧碳酸酯聚合物的方法，和将它用作引发剂的方法。美国专利4,433,099揭示了使用有机过氧化物引发剂制备Mv分子量为150,000-170,000的耐冲击苯乙烯聚合物。美国专利4,129,703揭示了在两个不同的热聚合阶段使用过氧碳酸酯引发剂制备聚苯乙烯，其中一个阶段约70℃，另一个150℃，每个阶段用不同的引发剂。
本发明通过提供含有聚丁二烯或苯乙烯-丁二烯橡胶的聚苯乙烯材料(PS)，克服了已知的高抗冲聚苯乙烯材料的缺陷，采用了可提供较常规PS引发剂有改进的ESCR性能的聚合引发剂材料的特定组合使所述PS材料与所述橡胶发生聚合。本发明所揭示的高抗冲聚苯乙烯(HIPS)表现出高抗环境应力开裂性、高冲击强度、良好的拉伸强度和良好的弯曲强度。
本发明揭示了含有用弹性体改性以提高其冲击强度和抗环境应力开裂性的单乙烯基芳族化合物的聚合物的热塑性组合物，该组合物通过在组合的聚合引发剂和弹性体存在下聚合单乙烯基芳族材料而获得。在所述组合物中，已经改性以提高其冲击强度的聚合物中的软组分含量低于聚合物的28％(重量)，软组分定义为已经改性以提高其冲击强度的聚合物中的不溶于甲苯的成分减去可能存在的任何颜料。用于本发明中的特定橡胶可以是几种类型中的一种，例如由Firestone出售的商品品为Diene55的类型，其门尼粘度约55，数均分子量约150,000，重均分子量约300,000，Z分子量约500,000，由凝胶渗透色谱技术测得。另一种较佳的橡胶材料类型包括高顺式橡胶。
只要采用上述成分，高抗冲聚合物可以根据任何常规方法制成。正常的制备方法包括本体聚合和溶液聚合，例如美国专利2,694,692所述，或本体悬浮聚合，例如美国专利2,862,906所述。也可以使用其他的聚合方法，只要该方法能够使用上述成分。
用于本发明的合适的单乙烯基芳族化合物包括苯乙烯和在环或侧链烷基化的苯乙烯，例如α-甲基苯乙烯和乙烯基甲苯。单乙烯基芳族化合物可以单独使用或混合使用。在一个优选实施方式中，苯乙烯是优选的单乙烯基芳族化合物。在橡胶和包含过缩酮与过氧碳酸酯的组合的新型组合引发剂存在下，通过聚合单乙烯基芳族化合物，就可形成根据本发明制备的高抗冲聚苯乙烯(HIPS)。橡胶的用量优选约为溶液的5-15％(重量)。由本体聚合、溶液聚合或在水中的分散聚合，以常规方式实施聚合，橡胶首先溶解于可聚合的单体中，接着，该溶液在组合引发剂存在下进行聚合。合适的过氧碳酸酯聚合引发剂可包括例如过氧碳酸叔戊基2-乙基己基酯(TAEC)，合适的过缩酮引发剂可以是宾夕法尼亚州Philadelphia的2000Market St.的Elf AtochemNorth America出售的，商品品为LUPERSOL233。当采用溶液聚合时，原料溶液可以与高达约10％(重量)的惰性稀释剂混合，以采用的单乙烯基芳族化合物为基准。优选的惰性稀释剂包括芳烃或芳烃的混合物，例如甲苯、乙苯、二甲苯或它们的混合物。也可以加入合适的链转移剂例如硫醇或α-甲基苯乙烯二聚体，来控制聚合物分子量和橡胶的粒度。
也可以以连续流程工艺应用本发明，采用预转化反应器来制备聚苯乙烯，在预转化反应器中，苯乙烯、橡胶和引发剂组合物聚合至低于转化点的某一点，接着，进入第二搅拌釜反应器。精确控制预转化器和第二搅拌釜反应器内溶液的粘度，以制成所要求的HIPS。在1988年10月11日授予Sosa等的美国专利4,777,210中可以发现制备优选实施例的具体工艺，其全部内容在这里引入参考。
优选将提高ESCR的过缩酮和过氧碳酸酯的引发剂组合物加入到起始的单体/橡胶进料中，或可以在聚合过程中的任意时刻加入至反应器包括最终的聚合反应器)。一种发现可出乎意料地提高ESCR性能的特定引发剂含有上述与过缩酮引发剂LUPERSOL233组合使用的过氧碳酸叔戊基2-乙基己基酯(TAEC)。TAEC可以不同的比例来使用，优选用量约为150-800PPM(重量)。LUPERSOL233的加入量约为200PPM。
在本发明的第一实施方式中，采用不同的TAEC和perkatal引发剂的量，由上述专利方法，将具有相应于门尼粘度约55的分子量的常规丁二烯橡胶与苯乙烯单体的混合物聚合成高抗冲聚苯乙烯材料。
下表1说明了与常规方法相比，采用本发明的组合引发剂所获得的ESCR的改善情况。
| 表1 ESCR的提高 | ||||
| A | B | C | D | |
| PPM引发剂#1 | 400 | 400 | ||
| PPM引发剂#2 | 400 | 400 | ||
| PPM引发剂#3 | 200 | 200 | 200 | 200 |
| PPM链转移剂 | 500 | 500 | 500 | 500 |
| 矿物油％ | 2 | 2 | 2 | 2 |
| PIB％ | 2 | 2 | 2 | 2 |
| 橡胶粒度分布的测量间距 | 1.8 | 1.6 | 1.0 | 1.4 |
| 橡胶粒度(微米) | 6.1 | 5.8 | 4.2 | 5.0 |
| ％橡胶 | 11.4 | 12.0 | 11.5 | 11.5 |
| 膨胀指数 | 12.2 | 12.1 | 12.8 | 13.0 |
| 凝胶％ | 23.3 | 24.8 | 24.5 | 22.8 |
| 接枝 | 104 | 107 | 113 | 99 |
| ESCR | 22.5 | 22.8 | 36.8 | 44.3 |
| 拉伸模量(PSI) | 228,300 | 214,300 | 210,900 | 221,900 |
*引发剂#1是Lupersol L-531，一种过缩酮
*引发剂#2是TAEC
*引发剂#3是Lupersol L-233，一种过缩酮
为了参考，根据下述ESCR指标，用于装脂肪或油的食品容器的HIPS材料是成功的：
ESCR 结果
10％ 过早应力开裂
20％ 刚刚合格
30％ 抗应力开裂性良好
40％ 抗应力开裂性优良
在另一组实施例中，利用本发明使HIPS材料内的材料的延展性最大化(提高凝胶含量)来制造杯子。下表2说明了两个橡胶用量比食品容器材料低的制杯子级HIPS材料的实施例。一个实施例采用常规的制杯子级HIPS材料，另一个采用本发明的材料。
| 表2 | ||
| A | B | |
| PPM引发剂L-331 | 400 | |
| PPM引发剂TAEC | 600 | |
| PPM引发剂L-233 | 200 | 200 |
| PPM链转移剂 | 200 | --- |
| 矿物油％ | 2 | 2 |
| PIB％ | - | - |
| 橡胶粒度分布的测量间距 | 2.0 | 1.5-- |
| 橡胶粒度(微米) | 3.3 | 3.6 |
| ％橡胶 | 4.2 | 4.4 |
| S.I. | 10.7 | 10.8 |
| 凝胶％ | 9.7 | 12.5 |
| 接枝 | 130 | 184 |
| 拉伸模量 | 339,500 | 332,300 |
从表1可清楚地看出，与常规材料A和B相比(ESCR值为22.5和22.8)，实施例C和D的过缩酮与过氧碳酸酯的组合引发剂可显著提高ESCR值(36.8和44.3)。
表2说明了利用本发明不仅能够提高ESCR值。在ESCR不重要的非食品级HIPS材料(即杯子级)中，本发明还可提高凝胶含量(相对于9.7为12.5)和接枝量(相对于130为184)。实施例B为使用本发明，实施例A为常规的方法。
由此，从上述结果能够清楚地说明，过缩酮引发剂与过氧碳酸酯引发剂组合可提高HIPS材料的ESCR，也可在其他方面有所改善例如凝胶含量和接枝量。
Claims (9)
1.一种提高弹性体改性的单乙烯基芳族聚合物材料的抗环境应力开裂性能的方法，它包括：
使单乙烯基芳族单体的进料流进入聚合反应器内；
使弹性体进料流进入所述聚合反应器内；
使聚合引发剂化合物进入所述反应器内，
所述引发剂化合物含有过缩酮和过氧碳酸酯，过缩酮的含量为200重量ppm，过氧碳酸酯的含量为150-800重量ppm，所述过缩酮是乙基-3，3-二(叔丁基过氧)丁酸酯，所述的过氧碳酸酯是叔戊基2-乙基己基过氧碳酸酯；
使所述单体、引发剂化合物和弹性体反应，形成弹性体改性的单乙烯基芳族聚合物，该聚合物的弹性组分含量低于聚合物重量的28重量％，该聚合物的抗环境应力开裂性能够提高30％或更多。
2.如权利要求1所述的方法，其特征在于所述过氧碳酸酯的加入量为400-800重量ppm。
3.如权利要求2所述的方法，它还包括向反应器加入至少一种链转移剂和至少一种润滑剂，所述润滑剂选自矿物油和聚异丁烯。
4.如权利要求3所述的方法，其特征在于所述的链转移剂是硫醇。
5.如权利要求3所述的方法，其特征在于所述加入的润滑剂是矿物油和聚异丁烯。
6.如权利要求1所述的方法，其特征在于所述单乙烯基芳族单体是苯乙烯单体，所述弹性体改性的单乙烯基芳族聚合物材料是高抗冲聚苯乙烯。
7.如权利要求4所述的方法，其特征在于所述硫醇的加入量为500重量ppm。
8.如权利要求6所述的方法，其特征在于所述的抗冲击聚苯乙烯的凝胶含量为12.5重量％。
9.如权利要求6所述的方法，其特征在于所述的抗冲击聚苯乙烯的接枝量大于130。
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| JP2001118098A JP2002327028A (ja) | 2001-04-17 | 2001-04-17 | 応力亀裂耐性が改善されたモノビニル芳香族重合体 |
| EP01201397A EP1251143B1 (en) | 2001-04-17 | 2001-04-17 | Monovinylaromatic polymer with improved stress crack resistance |
| CA002344284A CA2344284A1 (en) | 2001-04-17 | 2001-04-18 | Monovinylaromatic polymer with improved stress crack resistance |
| CN01116690.8A CN1249102C (zh) | 2001-04-17 | 2001-04-20 | 抗应力开裂性能提高的单乙烯基芳族聚合物 |
| US10/052,149 US6822046B2 (en) | 2000-04-10 | 2002-01-17 | Monovinylaromatic polymer with improved stress crack resistance |
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| EP01201397A EP1251143B1 (en) | 2001-04-17 | 2001-04-17 | Monovinylaromatic polymer with improved stress crack resistance |
| CA002344284A CA2344284A1 (en) | 2001-04-17 | 2001-04-18 | Monovinylaromatic polymer with improved stress crack resistance |
| CN01116690.8A CN1249102C (zh) | 2001-04-17 | 2001-04-20 | 抗应力开裂性能提高的单乙烯基芳族聚合物 |
| US10/052,149 US6822046B2 (en) | 2000-04-10 | 2002-01-17 | Monovinylaromatic polymer with improved stress crack resistance |
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| US7514516B2 (en) | 2003-05-27 | 2009-04-07 | Fina Technology, Inc. | Measurement and preparation of branched vinyl polymers |
| MXPA06005980A (es) * | 2003-11-26 | 2007-01-26 | Fina Technology | Uso de iniciadores tetrafuncionales para mejorar el volumen de fase de caucho del hips. |
| US20060160949A1 (en) * | 2004-03-24 | 2006-07-20 | Styranec Thomas J | Thermoplastic sheet containing a styrenic copolymer |
| US20070262667A1 (en) * | 2004-08-23 | 2007-11-15 | Charbonneau Robert A | Pneumatic powered electro-magnetic field generating device |
| US7754817B2 (en) * | 2005-10-31 | 2010-07-13 | Fina Technology, Inc. | Low temperature initiators for improving the rubber phase volume of HIPS formulations |
| US20080057294A1 (en) * | 2006-09-01 | 2008-03-06 | Fina Technology, Inc. | High impact polystyrene tile |
| US20090030095A1 (en) * | 2007-07-24 | 2009-01-29 | Laverdure Kenneth S | Polystyrene compositions and methods of making and using same |
| US20090110855A1 (en) * | 2007-10-30 | 2009-04-30 | Dixie Consumer Products Llc | Filled Polystyrene Compositions and Uses Thereof |
| EP2093238A1 (en) | 2008-02-21 | 2009-08-26 | Total Petrochemicals France | Process for preparing hydroperoxidized elastomers and their use in high impact monovinylaromatic polymers |
| US20090246501A1 (en) * | 2008-03-26 | 2009-10-01 | Fina Technology, Inc. | Reduced Weight Multilayer Polymeric Articles and Methods of Making and Using Same |
| US8246878B2 (en) * | 2008-04-30 | 2012-08-21 | Fina Technology, Inc. | Composites comprising a polymer and a layered compound and methods of preparing and using same |
| US20090281235A1 (en) * | 2008-05-06 | 2009-11-12 | Harris Iii Theodore G | Polystyrene compositions having improved mechanical properties and methods of using same |
| US20100015331A1 (en) * | 2008-07-16 | 2010-01-21 | Fina Technology, Inc. | Hot melt adhesive compositions and methods of making and using same |
| FR2933985B1 (fr) * | 2008-07-18 | 2010-08-20 | Arkema France | Melange de peroxydes pour la reticulation d'elastomeres |
| US20100087602A1 (en) * | 2008-10-08 | 2010-04-08 | Fina Technology, Inc. | Long chain branched polypropylene for cast film applications |
| US20100099822A1 (en) * | 2008-10-22 | 2010-04-22 | Fina Technology, Inc. | High impact polymeric compositions and methods of making and using same |
| US20100140835A1 (en) * | 2008-12-09 | 2010-06-10 | Fina Technology, Inc. | Styrenic polymers for injection stretch blow molding and methods of making and using same |
| US8093308B2 (en) * | 2009-01-30 | 2012-01-10 | Fina Technology, Inc. | Styrenic polymer compositions and methods of making and using same |
| US8563641B2 (en) * | 2009-03-12 | 2013-10-22 | Fina Technology, Inc. | Ionomer compositions and methods of making and using same |
| US20110218292A1 (en) * | 2010-03-08 | 2011-09-08 | Ineos Nova Llc | Monovinyl aromatic polymer compositions with a novel combination of stiffness and stress crack resistance |
| US9079982B2 (en) | 2010-10-29 | 2015-07-14 | Fina Technology, Inc. | Methods of making high impact polystyrene |
| US20120187019A1 (en) * | 2011-01-22 | 2012-07-26 | Fina Technology, Inc. | Methods to Produce Semi-Durable Foamed Articles |
| US9090715B2 (en) | 2011-03-30 | 2015-07-28 | Fina Technology, Inc. | Swell index of HIPS using additives |
| US8822597B2 (en) | 2011-04-28 | 2014-09-02 | Fina Technology, Inc. | Increasing rubber phase volume in rubber-modified polystyrene |
| US20230365773A1 (en) | 2022-05-13 | 2023-11-16 | Fina Technology, Inc. | High Melt Strength Polystyrene Compositions and Methods of Making and Using Same |
| US20240010766A1 (en) | 2022-07-07 | 2024-01-11 | Fina Technology, Inc. | High melt strength polystyrene compositions and methods of making and using same |
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| JP2002327028A (ja) | 2002-11-15 |
| EP1251143B1 (en) | 2012-07-18 |
| EP1251143A1 (en) | 2002-10-23 |
| US6822046B2 (en) | 2004-11-23 |
| CN1381506A (zh) | 2002-11-27 |
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