CN1371403A - 包含hfc-134和低溶解度助发泡剂的泡沫材料及其制备方法 - Google Patents
包含hfc-134和低溶解度助发泡剂的泡沫材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种挤制的、尺寸稳定的、闭孔链烯基芳烃聚合物泡沫材料。该泡沫材料包含具有超过50%重量的链烯基芳烃单体单元的链烯基芳烃聚合物材料。该泡沫材料的密度为约16-64千克/立方米。该泡沫材料的横截面厚度为15毫米或更高。该泡沫材料的发泡剂组合物包含约70-95%重量的主发泡剂1,1,2,2-四氟乙烷;和占所述发泡剂组合物总摩尔数约30-5%重量的次发泡剂。所述次发泡剂基本上选自1,1,1,2-四氟乙烷、二氧化碳、氮气、氩气和水。本发明还公开了该泡沫材料的制备方法。
Description
本发明涉及包含1,1,2,2-四氟乙烷(HFC134)与低溶解度助发泡剂的共混物的挤制链烯基芳烃聚合物泡沫材料及其制备方法。
由于环境法规不断严格,链烯基芳烃聚合物隔绝泡沫材料的生产正考虑将氟烃作为潜在的隔绝泡孔气剂(发泡剂)。其中一种试剂是HFC134。
HFC134是本领域已知的发泡剂,可用于制造链烯基芳烃聚合物泡沫材料。HFC134公开于加拿大专利1086450、日本公开申请5-287111和美国专利5278196和5182040。
在选择用于隔绝链烯基芳烃聚合物泡沫材料的发泡剂时,隔绝发泡剂的量必须足够高以产生合适的隔绝性能,但不应太高,否则导致泡沫材料产品的物理性能不理想。
使用HFC134时的问题在于,如果生产低密度(即,约16-64千克/立方米)和厚横截面(即,约15毫米或更高)的闭孔链烯基芳烃聚合物泡沫材料,在保持理想泡沫材料隔绝性能所需的含量(即,基于发泡剂总摩尔数的约70%重量或更高)下,结果发现尺寸稳定性不好。
已有技术没能有效地解决在制造低密度和厚横截面的闭孔链烯基芳烃聚合物泡沫材料时,与HFC134在发泡剂中的高用量有关的尺寸稳定性问题。
加拿大专利1086450涉及挤制链烯基芳烃聚合物泡沫材料,由30-70%重量的低渗透性发泡剂如HFC134和高渗透性助发泡剂如氟氯甲烷、甲基氯、乙基氯、氯二氟甲烷和1,1-二氟乙烷制备。该加拿大专利在采用明显较低量的HFC134时可避免上述问题。所公开的助发泡剂非常可溶于链烯基芳烃聚合物,而且在包含约70%重量或更高HFC134的发泡剂组合物中与HFC134一起使用时,对泡沫材料的尺寸稳定性产生负面影响。
日本公开申请5-287111涉及挤制聚苯乙烯泡沫材料,由HFC134与2-氯-1,1,1,2-四氟乙烷(HCFC124)的80/20重量比发泡剂制备。尽管没有描述所公开的泡沫材料的尺寸稳定性,但使用这种发泡剂会导致泡沫材料尺寸不稳定,因为HCFC124在聚苯乙烯中溶解度高且其透过聚苯乙烯泡沫材料的渗透速率低。
美国专利5182040涉及共沸和近共沸组合物,除了其它用途,据说可用作聚合物泡沫材料的发泡剂。该组合物包含HFC134和助发泡剂,选自1,1-二氟乙烷(HFC152a)、1-氯-1,1-二氟乙烷(HCFC142b)、二甲醚(DME)、1,1,1,2,3,3,3-七氟丙烷(HFC227ea)、全氟环丁烷(HFC318)、正丁烷、或异丁烷。一个特定的泡沫材料实施方案是具有特定物理性能的由60-99%重量HFC134与1-40%重量DME的组合物发泡的聚苯乙烯泡沫材料(权利要求1)。尽管没有描述任何可能泡沫材料的尺寸稳定性,但与约70%重量或更高的HFC134一起使用这种助发泡剂会导致泡沫材料尺寸不稳定,因为它们在聚苯乙烯中溶解度高,而且在某些助发泡剂的情况下,透过聚苯乙烯泡沫材料的渗透速率低。此外,DME非常易燃。
美国专利5278196涉及由1,1,1,2,3,3,3-七氟丙烷(HFC227ea)与HFC134(权利要求7)的组合物发泡的泡沫塑料。该参考文件没有描述一种由包含约70%重量或更高HFC134的组合物发泡的尺寸稳定的、低密度、挤制聚苯乙烯泡沫材料。
已经出人意料地发现,具有低密度和厚横截面的尺寸稳定的、低密度、挤制链烯基芳烃聚合物泡沫材料可通过一种包含约70%重量或更高HFC134a的发泡剂配方制备。
按照本发明,提供了一种挤制的、尺寸稳定的、闭孔链烯基芳烃聚合物泡沫材料。该泡沫材料包含具有超过50%重量的链烯基芳烃单体单元的链烯基芳烃聚合物材料。该泡沫材料的密度为约16-64千克/立方米。该泡沫材料的横截面厚度为15毫米或更高。该泡沫材料的发泡剂组合物包含约70-95%重量的主发泡剂1,1,2,2-四氟乙烷;和占所述发泡剂组合物总摩尔数约30-5%重量的次发泡剂。有用的次发泡剂在25摄氏度下的蒸汽压可以为约100psia或更高。具有这种蒸汽压水平的有用的次发泡剂包括1,1,1,2-四氟乙烷、二氧化碳、氮气、氦气和氩气。不具有这种蒸汽压的有用的次发泡剂是水。该泡沫材料具有优异的尺寸稳定性。
按照本发明,提供了一种制造上述泡沫材料的方法。该方法包括:a)将包含超过50%重量链烯基芳烃单体单元的链烯基芳烃聚合物材料加热,形成一种熔体聚合物材料;b)在升高的压力下,向所述熔体聚合物材料中加入上述发泡剂组合物;c)将该可发泡凝胶冷却至所希望的发泡温度;和d)将该可发泡凝胶挤过模头进入较低压力区以形成泡沫材料。
本发明解决了在制造低密度和厚横截面的闭孔链烯基芳烃聚合物泡沫材料时,与HFC134在发泡剂中的高用量有关的尺寸稳定性问题。所选的次发泡剂在链烯基芳烃聚合物、尤其是在聚苯乙烯中具有低溶解度。该次发泡剂不会明显增塑该聚合物基质,也不会使该泡沫材料过分膨胀或收缩(瘪泡)。某些有用的次发泡剂还具有迅速透过该泡沫材料的理想特性。迅速透过泡沫材料可提高尺寸稳定性,因为这样可平衡空气向该泡沫材料的渗透。在该隔绝泡沫材料的长期使用期限内,泡沫材料内的内部泡孔气压更易保持稳定或相对稳定。保持相对稳定的内部泡孔气压可使该泡沫材料不易膨胀或收缩。
最有用的次发泡剂在25摄氏度下的蒸汽压为约100psia或更高。由于发泡剂在基质聚合物中的溶解度难以精确测定,因此选择蒸汽压作为物理性能来表征该发泡剂。蒸汽压近似对应于溶解度,因为具有高蒸汽压的发泡剂往往在基质聚合物中溶解度较低;相反,具有低蒸汽压的发泡剂往往在基质聚合物中溶解度较高。有用的次发泡剂的用量至少为所述发泡剂组合物总摩尔数的约5%重量。有用的次发泡剂、但不具有这种蒸汽压的次发泡剂是水。
特别有用的次发泡剂是1,1,1,2-四氟乙烷、二氧化碳、氮气、氦气、氩气、水、以及前述物质的混合物。
特别有用的发泡剂组合包括HFC134/HFC134a和HFC134/二氧化碳。
发泡剂组合物可包含少量其它发泡剂,只要HFC134占基于发泡剂组合物总摩尔数的至少约70%重量且次发泡剂占至少约5%重量。其它的发泡剂包括物理发泡剂和化学发泡剂。有用的物理发泡剂包括具有1-9个碳原子的脂族烃、具有1-3个碳原子的脂族醇、以及具有1-4个碳原子的完全和部分卤化脂族烃。脂族烃的例子包括甲烷、乙烷、丙烷、正丁烷、异丁烷、正戊烷、异戊烷、新戊烷、和类似物。脂族醇的例子包括甲醇、乙醇、正丙醇和异丙醇。完全和部分卤化脂族烃包括氟烃、氯烃、和氯氟烃。氟烃的例子包括甲基氟、全氟甲烷、乙基氟、1,1-二氟乙烷(HFC-152a)、1,1,1-三氟乙烷(HFC-143a)、1,1,1,2-四氟乙烷(HFC-134a)、五氟乙烷、二氟甲烷、全氟乙烷、2,2-二氟丙烷、1,1,1-三氟丙烷、全氟丙烷、二氯丙烷、二氟丙烷、全氟丁烷、全氟环丁烷。部分卤化的氯烃和氯氟烃包括甲基氯、二氯甲烷、乙基氯、1,1,1-三氯乙烷、1,1-二氯-1-氟乙烷(HCFC-141b)、1-氯-1,1-二氟乙烷(HCFC-142b)、氯二氟甲烷(HCFC-22)、1,1-二氯-2,2,2-三氟乙烷(HCFC-123)、和1-氯-1,2,2,2-四氟乙烷(HCFC-124)。完全卤化的氯氟烃包括三氯一氟甲烷(CFC-11)、二氯二氟甲烷(CFC-12)、三氯三氟乙烷(CFC-113)、1,1,1-三氟乙烷、五氟乙烷、二氯四氟乙烷(CFC-114)、一氯七氟丙烷、和二氯六氟丙烷。化学发泡剂包括偶氮二甲酰胺、偶氮二异丁腈、苯磺酰肼、4,4-氧连苯磺酰基-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、和三肼基三嗪。
为了制造能形成泡沫材料的聚合物凝胶,发泡剂在聚合物熔体材料中的加入量为约0.2-5.0克分子/千克聚合物,优选约0.5-3.0克分子/千克聚合物,最优选约1.0-2.50克分子/千克聚合物。
本发明泡沫材料按照ASTM D-1622-88的密度为约16-64千克/立方米,最优选约25-48千克/立方米。该泡沫材料按照ASTM D3576-77的平均泡孔尺寸为约0.1-0.5毫米,优选约0.5-0.4毫米。
本发明泡沫材料特别适用于制成厚板,最好横截面积为约30平方厘米或更高,且横截面的短边(厚度)的尺寸为约15毫米或更高。
本发明泡沫材料是闭孔泡沫材料。按照ASTM D2856-87,本发明泡沫材料优选具有超过90%的闭孔。
本发明泡沫材料具有优异的尺寸稳定性。按照ASTM D2126/C578,该泡沫材料在任何方向上的尺寸变化为约四(4)%或更低。
本发明泡沫材料包含链烯基芳烃聚合物材料。合适的链烯基芳烃聚合物材料包括链烯基芳烃均聚物、以及链烯基芳烃化合物与可共聚烯属不饱和共聚单体的共聚物。链烯基芳烃聚合物材料还可包括少量的非链烯基芳烃聚合物。链烯基芳烃聚合物材料可仅由一种或多种链烯基芳烃均聚物、一种或多种链烯基芳烃共聚物、一种或多种链烯基芳烃均聚物和共聚物的共混物、或任何前述物质与非链烯基芳烃聚合物的共混物组成。与组成无关,该链烯基芳烃聚合物材料包含50%重量以上,优选约70%重量或更高的链烯基芳烃单体单元。最优选的是,该链烯基芳烃聚合物材料完全由链烯基芳烃单体单元组成。
合适的链烯基芳烃聚合物包括衍生自苯乙烯、α-甲基苯乙烯、乙基苯乙烯、乙烯基苯、乙烯基甲苯、氯苯乙烯和溴苯乙烯之类的链烯基芳烃化合物的那些聚合物。优选的链烯基芳烃聚合物为聚苯乙烯。可以将少量的单烯属不饱和化合物如C2-6烷基酸和酯、离聚体衍生物、和C4-6二烯与链烯基芳烃化合物进行共聚。可共聚化合物的例子包括丙烯酸、甲基丙烯酸、乙基丙烯酸、马来酸、衣康酸、丙烯腈、马来酸酐、丙烯酸甲酯、丙烯酸乙酯、丙烯酸异丁酯、丙烯酸正丁酯、甲基丙烯酸甲酯、乙酸乙烯酯和丁二烯。优选的结构基本上包含(即,大于90%重量,更优选大于95%重量)、最优选完全包含聚苯乙烯。
本发明链烯基芳烃聚合物泡沫材料一般这样制备:将链烯基芳烃聚合物材料加热形成一种塑化的或熔化的聚合物材料,向其中加入发泡剂以形成一种可发泡的凝胶,然后将该凝胶挤过模头,形成泡沫材料产品。在与发泡剂混合之前,将聚合物材料加热至其玻璃化转变温度或熔点或之上的温度。发泡剂可通过本领域已知的任何方式,例如使用挤出机、混合器、掺合机等加入或混入熔体聚合物材料中。发泡剂在足以防止熔体聚合物材料显著膨胀并一般将发泡剂均匀分散其中的升高压力下与熔体聚合物材料进行混合。视需要,可以将成核剂混入聚合物熔体中或在塑化或熔化之前与聚合物材料干混。可发泡凝胶通常冷却至较低温度以优化泡沫材料结构的物理特性。将凝胶在挤出机或其它混合设备中或在单独的冷却器中进行冷却。然后将凝胶挤过或传送经过一个具有所需形状的模头,进入一个较低压力区或低压区,形成泡沫材料结构。低压区的压力低于该可发泡凝胶在挤过模头之前所保持的压力。该低压可以是超大气压或低于大气压(真空),但优选大气压水平。
此外,可以加入成核剂以控制泡沫材料泡孔的大小。优选的成核剂包括无机物质,如碳酸钙、滑石、粘土、二氧化钛、硅石、硬脂酸钡、硅藻土、柠檬酸与碳酸氢钠的混合物、和类似物。成核剂的用量可以为约0.01-5重量份/100重量份聚合物树脂。优选范围为0.1-约3重量份。
可以将各种添加剂加入本发明泡沫材料结构中,例如无机填料、颜料、抗氧化剂、酸捕集剂、紫外线吸收剂、阻燃剂、加工助剂、挤出助剂和类似物。
在生产具有低导热率的最终产品泡沫材料的过程中,可以将红外减弱剂加入聚合物熔体或可发泡凝胶中,例如有炭黑、二氧化钛、或石墨。加入量通常为基于链烯基芳烃聚合物材料重量的约2-10%重量。
尽管已经特别详细地给出了本发明泡沫材料组合物和方法的实施方案,但应该理解,本发明可根据生产方法和制造商的要求进行各种变化和改进,这仍然明显在前述的新教导和原则的范围内。
Claims (14)
1.一种挤制的、尺寸稳定的、闭孔链烯基芳烃聚合物泡沫材料,包含:具有超过50%重量的链烯基芳烃单体单元的链烯基芳烃聚合物材料,该泡沫材料的密度为约16-64千克/立方米,该泡沫材料的横截面厚度为15毫米或更高,该泡沫材料的发泡剂组合物包含约70-95%重量的主发泡剂1,1,2,2-四氟乙烷、和占所述发泡剂组合物总摩尔数约30-5%重量的次发泡剂,所述次发泡剂选自1,1,1,2-四氟乙烷、二氧化碳、氮气、氩气和水。
2.根据权利要求1的泡沫材料,其中所述次发泡剂为1,1,1,2-四氟乙烷。
3.根据权利要求1的泡沫材料,其中所述次发泡剂为二氧化碳。
4.根据权利要求1的泡沫材料,其中所述次发泡剂为氮气。
5.根据权利要求1的泡沫材料,其中所述次发泡剂为氩气。
6.根据权利要求1的泡沫材料,其中所述次发泡剂为水。
7.根据权利要求1的泡沫材料,其中所述次发泡剂在25摄氏度下的蒸汽压为100psia或更高。
8.一种制造挤制的、尺寸稳定的、闭孔链烯基芳烃聚合物泡沫材料结构的方法,该泡沫材料的密度为约16-64千克/立方米,该泡沫材料的横截面厚度为15毫米或更高,该方法包括:
a)将包含50%重量或更多链烯基芳烃单体单元的链烯基芳烃聚合物材料加热,形成一种熔体聚合物材料;
b)在升高的压力下,向所述熔体聚合物材料中加入一种发泡剂组合物,该发泡剂组合物包含约70-95%重量的主发泡剂1,1,2,2-四氟乙烷、和选自1,1,1,2-四氟乙烷、二氧化碳、氮气、氩气和水的次发泡剂;
c)将该可发泡凝胶冷却至所希望的发泡温度;和
d)将该可发泡凝胶挤过模头进入较低压力区以形成泡沫材料。
9.根据权利要求8的方法,其中所述次发泡剂为1,1,1,2-四氟乙烷。
10.根据权利要求8的方法,其中所述次发泡剂为二氧化碳。
11.根据权利要求8的方法,其中所述次发泡剂为氮气。
12.根据权利要求8的方法,其中所述次发泡剂为氩气。
13.根据权利要求8的方法,其中所述次发泡剂为水。
14.根据权利要求8的方法,其中所述次发泡剂在25摄氏度下的蒸汽压为100psia或更高。
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US6998397P | 1997-12-18 | 1997-12-18 | |
US60/069,983 | 1997-12-18 |
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US (1) | US6225364B1 (zh) |
EP (1) | EP1042392A1 (zh) |
JP (1) | JP2002508419A (zh) |
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CN (1) | CN1371403A (zh) |
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CA (1) | CA2315229A1 (zh) |
HU (1) | HUP0004460A3 (zh) |
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TR (1) | TR200002398T2 (zh) |
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GB9701291D0 (en) * | 1997-01-22 | 1997-03-12 | Ici Plc | Closed cell polymer foam |
US6274640B1 (en) * | 2000-08-17 | 2001-08-14 | Owens Corning Fiberglas Technology, Inc. | Extruded foam product with 134a and alcohol blowing agent |
US6358434B1 (en) * | 2001-05-21 | 2002-03-19 | Ato Fina Chemicals, Inc. | Blowing agent blends |
JP4901026B2 (ja) * | 2001-06-29 | 2012-03-21 | 株式会社ジェイエスピー | ポリスチレン系樹脂押出発泡板の製造方法及びポリスチレン系樹脂押出発泡板 |
US9359481B2 (en) | 2003-11-26 | 2016-06-07 | Owens Corning Intellectual Capital, Llc | Thermoplastic foams and method of forming them using nano-graphite |
US9187608B2 (en) | 2005-09-08 | 2015-11-17 | Owens Corning Intellectual Capital, Llc | Polystyrene foam containing a modifier-free nanoclay and having improved fire protection performance |
US8119701B2 (en) * | 2005-10-24 | 2012-02-21 | Owens Corning Intellectual Capital, Llc | Method of manufacturing polystyrene foam with polymer processing additives |
US7624910B2 (en) | 2006-04-17 | 2009-12-01 | Lockheed Martin Corporation | Perforated composites for joining of metallic and composite materials |
US20070173554A1 (en) * | 2005-10-27 | 2007-07-26 | Yadollah Delaviz | Method of manufacturing polystyrene foam with polymer processing additives |
WO2007149418A2 (en) * | 2006-06-22 | 2007-12-27 | Meadwestvaco Corporation | Nucleating agents for plastic foams |
US20080242752A1 (en) * | 2007-03-28 | 2008-10-02 | Yadollah Delaviz | Polystyrene foams incorporating nanographite and HFC-134 |
RU2009141968A (ru) * | 2007-04-16 | 2011-05-27 | Дау Глобал Текнолоджиз Инк. (Us) | Алкенилароматический пенопласт с низкорастворимыми фторуглеводородами |
BRPI0822773A2 (pt) * | 2008-06-04 | 2015-06-30 | Owens Corning Intellectual Cap | Espuma de poliestireno extrudada contendo carbonato de propileno, carbonato de etileno ou carbonato de butileno como um auxiliar de processo |
CN102341226B (zh) * | 2009-03-04 | 2014-03-05 | 陶氏环球技术有限责任公司 | 具有分段成型的挤出聚合物发泡方法 |
CA2839446C (en) | 2011-06-27 | 2020-01-21 | Owens Corning Intellectual Capital, Llc | Organic infrared attenuation agents |
US10017618B2 (en) | 2013-12-20 | 2018-07-10 | Kaneka Corporation | Extruded polystyrene foam and method for producing same |
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CA1086450A (en) | 1976-02-03 | 1980-09-23 | Kyung W. Suh | Styrene polymer foam and preparation thereof |
EP0445847A3 (en) * | 1987-04-15 | 1992-01-15 | The Dow Chemical Company | Preparation of polymer foam and product |
US5182040A (en) | 1991-03-28 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of 1,1,2,2-tetrafluoroethane |
JPH05287111A (ja) | 1992-04-10 | 1993-11-02 | Asahi Glass Co Ltd | 熱可塑性樹脂発泡体を製造する方法 |
US5278196A (en) | 1993-03-25 | 1994-01-11 | Great Lakes Chemical Corp. | Hydrofluorocarbon compositions as blowing agents for cellular plastics |
WO1998003581A1 (en) * | 1996-07-24 | 1998-01-29 | E.I. Du Pont De Nemours And Company | Closed cell thermoplastic foams containing hfc-134 |
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1998
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- 1998-12-11 KR KR1020007006734A patent/KR20010033292A/ko not_active Application Discontinuation
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US6225364B1 (en) | 2001-05-01 |
CA2315229A1 (en) | 1999-06-24 |
WO1999031170A1 (en) | 1999-06-24 |
JP2002508419A (ja) | 2002-03-19 |
TR200002398T2 (tr) | 2000-11-21 |
KR20010033292A (ko) | 2001-04-25 |
HUP0004460A3 (en) | 2003-02-28 |
AU1722399A (en) | 1999-07-05 |
EP1042392A1 (en) | 2000-10-11 |
NO20003148D0 (no) | 2000-06-16 |
NO20003148L (no) | 2000-07-18 |
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