CN1204173C - 包含氢氟碳、低沸点醇和/或低沸点羧基化合物的发泡剂组合物 - Google Patents
包含氢氟碳、低沸点醇和/或低沸点羧基化合物的发泡剂组合物 Download PDFInfo
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- CN1204173C CN1204173C CNB018211275A CN01821127A CN1204173C CN 1204173 C CN1204173 C CN 1204173C CN B018211275 A CNB018211275 A CN B018211275A CN 01821127 A CN01821127 A CN 01821127A CN 1204173 C CN1204173 C CN 1204173C
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- foaming agent
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- polymers
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/127—Mixtures of organic and inorganic blowing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及发泡剂组合物,该组合物包含至少一种沸点为30℃或更高,并低于120℃的氢氟碳;至少一种沸点低于30℃的氢氟碳;和至少一种选自低沸点醇和低沸点羰基化合物的组分。本发明也涉及使用这样发泡剂组合物制备聚合物泡沫的方法,以及包含这样发泡剂组合物的聚合物泡沫和可发泡聚合物组合物。
Description
本发明涉及一种发泡剂组合物,该组合物包含沸点为30℃或更高,并低于120℃的氢氟碳(HFC)(中等范围低沸点HFC);沸点低于30℃的氢氟碳HFC(低范围低沸点HFC);和至少一种选自低沸点醇和低沸点羰基化合物的组分。本发明进一步涉及聚合物泡沫和这样发泡剂组合物生产聚合物泡沫的用途,和包括聚合物的可发泡剂聚合物组合物,该聚合物组合物含有分散在其中的这样发泡剂组合物。
低沸点醇是制备聚合物泡沫的发泡剂组合物中的有用组分。“低沸点醇”和“LBA”在此是可互换的术语并表示沸点低于120℃的醇。LBAs可塑化聚合物(参见,例如,U.S.专利No.4,663,360的12栏50-52行),在比非塑化聚合物更低压力下促进聚合物的膨胀。此外,甚至在相对高浓度下,其中其它发泡剂倾向于用作成核剂和降低泡沫孔度的浓度,LBAs倾向于保持或增加泡沫孔度。结果是,人们可以使用相对高浓度的醇以降低泡沫密度而不降低泡沫孔度。降低密度而不降低泡沫孔度对于制备隔热聚合物泡沫是有吸引力的。
令人遗憾地,当用作发泡剂时醇具有缺点。醇可以与泡沫中存在的卤代组分,如卤代阻燃剂反应,以产生腐蚀性酸。酸倾向于腐蚀金属设备。此外,醇可逸出到大气中,因此它们会导致不需要的挥发性有机化合物(VOC)散发。
低沸点羰基化合物,如酮和醛,可相似于醇促进聚合物泡沫的生产,但这样做而不显著引起酸形成。“低沸点羰基化合物”和“LBC”是可互换的术语,表示沸点低于120℃的醛或酮。令人遗憾地,残余的LCBs也可逸出到大气中,因此它们会导致不需要的挥发性有机化合物(VOC)散发。
由于规则鼓励替代氢氯氟碳(HCFC)和氯氟碳(CFC)发泡剂组分,它们两者可引起臭氧消耗,含有HFCs的发泡剂得到普遍认可。HFCs具有低于大多数聚合物或发泡剂(不是HCFCs和CFCs)的导热系数,使得聚合物泡沫中的HFC可降低泡沫的导热系数。
令人遗憾地,低范围低沸点HFCs倾向于从聚合物泡沫逸出,因此引起聚合物泡沫导热系数的不需要增加及随着时间的有机散发。中范围低沸点HFCs如1,1,1,3,3-五氟丁烷(HFC-365mfc)作为发泡剂的研究正在进行中。中范围低沸点HFCs也可降低聚合物泡沫导热系数,并倾向于比低范围低沸点HFCs在聚合物泡沫中停留更长。
需要一种得益于LBA和/或LBC化合物优点的发泡剂组合物,该组合物仍然具有较少醇和/或羰基化合物的不利效果。也需要进一步包括HFCs以降低通过聚合物泡沫的导热系数的发泡剂组合物,特别是如果中范围低沸点HFC部分代替低范围低沸点HFC。
“氢氟碳”和“HFC”是可互换的术语,表示包含氢、碳和氟的有机化合物,化合物基本没有除了氟的卤素。
“沸点”表示在一个大气压下的沸点。
“中范围低沸点氢氟碳”,“中范围低沸点HFC”,和“MRLB HFC”是可互换的术语,表示沸点为30℃或更高,并低于120℃的HFC。
“低范围低沸点氢氟碳”,“低范围低沸点HFC”,和“LRLB HFC”是可互换的术语,表示沸点小于30℃的HFC。
“新鲜”表示在一个月内,优选在一周内,更优选在一天内,仍然更优选在一小时内,最优选就在制造之后。
“LBA和/或LBC”表示“LBA,LBC,或LBA和LBC”。
“基本没有”规定组分的聚合物泡沫或发泡剂组合物分别表示包含10重量百分比(wt%)或更小,优选5wt%或更小,更优选1wt%或更小,仍然更优选0.5wt%或更小,最优选0wt%规定组分的聚合物泡沫或发泡剂组合物。
在第一方面,本发明是一种发泡剂组合物,包括:(a)至少一种沸点为30℃或更高,并低于120℃的氢氟碳;(b)至少一种沸点低于30℃的氢氟碳;和(c)至少一种选自低沸点醇和低沸点羰基化合物的组分。第一方面的实施方案包括基本没有低沸点羰基化合物的组合物和包含乙醇,丙酮,和另外发泡剂至少一种的组合物。第一方面的一个优选实施方案进一步包括浓度小于组合物50wt%的二氧化碳。第一方面的另一个优选实施方案包括1,1,1,3,3-五氟丁烷,1,1,1,2-四氟乙烷,乙醇,和二氧化碳,其中二氧化碳小于组合物的50wt%。
在第二方面,本发明是一种生产聚合物泡沫的方法,包括如下步骤:(a)从聚合物和第一方面的发泡剂组合物形成可发泡聚合物组合物;和(b)将该可发泡聚合物组合物膨胀成聚合物泡沫。
在第三方面,本发明是一种聚合物泡沫,该泡沫包括:(a)聚合物;(b)沸点为30℃或更高,并低于120℃的氢氟碳;(c)沸点低于30℃的氢氟碳;和(d)至少一种选自低沸点醇和低沸点羰基化合物的组分。
在第四方面,本发明是一种包括聚合物的可发泡聚合物组合物,含有分散在其中的第一方面的发泡剂组合物。
令人惊讶地,可通过用MRLB HFC部分代替LRLB HFC,LBA和LBC的至少一种,达到低泡沫导热系数和与由LRLB HFC和LBA和/或LBC组成的发泡剂组合物相关的容易加工。此外,在泡沫的发泡剂组合物中,人们可以由MRLB HFC部分代替LRLB HFC,LBA和LBC的至少一种在形成之后90天达到更低的泡沫导热系数。
本发明的发泡剂组合物特别用于制备隔热聚合物泡沫。
本发明涉及包括至少一种MRLB HFC,至少一种LRLB HFC,和至少一种选自LBAs和LBCs的组分的发泡剂组合物。
合适的LBAs包括含有1-5个碳(C1-C5)的脂族醇如甲醇、乙醇、正丙醇和异丙醇。LBAs可以是无水的或可以不是无水的,但优选是无水的(包含小于1重量百分比(wt%)水,基于醇的重量)。LBA优选是乙醇或异丙醇,更优选无水乙醇。
合适的LBCs包括沸点低于120℃的酮或醛。说明性LBCs包括丙酮、2-丁酮和乙醛。
发泡剂组合物可以没有LBA,条件是存在LBC,和没有LBC,条件是存在LBA,或可以包含LBA和LBC两者。LBA和LBC的结合浓度,基于发泡剂组合物重量,大于0wt%,优选至少1wt%,更优选至少5wt%,仍然更优选至少10wt%,和典型地60wt%或更小,优选50wt%或更小,更优选40wt%或更小,仍然更优选20wt%或更小。大于60wt%的LBA和/或LBC浓度倾向于过量塑化聚合物,使加工困难并导致不适当的聚合物泡沫导热系数。
合适的MRLB HFCs包括沸点为30℃或更高,并低于120℃的任何HFC。合适MRLB HFCs的例子包括脂族化合物如HFC-365mfc、1-氟丁烷、九氟环戊烷、全氟-2-甲基丁烷、1-氟己烷、全氟-2,3-二甲基丁烷、全氟-1,2-二甲基环丁烷、全氟己烷、全氟异己烷、全氟环己烷、全氟庚烷、全氟乙基环己烷、全氟-1,3-二甲基环己烷和全氟辛烷;以及芳族化合物如氟苯、1,2-二氟苯、1,4-二氟苯、1,3-二氟苯、1,3,5-三氟苯、1,2,4,5-四氟苯、1,2,3,5-四氟苯、1,2,3,4-四氟苯、五氟苯、六氟苯和1-氟-3-(三氟甲基)苯。由于它的增加可得性和使用容易,特别需要HFC-365mfc。如果在HFC和聚合物之间的增强相容性有助于在形成之后在聚合物泡沫中保留HFC,芳族HFCs对于使用芳族聚合物制备聚合物泡沫也可能有吸引力。MRLB HFCs相对于LRLB HFCs具有的一个优点,一般在于它们典型地在聚合物泡沫中保留更长。HFC保留对于减缓导热系数增加和与逸出HFC有关的有机物散发是有吸引力的。MRLBHFCs也比LRLB HFCs容易处理,这是由于它们在大气压下(760mm汞)为缩合相,因此在发泡工艺期间并不要求液化。
本发明的发泡剂组合物包括相对于发泡剂组合物重量浓度如下的MRLB HFC:大于0wt%,一般10wt%或更大,更一般5wt%或更大,仍然更一般3wt%或更大,和一般40wt%或更小,更一般60wt%或更小,仍然更一般80wt%或更小,和最一般95wt%或更小。
在大于95wt%的浓度下,MRLB HFC会过量塑化聚合物,使发泡困难。
发泡剂组合物也包括LRLB HFC。LRLB HFC典型地在聚合物泡沫中作为发泡剂和隔热剂。LRLB HFCs具有低导热系数,相似于MRLB HFCs。因此,在发泡聚合物泡沫中的残余LRLB HFC有助于降低泡沫的导热系数。LRLB HFC残余物一般占据泡孔空间而MRLB HFC残余物一般缩合到泡孔壁上或缩合入泡孔壁中。因此,LRLB HFCs一般在降低的聚合物泡沫导热系数下比MRLB HFCs更有效。
合适的LRLB HFCs包括氟甲烷、二氟甲烷(HFC-32)、全氟甲烷、氟乙烷(HFC-161)、1,1-二氟乙烷(HFC-152a)、1,1,1-三氟乙烷(HFC-143a)、1,1,2,2-四氟乙烷(HFC-134)、1,1,1,2-四氟乙烷(HFC-134a)、五氟乙烷(HFC-125)、全氟乙烷、2,2-二氟丙烷(HFC-272fb)、1,1,1-三氟丙烷(HFC-263fb)、1,1,1,2,3,3,3-七氟丙烷(HFC-227ea)、1,1,1,3,3-五氟丙烷(HFC-245fa)、及其混合物。优选的LRLB HFC是HFC-134a。
相对于总组合物重量,发泡剂组合物中的LRLB HFC浓度大于0wt%,通常10wt%或更大,更通常15wt%或更大,仍然更通常30wt%或更大,最优选大于50wt%。
LRLB HFC的浓度上限主要依赖于聚合物中LRLB HFC的溶解度极限。聚合物中超过溶解度极限的LRLB HFC浓度与剩余的发泡剂组合物结合,导致在聚合物膨胀期间的过量成核(泡沫的发泡)。熟练技术人员可以不进行过度试验而确定在给定发泡剂组合物中的LRLB HFC上限。LRLB HFC的浓度是95wt%或更小(相对于发泡剂组合物重量),所需地80wt%或更小,优选75wt%或更小,更优选60wt%或更小。
尽管另外的发泡剂不是必须的,发泡剂组合物优选包括至少一种另外的发泡剂。另外的发泡剂用于降低泡沫密度。另外发泡剂的合适选择可增加发泡剂的总摩尔数而不降低孔度,增加密度,和/或降低尺寸稳定性。
合适的另外发泡剂包括无机和有机发泡剂以及分解成无机和/或有机发泡剂的化学发泡剂。合适的无机发泡剂包括氮气、氩气、水、空气和氦气。有机发泡剂包括二氧化碳(CO2)、醚、含有1-9个碳的(C1-9)脂族烃、完全和部分卤代的C1-4脂族烃。脂族烃包括甲烷、乙烷、丙烷、正丁烷、异丁烷、正戊烷、异戊烷、新戊烷、环丁烷和环戊烷。优选另外的发泡剂包括水、CO2、异丁烷和环戊烷。最优选的发泡剂是CO2。
一般情况下,发泡剂组合物中任何单个另外发泡剂的浓度小于聚合物中,在工艺温度(典型地聚合物的玻璃化转变温度)下和在整个发泡剂组合物存在下的发泡剂溶解度极限。一般情况下,另外的发泡剂包括发泡剂组合物的50wt%或更小,30wt%或更小,甚至10wt%或更小。
CO2,MRLB HFC,LRLB HFC,LBA,LBC,和任何另外的发泡剂的总和占发泡剂组合物的100wt%。
优选发泡剂组合物的例子是45-60wt%HFC-134a,25-40wt%HFC-365mfc,10-20wt%乙醇,和1-10wt%CO2。
本发明也涉及包括LBA和/或LBC,MRLB HFC,和LRLB HFC的发泡剂组合物用于制备可发泡聚合物组合物和聚合物泡沫的用途。
任何常规的发泡泡沫工艺适于使用本发明的发泡剂组合物制备发泡聚合物泡沫。一般情况下,通过塑化聚合物,在初始压力下在其中引入发泡剂以形成可发泡组合物,和然后将可发泡组合物曝露于低于初始压力的发泡压力和允许可发泡组合物膨胀成聚合物泡沫,而制备聚合物泡沫。典型地,在相对于聚合物树脂的重量份,在大于0份每一百(pph),优选大于5pph,和典型地小于25pph,优选小于20pph,和更优选小于15pph的浓度下引入发泡剂组合物以形成可发泡聚合物组合物。使用大于25pph的发泡剂组合物可产生具有不期望密度和孔度的泡沫。
形成可发泡聚合物组合物的典型方法包括:(1)塑化聚合物,典型地通过加热它到处于或大于其玻璃化转变温度或熔融温度的加工温度,以形成塑化的聚合物,和(2)在初始压力下向塑化的聚合物中加入发泡剂组合物以形成可发泡聚合物组合物。单独或以结合的方式加入发泡剂组合物的组分。由间歇或连续工艺,使用常规设备如挤出机或混合共混机,向塑化的聚合物中引入发泡剂组合物。初始压力足以防止可发泡组合物的实质膨胀和一般将发泡剂组合物分散入塑化的聚合物中。尽管不必须,初始压力通常大于大气压。
通过降低可发泡组合物周围的压力到发泡压力或将可发泡组合物转移到在发泡压力下的发泡区中,发泡可发泡的聚合物组合物。发泡压力低于初始压力和可以大于或小于大气压,但典型地是大气压。发泡剂组合物中的发泡剂在发泡压力下膨胀,将可发泡聚合物组合物膨胀成聚合物泡沫。
在将可发泡组合物曝露于发泡压力之前,冷却热塑化的可发泡组合物至低于加工温度用于优化泡沫性能。在挤出机或其它混合设备中或在单独的换热器中冷却可发泡组合物。
熟练技术人员确认存在通用程序的许多变化以及其它方式以制备适于本发明目的的聚合物泡沫。例如,U.S.专利No.4,323,528公开了通过积累挤出工艺制备聚合物泡沫的方法。方法包括:1)混合热塑性材料和发泡剂组合物以形成可发泡聚合物组合物;2)将可发泡聚合物组合物挤出到保持在阻止可发泡聚合物组合物发泡的温度和压力下的保持区中;保持区有一个限制孔板开口进入更低压力区的模头和可开放的门关闭模头孔板;3)周期地开启闸门;4)基本与3)同时通过移动柱塞在可发泡聚合物组合物上施加机械压力以将它从保持区通过模头孔排出到更低压力的区域,和5)允许排出的可发泡聚合物组合物在更低压力的区域中膨胀以形成聚合物泡沫。
用于本发明的合适聚合物包括热塑性聚合物。合适的热塑性聚合物包括选自如下的那些:乙烯基芳族聚合物如聚苯乙烯;橡胶改性的乙烯基芳族聚合物如高抗冲聚苯乙烯(HIPS);乙烯基芳族共聚物如苯乙烯/丙烯腈或苯乙烯/丁二烯共聚物;氢化乙烯基芳族聚合物和共聚物如氢化聚苯乙烯和氢化苯乙烯/丁二烯共聚物;α-烯烃均聚物如低密度聚乙烯、高密度聚乙烯和聚丙烯;线性低密度聚乙烯(乙烯/辛烯-1共聚物)和乙烯与可共聚,单烯属不饱和单体如含有3-20个碳原子的α-烯烃的其它共聚物;丙烯与可共聚,单烯属不饱和单体如含有4-20个碳原子的α-烯烃的其它共聚物;乙烯与乙烯基芳族单体的共聚物,如乙烯/苯乙烯共聚体;乙烯/丙烯共聚物;乙烯与烷烃的共聚物如乙烯/己烷共聚物;热塑性聚氨酯(TPU’s);及其共混物或混合物,特别是聚苯乙烯和乙烯/苯乙烯共聚体的共混物。
其它合适的聚合物包括聚氯乙烯、聚碳酸酯、聚酰胺、聚酰亚胺、聚酯如聚对苯二甲酸乙二醇酯、聚酯共聚物和改性聚酯如聚对苯二甲酸乙二醇酯-二醇(PETG)、苯酚-甲醛树脂、热塑性聚氨酯(TPUs)、生物降解多糖如淀粉和聚乳酸聚合物和共聚物。
聚合物优选是聚乙烯(PE)、聚苯乙烯(PS)、聚丙烯(PP)、PS和乙烯/苯乙烯共聚体(ESI)的共混物、ESI和PE的共混物、ESI和PP的共混物、PS,PE和ESI的共混物或ESI与任何一种或多种如下物质的共混物:使用金属茂催化剂或受限几何催化剂(如The Dow ChemicalCompany’s INSITETM催化剂,INSITE是The Dow Chemical Company的商标)生产的聚烯烃或乙烯/α-烯烃共聚物、三元共聚物或共聚体。
另外的添加剂,如通常用于制备聚合物泡沫的那些,可以包括在可发泡组合物中。另外的添加剂可包括颜料,粘度改性剂,阻燃剂,红外阻滞剂(例如,炭黑和石墨),成核剂,渗透改性剂,和挤出助剂。有趣地,含有成核剂对于使用本发明的发泡剂组合物以制备聚合物泡沫不是必须的。
本发明进一步涉及包括聚合物,MRLB HFC,LRLB HFC,和LBA和/或LBC的聚合物泡沫。典型地,聚合物泡沫包含用于它制造的发泡剂残余物。然而,发泡剂倾向于从聚合物泡沫逸出和空气倾向于随时间渗透入聚合物泡沫中。因此,优选表征聚合物泡沫在说明为“新鲜”的时间范围内,最优选就在制造之后,以保证发泡剂不逸出和空气不污染泡沫。当它们包括在用于制备泡沫的发泡剂组合物中时,聚合物泡沫可进一步包含另外的发泡剂,如CO2。人们可使用标准分析技术,如气相色谱识别发泡剂残余物的存在。
本发明的聚合物泡沫可采取本领域已知的任何物理构型,如片材、棒、厚板、或聚结平行条和/或片材。形式优选是厚板,更优选横截面为30平方厘米(cm2)或更大和以较小尺寸的截面厚度为0.25英寸(6.4毫米(mm))或更大,更优选0.375英寸(9.5mm)或更大,和仍然更优选0.5英寸(12.7mm)或更大的厚板。较小尺寸至多为8英寸(200mm)的聚合物泡沫是可能的。较小尺寸的上限由发泡设备限制条件限制。给定足够大的设备,大于8英寸(200mm)的较小尺寸是可以想象得到的。
本发明的聚合物泡沫的密度为10千克每立方米(kg/m3)或更大,正常地25kg/m3或更大和正常地100kg/m3或更小,最通常45kg/m3或更小。密度小于10kg/m3的聚合物泡沫一般缺乏所需的结构整体性。本发明的聚合物泡沫的密度可至多到,但不包括,用于制备泡沫的聚合物和添加剂的结合物的密度。
本发明的聚合物泡沫可以是开孔的(大于20百分比(%)开孔的)或闭孔的(小于20%开孔的),但由于它一般具有更低的导热系数,优选是小于10%开孔的泡沫。根据ASTM D2856-A确定开孔百分比。典型地,本发明聚合物泡沫在制备之后60天,优选在制备之后90天的导热系数(根据ASTM方法C-518-98使用24℃的样品温度测量)为35毫瓦每米-开尔文(mW/m·K)或更小,优选30mW/m·K或更小。
本发明聚合物泡沫的平均孔度大于0.05毫米(mm),优选大于0.075mm,更优选大于0.1mm,和小于2mm,优选小于1.2mm。使用ASTM方法D3576采用如下改进测量平均孔度:(1)使用光学或电子显微镜将泡沫成象而不是将图象投影在屏幕上;和(2)划已知长度但间隔大于15个泡孔的线而不是划30mm线。
如下实施例进一步说明,但并不限制本发明的范围。
对比例(Comp Ex)A和实施例(Ex)1
将100重量份PS(购自The Dow Chemical Company的F168PS,168,000重均分子量)与1.2份每一百(pph)六溴环十二烷(HBCD),0.15pph焦磷酸四钠(TSPP),0.15pph硬脂酸钡,0.15pph蓝色浓缩物(在PS中20wt%铜酞菁,按浓缩物重量计),和0.2pph线性低密度PE2247a(购自The Dow Chemical Company)一起加入到64mm单螺杆挤出机中和加热到200℃以制备熔融混合物。根据PS的重量确定pph。
对于Comp Ex A,在14.5兆帕(MPa)的初始压力下,向熔融混合物中加入由73wt%HFC-134a,19wt%无水乙醇,和8wt%CO2(其中wt%是相对于总发泡剂组合物重量)构成的发泡剂组合物以形成可发泡聚合物组合物。Comp Ex A中发泡剂的总数量是8.54pph,基于PS重量,或0.12摩尔每100克PS(mol/100gPS)。
对于Ex 1,在13.2MPa的初始压力下,向熔融混合物中加入由60wt%HFC-134a,16wt%无水乙醇,8wt%CO2,和16wt%HFC-365mfc(其中wt%是相对于总发泡剂组合物重量)构成的发泡剂组合物以形成可发泡聚合物组合物。Ex 1中发泡剂的总数量是8.86pph,基于PS重量,或0.12mol/100gPS。
对于Comp Ex A和Ex 1两者,将可发泡聚合物组合物通过一系列换热器以冷却可发泡聚合物组合物到大约125℃。通过狭缝模头(50mm宽有2mm间隙)将可发泡聚合物组合物膨胀到大气压的区域中。将膨胀的泡沫成形为大约30mm厚和200mm宽的板。
表1包含Comp Ex A和Ex 1两者的泡沫密度和导热系数值以及残余发泡剂浓度。在除去泡沫皮层之后,根据ASTM方法D-1622-98测量泡沫密度。就在制造之后(新鲜λ)和在制造之后90天(90天λ),根据ASTM方法C518-98(在24℃下)对Comp Ex A和Ex 1测量导热系数。
使用气相色谱与质量选择性检测(GC/MSD)测量残余发泡剂浓度。通过将0.46-0.54克泡沫溶解入包含五毫升四氢呋喃的小瓶中,制备GC/MSD的样品。加入十毫升甲醇以沉淀聚合物。直接将THF/甲醇上清液注入装配有Hewlett-Packard 5971A质量选择性检测器的Hewlett-Packard 5890II气相色谱中。使用DB-5柱(J&W ScientificCompany,30米乘0.25mm直径有0.25微米涂料厚度)。仪器设定情况是:柱压力(5psi),样品洗涤(2),样品泵(4),粘度(0),溶剂A(2),溶剂B(2),净化B(关),检测器温度(260℃),注射器温度(260℃),烘箱平衡(0.50分钟),烘箱程序(50℃下2分钟,然后以15℃/分钟升温到65℃和保持2分钟)。检测器设定情况是:溶剂延迟(0),EM绝对(1360),低量(35),高量(100),EMV偏移(0),取样(2),扫描/秒(10.2),电压(1360),阈值(150)。监视器离子质量83对于HFC-134a,离子质量65对于HFC-365mfc,和离子质量43对于乙醇。
此方法并不检测(ND)CO2,故表1中没有CO2数值。在制造之后125-130天测量残余发泡剂浓度。期望在测量残余发泡剂浓度之前,基本上所有的CO2从泡沫逸出。
泡沫密度以磅每平方英尺(pcf)和千克每立方米(kg/m3)计。表1中的pph数值是相对于PS树脂重量。导热系数是以毫瓦每米-开尔文(mW/m*K)计。
表1
测量 | 单位 | Comp Ex A | Ex 1 |
泡沫密度 | Kg/m3(pcf) | 39.1(2.44) | 37.3(2.33) |
残余HFC-134a | pph | 4.37 | 3.75 |
残余HFC-365mfc | pph | 0.00 | 1.11 |
残余乙醇 | pph | 0.00 | 0.00 |
残余CO2 | pph | ND | ND |
残余总发泡剂 | pph | 4.37 | 4.86 |
%剩余的总发泡剂 | % | 51 | 55 |
新鲜λ | mW/m*k | 21.5 | 21.6 |
90天λ | mW/m*k | 27.8 | 27.4 |
Ex 1对Comp Ex A的比较说明在PS泡沫中,导热系数并不被降低乙醇和HFC-134a和在用于制备PS泡沫的发泡剂组合物中包括HFC-365mfc显著影响。同时,Ex 1展示比Comp Ex B更多的残余发泡剂,说明发泡剂组合物的改进保留和因此采用HFC-365mfc发泡剂配方剂,说明发泡剂组合物的改进保留和因此采用HFC-365mfc发泡剂配方相对于没有HFC-365mfc的发泡剂配方,较小的发泡剂散发。
Ex 1进一步说明HFC-365mfc保留在PS泡沫中比HFC-134a更长。发泡剂组合物中的83%HFC-365mfc在125天之后保留在泡沫中,正如与HFC-134a的71%相比较。
Comp Ex B和Ex 2-6
以相似于Comp Ex A和Ex 1的方式制备Comp Ex B和Ex 2-6,区别在于使用表2中的发泡剂组合物和发泡剂加入压力。Comp Ex A没有HFC-365mfc和Ex 2-6包括作为HFC-134a部分替代的HFC-365mfc,乙醇,和水。
发泡剂浓度以相对于PS重量的wt%计(在圆括号中的数值是相对于总发泡剂重量)。初始压力以MPa计。总发泡剂浓度以相对于PS树脂重量的pph计和以摩尔每一百克PS(mol/100gPS)计。
表2
测量 | Comp Ex B | Ex2 | Ex3 | Ex4 | Ex5 | Ex6 |
HFC-134a,以wt%计 | 6.15(66) | 5.40(55) | 4.77(47) | 5.28(59) | 4.79(49) | 4.76(47) |
HFC-365mfc,以wt%计 | 0.00(0) | 1.77(18) | 2.65(26) | 1.34(15) | 2.66(27) | 3.09(30) |
乙醇,以wt%计 | 2.23(24) | 1.77(18) | 1.77(18) | 1.43(16) | 1.42(15) | 1.41(14) |
CO2,以wt%计 | 0.71(8) | 0.71(7) | 0.71(7) | 0.72(8) | 0.71(7) | 0.71(7) |
水,以wt%计 | 0.19(2) | 0.16(2) | 0.17(2) | 0.16(2) | 0.16(2) | 0.16(2) |
总发泡剂浓度(以pph计) | 9.28 | 9.81 | 10.07 | 8.93 | 9.74 | 10.13 |
(以mol/100gPS计) | 0.15 | 0.14 | 0.14 | 0.13 | 0.14 | 0.14 |
初始压力(MPa) | 10.8 | 12.1 | 14.9 | 12.9 | 11.6 | 10.9 |
如在实施例1中测量泡沫密度,新鲜λ和90天λ。同样测量在制造之后124-128天,每种发泡剂在泡沫中保留多少(参见表3关于对于每种泡沫多少天)。表3包含Comp Ex B和Ex 2-6的这些数值。如在CompEx A和Ex 1中确定残余发泡剂浓度。当测量残余发泡剂时,CO2是不可检测的,水也是不可检测的。对于确定表3中的总发泡剂浓度,假定CO2和水两者从泡沫逸出。
泡沫密度是以kg/m3计(在圆括号中的数值是pcf)。浓度以相对于PS树脂的pph计,导热系数以mW/m*K计。总发泡剂以相对于PS树脂重量的pph计。
表3
测量 | CompEx B | Ex2 | Ex3 | Ex4 | Ex5 | Ex6 |
泡沫密度,以kg/m3(pcf)计 | 34.0(2.12) | 34.6(2.16) | 34.5(2.15) | 37.2(2.32) | 36.2(2.26) | 36.4(2.27) |
测试之前的天数 | 128 | 125 | 126 | 124 | 126 | 125 |
残余HFC-134a,以wt%计 | 4.35 | 3.97 | 3.29 | 3.86 | 3.78 | 3.49 |
残余HFC-365mfc,以wt%计 | 0.00 | 1.56 | 2.05 | 1.23 | 2.30 | 2.47 |
残余乙醇,以wt%计 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
残余CO2,以wt%计 | ND | ND | ND | ND | ND | ND |
残余水,以wt%计 | ND | ND | ND | ND | ND | ND |
残余总发泡剂,以pph计 | 4.35 | 5.53 | 5.34 | 5.09 | 6.08 | 5.96 |
%剩余HFC-134a | 71 | 74 | 69 | 73 | 79 | 73 |
%剩余HFC-365mfc | -- | 88 | 77 | 92 | 86 | 80 |
%剩余的总发泡剂 | 47 | 56 | 53 | 57 | 62 | 59 |
新鲜λ,以mW/m*K计 | 21.8 | 22.3 | 21.9 | 22.0 | 21.5 | 22.5 |
90天λ,以mW/m*K计 | 28.4 | 27.7 | 27.5 | 27.5 | 27.3 | 27.3 |
Ex2-6说明在聚苯乙烯泡沫的发泡剂组合物中,采用HFC-365mfc部分代替HFC-134a,乙醇,CO2,和水可降低90天λ数值和增加泡沫中剩余的发泡剂组合物两者。
Ex2-6进一步说明HFC-365mfc比HFC-134a从聚合物泡沫逸出到更小的程度。
在发泡剂组合物中代替其它LRLB HFCs,LBAs和LBCs时和当从不是PS的聚合物制备泡沫时,希望相似的优点是期望的。
Comp Ex C和Ex 7
在50mm单螺杆挤出机中在200℃下,将100pph PS树脂(购自TheDow Chemical Company的XZ40 PS树脂)与2.8份每一百(pph)六溴环十二烷,0.15pph铜酞菁浓缩物(在PS中20wt%铜酞菁),0.2pph硬脂酸钡,0.4pph线性低密度聚乙烯(DOWLEX2247a,2247a是The Dow物熔体。所有的pph数值相对于PS树脂重量。XZ40 PS树脂是重均分子量(Mw)为151,000,多分散性(Mw/Mn)为3.1,和熔体流动指数(MFI)为33克每10分钟(g/10min)的共混物。使用ASTM方法D-1238(190℃,5kg负荷)测量MFI。
在164巴(16.4兆帕(MPa))压力下向聚合物熔体注入发泡剂组合物(参见如下)和混合以形成可发泡聚合物组合物。冷却到125℃和通过狭缝模头(50mm宽具有0.8mm开口)挤出可发泡聚合物组合物到大气压以形成30mm厚和180mm宽聚合物泡沫。
Comp Ex C和Ex 7的发泡剂组合物(以相对于PS树脂重量的wt%计和,在圆括号中,相对于总发泡剂重量)和获得的泡沫参数见表4。
表4
测量 | Comp Ex C | Ex 7 |
HFC-245fa浓度,以wt%计 | 2.8(38) | 3.0(33) |
HFC-365mfc浓度,以wt%计 | 0(0) | 2.5(28) |
乙醇浓度,以wt%计 | 1.4(19) | 1.0(11) |
CO2,以wt%计 | 3.2(43) | 2.5(28) |
总发泡剂,以相对于PS重量的pph计 | 7.4 | 9 |
以mol/100g PS计的总发泡剂 | 0.12 | 0.12 |
密度,以kg/m3计 | 33 | 34 |
孔度,以mm计 | 0.3 | 0.3 |
90天λ*,以mW/m*K计 | 33 | 31 |
*根据标准方法EN28301使用10℃的样品温度,测量Comp Ex C和Ex 7的λ数值。
Ex 7说明采用MRLB HFC(HFC-365mfc)部分代替CO2,乙醇,和LRLBHFC(HFC-245fa),同时保持发泡剂的总摩尔数恒定可在制造之后90天降低泡沫的导热系数。
当使用其它聚合物,发泡剂组合物和添加剂时,有期望与Ex 1-7那些相似的结果。
Claims (9)
1.一种发泡剂组合物,包括:
(a)至少一种沸点为大于30℃,并低于120℃的氢氟碳;
(b)至少一种沸点低于30℃的氢氟碳;和
(c)至少一种选自低沸点醇和低沸点羰基化合物的组分。
2.根据权利要求1所述的组合物,其中所述的组合物含有10wt%或更少的低沸点羰基化合物。
3.根据权利要求1所述的组合物,其中所述的低沸点醇是乙醇。
4.根据权利要求1所述的组合物,其中所述的低沸点羰基化合物是丙酮。
5.根据权利要求1所述的组合物,进一步包括至少一种选自如下的另外发泡剂:二氧化碳、氮气、氩气、水、空气、氦气、醚、甲烷、乙烷、丙烷、正丁烷、异丁烷、正戊烷、异戊烷、新戊烷、环丁烷和环戊烷;其中另外的发泡剂占发泡剂组合物的50wt%或更小。
6.根据权利要求1所述的组合物,进一步包括二氧化碳,其中所述的二氧化碳占发泡剂组合物的50wt%或更小。
7.根据权利要求1所述的组合物,其中所述的(a)是1,1,1,3,3-五氟丁烷。
8.根据权利要求1所述的组合物,其中所述的(b)是1,1,1,2-四氟乙烷。
9.根据权利要求1所述的发泡剂组合物,进一步包括水。
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US25748300P | 2000-12-21 | 2000-12-21 | |
US60/257,483 | 2000-12-21 |
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JP (1) | JP3934552B2 (zh) |
KR (1) | KR20030064853A (zh) |
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AT (1) | ATE371697T1 (zh) |
AU (1) | AU2002219980A1 (zh) |
CA (1) | CA2431694A1 (zh) |
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DK (1) | DK1353981T3 (zh) |
ES (1) | ES2290097T3 (zh) |
HU (1) | HUP0400742A3 (zh) |
MX (1) | MX234823B (zh) |
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2001
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- 2001-11-29 HU HU0400742A patent/HUP0400742A3/hu unknown
- 2001-11-29 EP EP01272470A patent/EP1353981B1/en not_active Expired - Lifetime
- 2001-11-29 JP JP2002553404A patent/JP3934552B2/ja not_active Expired - Fee Related
- 2001-11-29 DK DK01272470T patent/DK1353981T3/da active
- 2001-11-29 AT AT01272470T patent/ATE371697T1/de active
- 2001-11-29 ES ES01272470T patent/ES2290097T3/es not_active Expired - Lifetime
- 2001-11-29 DE DE60130258T patent/DE60130258T2/de not_active Expired - Lifetime
- 2001-11-29 AU AU2002219980A patent/AU2002219980A1/en not_active Abandoned
- 2001-11-29 KR KR20037008350A patent/KR20030064853A/ko not_active Application Discontinuation
- 2001-11-29 US US09/999,277 patent/US6476080B2/en not_active Expired - Lifetime
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- 2001-11-29 CA CA002431694A patent/CA2431694A1/en not_active Abandoned
- 2001-11-29 RU RU2003122204/04A patent/RU2275395C2/ru not_active IP Right Cessation
- 2001-11-29 CN CNB018211275A patent/CN1204173C/zh not_active Expired - Fee Related
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Also Published As
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US20020132868A1 (en) | 2002-09-19 |
RU2275395C2 (ru) | 2006-04-27 |
ATE371697T1 (de) | 2007-09-15 |
DK1353981T3 (da) | 2008-01-21 |
NO20032832L (no) | 2003-08-20 |
CA2431694A1 (en) | 2002-07-04 |
JP2004516375A (ja) | 2004-06-03 |
MX234823B (es) | 2006-03-13 |
AU2002219980A1 (en) | 2002-07-08 |
NO20032832D0 (no) | 2003-06-20 |
DE60130258D1 (de) | 2007-10-11 |
CN1483059A (zh) | 2004-03-17 |
EP1353981B1 (en) | 2007-08-29 |
WO2002051919A3 (en) | 2003-04-10 |
EP1353981A2 (en) | 2003-10-22 |
KR20030064853A (ko) | 2003-08-02 |
ES2290097T3 (es) | 2008-02-16 |
MXPA03005693A (es) | 2004-04-21 |
US6476080B2 (en) | 2002-11-05 |
DE60130258T2 (de) | 2008-05-21 |
HUP0400742A3 (en) | 2008-03-28 |
AU2002219980A8 (en) | 2005-10-13 |
HUP0400742A2 (hu) | 2004-07-28 |
JP3934552B2 (ja) | 2007-06-20 |
WO2002051919A2 (en) | 2002-07-04 |
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