CN1065870A - 含氢氟烃发泡剂的微孔和超微孔材料 - Google Patents
含氢氟烃发泡剂的微孔和超微孔材料 Download PDFInfo
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Abstract
公开了含氢氟烃(HFC)发泡剂的改进微孔和超
微孔材料。这些发泡剂比全卤代氯氟烃(CFCs)对环
境更为有利。
Description
本发明涉及含氢氟烃(HFC)发泡剂的改进微孔和超微孔聚合物材料。这些对环境更为有利的发泡剂耗损地球同温层臭氧层的潜力为零,其全球变暖潜力比全卤代氯氟烃(CFCS)低得多。
本文中所使用的“微孔”这一术语,系指一种具有下列通性的合成有机聚合物结构:1)该聚合物基本上全部以由厚度小于2微米、较好小于0.5微米的膜状孔壁围成的密闭多面体形孔形式存在,2)孔壁有基本上均匀的厚度和密度。
本文中所使用的“超微孔”这一术语,系指一种具有下列通性的结晶合成有机聚合物结构:1)该聚合物基本上全部以由厚度小于2微米、较好小于0.5微米的膜状孔壁围成的密闭多面体形孔形式存在,2)孔壁有基本上均匀的厚度和密度,3)有均匀结晶的聚合物取向,4)有单平面结晶的聚合物取向。这些超微孔结构和用于产生此类结构的工艺方法详见Blades和White美国专利3,227,664和3,227,784。
Parrish美国专利3,375,211公开的超微孔聚合物结构含有一种发泡剂,其穿透孔壁扩散的渗透系数比空气小。这种发泡剂在该聚合物软化点以下的温度能产生至少30mmHg的蒸气压。该专利公开了适用的发泡剂,例如,从由六氟化硫以及具有至少一个氟-碳共价键且其中氟原子数超过碳原子数的饱和脂族和环脂族化合物组成的这一组中选择的那些发泡剂。较好的是,饱和的脂族和环脂族化合物分别是全卤代链烷和全卤代环烷烃,其中至少50%的卤素是氟。适用发泡剂的具体实例包括一氯三氟甲烷,二氯二氟甲烷,1,1,2-三氯-1,2,2-三氟乙烷,对称二氯四氟乙烷,全氟环丁烷等。
Bonner美国专利3,375,212公开了由玻璃化温度至少40℃的高分子量合成有机聚合物组成的微孔结构的制备。这些结构含有上述美国专利3,375,211中所述的发泡剂。该专利包括一个生产含有全氟环丁烷发泡剂的聚氯乙烯微孔纤维的实例。
虽然全卤代氯氟烃化合物已经是非常有效的发泡剂,但人们担心这样的化合物释放到大气中可能是造成地球同温层臭氧层耗损的一个因素。此外,这些化合物可能是全球变暖的一种根源。(参阅P.S.Zurer,“Search Intensifies for Alternatives to Ozone-Depleting Halocarbons”(加强对耗损臭氧的卤代烃的替代物的探索),Chemical & Engineering News,1988年2月8日,17-20页)。
本发明涉及含有耗损地球同温层臭氧层的潜力为零且全球变暖潜力比全卤代氯氟烃低得多的、对环境更为有利的发泡剂的微孔和超微孔聚合物材料的提供。
本发明提供含有对环境更为有利的发泡剂的改进微孔和超微孔聚合物材料。所做的改进包括从由实验式为CnF2n+1H(其中n是2~5的一个整数)的氢氟烃化合物组成的这一组中选择发泡剂。较好是,这种超微孔材料是由一种选自由聚丙烯、聚乙烯和聚对苯二甲酸乙二醇酯组成的这一组的聚合物组成的,而微孔材料则是由聚氯乙烯组成的。更好的是,聚合物是聚对苯二甲酸乙二醇酯,而发泡剂是五氟乙烷或1,1,1,2,3,3,3-七氟丙烷。微孔和超微孔材料可以呈短纤维、长丝或片材的形式。
本发明涉及含有氢氟烃发泡剂的微孔和超微孔聚合物材料。这些发泡剂耗损地球同温层臭氧层的潜力为零,其全球变暖潜力比全卤代氯氟烃低得多。
本门技术熟练人员都了解用于生产微孔和超微孔聚合物材料的瞬时纺丝法,这样的方法可用于本发明。这些材料可呈诸如片材、长丝或短纤维等形式。在如上述美国专利3,227,784和3,375,212中所述的已知瞬时纺丝工艺中,首先制备一种合成有机成膜聚合物在活化液体中的溶液。随后将该溶液挤压到一个具有低得多的压力和温度的区域,其中该活化液体迅速蒸发,使该溶液冷却到该聚合物能发生沉淀和定向凝固的温度。
适合于制备微孔和超微孔结构的聚合物类别,在技术上是众所周知的。这些聚合物包括聚烯烃如聚乙烯和聚丙烯,聚酰胺如尼龙66,聚酯如聚对苯二甲酸乙二醇酯,及卤代聚合物如聚氯乙烯。所谓“聚烯烃”这一术语,系指一系列仅由碳和氢组成的高度饱和开链聚合的烃类中的任何一种。所谓“聚乙烯”这一术语,系指乙烯的均聚物和共聚物,其中至少80%(重量)的重复单元是乙烯单元。所谓“聚丙烯”这一术语,系指丙烯的均聚物和共聚物,其中至少80%(重量)的重复单元是丙烯单元。在本发明中,较好使用聚对苯二甲酸乙二醇酯。
适用于这样的结构的瞬时纺丝的活化液体类别也是众所周知的。这种活化液体的主要目的是在急骤蒸发时产生小孔,这样的液体一般具有下列性质:
a)沸点比所用聚合物的熔点低至少10℃、较好是低至少60℃,
b)在混合和挤压期间基本上不与该聚合物反应,
c)在该溶剂的沸点或沸点以下,溶解不到1%的聚合物,和
d)在高温度压下能与该聚合物形成均匀溶液。适用的活化液体包括诸如二氯甲烷和三氯氟甲烷。
如果使用聚乙烯或聚丙烯,则该溶液也可以包括一种固体成核剂,以有助于在该溶液挤压的特定时刻提供足够数目的泡核。这些已知的成核剂包括诸如气相二氧化硅(可从Cabot公司购买“Cab-O-Sil”产品)、高岭土和滑石。此外,该溶液可含有这样一些已知的瞬时纺丝添加剂,如染料、紫外光稳定剂、抗氧剂、增强颗粒等。
如Parrish美国专利3,375,211和Bonner美国专利3,375,212中所述(其公开文书列为本文参考文献),一般有两种方法用于把一种发泡剂引进到微孔和超微孔结构中。这些方法中任意一种都可用于引进本发明的发泡剂。这些方法可用间歇法即非连续工艺或连续工艺执行。
一种现在通常称为“后发泡”法的方法一般涉及用一种能使孔壁增塑即溶胀的增塑剂和一种专用发泡剂处理事先形成的聚合物结构。然后迅速脱除该增塑剂,使发泡剂截留在孔内。当随后将这些孔暴露于空气时,渗透压梯度随即形成,使空气能渗透这些孔并使之膨胀,同时该发泡剂仍基本上截留在这些孔内。
另一种方法现在通常称为“纺入发泡”法,是一种瞬时纺丝法,一般涉及在一个压力容器中混合该聚合物、发泡剂和活化液体,形成一种可纺溶液。然后通过一个喷丝孔将该溶液挤压到一个压力和温度都低得多的区域,形成该聚合物结构。
已知微孔和超微孔材料的适用发泡剂必须有某些最起码的性质。本发明的氢氟烃发泡剂具有这样的性质,包括下列方面:
a)该发泡剂必须是基本上“不渗透”的。所谓“不渗透”这一术语,在本文中使用时系指该发泡剂通过孔壁扩散的渗透系数不仅在25℃比空气小,而且该发泡剂在室温,例如低于40℃,也不能以如下速度渗透同样的孔壁:该发泡剂的50%或更多将在一天时间内,较好是一个月时间内或更长时间扩散到周围大气中。
b)该发泡剂必须能在该聚合物软化点以下的温度产生至少30mmHg的蒸气压。
c)由于发泡剂的渗透速度随着其扩散系数和溶解度增大而增大,所以,发泡剂的分子尺寸应当尽可能大,要与30mmHg的最低蒸气压相一致,而且对闭合的聚合物孔壁基本上没有溶剂能力或亲合力。
本发明的关键改进是使用一种氢氟烃化合物作为发泡剂,其实验式为CnF2n+1H,式中n是2~5的一个整数。具体的氢氟烃化合物包括,例如,五氟乙烷和1,1,1,2,3,3,3-七氟丙烷。这些发泡剂的制造可能产生该发泡剂结构异构体的混合物,这些异构体也会是适用的。
本发明的氢氟烃发泡剂是一组有特色的氢氟烃化合物。尽管目前已经有数百种氢氟烃化合物,但据发现,只有那些实验式为CnF2n+1H(式中n是2~5的一个整数)的化合物才是有效的发泡剂,也才有理想的环境性质。下列表Ⅰ列举了含有本发明的氢氟烃发泡剂(五氟乙烷或1,1,1,2,3,3,3-七氟丙烷)、对比的已知发泡剂(全氟环丁烷或六氟化硫)和本发明范围以外的氢氟烃发泡剂的聚对苯二甲酸乙二醇酯超微孔纤维的明显的性质。
表Ⅰ
发泡剂 化学式 *厚度回复率 *发泡剂
保留率
全氟环丁烷 C4F882% 84%
(FC-318)**
五氟乙烷 C2F5H 76% 87%
(HFC-125)
1,1,1,2,3,3,3-七氟丙烷 C3F7H 88% 81%
(HFC-227ea)
六氟化硫 SF697% 90%
(SF6)
1,1,1,2-四氟乙烷 C2F4H228% 17%
(HFC-134A)
1,1,2,2-四氟乙烷 C2F4H233% 12%
(HFC-134)
1-氯-1,2,2,2-四氟乙烷 C2F4ClH 38% 35%
(HCFC-124)
2-(三氟甲基)-1,
1,1,3,4,5,5,5-
九氟戊烷 C6F12H26% 20%
(HFC-53-12)
*厚度回复率/发泡剂保留率:这些测量是200磅/平方英寸静压负荷测试步骤的结果,对此还要在下面“测试方法”一节中进一步介绍。
**括号名称:FC-318,HFC-125等这些名称代表发泡剂化学式的缩略语。
较好的是使用发泡剂五氟乙烷和1,1,1,2,3,3,3-七氟丙烷,因为如表Ⅰ中所示,这些发泡剂使聚对苯二甲酸乙二醇酯超微孔纤维能表现出大于70%的厚度回复率和80%的发泡剂保留率。这样一些性质对于在聚对苯二甲酸乙二醇酯超微孔材料支撑重负荷的情况下的应用是理想的。
本发明的发泡剂全都是特别理想的,因为若释放到地球的大气中,它们比全卤代氯氟烃(CFC)发泡剂对环境更为有利。人们大都认为,CFCS的环境危险可归因于两个决定性因素。第一个因素是氯在CFC化合物中的重量百分率。第二个因素是CFC化合物的稳定性或在大气中的寿命。
CFC化合物是如此稳定,以致它往往穿透到地球的同温层中,在那里,氯原子终究被释放出来破坏臭氧分子。结果,已开发出有一个或多个氢原子的新型卤代烃化合物,即氢氯氟烃(HCFCS)。由于这些HCFC化合物含有氢,它们在大气中通过脱卤化氢反应发生破坏,因此,在大气中的寿命比CFCS短。然而,尽管有这个特征,但由于氯的存在,HCFCS仍然有某种臭氧耗损潜力。相反,本发明的发泡剂属于一类有一个氢原子而没有氯原子的卤代烃化合物,通常称之为氢氟烃(HFCS)。由于本发明的氢氟烃发泡剂不含有任何氯原子,所以它们的臭氧耗损潜力为零。此外,由于这些氢氟烃发泡剂也含有一个氢原子,所以这种发泡剂在大气中的寿命缩短到它不会对地面烟雾和全球变暖做出显著贡献的程度。
测试方法
聚对苯二甲酸乙二醇酯发泡超微孔纤维的厚度回复率、发泡剂含量和发泡剂保留率是用下列步骤测定的。
厚度回复率:
把外形尺寸大于2英寸×2英寸的纤维样品捆札到一块尺寸为4英寸×4英寸×1/4英寸的金属板上,直至该板覆盖一层平行紧密排列的纤维为止。然后把该板翻转90°,并把第二层纤维放在该板上,从而使第二层的纤维轴与第一层成直角。
然后,用一支Ames规测量这些纤维的初始厚度(Ti)。然后把该板插在一台静负荷试验机的柱塞下,把一个200磅/平方英寸的负荷加到样品纤维上。这个200磅/平方英寸的负荷施加64.5小时,然后撤除。在3天的回复期之后,测量纤维的最终厚度(Tf),用下列公式计算厚度回复率(%)。
厚度回复率(%)= (最终厚度(Tf))/(初始厚度(Ti)) ×100
发泡剂含量/发泡剂保留率:
一片铝箔在一台Mettler天平上称重,记为重量A。把至少0.04克样品纤维放在该铝箔上,然后和铝箔一起称重。这个重量记为重量B。然后把铝箔摺叠起来,使其3个开边各为约3/8英寸。然后把铝箔插在一台温度为280℃的Carver热压机的压板之间。慢慢泵该压机的杠杆直至表压达到约5000磅/平方英寸为止,使压板合龙。45秒钟后,把压板打开,且镊子取出铝箔。将铝箔冷却,称重精确到0.0001克。这个重量记为重量C,然后用下列公式计算样品的发泡剂含量(%)。
聚合物重量=重量C-重量A
发泡剂重量=重量B-重量C
发泡剂含量(%)= (发泡剂重量)/(聚合物重量) ×100
然后对一个新鲜纤维样品进行上述的200磅/平方英寸静负荷测试,测定该样品的发泡剂含量。然后用下列公式计算该样品的发泡剂保留率(%)。
发泡剂保留率(%)= (静负荷样品的发泡剂含量)/(对照样品的发泡剂含量) ×100
以下实例说明本发明。实例3~8是对比实例,并在本发明的范围之外。虽然这些实例说明了用相对小型的设备进行的间歇式工艺方法,但它们能进行放大和转变成连续工艺方法。
实例
先用如下瞬时纺丝工艺制备不含发泡剂的聚对苯二甲酸乙二醇酯超微孔纤维。
在一个用干燥氮气吹扫的干燥箱子中,在一个3升镍高压釜中装入1600克相对粘度(HRV)为72.1的聚对苯二甲酸乙二醇酯和1000毫升无水二氯甲烷。高压釜装配一个长度和直径为0.008英寸(0.020毫米)的喷丝孔。喷丝头用一个移动式密封套密封。然后,把这个组装单元从干燥箱中取出,缠上电热丝,放进一个保温、抽气的箱子内。将高压釜围绕它的重心旋转,以便当其内部温度上升到预期的230℃时使其溶解的内容物混合。然后将高压釜定位,给溶液上方的蒸气空间施加1000磅/平方英寸(表压)的氮气压力。打开喷丝头,当超微孔纤维自由落入空气中时,随时将其收集起来。超微孔纤维的HRV为38。
然后对该纤维进行如下的后发泡工艺过程,其中用一种增塑剂和所希望的发泡剂处理该纤维。
一个一升树脂釜装配一支温度计,一个干冰冷凝器和一个气体注入口。将大约150毫升二氯甲烷(增塑剂)放入树脂釜中,冷凝器装入干冰,通入所希望的发泡剂,通常以气体形式通过一个调节器和减压装置,再通过气体注入口。随着发泡剂气体在指形冷冻器上冷凝以及回流物返回釜中,二氯甲烷便冷却下来,并逐渐为一个大气压的发泡剂所饱和。继续通入发泡剂,直至釜中饱和溶液的温度下降到预期点,通常是在0~15℃这一范围。将一束超微孔纤维称重,连同一个用来使其沉没的金属网一起放进冷的但不断回流的发泡剂溶液中。在经过预期时间之后,通常约5~15分钟,取出这束纤维,迅速浸入55℃水中约30秒钟。(采取这个步骤是为了使该纤维快速脱增塑剂并使发泡剂截留于其中。)然后将这束纤维放进一个温度约110℃的鼓风烘箱内,使该纤维充分膨胀并与空气达成平衡。然后将这束纤维冷却、称重,以确定渗入的发泡剂数量,用水置换法测量纤维的体积,以确定其密度。这些实例全都是用上述瞬时纺丝法和后发泡法在规定条件下以如下表Ⅱ中所示的特定发泡剂进行的。表Ⅱ也记录了这些聚对苯二甲酸乙二醇酯超微孔纤维的性质。
密度:纤维中的聚合物克数/立方厘米(不包括发泡剂)
分压:发泡剂分压,用大气压单位表示,用如下公式确定:
分压= (发泡剂含量×密度×224)/(发泡剂的分子量)
发泡剂含量,厚度回复率和发泡剂保留率:这些性质是用上节“测试方法”中所述的测试步骤测定的。
Claims (15)
1、一种含有合成结晶有机聚合物密闭多面体孔的改进超微孔材料,其中这些孔含有一种发泡剂,所做的改进包括从由具有如下实验式的氢氟烃化合物组成的一组中选择发泡剂:
式中,n是2~5的一个整数。
2、权利要求1中所定义的一种改进超微孔材料,其中发泡剂是五氟乙烷。
3、权利要求1中所定义的一种改进超微孔材料,其中发泡剂是1,1,1,2,3,3,3-七氟丙烷。
4、权利要求1中所定义的一种改进超微孔材料,其中聚合物选自由聚乙烯、聚丙烯和聚对苯二甲酸乙二醇酯组成的一组。
5、权利要求1中所定义的一种改进超微孔材料,其中聚合物是聚、对苯二甲酸乙二醇酯。
6、权利要求5中所定义的一种改进超微孔材料,其中发泡剂是五氟乙烷。
7、权利要求5中所定义的一种改进超微孔材料,其中发泡剂是1,1,1,2,3,3,3-七氟丙烷。
8、权利要求1中所定义的一种改进超微孔材料,其中该材料呈短纤维形式。
9、权利要求1中所定义的一种改进超微孔材料,其中该材料呈长丝形式。
10、权利要求1中所定义的一种改进超微孔材料,其中该材料呈片材形式。
11、一种含有合成有机聚合物密闭多面体孔的改进微孔材料,其中这些孔含有一种发泡剂,所做的改进包括从由具有如下实验式的氢氟烃化合物组成的一组中选择发泡剂:
式中,n是2~5的一个整数。
12、权利要求11中所定义的一种改进微孔材料,其中该聚合物是聚氯乙烯。
13、权利要求11中所定义的一种改进微孔材料,其中该材料呈短纤维形式。
14、权利要求11中所定义的一种改进微孔材料,其中该材料呈长丝形式。
15、权利要求11中所定义的一种改进微孔材料,其中该材料呈片材形式。
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EP1708895B1 (en) * | 2004-01-28 | 2012-01-25 | SAPIO PRODUZIONE IDROGENO OSSIGENO S.r.l. | Method for minimizing heat retention within a tyre filled with a gas and rotating on a surface. |
US20060157882A1 (en) * | 2004-12-10 | 2006-07-20 | Simona Percec | Filled ultramicrocellular structures |
US20060159907A1 (en) * | 2004-12-10 | 2006-07-20 | Simona Percec | Filled ultramicrocellular structures |
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DE345580C (de) * | 1919-09-21 | 1921-12-16 | Johannes Gotthilf Dietrich | Schablonierverfahren und Vorrichtung zu seiner Durchfuehrung |
US3227664A (en) * | 1961-12-07 | 1966-01-04 | Du Pont | Ultramicrocellular structures of crystalline organic polymer |
US3375211A (en) * | 1963-08-16 | 1968-03-26 | Du Pont | Ultramicrocellular polymeric structures containing an inflatant |
US3381077A (en) * | 1966-01-26 | 1968-04-30 | Du Pont | Method for inflating closed cell foams |
US3521328A (en) * | 1966-06-23 | 1970-07-21 | Du Pont | Process for carding microcellular fibers |
US3375212A (en) * | 1967-02-14 | 1968-03-26 | Du Pont | Microcellular polymeric structure |
US3743694A (en) * | 1971-07-13 | 1973-07-03 | Du Pont | Method for rendering microcellular staple fibers self-inflatable in air involving the continuous transporting of the fibers through a reaction pipeline |
US3730916A (en) * | 1971-07-13 | 1973-05-01 | Du Pont | Process of treating microcellular polymeric staple fibers to render them postinflatable |
JPS63260416A (ja) * | 1986-04-15 | 1988-10-27 | Japan Styrene Paper Co Ltd | 発泡成形体の製造方法 |
DE3819630A1 (de) * | 1988-06-09 | 1989-12-14 | Bayer Ag | Verfahren zum einbringen von treibmitteln in mindestens eine der fliessfaehigen reaktionskomponenten fuer die herstellung von polyurethanschaumstoffen |
DE3824354A1 (de) * | 1988-07-19 | 1990-01-25 | Basf Ag, 67063 Ludwigshafen | Verfahren zur herstellung von zellhaltigen kunststoffen nach dem polyisocyanat-polyadditionsverfahren mittels lagerstabiler, treibmittelhaltiger emulsionen und diese emulsionen |
JPH02265933A (ja) * | 1989-04-07 | 1990-10-30 | Asahi Glass Co Ltd | 発泡合成樹脂の製造方法 |
JP2773233B2 (ja) * | 1989-05-09 | 1998-07-09 | 旭硝子株式会社 | フェノール樹脂発泡体の製造方法 |
US4997706A (en) * | 1990-02-09 | 1991-03-05 | The Dow Chemical Company | Foaming system for closed-cell rigid polymer foam |
-
1991
- 1991-04-18 US US07/687,057 patent/US5254400A/en not_active Expired - Lifetime
-
1992
- 1992-04-16 DE DE69230639T patent/DE69230639T2/de not_active Expired - Fee Related
- 1992-04-16 CN CN92102682.XA patent/CN1065870A/zh active Pending
- 1992-04-16 WO PCT/US1992/003037 patent/WO1992018562A1/en active IP Right Grant
- 1992-04-16 JP JP51139692A patent/JP3154722B2/ja not_active Expired - Fee Related
- 1992-04-16 EP EP92911496A patent/EP0580771B1/en not_active Expired - Lifetime
- 1992-04-16 ES ES92911496T patent/ES2143472T3/es not_active Expired - Lifetime
- 1992-04-16 CA CA002108694A patent/CA2108694A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1307244C (zh) * | 2001-02-02 | 2007-03-28 | 阿托菲纳公司 | 以hfc-134a和环戊烷为基础的聚合物发泡剂 |
WO2021208192A1 (zh) * | 2020-04-16 | 2021-10-21 | 博聚(上海)生态科技有限公司 | 一种快速生物降解的微多孔聚酯纤维的生产工艺 |
Also Published As
Publication number | Publication date |
---|---|
JP3154722B2 (ja) | 2001-04-09 |
CA2108694A1 (en) | 1992-10-19 |
JPH06506975A (ja) | 1994-08-04 |
WO1992018562A1 (en) | 1992-10-29 |
DE69230639D1 (de) | 2000-03-09 |
ES2143472T3 (es) | 2000-05-16 |
EP0580771B1 (en) | 2000-02-02 |
US5254400A (en) | 1993-10-19 |
EP0580771A1 (en) | 1994-02-02 |
DE69230639T2 (de) | 2000-08-31 |
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