CN101657496A - 聚合物泡沫 - Google Patents
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Abstract
本发明涉及聚合物泡沫,其可通过制备包含真空或充气隔间的聚合物泡沫的方法通过以下步骤制备:a)制备在溶剂中的1-20重量%聚合物溶液;b)在聚合物溶液中添加颗粒;c)通过加热、冷却、老化或凝结来固化其中含有颗粒的聚合物以获得包含颗粒的聚合物泡沫或基体,并由该聚合物基体获得含有隔间的聚合物泡沫;及d)任选洗涤、干燥和/或加热所述聚合物泡沫;其中在步骤b)中,i)所述颗粒为其中中空部分为真空或充气隔间以得到聚合物泡沫的惰性中空颗粒;或ii)所述颗粒为在溶剂中不可溶以得到聚合物基体的固体颗粒;从而在步骤c)中在加热、冷却、老化或凝结之后通过将固体颗粒溶解于其中所述固体颗粒可溶且所述聚合物不可溶的第二溶剂中而除去聚合物基体中的固体颗粒以得到聚合物泡沫;或iii)所述颗粒为可膨胀颗粒,在步骤b)中溶解于溶剂时和/或在步骤c)中加热过程中释放出气泡而得到聚合物泡沫,其中所述聚合物选自芳族聚酰胺和刚性杆形聚合物。
Description
本发明涉及一种制备聚合物泡沫的方法、这些泡沫及由其制备的成型制品。
芳族聚酰胺是众所周知的作为纤维(包括纸浆)和膜市售的聚合物。这类产品的实例以商品名例如和市售。芳族聚酰胺也以与其它聚合物材料的复合材料应用。其它聚合物为以市售的PBO、也称为M5的PIPD和以市售的共聚(对亚苯基/3,4’-氧联二亚苯基对苯二甲酰胺)。成型制品可由该类复合材料制成,但对许多应用而言,它们具有的缺点是太密实且太重以致于不实用。因此需要可以任何所需形状成型的轻聚合物材料。在传统上,如果需要轻聚合物成型材料,则通常使用泡沫,例如用于建筑材料、隔绝材料和防火或阻燃材料中。
US 4,178,419描述了密度为0.025-0.7g/cm3的泡沫材料。这些泡沫使用N,N’-二烷基芳族聚酰胺制备,将其加热以使该聚酰胺脱烷基化而形成泡沫。该方法具有许多缺点。应在250-340℃下加热以进行脱烷基化和产生泡沫。为了避免聚合物降解,加热应在与获得基本上脱烷基化产物相适应的短时间和低温下进行。实际上获得了不完全脱烷基化或分解产物。特别不完全的脱烷基化可能非常危险,因为该产物可能由于在燃烧条件下分裂出其它链烯而过度可燃。其它缺点是必定产生N-烷基化单体并且聚合该类单体,然而使用标准聚酰胺聚合物则更加经济。此外,密度,即平均孔大小难以控制,并且实际上该类孔的均匀分布是不可能的。
US 2005/0256214描述了通过将溶剂THF吸收至聚合物基体中,然后将其加热蒸发出THF而制备PBO泡沫。该方法具有类似于上述US4,178,419在工艺可控性和可能存在可燃且有毒的痕量THF方面的缺点,因此较不优选该方法。
JP 2001098106描述了通过形成分散有金属氧化物细颗粒的膜,然后除去金属氧化物颗粒以形成多孔膜而制备的多孔膜。该方法不能用于制备泡沫。
因此本发明目的为提供一种制备由任何聚合物组成的泡沫和泡沫状材料的更通用的方法,从而可容易地控制泡沫性能。
为此,本发明涉及一种通过以下步骤制备包含真空或充气隔间的聚合物泡沫的方法:
a)制备在溶剂中的1-20重量%聚合物溶液;
b)在聚合物溶液中添加颗粒;
c)通过加热、冷却、老化或凝结来固化其中含有颗粒的聚合物以获得包含颗粒的聚合物泡沫或基体,并由该聚合物基体获得含有隔间的聚合物泡沫;及
d)任选洗涤、干燥和/或加热所述聚合物泡沫;
其中在步骤b)中,
i)所述颗粒为其中中空部分为真空或充气隔间以得到聚合物泡沫的惰性中空颗粒;或
ii)所述颗粒为在溶剂中不可溶以得到聚合物基体的固体颗粒;从而在步骤c)中在加热、冷却、老化或凝结之后通过将固体颗粒溶解于其中所述固体颗粒可溶且所述聚合物不可溶的第二溶剂中而除去聚合物基体中的固体颗粒以得到聚合物泡沫;或
iii)所述颗粒为可膨胀颗粒,在步骤b)中溶解于溶剂时和/或在步骤c)中加热过程中释放出气泡而得到聚合物泡沫,其中所述聚合物选自芳族聚酰胺和刚性杆形聚合物。
所述聚合物可为任何芳族聚酰胺,包括芳族羟基官能化聚酰胺,或刚性杆形聚合物。刚性杆形聚合物为芳族聚二噁唑和芳族聚二咪唑。芳族聚酰胺的实例为对芳族聚酰胺如以商品名和市售的聚(对亚苯基-对苯二甲酰胺)(PPTA)、芳族羟基官能化聚酰胺如聚-4,4’-(3,3’-二羟基)-二亚苯基-对苯二甲酰胺(OH-BPTA)、以商品名市售的共聚(对亚苯基/3,4’-氧联二亚苯基对苯二甲酰胺)。典型的刚性杆形聚合物为以商品名市售的聚(对亚苯基-苯并二噁唑)(PBO)和聚(对亚苯基-吡啶并二咪唑)(PIPD,M5)。
将聚合物溶于溶剂中。合适的溶剂可选自例如NMP/CaCl2、硫酸、(聚)磷酸和含有强碱的碱水溶液(pKa>9)。
当使用PPTA-NMP/CaCl2溶液时,固化步骤可最容易通过升高的温度如50-250℃,更优选80-120℃,然后通过用合适溶剂洗涤除去该溶剂而进行。这导致聚合物固化,在特定条件下可导致结晶聚合物。该固化步骤导致其中已含有隔间或其隔间可通过另一工艺步骤获得的聚合物基体。固化聚合物基体的另外方法可通过在非溶剂(即聚合物在其中不可溶的溶剂)中凝结而进行。合适的溶剂可选自例如水、甲醇、丙酮和pKa<5的含酸的酸水溶液。
在第一个实施方案中,所述颗粒为惰性中空颗粒,其中空部分为真空或充有气体如氧气、空气、氮气、二氧化碳等。该类颗粒可为例如中空玻璃、陶瓷,或软木珠。就本发明而言,惰性指的是对所述方法中使用的溶剂呈惰性。因此,其它材料如金属也是可以的,但是它们通常更昂贵且通常更重。玻璃颗粒可以商品名例如(购自Trelleborg Emerson&Cuming,Inc.)和3MTM玻璃泡市售。它们为例如硼硅酸钠制成的中空玻璃微球。这些含中空部分的玻璃微球成为与聚合物混合的整体材料,从而所述中空部分形成泡沫的隔间。通常所述颗粒为其至少50体积%的直径为1-500μm,优选10-100μm,更优选40-70μm的珠粒。该类玻璃泡的尺寸分布非常窄且可容易地选自大量市售种类。
在聚合物固化之后,使其中含有玻璃微球而得到泡沫。泡沫密度优选为0.1-1g/cm3。更具体地,密度为0.1-0.3g/cm3,但应考虑到它们还取决于玻璃的壁厚。玻璃(或陶瓷材料)越厚就越重且密度由此越大。这些微球的中空部分可填充气体如空气、氧气、氮气、二氧化碳等,或者这些中空部分为真空。因此当使用该方法时,密度的差别不必与隔间尺寸完全相关。该实施方案在工艺简化方面为最容易的方法。
在第二个实施方案中,所述颗粒为在溶剂中不可溶的固体颗粒。因此当所述聚合物固化时,这些固体颗粒保留在聚合物中而得到聚合物基体。在该阶段,聚合物基体还不包含隔间,也不是泡沫。然后,应在另一工艺步骤中将这些固体颗粒溶于与用于溶解聚合物的溶剂不同的(第二)溶剂中。重要的是所述聚合物在该第二溶剂中不可溶。通过使用该方法,当从聚合物基体中洗出固体颗粒而留下空的隔间时形成泡沫,其中所述空的隔间在干燥和任选加热之后充入空气。合适的固体材料为无机盐如氯化钠、氯化钙、碳酸钠、氢氧化钠、碳酸氢钾,碳水化合物如蔗糖等。非常合适的第二溶剂为水,其一方面不是聚合物的溶剂,另一方面是大部分盐的极好溶剂。这些固体颗粒的粒度可与第一个实施方案的颗粒相同。所述固体颗粒可通过使用合适的筛子以所需且窄的尺寸分布获得。泡沫密度与上述相同。
在第三个实施方案中,所述颗粒为在溶解聚合物的溶剂中可溶或不可溶的可膨胀颗粒。可膨胀颗粒例如以作为可膨胀微球产品的(购自Akzo Nobel)已知。包含填充有气体的塑料微粒。当加热气体时,压力增加,塑料壳软化且微球体积增加超过40倍。将未膨胀颗粒加入聚合物溶液中,然后加热以使微球膨胀以及使聚合物固化而得到发泡产品。当未膨胀颗粒溶于溶剂中时,即使不加热,它们也释放出气泡。在释放气泡过程中,目前作为所用聚合物和用于可膨胀颗粒的聚合物的混合物的聚合物固化而形成泡沫,泡沫中吸收有可膨胀颗粒释放出的小气泡。或者,还可以使用市售膨胀类型,因为聚合物没有完全渗入这些颗粒的孔中。因此,虽然较难控制,还是加热含有膨胀颗粒的聚合物溶液以获得在其中含有的膨胀颗粒中具有隔间的聚合物泡沫。所述膨胀颗粒的粒度可与第一个实施方案的颗粒相同。泡沫密度在上述给定的范围内。
还可以将本发明方法用于可转化成其它聚合物的聚合物。因此,例如可在实际上作为另外聚合物前驱体的聚合物上应用该方法,其在工艺步骤d)中通过加热而由起始聚合物形成。
上述含有非纤维基体的泡沫可用于制备成型制品,包括建筑材料、地毯衬垫、汽车部件、汽车车身填料等。该泡沫也可直接用作例如缝隙填料、隔绝材料等。成型泡沫和泡沫本身具有优异的耐温性和机械性能如高弯曲强度和剪切强度,并且由此特别适合于其中耐火性很重要的应用。当制备成型制品时,有利的是在模具中进行固化工艺而直接获得制品。
包含颗粒的聚合物溶液还可进一步含有其它成分如填料、颜料、导电剂、阻燃剂等。非纤维泡沫的添加剂的实例为纸浆、纤维如芳族聚酰胺纤维、二氧化硅、碳、纳米管、颜料、木屑、陶瓷、砂等。
本发明通过以下非限制性实施例进一步说明。
实施例1
在将200g玻璃微球SI-250(购自Emerson & Cuming Ltd.)与在NMP/CaCl2(NMP=N-甲基吡咯烷酮)中的750g PPTA(聚合物浓度为3.6重量%)混合之后(21.1重量%微球),制备可模塑成任何所需形状的面团状材料。
在该实施例中,使用扁平容器盛装该面团状材料。将所述容器置于100℃温度下的烘箱中约1.5小时。混合物结晶成片状。通过用热水洗涤该片状物约24小时而除去残留NMP。洗涤之后干燥该片状物。所述方法得到226g泡沫密度为0.17g/cm3的发泡片。
实施例2-5
类似于实施例1通过在实施例1的PPTA-NMP/CaCl2混合物中混合不同浓度的微球而制备具有不同密度的泡沫。
获得以下泡沫:
实施例 | 微球重量% | 泡沫密度[g/cm3] |
2 | 10.7 | 0.23 |
3 | 15.3 | 0.20 |
4 | 21.3 | 0.16 |
5 | 29.1 | 0.16 |
实施例6-9
类似于实施例1在实施例1的PPTA-NMP/CaCl2混合物中制备含有微球的不同密度泡沫。
这些泡沫具有以下密度:
实施例 | 微球类型 | 微球重量% | 泡沫密度[g/cm3] |
6 | E&C[0.25g/cm3]* | 21.3 | 0.11 |
7 | 3M;K1[0.125g/cm3]** | 13.8 | 0.06 |
8 | 3M;K25V[0.25g/cm3]** | 23.1 | 0.12 |
9 | 3M;K46[0.46g/cm3]** | 37.2 | 0.24 |
*购自Emerson & Cuming Ltd.
**购自3M Company
实施例10
类似于实施例1方法制备由含有3M微球(3M;K25V)的在NMP中的重量%聚合物溶液制成的泡沫(23.1重量%微球)。然而,因为溶液没有固化成晶体,所以将该混合物倾入模具中,用水凝结并洗涤以获得泡沫密度为0.12g/cm3的固体成型制品。
实施例11
该实施例由含有3M微球(3M;K25V)的在H2SO4中的20重量%PPTA制成。在90℃温度下,将178g该聚合物溶液与27g微球混合(13.2重量%微球)。将混合物倾入模具中并且冷却固化。在凝结之后,洗涤该固体成型产品以除去硫酸。该泡沫密度为0.36g/cm3。
实施例12
在该实施例中,使用在NMP中的重量%聚合物溶液并与盐颗粒(NaCl)混合。将70g聚合物溶液与128g NaCl混合约10分钟之后,将该混合物倾入模具中。使该混合物凝结并且洗出NMP和NaCl盐而获得泡沫。该泡沫密度为0.18g/cm3。
实施例13
Claims (14)
1.一种通过以下步骤制备包含真空或充气隔间的聚合物泡沫的方法:
a)制备在溶剂中的1-20重量%聚合物溶液;
b)在聚合物溶液中添加颗粒;
c)通过加热、冷却、老化或凝结来固化其中含有颗粒的聚合物以获得包含颗粒的聚合物泡沫或基体,并由所述聚合物基体获得含有隔间的聚合物泡沫;及
d)任选洗涤、干燥和/或加热所述聚合物泡沫;
其中在步骤b)中,
i)所述颗粒为其中中空部分为真空或充气隔间以得到聚合物泡沫的惰性中空颗粒;或
ii)所述颗粒为在溶剂中不可溶以得到聚合物基体的固体颗粒;从而在步骤c)中在加热、冷却、老化或凝结之后通过将固体颗粒溶解于其中所述固体颗粒可溶且所述聚合物不可溶的第二溶剂中而除去聚合物基体中的固体颗粒以得到聚合物泡沫;或
iii)所述颗粒为可膨胀颗粒,在步骤b)中溶解于溶剂时和/或在步骤c)中加热过程中释放出气泡而得到聚合物泡沫,其中所述聚合物选自芳族聚酰胺和刚性杆形聚合物。
2.根据权利要求1的方法,其中所述聚合物选自聚(对亚苯基-对苯二甲酰胺)、聚-4,4’-(3,3’-二羟基)-二亚苯基-对苯二甲酰胺、聚(对亚苯基-苯并二噁唑)、聚(对亚苯基-吡啶并二咪唑)和共聚(对亚苯基/3,4’-氧联二亚苯基对苯二甲酰胺)。
3.根据权利要求1或2的方法,其中所述颗粒为惰性中空颗粒,其中惰性材料为玻璃或陶瓷材料;或者所述颗粒为固体颗粒,其中所述固体为无机盐且所述第二溶剂为水。
4.根据权利要求3的方法,其中所述颗粒为玻璃或陶瓷材料的惰性中空颗粒,其中所述中空部分填充有气体。
5.根据权利要求1的方法,其中所述颗粒为其至少50体积%的直径为1-500μm,优选10-100μm,更优选40-70μm的珠粒。
6.根据权利要求1-5中任一项的方法,其中步骤c)的固化在模具中进行。
7.一种包含具有隔间的聚合物基体的泡沫,其隔间被惰性或膨胀材料包围,或者一种包含选自芳族聚酰胺和刚性杆形聚合物的聚合物与可膨胀颗粒的聚合物的混合物的基体的泡沫,其中所述隔间为真空或填充有气体。
8.根据权利要求7的泡沫,其中所述隔间被玻璃或陶瓷材料的惰性材料包围。
9.根据权利要求7或8的泡沫,其中所述聚合物选自聚(对亚苯基-对苯二甲酰胺)、聚-4,4’-(3,3’-二羟基)-二亚苯基-对苯二甲酰胺、聚(对亚苯基-苯并二噁唑)、聚(对亚苯基-吡啶并二咪唑)和共聚(对亚苯基/3,4’-氧联二亚苯基对苯二甲酰胺。
10.一种包含具有隔间的聚合物基体的泡沫,所述隔间为真空或填充有气体,其中所述聚合物选自芳族聚酰胺和刚性杆形聚合物,条件是所述聚合物不为PPTA。
11.根据权利要求10的泡沫,其中所述聚合物选自聚-4,4’-(3,3’-二羟基)-二亚苯基-对苯二甲酰胺、聚(对亚苯基-苯并二噁唑)、聚(对亚苯基-吡啶并二咪唑)和共聚(对亚苯基/3,4’-氧联二亚苯基对苯二甲酰胺)。
12.根据权利要求7-11中任一项的泡沫,其中所述隔间的平均直径为1-500μm,优选10-100μm。
13.根据权利要求7-12中任一项的泡沫,其密度为0.01-1g/cm3,优选0.1-0.3g/cm3。
14.包含权利要求7-13中任一项的芳族聚酰胺泡沫的成型制品。
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- 2008-03-28 BR BRPI0809606-6A patent/BRPI0809606A2/pt not_active IP Right Cessation
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2012
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107922663B (zh) * | 2015-09-04 | 2022-02-08 | 东京应化工业株式会社 | 多孔膜的制造方法 |
CN108649114A (zh) * | 2018-04-26 | 2018-10-12 | 东华大学 | 一种无机热电材料基柔性热电转换器件 |
CN108649114B (zh) * | 2018-04-26 | 2021-03-23 | 东华大学 | 一种无机热电材料基柔性热电转换器件 |
CN110394936A (zh) * | 2019-07-31 | 2019-11-01 | 太仓富宇塑胶科技有限公司 | 汽车遮阳板的epp本体制备方法 |
CN112679793A (zh) * | 2021-01-25 | 2021-04-20 | 华东理工大学 | 一种轻质、隔热、阻燃pipd纳米纤维气凝胶制备和应用 |
Also Published As
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WO2008122373A3 (en) | 2009-03-19 |
US8142695B2 (en) | 2012-03-27 |
JP5622320B2 (ja) | 2014-11-12 |
WO2008122373A2 (en) | 2008-10-16 |
US20120165423A1 (en) | 2012-06-28 |
EP2155809B1 (en) | 2017-10-25 |
RU2461589C2 (ru) | 2012-09-20 |
EP2155809A2 (en) | 2010-02-24 |
US20100036007A1 (en) | 2010-02-11 |
BRPI0809606A2 (pt) | 2014-09-30 |
KR20100015352A (ko) | 2010-02-12 |
CN101657496B (zh) | 2013-02-13 |
KR101525836B1 (ko) | 2015-06-05 |
RU2009140754A (ru) | 2011-05-10 |
CA2683482A1 (en) | 2008-10-16 |
JP2010523743A (ja) | 2010-07-15 |
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