CN103167939A - 包含二酰肼的聚合物纤维垫和其用途 - Google Patents

包含二酰肼的聚合物纤维垫和其用途 Download PDF

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Publication number
CN103167939A
CN103167939A CN2011800356006A CN201180035600A CN103167939A CN 103167939 A CN103167939 A CN 103167939A CN 2011800356006 A CN2011800356006 A CN 2011800356006A CN 201180035600 A CN201180035600 A CN 201180035600A CN 103167939 A CN103167939 A CN 103167939A
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CN
China
Prior art keywords
pad
polymer
hydrazides
fiber
formaldehyde
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Granted
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CN2011800356006A
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English (en)
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CN103167939B (zh
Inventor
B.布朗夏尔
B.雅弗雷努
K.楚达
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Saint Gobain Technical Fabrics Canada Ltd
Saint Gobain Adfors SAS
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Saint Gobain Adfors SAS
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    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N7/00—After-treatment, e.g. reducing swelling or shrinkage, surfacing; Protecting the edges of boards against access of humidity
    • B27N7/005—Coating boards, e.g. with a finishing or decorating layer
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Abstract

本发明涉及可以捕集甲醛的试剂的聚合物纤维垫，其包含至少一种二酰肼。本发明的目的还是所述垫的用途，特别地作为用于隔热和/或隔声产品，特别地基于矿棉，聚苯乙烯或者有机或者无机泡沫的隔热和/或隔声产品的表面覆盖物。

Description

包含二酰肼的聚合物纤维垫和其用途
本发明涉及包含二酰肼作为可以捕集甲醛的试剂的聚合物纤维垫。
非常不同的复合材料使用在寓所和办公室建筑的构造和装修领域中以及运输交通工具的领域中。这些材料中一些，如声音和/或热绝缘体、木制面板、家具部件和修饰部件，使用包含甲醛基树脂的粘结剂、油漆和清漆。在这些材料中的游离甲醛的比例尤其由于加入少量可以捕集甲醛的试剂而保持在非常低的水平。
然而，关于防止产品的不希望的排放物(如甲醛，其可显示出对人的健康的危险)的规章变得更严厉的并且要求进一步地减少在材料中存在的或者可随着时间由材料放出的游离甲醛的量。
用于减少在建筑物内部的甲醛含量的手段是已知的。
已经提出在油漆或者由石膏制成的材料中(US-A-2005/0226761)、在纸或者织物、塑料或者木制材料(EP-A-1437397)中包括光催化二氧化钛的颗粒。
还已知在基于石膏或者水泥的建筑材料中使用酰肼(US-A-2004/0101695和JP-A-2004115340)或在木纤维板中使用二肼羰(EP1905560)。
本发明的目的是减少在建筑物，特别地寓所，和运输交通工具内部存在的甲醛的量。
为了实现这种目的，本发明提供包含至少一种二酰肼。
本发明的另一主题涉及该前述的垫的用途，特别地作为基于矿棉的隔热和/或隔音产品的表面覆盖物的用途。
根据本发明的二酰肼对应于下式：
H2N–NH–CO–R–CO–NH–NH2
其中R表示
-线性或支化亚烷基，其优选地包含1至18个碳原子，任选地被一个或多个羟基取代；或
-亚芳基，优选地亚苯基或亚联苯基，其任选地被一个或多个羟基、一个或多个卤素原子，特别地F，Cl或Br、或一个或多个包含1至4个碳原子的线性或支化烷基取代。
有利地，二酰肼选自其中基团R是C1-C12，优选地C1-C8亚烷基的二酰肼。优选的二酰肼是己二酸二酰肼。
优选地，二酰肼的量占该聚合物纤维垫的重量的0.1-50%，有利地0.2-20%，更好地至少等于0.3-10%。
有利地，二酰肼与表面活性剂一起使用，该表面活性剂的目的是提高纤维与二酰肼的亲合力。由此引起二酰肼在垫中的更均匀分布。
根据本发明的表面活性剂可以是阴离子、阳离子或者非离子型表面活性剂。阴离子型表面活性剂是优选的，尤其为烷基二苯醚二磺酸盐。
表面活性剂的量通常占二酰肼的重量的低于90%，优选地20-80%，有利地55-65%。
根据本发明的垫基于纤维，该纤维优选地由有机聚合物构成。
作为实例，可以提到聚烯烃纤维，例如聚乙烯纤维，聚丙烯纤维，聚异丁烯纤维和聚甲基戊烯纤维，聚醋酸乙烯酯(均聚物或者共聚物)纤维，例如乙烯-醋酸乙烯酯(EVA)纤维，聚乙烯醇(均聚物或者共聚物)纤维，例如乙烯-乙烯醇纤维，聚乳酸纤维，丙烯腈纤维，例如改良丙烯腈纤维(modacrylique)(包含35-85%的丙烯腈单元)，聚氧化烯纤维，例如聚氧乙烯纤维，聚氧亚苯基纤维，聚丙烯酸纤维或者聚丙烯酸酯纤维，例如聚甲基丙烯酸甲酯(PMMA)纤维，聚酯纤维，特别地聚对苯二酸亚烷基酯纤维，例如聚对苯二酸乙二醇酯纤维和聚对苯二甲酸丁二醇酯纤维，聚酰胺纤维，聚酰亚胺纤维，含氯和/或氟的聚合物纤维，例如聚氯乙烯纤维，聚氯氟乙烯纤维，全氟乙烯纤维和全氟丙烯纤维，聚砜纤维，例如聚醚砜纤维，聚氨酯纤维，特别地弹性纤维(至少85%的热塑性聚氨酯弹性体)，聚苯并咪唑纤维和芳族聚酰胺的纤维。
该优选的纤维是热塑性聚合物纤维，这是由于它们可以容易地由传统方法获得，该传统方法通过拉丝或者共拉丝熔融塑料，特别地聚酯，有利地聚对苯二酸乙二醇酯进行。
该垫可以由纤维(其由单一聚合物构成)构成或者由不同聚合物的纤维混合物构成。
聚合物纤维垫可以由连续长丝组成，或者具有可达到1000mm，优选地为5-500mm，有利地50-100mm的长度的不连续长丝组成。
纤维的线密度可以在很大范围内变化，例如最多30特，优选地至少等于0.9特，有利地2至20特，更好是3至10特。
虽然本发明更特别地涉及合成聚合物的纤维垫，它还适用于天然来源的聚合物的纤维，其特别地包含多糖和/或蛋白质，如动物纤维(羊毛或者丝)和植物纤维(棉花，亚麻，大麻，剑麻，椰子，竹，等等)。
根据本发明的垫可以由上述合成或者天然纤维或者这些纤维的混合物构成。
聚合物纤维垫还可以包含呈其直径大于构成该垫的聚合物纤维的直径的纤维形式或者呈由多个长丝(其已经受或者未经受捻操作)组成的丝束形式的增强元件。增强元件可以由与构成该垫的纤维相同或者不同的聚合物材料构成，或者由另一种材料，例如玻璃构成。
增强元件在聚合物纤维垫中的比例保持低的并且通常占该聚合物纤维的重量的最多10%。
根据本发明的聚合物纤维垫具有5至1000g/m2，优选地10至800g/m2，有利地15至300g/m2，更好地最多等于100g/m2的面密度。
当然，更高的面密度可以通过重叠多个根据本发明的聚合物纤维垫获得。
在本发明的范围内可以使用的垫可以根据允许获得聚合物纤维的已知方法进行制备，特别地通过干法(其通过梳理或者通过气动分离纤维(“air laid”)，通过熔融途径方法(其通过直接拉丝(“spunlaid”)或者通过挤出(“spundbonding”或者“熔融吹塑”)进行)，通过与用于获得纸实施的方法相似的湿法(其使用纤维在水中的悬浮液进行操作)或者通过特定技术(例如“静电纺纱”和“闪蒸纺纱”)进行制备。
通常，该聚合物纤维垫还可以包含粘结剂，其粘结所述纤维并且为其提供适合于该希望的用途的机械性质，特别地足以能容易操作的硬度。
该粘结剂通常包含至少一种可以粘结该纤维的聚合物，其中所述聚合物可以是与构成该纤维的聚合物相同的本质或者不同的本质。
这种聚合物可以是热塑性聚合物，例如苯乙烯-丙烯腈，丙烯腈-丁二烯-苯乙烯，纤维素(三)乙酸酯，膨胀性聚苯乙烯，聚烯烃，如聚乙烯和聚丙烯，聚(甲基)丙烯酸酯，聚醋酸乙烯酯或者聚甲醛；热固性聚合物，例如不饱和聚酯，环氧化物，酚醛树脂，如酚醛清漆或者可熔酚醛树脂，特别地具有低于0.05%的含量的游离醛(一种或多种)的那些，聚酰亚胺，聚氨酯，酚醛塑料或者生物聚合物，例如多糖或者蛋白；弹性聚合物，例如含氟聚合物，特别地基于1,1-二氟乙烯的聚合物，氯丁橡胶，聚丙烯酸，聚丁二烯，聚醚酰胺，硅氧烷，天然橡胶或者丁苯橡胶(SBR)，或者生物聚合物，例如多糖或者蛋白。
该粘结剂通常按重量计占该聚合物纤维垫的5至300%，优选地低于100%。
在这种情况下，需要在足够的温度下处理该聚合物纤维垫使得该粘结剂可以交联。该处理温度取决于构成该垫的纤维的聚合物和取决于进入该粘结剂的组成中的聚合物：它必须保持远低于该纤维的聚合物的分解温度以避免该垫的破坏。
将二酰肼施用至聚合物纤维垫上可以通过任何已知的手段实施，例如通过浸渍、涂覆或者喷雾所述二酰肼的溶液、分散体或者乳液。
可用于使二酰肼溶解、分散或者乳化的液相通常是水。
该液相还可以包含小比例的与水能混溶的共-溶剂，其提高聚合物纤维的润湿性。
该共-溶剂选自极性有机溶剂，如醇，特别地乙醇或者丙醇，和酮，特别地丙酮。
通常，共-溶剂的量不超过水和共-溶剂的总重量的30%，优选地保持低于20%。
根据本发明的聚合物纤维垫可以使用在许多应用中，例如:
- 在建筑物中，作为用于墙壁、地板和/或天花板的覆盖物，用于石膏板或者水泥板的表面或者衔接头的覆盖物，用于隔热和/或隔音产品(特别地基于矿棉，聚苯乙烯或者有机或者无机泡沫，特别地用于屋顶下隔层(sous-toiture)的应用)的表面的覆盖物；
- 在机动车辆中，作为填充材料或者装饰织物(支架，箱体，门，座位，地毯)或者声阻尼材料(防护罩，地板，车顶内衬)，
- 在地质领域中，作为土工织物，特别地用于沥青或者土体稳定材料的覆盖物，
- 在工业中，作为涂覆织物、用于气体(换气、空调)或者液体(如油)的过滤器、用于种子和作物的保护的覆盖物或者用于家具的覆盖物(壁纸载体或者地毯衬层)。
以下实施例可以举例说明本发明而不限制它。
实施例1
a)垫的获得
在容器中，倒入141.1g水、5.9g己二酸二酰肼和3g烷基二苯醚二磺酸盐(由Dow Chemical销售的Dowfax?)。
将聚对苯二酸乙二醇酯纤维垫(18g/m2)浸入获得的溶液中，然后取出它并且在110℃的烘箱中干燥它1分钟。
在该垫上沉积的己二酸二酰肼的量等于4g/m2。
b)在静态条件下捕集甲醛的能力
将垫(25cm×5cm)放置于包含0.4g/l甲醛水溶液的容器中。将该垫放置在该溶液之上使得它不与溶液接触。该容器被密封，然后将它放置于50℃的烘箱中16小时。
取出该垫并且用水洗涤以除去还未与己二酸二酰肼起反应的甲醛。
然后将垫切成多个碎片，在搅拌下将它们放置于包含100ml蒸馏水的容器中。在60℃加热该容器24小时。回收水相，过滤它并通过光谱色度学测量包含的甲醛的量。
根据实施例1的垫的捕集甲醛的能力等于930.44mg/m2。
通过比较，在相同的条件下处理的不包含己二酸二酰肼的相同的垫不可以捕集甲醛。
c)在动态条件下捕集甲醛的能力
将在a)下获得的垫的样品放置于根据标准ISO 16000-9的装置(其改变之处为特定的换气流速等于0.5m3/(m2.h)和负载率等于1m2/m3)中。
1.首先，在8天期间内该装置的试验腔室用包含95μg/m3的甲醛的连续空气流进料。在8天时间内测量在进入和离开的空气中的甲醛量，并且计算每单位体积空气的甲醛量的减少。
甲醛通过在标准ISO 16000-3的条件下的液相色谱(HPLC)进行测量。
在表1中，使用包含己二酸二酰肼的垫实施的甲醛量的减少通过与不包含可以捕集甲醛的试剂的垫(参照物)比较进行指出。
表1
Figure 183128DEST_PATH_IMAGE001
2. 其次在7天期间向该腔室供应不包含甲醛的空气并且测量在该腔室出口处的空气中存在的甲醛量。
在与在部分1中相同的条件下测量甲醛。
由根据本发明的实施例的垫放出的甲醛量等于当腔室不包含垫时测量的甲醛量。可以由此得到结论甲醛以强烈的并且持久的方式与己二酸二酰肼连接。
实施例2
在实施例1的条件下进行实施，但是改变在于：将聚酯垫浸入通过混合121.9 g水、5.1 g己二酸二酰肼、20g包含热固性聚合物的粘结剂溶液(Aquaset ? TF 150，由Rohm & Haas销售；固体含量:54%)和3 g烷基二苯醚二磺酸盐(Dowfax?，由Dow Chemical公司销售)获得的溶液中，并在210℃进行干燥。
沉积在该垫上的己二酸二酰肼的量等于3 g/m2。
在b)的静态条件下，来自实施例2的垫捕集甲醛的能力等于694.44 mg/m2。
通过比较，在相同条件下处理的不包含己二酸二酰肼的相同垫不能够捕集甲醛。

Claims (17)

1.聚合物纤维垫，其特征在于它包含至少一种二酰肼。
2.根据权利要求1的垫，特征在于二酰肼对应于下式：
H2N–NH–CO–R–CO–NH–NH2
其中R表示
-线性或支化亚烷基，其优选地包含1至18个碳原子，任选地被一个或多个羟基取代；或
-亚芳基，优选地亚苯基或亚联苯基，其任选地被一个或多个羟基，一个或多个卤素原子，特别地F、Cl或Br，或者一个或多个包含1至4个碳原子的线性或支化烷基取代。
3.根据权利要求2的垫，特征在于二酰肼选自其基团R是C1-C12，优选地C1-C8亚烷基的二酰肼。
4.根据权利要求3的垫，特征在于二酰肼是己二酸二酰肼。
5.根据权利要求1-4任一项的垫，特征在于二酰肼的量占该垫的重量的0.1-50%，优选地0.2-20%，有利地0.2-20%，更好地至少等于0.3-10%。
6.根据权利要求1-5任一项的垫，特征在于它还包含阴离子、阳离子或者非离子型表面活性剂。
7.根据权利要求6的垫，特征在于表面活性剂占二酰肼的重量的低于90%，优选地20-80%，有利地55-65%。
8.根据权利要求1-7任一项的垫，特征在于纤维由有机聚合物构成。
9.根据权利要求8的垫，特征在于聚合物是聚烯烃、聚醋酸乙烯酯、聚乙烯醇、聚乳酸、丙烯腈、聚(氧化烯)、聚(氧亚苯基)、聚丙烯酸或者聚丙烯酸酯、聚酯、聚酰胺、聚酰亚胺、含氯和/或氟的聚合物、聚砜、聚氨酯、聚苯并咪唑或芳族聚酰胺。
10.根据权利要求9的垫，特征在于所述聚合物是聚酯。
11.根据权利要求1-10任一项的垫，特征在于其具有5至1000g/m2，优选地10至800g/m2，有利地15至300g/m2，更好地最多等于100g/m2的面密度。
12.根据权利要求1-11任一项的垫，特征在于其还包含粘结剂，该粘结剂包含可以粘结所述纤维的聚合物，该聚合物是与构成该纤维的聚合物相同的本质或者不同的本质。
13.根据权利要求12的垫，特征在于可以粘结所述纤维的聚合物是热塑性聚合物、热固性聚合物或弹性体聚合物，或者生物聚合物。
14.根据权利要求12或13的垫，特征在于该粘结剂按重量计占该聚合物纤维垫的5至300%，优选地低于100%。
15.根据权利要求1-14任一项的垫的用途，其作为用于墙壁、地板和/或天花板的覆盖物。
16.根据权利要求1-14任一项的垫的用途，其作为用于石膏板或者水泥板的表面或者衔接头的覆盖物。
17.根据权利要求1-14任一项的垫的用途，其作为用于隔热和/或隔音产品，特别地基于矿棉、聚苯乙烯、或者有机或者无机泡沫的隔热和/或隔音产品的表面的覆盖物。
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EP2576166B1 (fr) 2017-11-15
RU2012156219A (ru) 2014-06-27
US20130115447A1 (en) 2013-05-09
CA2800505A1 (fr) 2011-12-01
FR2960565B1 (fr) 2012-07-27
RU2570040C2 (ru) 2015-12-10
WO2011148076A1 (fr) 2011-12-01
EP2576166A1 (fr) 2013-04-10
CN103167939B (zh) 2016-12-21

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