CN101203545B - 用于制备阻燃性聚酯纱线的组合物 - Google Patents
用于制备阻燃性聚酯纱线的组合物 Download PDFInfo
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Abstract
用于制备阻燃性聚酯纱线的组合物,其包含约93-99.5重量%的聚酯、约0.25-4重量%的增链剂和约0.25-3重量%的聚氧亚烷基胺。
Description
本申请涉及2005年3月3日递交的临时申请第60/657,734号,并要求其优先权。
技术领域
本发明总体涉及用于制备纺织品和铺地织物的聚酯纱线,并更特别涉及用于制备此纱线的组合物,其提供具有改进阻燃性的纱线。
在现代生活中,由具有充分阻燃性的聚酯纤维制备的诸如纺织品和铺地织物的产品是非常重要的。我们已经发明了一种新组合物,其在提供用于制备纺织物和铺地织物中使用的阻燃性聚酯纤维方面是非常有效和经济的,该纱线另外保持其他的所希望的物理性能。
发明内容
根据我们的发明,用于制备具有改进阻燃性的聚酯基纱线的组合物包括聚酯、一种或多种聚氧亚烷基胺和一种或多种增链剂。优选所述组合物包含约93-99.5重量%的聚酯、约0.25-4重量%的增链剂和约0.25-3重量%的聚氧亚烷基胺。最优选地,所述组合物包含约96-99重量%的聚酯、约0.5-2重量%的增链剂和约0.5-2重量%的聚氧亚烷基胺
聚氧亚烷基胺可以直接加入到聚酯中,或者以将其混配在合适的热塑性载体中得到的热塑性浓缩物或母料的形式加入。合适的热塑性载体是聚酯或聚酰胺或它们的混合物。聚酰胺包括由内酰胺、α-氨基酸、ω-氨基酸、以及二酸和二胺合成的那些。这样的聚酰胺包括但不限于聚己内酰胺[聚酰胺6]、聚十一内酰胺[聚酰胺11]、聚己二酰己二胺[聚酰胺66]、聚十二内酰胺[聚酰胺12]、聚十二烷二酰己二胺[聚酰胺6,12]、聚癸二酰己二胺[聚酰胺6,10]、聚对苯甲酸乙二醇酯、聚对苯甲酸丁二醇酯、聚对苯二甲酸三亚甲酯。如果聚氧亚烷基二胺以此母料形式使用,那么调节上述配方中的聚酯量以考虑氧亚烷基二胺母料中的热塑性载体的量。
优选的聚氧亚烷基胺是分子量为约2000的聚氧亚乙基二胺(POED)。可用于本发明中的另外优选聚氧亚烷基胺是聚氧亚丙基二胺,其也具有2000的分子量。这些化合物可从Huntsman Corporation以Jeffamine商标购得。适合的聚氧亚乙基二胺的其他细节描述于USP3,654,370中。
增链剂,也称作偶联剂,其具有至少两个能够与其他化合物反应的官能团,以便将两个或多个所述化合物连接在一起。原则上,可以使用任何二官能(或更高官能)化合物用于增链或偶联。适合的增链剂的实例是多官能活性材料,其另外的实例是环氧官能的苯乙烯(甲基)丙烯酸共聚物。合适的多官能环氧化合物描述于Blasius等人的美国专利申请公开号US 2004/0138381 Al中。由Clariant Corporation购得的CESA(R)-extend 1598是低聚多官能活性材料在苯乙烯类基础中的20%母料。此母料形式的其他细节详细描述于也属于Blasius等人的美国专利申请公开号US 2004/0147678 A1中。适合的增链剂另外实例是由CibaSpecialty Chemicals,Inc.以商标Irgamod购得的那些,例如Irgamod RA 20。其他可能的增链剂包括但不限于均苯四甲酸二酐、亚苯基二唑啉、羰基二(1-己内酰胺)、基于双酚A-二缩水甘油醚的二环氧化物、基于四缩水甘油基二氨基二苯甲烷的四环氧化物。
增链剂以多种不同方式加入到组合物中。最优选地,增链剂在加入到聚酯中之前与聚氧亚烷基胺或聚氧亚烷基胺母料熔融配混或预掺混。或者,增链剂可以作为浓缩物或以母料形式加入到聚酯中。母料的增链剂的载体的选择取决于增链剂官能团与载体树脂的反应性,选择范围为从基于聚烯烃的树脂到类似的用于制备聚氧亚烷基胺母料的载体树脂到母料制备领域技术人员已知的其他类型。在某些情况下,取决于增链剂的化学和物理性质,可以直接加入到纤维纺丝挤出机处的聚酯和聚氧亚烷基胺中。
聚酯包括热塑性聚酯,例如由一种或多种二酸和一种或多种二醇合成的那些。这样的聚酯包括但不限于聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丙二醇酯、聚萘二甲酸丁二醇酯、聚对苯二甲酸环己烷二甲醇酯和聚乳酸、或它们的混合物。
除了以上描述的聚酯、聚氧亚烷基胺和增链剂之外,本发明实践中所用的组合物可以包含其他组分。这些包括但不限于着色剂、抗氧化剂、UV稳定剂、抗臭氧剂、防尘剂、防污剂、抗静电剂、阻燃剂、抗微生物剂、润滑剂、熔融粘度和熔融强度增强剂、固态聚合促进剂和加工助剂。
由该组合物制备的纤维可以使用各种方法熔融纺丝,从而生成用于大量终端用途的不同产品。纤维可以使用本领域技术人员已知的标准纺丝机械来纺丝,包括使用慢速和高速纺丝方法。旦尼尔每丝(dpf)的范围可以根据所述纤维可以使用的最终末端用途来制备,例如低dpf用于纺织品用途,较高dpf用于地毯。纤维的截面形状也可以是宽范围的可能形状的任何一种,包括圆形,三叶形、四叶形、有沟槽的形状或不规则形状。
这些产品纤维可以进行通常用于熔融纺丝纤维上的已知下游处理,包括卷曲、膨化、加捻等,从而制备适合于加入多种制造物品的纱线,所述制造物品例如为衣服、线、纺织品、室内装饰物、地毯和其他铺地制品。可以将纤维掺混、缠绕、加捻或与其他纤维类型混合,所述其他纤维类型包括但不限于合成纤维,例如聚酯、聚烯烃或丙烯酸类,或者是天然纤维例如羊毛或棉花,以及它们的混合物。
本发明的实施例
实施例1
15重量%的POED与尼龙6,RV=2.8,在带孔的双螺杆挤出机中配混,绞合、造粒并干燥。该POED母料进一步在带孔的双螺杆挤出机中以10%水平与PET,IV=O.67,和2%的CESA(R)-Extend 1598及5%的由在聚酯载体中的无机和有机颜料组成的浅褐色母料(“Rye”)配混。所得配混物在熔融挤出机纤维纺丝线上纺丝,并喷气变形,从而得到由60个具有Y或三叶形界面的长丝构成的膨化连续长丝(BCF)1300旦尼尔纱线(1300/60Y)。BCF纱线的两端在是在Gilbos-型空气加捻机上空气加捻在一起的,从而制备标称2600/120Y BC纱线束。此纱线在1/10th绒圈间距簇绒机(gauge tufter)上被簇绒以制造level-loop构造中的地毯,从而得到的面重量为26oz。所述簇绒被乳胶背面固定。
实施例2
2%的具有PET,IV=0.67的CESA(R)-Extend 1598和5%的Rye有色母料在双螺杆挤出机中熔融配混。所得配混物以类似于实施例1的方式加工,从而制备2600/120Y BCF纱线。以与实施例1中所述构造类似由该BCF纱线制备地毯。
实施例3
以类似实施例1的方式将对比的(非发明的)2600/120Y BCF纱线纺丝、喷气变形和喷气加捻,其包括5%的Rye有色母料和相同的IV=0.67PET。在熔融纺丝该纱线之前,将所述有色母料和PET预熔融配混。将BCF纱线簇绒并背面固定,从而得到类似于实施例1中所述结构的地毯。
实施例4
在双螺杆挤出机中将10重量%的实施例1中所述POED母料与PET,IV=0.67,和5重量%的Rye有色母料熔融配混。所得配混物以类似于实施例1的方式加工,从而制备2600/120Y BCF纱线。以与实施例1中所述构造类似由该BCF纱线制备地毯。
根据ASTM E648-03,″Standard Test Method for Critical Radiant Flux ofFloor-Covering Systems Using a Radiant Heat Energy Source″,测试在实施例1-4中制备的地毯的阻燃性。结果显示在以下表1中。临界辐射通量表明地毯一旦已经点燃时维持地毯中的火焰传播所需的辐射热能水平。较高的临界辐射通量表示该地毯具有较大的阻燃性。
表1
实施例号 | 临界辐射通量/Wcm-2 |
实施例1 | 0.53 |
实施例2 | 0.38 |
实施例3 | 0.32 |
实施例4 | 0.40 |
在表1中列出的实施例1-4的阻燃性测试结果表明:当加入到聚酯聚合物基体中时,分别包括增链剂和聚氧亚烷基胺(分别为实施例2和4)在阻燃性方面比未改性聚酯(实施例3)有小的改进。惊奇地发现既加入增链剂又加入聚氧亚烷基胺到聚酯基体中(实施例1)在阻燃性方面比未改性聚酯(实施例3)有相当大的改进。
实施例5
在双螺杆挤出机中将10份实施例1中所述POED母料与2份Irgamod RA 20配混。所得配混物直接在纤维纺丝线上以1 2%的水平加入到PET,IV=0.67中,并喷气变形,从而制备1300/60Y BCF天然纱线。所制备纱线的两端被喷气加捻在一起,并被簇绒为level-loop地毯构造,具有的纱线面重量为20oz,并被乳胶背面固定。
实施例6
直接在纤维纺丝线上以7%的速率,以5份POED母料对2份Irgamod RA 20的比例,将第二种POED母料/Irgamod RA 20类似于实施例5的方式配混加入到PET,IV=O.67中,并喷气变形,从而制备1300/60Y BCF天然纱线。所制备纱线的两端被喷气加捻在一起,并被簇绒为level-loop地毯构造,从而得到的纱线面重量为20oz,并被乳胶背面固定。
实施例7
将天然纱线(不包含添加物)纺丝,并由PET树脂,IV=0.67喷气变形,从而制备1300/60Y BCF纱线。该BCF纱线的两端被喷气加捻在一起,并被簇绒为level-loop地毯构造,从而得到的纱线面重量为20oz,并被乳胶背面固定。
根据ASTM E648-03,测试在实施例5-7中制备的地毯的阻燃性。实施例5和6的临界辐射通量分别是0.51Wcm-2和0.49Wcm-2。实施例7的临界辐射通量是0.33Wcm-2。与对照例7相比,两种本发明的组合物(实施例5和6)都显示了改进的阻燃性。
前述实施例说明了本发明的优点。用于说明本发明规律的具体技术、条件、材料、比例和报告数据是示例性的,并不应理解为限制本发明的范围。
实施例8
在带孔的双螺杆挤出机中将10份实施例1中所述POED母料与0.6份50%二氧化钛母料、2份CES A(R)-extend 1598和87.4份聚对苯二甲酸丙二醇酯树脂,IV=0.90配混。将所得配混物纺丝,并喷气变形,从而制备1300/60Y BCF纱线。该BCF纱线的两端被空气绞合在一起,并且该绞合的纱线被簇绒为level-loop地毯构造,其面重量为20oz,并被乳胶背面固定。
实施例9
将0.6份50%二氧化钛母料和99.4份聚对苯二甲酸丙二醇酯树脂,IV=0.90配混,纺丝,并喷气变形,从而制备1300/60Y BCF纱线。该BCF纱线的两端被喷气加捻在一起,并且该加捻的纱线被簇绒为level-loop地毯构造,其面重量为20oz,并被乳胶背面固定。
根据ASTM e648-03,测试实施例8和9的阻燃性。实施例8的临界辐射通量是0.33Wcm-2。(对照)实施例9的试样给出的临界辐射通量为0.19Wcm-2。如先前实施例,与非发明的(实施例9)对照试样相比,本发明的组合物(实施例8)显示了相当大改进的阻燃性。
前述实施例说明了本发明的优点。用于说明本发明规律的具体技术、条件、材料、比例和报告数据是示例性的,并不应理解为限制本发明的范围。
Claims (15)
1.一种阻燃性组合物,其包括:
(a)热塑性聚酯,
(b)聚氧亚烷基胺,以及
(c)增链剂,
其中所述聚氧亚烷基二胺包括选自以下组中的化合物:聚氧亚乙基二胺和聚氧亚丙基二胺,以及它们的混合物。
2.权利要求1的组合物,其中所述热塑性聚酯是形成纤维的热塑性聚酯。
3.权利要求1的组合物,其中所述热塑性聚酯包括选自以下组中的聚酯:聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丙二醇酯、聚萘二甲酸丁二醇酯、聚对苯二甲酸环己烷二甲醇酯和聚乳酸以及它们的混合物。
4.权利要求1的组合物,其中所述增链剂是多官能活性材料。
5.权利要求4的组合物,其中所述多官能活性材料是环氧官能的苯乙烯(甲基)丙烯酸共聚物。
7.权利要求1的组合物,其包含93-99.5重量%的聚酯、0.25-4重量%的增链剂,0.25-3重量%的聚氧亚烷基胺。
8.权利要求7的组合物,其包含96-99重量%的聚酯、0.5-2重量%的增链剂和0.5-2重量%的聚氧亚烷基胺。
9.一种阻燃性组合物,其包括:
(a)热塑性聚酯,
(b)包括聚氧亚烷基二胺和热塑性聚酰胺或热塑性聚酯载体树脂的浓缩物,
以及
(c)增链剂,
其中所述聚氧亚烷基胺包括选自以下组中的化合物:聚氧亚乙基二胺和聚氧亚丙基二胺,以及它们的混合物。
10.权利要求7的组合物,其中所述热塑性聚酯是形成纤维的热塑性聚酯。
11.权利要求7的组合物,其中所述热塑性聚酯包括选自以下组中的聚酯:聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丙二醇酯、聚萘二甲酸丁二醇酯、聚对苯二甲酸环己烷二甲醇酯和聚乳酸以及它们的混合物。
12.权利要求7的组合物,其中所述增链剂是多官能活性材料。
13.权利要求11的组合物,其中所述多官能活性材料是环氧官能的苯乙烯(甲基)丙烯酸共聚物。
15.权利要求7的组合物,其中所述热塑性聚酰胺或热塑性聚酯载体树脂包括选自以下组中的聚酰胺:聚酰胺6、聚酰胺11、聚酰胺66、聚酰胺12、聚酰胺6,12、聚酰胺6,10、聚对苯甲酸乙二醇酯、聚对苯甲酸丁二醇酯、聚对苯二甲酸三亚甲酯、以及它们的混合物。
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