CN1758997A - 控制聚合物分子量的方法 - Google Patents
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Abstract
本发明涉及一种从固态高分子量原料切片制造低分子量聚合物的方法。特别是通过引入乙二醇,以可控方式降低工业树脂或瓶树脂的分子量。如果采用工业树脂用于工业纤维,可以在用于纺丝工业纤维的挤出机处加入乙二醇。另一方面,必须将高分子量切片用于瓶树脂时,通过在用于注塑低分子量预制品的挤出机处引入乙二醇,可以降低分子量。乙二醇/聚合物的比率是根据所需的分子量减小量而定的。优选的树脂是聚酯聚合物或共聚物,特别是聚对苯二甲酸乙二酯(PET)。本发明包括一种用于降低固态聚酯原料树脂分子量的方法,该方法包括获得IV大于约0.8dl/g的聚酯树脂,并且将乙二醇和所述聚酯混合,其中所述乙二醇是以化学计量比的量存在的,以将IV降低到所需水平。
Description
发明背景
1)发明领域
本发明涉及从固态高分子量原料切片制造低分子量聚合物的方法。特别是本发明涉及一种方法,其中通过引入乙二醇以可控方式降低工业树脂或瓶树脂的分子量。更具体而言,可以在挤出机中引入乙二醇。如果采用工业树脂用于工业纤维,可以在用于纺丝工业纤维的挤出机处加入乙二醇。另一方面,必须将高分子量切片用于瓶树脂时,通过在用于注塑低分子量预制品的挤出机处引入乙二醇,可以降低分子量。乙二醇/聚合物的比率是根据所需的分子量减小量而定的。优选的树脂是聚酯聚合物或共聚物,特别是聚对苯二甲酸乙二酯(PET)。
2)现有技术
通常采用聚酯切片制造容器,例如软饮料瓶;多种用途的薄膜,包括例如食品包装;用于例如器具或汽车工业的模制部件;以及用于纺织品或工业用途的纤维。在聚酯切片的众多用途中,容器和工业纤维要求高分子量切片。起初,高分子量是通过将聚酯切片经过固态聚合处理以增加其分子量而获得的。
在纤维制造技术中,可以使用低分子量切片来制造纺织产品。纺织产品不要求高拉伸强度和工业纤维用途所要求的高物理性质。典型的工业纤维用途包括安全带,气袋,轮胎帘布,以及用于例如传送带、软管和V形皮带的其他加强件。
用于高分子量切片的标准方法是固态聚合来自低分子量的熔融相聚合法的切片。通常,能够生产高分子量切片的生产线也能够被改装来生产低分子量切片。但是,必须中断生产以消除固态聚合的影响,或者改变固态聚合法条件以制造低分子量切片。从高分子量切片到低分子量切片以及从低分子量切片到高分子量切片的生产线中方法的转换不仅费时而且成本高。因此,希望开发一种不需要停止和改装生产线以制造低分子量切片的方法。特别希望在恒定的条件下生产高分子量切片,并且以可控的和精确的方式降低其分子量而不改变生产线,以生产出所需分子量的产品。
在聚酯的循环利用研究成果中,已知可以采用乙二醇醇解法或水解法来循环利用聚酯。水解法使用水或蒸汽将聚酯断裂成其单体以循环利用。本发明不需要进一步讨论这种方法。
在乙二醇醇解循环法中,将用于循环利用的聚酯加热并经历高温乙二醇流,使生产聚酯的反应逆转而生产单体(制造聚酯的原材料),从而可以再次使用单体制造聚酯。因此,向聚酯中加入乙二醇以进行乙二醇醇解法反应是本行业中已知的。
向聚酯中加入乙二醇作为母料操作的载体也是本行业中已知的。母料操作通常是在希望将少量添加剂均匀地混合到例如聚酯的大量聚合物中时采用的。为了获得必要的均匀度,可以将母料,例如包含10%添加剂,其余是乙二醇的母料,加入到聚酯中,以生产具有一半百分比添加剂的最终聚酯组合物。为了实现添加剂在母料中的良好分散,在混合母料的过程中加入乙二醇。选择母料的分子量使其和不含添加剂的聚合物匹配,以获得所需的分子量。
向聚酯树脂中加入乙二醇以防止起球也是在纺织行业中已知的。起球现象发生在含有合成纤维,例如聚酯纤维的衣服中。当纺织衣服中聚酯的长丝或双丝(filament or two)断裂时,其趋向于卷成非常小的球而使衣服不美观。为了避免起球,在纺丝时将乙二醇加入到聚酯树脂中,这样做导致形成减小的或较低强度物理性质的纤维(但是这样的纤维仍然具有优良的物理性质,例如优于棉花)。
总之,现有技术中有三种向聚酯中加入乙二醇的情况,即:1)聚酯的循环利用;2)母料操作;以及3)在纺织衣服中减少起球。这些情况的每一种中,聚酯切片或聚酯树脂的最终分子量,以特性粘度(IV)表示,都小于0.7,大多数情况下在0.4到0.6IV之间。具有这样的低IV的聚酯切片或树脂将不适合用于要求高分子量以获得良好物理性质的工业应用。
Zickler等人的美国专利5,308,892公开了一种聚酯母料,该母料是用每摩尔聚酯0.01到5摩尔的二元醇(乙二醇)生产的。用于母料的聚酯最初的IV至少为0.5dl/g,并且通过在母料处理中加入乙二醇而进一步降低。
Watkins等人的美国专利4,359,557公开了一种通过在挤出机中加入乙二醇/将乙二醇和聚对苯二甲酸乙二酯混合,制造具有改善了的低起球性的聚对苯二甲酸乙二酯纤维的方法。最初的聚合物材料的IV为约0.56至约0.60,其中混有约0.25重量%的乙二醇。生成物分子量为约0.39至约0.43。基于聚酯的重量,这意味着加入2500ppm的乙二醇以减小权利要求1中的固有分子量,例如从0.56减小到0.40。
Iwaki等的日本专利公布49-1256公开了一种通过和聚酯乙二醇或丙二醇混合而制造具有改善起球性质的低分子量聚酯纤维的方法。但是,在各个实施例中,都加入了硬脂酸镁作为降低分子量的必要组分。
发明概述
最广泛而言,本发明包括一种用于降低固态聚酯原料树脂分子量的方法,该方法包括获得IV大于约0.8dl/g的聚酯树脂;并且将乙二醇和所述聚酯混合,其中所述乙二醇是以化学计量比的量存在的,以将IV降低到所需水平。
而且,在本发明的最广泛含义中,所述树脂具有约和聚酯树脂相同的色性质,而不用引入乙二醇组分。
本发明的最广泛含义中还包括一种降低适合纺丝的固态聚酯树脂原料的IV的方法,该方法包括获得IV大于约0.8的聚酯树脂,将所述聚酯树脂引入到用于将树脂挤出/纺丝成纤维的挤出机中,将乙二醇引入到所述挤出机中,并且挤出/纺丝所述聚酯树脂,以生产IV低于在没有加入乙二醇情况下获得的纤维的IV的纤维。
本发明的最广泛含义中还包括一种降低合适注塑的固态聚酯树脂原料的IV的方法,该方法包括获得IV大于约0.8的聚酯树脂,将所述聚酯树脂引入到用于将树脂注塑成物品(例如塑料瓶的预制品)的挤出机中,将乙二醇引入到所述挤出机中,并且挤出/注塑所述聚酯树脂,以生产IV低于在没有加入乙二醇情况下获得的物品的IV的物品。
此外,本发明在将乙二醇和聚酯在挤出机喉管处加入并且在纺成纤维之前在挤出机中混合的方法中,沿着纺丝箱体(spin beam manifold)的IV标准偏差在小于约0.01的范围内。
优选实施方案描述
聚对苯二甲酸乙二酯是用如下两种方法之一制备的,即:1)DMT法和2)TA法。在DMT法中,将对苯二甲酸二甲酯(DMT)和乙二醇进行酯交换反应(酯基转移反应),得到对苯二甲酸二(2-羟基乙)酯(单体)和甲醇。由于反应是可逆的,必须除去甲醇以将原材料完全转化成单体。已知在酯交换反应中使用镁和/或钴和/或锌。在酯交换反应结束时,通过引入磷,例如以多磷酸(PPA)形式引入磷,消除催化剂活性。然后将单体进行缩合反应(缩聚),将单体聚合成PET。当单体进行缩聚时,最经常采用的催化剂是锑。如果酯交换反应中采用的催化剂没有被磷所阻止,则所得到的聚合物容易降解(热降解),并且有极其不可接受的黄色。
制造PET的第二种方法是将对苯二甲酸(TA)和乙二醇进行直接酯化反应,制造对苯二甲酸二(2-羟基乙)酯和低聚物以及水。该反应也是可逆的,因而可以通过在反应过程中除去水而使反应进行完全。直接酯化步骤不需要催化剂,并且按照常规也不使用催化剂。如同DMT法一样,然后将单体进行缩聚形成PET。缩聚反应典型地使用锑作为催化剂。
在合成纤维的生产中,将含或不含各种添加剂的熔融聚酯树脂经由挤出机输送到喷丝头。经过喷丝头,制造出许多长丝,然后将这些长丝拉伸以提高物理性质,并且在卷成筒管之前可以任选松弛。挤出温度和压力,连同拉伸比,松弛量和卷起速度都是生产工业纤维领域中的技术人员所知的。熔融聚酯通常是由已经被固态聚合了的高分子量(高IV)切片制造的。然后将来自固态聚合器的切片输送到挤出机中,该挤出机熔化切片,并迫使熔融的聚酯树脂通过喷丝头的小孔,从而生产出纤维或长丝。
在聚酯瓶的生产中,将挤出机中的含或不含各种添加剂的熔融聚酯树脂输送到注塑机中,形成瓶子预制品。然后通常用红外加热装置将瓶子预制品加热并在模具中吹成瓶子。这样的瓶子典型地用于软饮料,啤酒或其他酒精饮料,以及用于矿泉水。
本发明采用的挤出机在其喉管处有一个末端状(end-like)开口,通过该开口可以引入添加剂,特别是和本发明有关的添加剂,即乙二醇。
本发明中,将已经固态聚合成高分子量(至少0.80IV)的聚酯切片和乙二醇一起引入到挤出机中(典型的乙二醇/聚酯比率在约0.0001和约0.001之间),以与不含乙二醇的挤出的聚酯树脂相比,降低分子量(减小IV)。随着切片被熔化,乙二醇均匀地与其混合,导致IV的减小。没有可检测到的降解气味,没有明显可见的降解,也没有表示任何降解的测试数据。
测试方法
在25℃下,使用Ubbelhode粘度计测量3%的聚合物邻氯苯酚溶液的相对粘度(RV)。由如下关系式计算特性粘度(IV):
RV=1+IV×C+0.305×IV2×C2+1.85×10-5×exp(4.5×IV)×C4其中C是克/100毫升浓度。
聚合物的羧基端基(CEG)值是用如下方法测定的:将样品溶解在试剂级苄醇中,并用0.03N氢氧化钠/苄醇溶液滴定到酚红指示剂的紫色终点。结果以毫当量氢氧化钠/千克样品形式表示。
颜色用使用D65光源、2”观测器的Hunter ColorQuest II仪器测量,以颜色和亮度的1976CEI值,L、a*和b*表示。
实施例1
使用单位置工业纺丝-拉伸机器,试验用切片速度为47.7kg/hr,使用标准挤出机、纺丝箱和dow箱温度。安装两包以检查纺丝特性并检查来自每包的聚合物的均匀度。表1显示了各种试验组,包括注射速度,乙二醇/聚合物比率,以及测量结果,IV,CEG和颜色。
表1
试验组 | 乙二醇/聚合物比率 | 包装聚合物温度℃ | IV | CEG | b*/L* |
切片 | 0.955 | 13.3 | |||
1 | 0 | 318.0 | 0.876 | 17.1 | 3.27/88.4 |
2 | 0.00033 | 311.5 | 0.812 | 17.8 | |
3 | 0.00052 | 308.8 | 0.790 | 18.3 | |
4 | 0.00075 | 306.2 | 0.747 | 16.3 | 3.10/89.1 |
5 | 0.00109 | 303.3 | 0.707 | 16.2 | |
6 | 0.00138 | 301.0 | 0.656 | 17.5 |
在没有乙二醇加入的情况下,由于热降解,高产量的高聚合温度导致相当低的IV,从0.955到0.876。在各种乙二醇加入比率下,IV由于乙二醇醇解作用而不断下降。正如所预期的,没有加入乙二醇的组的CEG水平没有统计意义上的变化。聚合物颜色也没有变差。
实施例2
该试验是在生产工业长丝的纺丝-拉伸机器上进行的。用1/4”管和套管制造注射管,并将其安装在未使用的气体排放器中,所述气体排放器接入在挤出机进料喉中。使用具有可变速度驱动的齿轮泵来计量乙二醇的加入。监测挤出机操作的过程响应,通过纺丝箱的熔融体中的聚合物温度和聚合物压力。SSP切片IV为0.955,CEG为12,并将其以474.2kg/小时的速度输送到挤出机中。表2显示了组别、乙二醇加入比率和纱线性质的结果。
表2
组 | 乙二醇/聚合物比率 | IV | CEG |
1 | 0 | 0.891 | 21 |
2 | 0.0005 | 0.787 | 18.3 |
3 | 0.0008 | 0.731 | 18.3 |
4 | 0.0010 | 0.699 | 18.5 |
5 | 0.0012 | 0.672 | 17.8 |
表3显示了无乙二醇组和第4组在纺丝箱体的奇数剥离器接头处测量的IV。结果的标准偏差是相等的。CEG不随着IV降低而增加,并且实际上由于排出挤出机的聚合物温度较低而略微下降。
表3
IV | ||
纺丝箱接头 | 组1 | 组4 |
1 | 0.878 | 0.704 |
3 | 0.889 | 0.700 |
5 | 0.893 | 0.691 |
7 | 0.887 | 0.702 |
平均 | 0.887 | 0.699 |
标准偏差 | 0.0063 | 0.0061 |
范围 | 0.015 | 0.014 |
因此,很显然,依照本发明,提供了一种完全满足上述目的、目标和优点的减小分子量的方法。尽管本发明结合其具体实施方案进行了描述,显然对于本领域技术人员而言,根据上述描述,许多选择、修改和变化是显而易见的。因此,所有这样的选择、修改和变化将都落入所附权利要求的精神和广泛范围之内。
Claims (13)
1、一种减小适合纺丝的聚酯树脂分子量的方法,该方法包括:获得IV大于约0.8的固态聚酯树脂原料,将所述聚酯树脂引入到挤出机中,将乙二醇引入到所述挤出机中和所述聚酯树脂混合,并且在纺丝机中将所得到的聚酯树脂纺丝,以生产IV低于在没有加入乙二醇情况下获得的纤维的IV的纤维。
2、权利要求1的方法,其中所述乙二醇是以化学计量比的量存在的,以获得所需的IV的降低。
3、权利要求2的方法,其中所述乙二醇是以乙二醇/聚酯树脂比从约0.0001到约0.001的比率存在的。
4、权利要求1的方法,其中所述纤维除了IV降低之外没有可检测到的降解。
5、权利要求2的方法,其中所述纤维具有和不加入乙二醇生产的聚酯树脂大约相同的亨特色度性质。
6、权利要求1的方法,其中所述纤维IV是在所述纺丝机的多个位置处测量的,并且IV的变化率和不加入乙二醇的方法相同。
7、权利要求6的方法,其中所述的变化率小于0.01。
8、一种降低聚酯分子量的方法,该方法包括:获得IV大于约0.8的固态聚酯树脂原料,将所述聚酯树脂引入到挤出机中,在所述挤出机中将乙二醇和所述聚酯混合,其中所述乙二醇是以化学计量比的量存在的,从而所得到的聚酯树脂的IV低于在没有加入乙二醇情况下获得的聚酯树脂的IV。
9、权利要求8的方法,该方法还包括将所得到的聚酯树脂挤出成物品的步骤。
10、权利要求9的方法,其中所述物品是瓶子预制品。
11、权利要求8的方法,其中所述乙二醇是以约0.0001到约0.001的乙二醇/聚酯树脂比率存在的。
12、权利要求9的方法,其中所述物品除了IV降低之外没有可检测到的降解。
13、权利要求9的方法,其中所述物品具有和不加入乙二醇生产的聚酯树脂大约相同的亨特色度性质。
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CN104861095A (zh) * | 2014-02-26 | 2015-08-26 | 中国石油化工股份有限公司 | 一种降低聚合物分子量的方法 |
CN104861093A (zh) * | 2014-02-26 | 2015-08-26 | 中国石油化工股份有限公司 | 一种降低聚合物分子量的方法 |
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US7014914B2 (en) * | 2004-01-09 | 2006-03-21 | Milliken & Company | Polyester yarn and airbags employing certain polyester yarn |
WO2009026092A1 (en) * | 2007-08-17 | 2009-02-26 | Fiberweb, Inc. | Area bonded nonwoven fabric from single polymer system |
WO2012115984A2 (en) | 2011-02-21 | 2012-08-30 | Felice Kristopher M | Polyurethane dispersions and methods of making and using same |
EP2718383A4 (en) | 2011-06-10 | 2015-05-20 | Kristopher M Felice | CLEAR VARNISH, ACRYLIC COATINGS |
CN105780159A (zh) * | 2014-12-23 | 2016-07-20 | 苏州千色纺化纤有限公司 | 采用回收瓶片的纺织机械 |
JP6928682B2 (ja) | 2017-08-22 | 2021-09-01 | エルジー・ケム・リミテッド | プラスチック樹脂の射出物性評価方法および射出成形用ポリエチレン樹脂 |
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CN104861093A (zh) * | 2014-02-26 | 2015-08-26 | 中国石油化工股份有限公司 | 一种降低聚合物分子量的方法 |
CN104861093B (zh) * | 2014-02-26 | 2017-08-25 | 中国石油化工股份有限公司 | 一种降低聚合物分子量的方法 |
CN104861095B (zh) * | 2014-02-26 | 2017-09-26 | 中国石油化工股份有限公司 | 一种降低聚合物分子量的方法 |
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