CN113316605A - 挥发性有机化合物含量低的基于高温热塑性塑料的易溶解和自由流动的颗粒材料 - Google Patents
挥发性有机化合物含量低的基于高温热塑性塑料的易溶解和自由流动的颗粒材料 Download PDFInfo
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Abstract
本发明涉及基于高温热塑性塑料的颗粒材料，其根据DIN ISO 697：1984的堆积密度为100至650kg/m3且挥发性有机化合物含量低于1重量％，涉及制备它们的方法及其用于制备膜、涂层或用于反应性树脂的橡胶改性的用途。
Description
本发明涉及挥发性有机化合物含量低的基于高温热塑性塑料的易溶解和可流动颗粒及其制备方法和用途。
膜或涂层的制备通常需要高温热塑性塑料、特别是聚醚砜的溶液。为此目的，优选使用可快速溶解在所用溶剂中的可流动高温热塑性塑料。致密颗粒通常仅缓慢溶解。粉末或薄片经常容易结块。
WO 94/15999记载了由聚亚芳基醚砜或聚亚芳基醚酮制成的微粉末，在每种情况下都含有具有基本上光滑的表面结构的球形颗粒，这些微粉末可通过将聚亚芳基醚砜在N-甲基吡咯烷酮、二甲基亚砜或二甲基甲酰胺中的溶液喷雾干燥而获得。微粉末具有窄的粒度分布，平均粒径为2-70μm，特别适用于金属表面的涂层。为了减少残余溶剂的含量，通常需要进行后干燥阶段，例如在流化床或移动床中。
US 2012/0245239 A1记载了具有大表面积和高孔隙率的聚醚酰亚胺颗粒或粉末，其可通过由聚合物溶液在热水或蒸汽中的沉降而获得。尽管聚醚酰亚胺粉末在80℃下在N-甲基甲酰胺中的溶解度低于机械粉碎的聚醚酰亚胺，但所需时间仍然在1小时左右。
尚未公布的PCT/EP2018/070084记载了基于高温热塑性塑料的可膨胀的、含发泡剂的颗粒及其制备方法。可膨胀的含有发泡剂的颗粒可以发泡以得到堆积密度为10至200kg/m3(根据DIN ISO 697：1984)的泡沫颗粒。
残余量的溶剂如丙酮、甲乙酮、乙醇、异丙醇、N-甲基吡咯烷酮、二甲基甲酰胺、环丁砜或二甲基亚砜——这些溶剂用于上述制备高温热塑性塑料的方法中——在进一步加工以得到涂层或膜(例如透析膜)的过程中通常存在问题。因此，需要将溶剂从聚合物颗粒中昂贵地去除。
WO 2014/033321记载了一种通过使二氯二苯砜组分与双酚组分在碱金属碳酸盐的存在下以熔体形式在混合捏合机中反应而制备芳族聚醚砜的无溶剂方法。该方法产生无溶剂颗粒，但这些颗粒只能缓慢地重新溶解在溶剂中，例如N-甲基吡咯烷酮。
因此，本发明的一个目的是提供挥发性有机化合物含量低的易溶解和可流动的颗粒及其制备方法。
该目的通过基于高温热塑性塑料的颗粒实现，颗粒的根据DIN ISO 697：1984的堆积密度为100至650kg/m3，挥发性有机化合物含量低于1重量％。
优选的实施方案可见于从属权利要求。
根据本发明，以下可用作高温热塑性塑料：无定形热塑性聚合物，其玻璃化转变温度Tg至少为165℃，优选为180℃至240℃，通过差示扫描量热法(DSC)根据ISO 11357-2：1999在10K/min的加热速率下测得，以及半结晶热塑性聚合物，其根据ISO 11357-3：2011-05-01的熔融峰值温度Tpm至少为250℃，优选为260至350℃。
优选的高温热塑性塑料为聚芳醚砜、聚芳醚酮、聚苯硫醚、聚醚酰亚胺、聚亚苯基酰胺、聚碳酸酯、芳族聚酯碳酸酯、高温聚酰胺(HTPA)、热塑性聚噁唑烷酮和衍生自BPA和BPTMC的共聚碳酸酯(PC-HAT)。特别优选聚砜(PSU)、聚苯砜(PPSU)和聚醚砜(PESU)。
根据本发明，根据DIN ISO 697：1984，颗粒的堆积密度为100至650kg/m3，优选为210至390kg/m3。在堆积密度低于100kg/m3的情况下，颗粒可在溶解在溶剂中的过程中漂浮，而在堆积密度高于700kg的情况下，颗粒完全溶解所需的时间增加。
颗粒的挥发性有机化合物(VOC)含量优选小于0.1重量％，特别优选小于0.01％。表述“挥发性有机化合物”意指沸点介于异戊烷的沸点(28℃)和正十六烷的沸点(287℃)之间的化合物。基于颗粒计，丙酮、乙醇、异丙醇、N-甲基吡咯烷酮、二甲基甲酰胺、环丁砜和二甲基亚砜的总含量特别优选低于1重量％，非常特别优选低于0.1重量％。挥发性有机化合物(VOC)的含量可例如通过顶空GC/MS或如DIN ISO 16000-6：2012-11中所述确定。
颗粒的平均质量通常为1至50mg，优选为3至20mg，特别优选为3至8.5mg。平均质量是通过称重约100个颗粒并确定一个颗粒的平均值来确定。
颗粒通常为球形、椭圆形或圆柱形。它们优选为球形或椭圆形，其中L/D比(颗粒的最长尺寸(L)与直径(D)之比)为1/1至2.5/1，优选为1/1至2/1。在L/D比高于2.5/1或低于1/2的情况下，流动性大大降低。L/D比可以通过测量至少20个颗粒并计算平均值来确定，或者优选通过动态图像分析(Camsizer)来确定，其中使用照相机记录流过槽的颗粒的阴影投影。
本发明的颗粒可以迅速溶解在常规的溶剂中。优选2g颗粒在80℃下在小于100分钟、优选小于60分钟内完全溶解在100ml N-甲基吡咯烷酮中。
本发明的颗粒是可流动的。其流动性值优选为1至6秒，特别优选为2至5秒，根据DIN EN ISO 6186-1998测得。
颗粒优选由高温热塑性塑料组成，特别优选由特性粘度为40至100cm3/g的聚芳醚砜作为高温热塑性塑料组成，特性粘度根据ISO 307,1157,1628在0.01g/ml的苯酚/1，2-邻二氯苯，1∶1中测得。
颗粒优选不包含固体作为添加剂，特别是不包含填料或成核剂，例如滑石。
本发明还提供通过挤出含发泡剂的高温热塑性塑料熔体来制备本发明颗粒的方法。
一种优选的制备本发明上述颗粒的方法包括以下阶段：
a)通过熔融至少一种高温热塑性塑料制备聚合物熔体，所述高温热塑性塑料的挥发性有机化合物含量低于1重量％，优选低于0.1重量％，
b)向聚合物熔体中加入发泡剂，
c)任选地通过齿轮泵输送聚合物熔体，
d)将含发泡剂的聚合物熔体在250℃至350℃的温度下输送通过造粒模，以及
e)将负载有发泡剂的聚合物熔体造粒。
另一种优选的制备本发明上述颗粒的方法包括以下阶段：
a)通过使作为单体的二氯二苯砜组分与双酚组分在碱金属碳酸盐存在下以熔体形式在不存在溶剂或稀释剂的情况下反应，然后除去盐而制备聚合物熔体，
b)向聚合物熔体中加入发泡剂，
c)任选地通过齿轮泵和熔体过滤器输送聚合物熔体，
d)将含发泡剂的聚合物熔体在250℃至350℃的温度下输送通过造粒模，以及
e)将负载有发泡剂的聚合物熔体造粒。
两种优选方法中的造粒均可通过挤出造粒、水冷模面造粒或水下造粒来实现。两种优选方法的阶段e)中的造粒优选在水下造粒机中进行，所述水下造粒机在75至99℃的水温和1至10巴的压力下操作。
优选使用氮气、二氧化碳、水或其混合物作为发泡剂。发泡剂或发泡混合物的加入量为1至10重量％，优选2至5重量％，基于高温热塑性塑料计。
本发明颗粒的堆积密度可通过选择发泡剂和水下造粒机中的压力来控制。通过较低的压力和/或较少量的发泡剂实现低堆积密度。
上述用于本发明颗粒的聚合物可用作高温热塑性塑料。优选使用特性粘度为40至100cm3/g的聚亚芳基醚砜作为高温热塑性塑料，特性粘度根据ISO 307,1157,1628在0.01g/ml的苯酚/1，2-邻二氯苯，1∶1中测得。
具有低残余单体含量的合适聚醚砜可例如通过使作为单体的二氯二苯砜组分与双酚组分在碱金属碳酸盐的存在下以熔体形式在不存在溶剂或稀释剂的情况下反应，然后去除盐而获得，如WO 2014/033321和WO 2017/162485中所述。
优选不向聚合物熔体加入固体作为添加剂，特别是不加入填料或成核剂，例如滑石。
本发明的颗粒可优选用于制备膜，特别是透析膜，涂层，或用于反应性树脂的韧性改性。
实施例
所使用的原料：
Ultrason E2010 natural 聚醚砜颗粒，购自BASF SE，密度为1370kg/m3，特性粘度为56cm3/g，DSC玻璃化转变温度(10℃/min)为225℃，堆积密度为750g/l。
Ultrason E3010 natural 聚醚砜颗粒，购自BASF SE，密度为1370kg/m3，特性粘度为66cm3/g，DSC玻璃化转变温度(10℃/min)为225℃，堆积密度为750g/l。
发泡剂：H2O
测试方法：
堆积密度的测定：
无发泡剂的多孔颗粒的堆积密度根据DIN ISO 697：1984测定。
溶解度的测定
在每种情况下，通过以下方式测定溶解度：在150rpm下，在振动板上，在80℃下，将2g聚醚砜溶解在玻璃烧杯中的100ml N-甲基吡咯烷酮(NMP)中。测量颗粒完全溶解所需的时间。振动板的转速为150rpm，持续30分钟，然后为300rpm。
流动性的测定
颗粒的流动性值根据DIN EN ISO 6186：1998方法B，使用出口直径为15mm的测试漏斗测定。
挥发性有机化合物(VOC)含量的测定
挥发性有机化合物(VOC)的含量通过顶空GC/MS如下测定。
顶空测量条件：
样品温度：70℃
温度控制时间：60min
接口温度：150℃
标准压力：115kPa
高压：180kPa
进样时间：0.20min
冷集(cryofocusing)：2.5/2.5min(前/后)
起始重量：152mg样品+2ml DMAA
GC/MS测量条件
分离毛细管：DB-130m 0.25mm 1μm
温度程序：40℃；8.5min；5℃/分钟；260℃；10min
入口压力：70kPa
分流：约20ml/min
扫描：25-400amu
丙酮和异丙醇用作定量测定的参考。
L/D比的确定：
L/D比通过动态图像分析(Camsizer)确定，其中使用照相机记录流经槽的颗粒的阴影投影。特征变量L/D由Camsizer尺寸b/l3确定，b/l3＝xc，min/xFe，max，其中xc，min为投影平面中的最短弦，xFe，max为投影平面中的最大Feret直径。L/D＝l3/b。
实施例B-1-B-6：由聚醚砜制备多孔颗粒
多孔颗粒的制备在设备中进行，所述设备由下述组成：购自Leistritz的双螺杆挤出机，分为八个区域(Z1……Z8)，螺杆直径为18mm，长径比为40，具有熔体泵(齿轮泵GP)、启动阀(SUV)、熔体过滤器、造粒模(PD)和水下造粒机(UWP)。
将聚醚砜(PESU)计量加入双螺杆挤出机中并熔融。在挤出机长度的大约2/3的下游，借助Isco泵(购自Axel Semrau的活塞泵)和纳入挤出机中的注射器将发泡剂H2O注入挤出机中。使用熔体泵(GP)调节挤出机中的压力分布(压力-旋转-速率控制)，以使发泡剂完全混合到聚合物熔体中。熔体泵不仅用于调节双螺杆挤出机的压力分布，而且还用于将浸渍了发泡剂的聚合物熔体输送通过下游设备(启动阀、熔体筛和造粒模)。将通过造粒模(1个直径为1.0mm的孔)形成的熔体挤出物在水下造粒机(UWP)中在反压下膨胀，并切碎以得到颗粒重量为3-10mg的聚醚砜颗粒。在本文中，挤出机的总通过量保持恒定在4.6kg/h。水箱中的挤出物被连接到刀片环上的6个刀片切碎。在本文中，刀片环以3600rpm旋转。得到多孔颗粒，将多孔颗粒通过水回路从造粒模输送到干燥器，并由干燥器沉积到收集容器中。
表1整理了所用原料的重量比例。水的比例基于每100重量比例的聚合物所添加的量。表2整理了工艺参数。
对比实验：
对比实验V1以与实施例B-1至B-6相同的方式进行，工艺参数列于表1中。
表2：性能
Claims (14)
1.一种基于高温热塑性塑料的颗粒，所述高温热塑性塑料选自聚芳醚砜、聚芳醚酮、聚苯硫醚、聚醚酰亚胺、聚亚苯基酰胺、聚碳酸酯、芳族聚酯碳酸酯、高温聚酰胺(HTPA)、热塑性聚噁唑烷酮和共聚碳酸酯或其混合物，所述颗粒的根据DIN ISO 697：1984的堆积密度为100至650kg/m3，挥发性有机化合物含量小于1重量％。
2.根据权利要求1所述的颗粒，其中所述颗粒的挥发性有机化合物含量小于0.01％。
3.根据权利要求1或2所述的颗粒，其中所述颗粒每个颗粒的质量为3至8.5mg。
4.根据权利要求1至3中任一项所述的颗粒，其中所述颗粒的L/D比为1/1至2.5/1。
5.根据权利要求1至4中任一项所述的颗粒，其中2g颗粒在80℃下在小于60分钟内溶解在100ml N-甲基吡咯烷酮中。
6.根据权利要求1至5中任一项所述的颗粒，其中所述颗粒的流动性值为1至6秒，根据DIN EN ISO 6186：1998测得。
7.根据权利要求1至6中任一项所述的颗粒，其中所述颗粒由高温热塑性塑料组成，所述高温热塑性塑料的特性粘度为40至100cm3/g，根据DIN EN ISO 1628-1：2012-10在0.01g/ml的苯酚/1.2-邻二氯苯，1∶1中测得。
8.根据权利要求1至7中任一项所述的颗粒，其中所述颗粒由聚芳醚砜作为高温热塑性塑料组成。
9.一种制备根据权利要求1至8中任一项所述的基于高温热塑性塑料的颗粒的方法，其包括以下阶段：
a)通过熔融至少一种挥发性有机化合物含量低于1重量％的高温热塑性塑料制备聚合物熔体，
b)向聚合物熔体中加入发泡剂，
c)任选地通过齿轮泵输送聚合物熔体，
d)将含发泡剂的聚合物熔体在250℃至350℃的温度下输送通过造粒模，以及
e)将负载有发泡剂的聚合物熔体造粒。
10.一种制备根据权利要求8所述的基于聚芳醚砜的颗粒的方法，其包括以下阶段：
a)通过使作为单体的二氯二苯砜组分与双酚组分在碱金属碳酸盐存在下以熔体形式在不存在溶剂或稀释剂的情况下反应，然后除去盐而制备聚合物熔体，
b)向聚合物熔体中加入发泡剂，
c)任选地通过齿轮泵输送聚合物熔体，
d)将负载有发泡剂的聚合物熔体在250℃至350℃的温度下输送通过造粒模，以及
e)将负载有发泡剂的聚合物熔体造粒。
11.根据权利要求9或10所述的方法，其中阶段e)中的造粒在水下造粒机中进行，所述水下造粒机在75至99℃的水温和1至10巴的压力下操作。
12.根据权利要求9或10所述的方法，其中使用氮气、二氧化碳、水或其混合物作为发泡剂。
13.根据权利要求9至12中任一项所述的方法，其中使用特性粘度为40至100cm3/g的聚亚芳基醚砜作为高温热塑性塑料，特性粘度根据DIN EN ISO 1628-1：2012-10在0.01g/ml的苯酚/1，2-邻二氯苯，1∶1中测得。
14.根据权利要求1至8所述的颗粒用于制备膜或涂层，或用于反应性树脂的韧性改性的用途。
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| US5091126A (en) * | 1989-08-03 | 1992-02-25 | Basf Aktiengesellschaft | Preparation of expandable granules, and the production of foams therefrom |
| US20040167241A1 (en) * | 2003-02-24 | 2004-08-26 | Dietrich Scherzer | Open-cell foam composed of high-melting point plastics |
| CN103842411A (zh) * | 2011-09-30 | 2014-06-04 | 巴斯夫欧洲公司 | 基于聚亚芳基醚的高强度混合物 |
| CN104854781A (zh) * | 2012-12-06 | 2015-08-19 | 大众汽车有限公司 | 电机及其制造方法 |
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| DE4436046B4 (de) * | 1994-10-10 | 2005-03-03 | Trevira Gmbh | Verfahren zum Trocknen von abbaugefährdeten thermoplastischen Polymeren |
| US9469734B2 (en) | 2011-03-25 | 2016-10-18 | Sabic Global Technologies B.V. | Fast dissolving polyimide powders |
| CN109880099A (zh) | 2012-09-03 | 2019-06-14 | 巴斯夫欧洲公司 | 用于制备芳族聚醚砜的方法 |
| KR102399386B1 (ko) * | 2014-12-15 | 2022-05-17 | 닛산 가가쿠 가부시키가이샤 | 정공 캐리어 물질 및 폴리(아릴 에테르 술폰)을 함유하는 조성물 및 그의 용도 |
| EP3222651A1 (de) | 2016-03-21 | 2017-09-27 | Basf Se | Entsalzung von polyarylethern mittels schmelzeextraktion |
| KR102614476B1 (ko) * | 2017-08-04 | 2023-12-15 | 바스프 에스이 | 고온 열가소성 물질에 기반한 발포성, 발포제 함유 펠릿 |
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| US5091126A (en) * | 1989-08-03 | 1992-02-25 | Basf Aktiengesellschaft | Preparation of expandable granules, and the production of foams therefrom |
| US20040167241A1 (en) * | 2003-02-24 | 2004-08-26 | Dietrich Scherzer | Open-cell foam composed of high-melting point plastics |
| CN103842411A (zh) * | 2011-09-30 | 2014-06-04 | 巴斯夫欧洲公司 | 基于聚亚芳基醚的高强度混合物 |
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