CN109789651A - 透明拉伸制品 - Google Patents
透明拉伸制品 Download PDFInfo
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- CN109789651A CN109789651A CN201780058868.9A CN201780058868A CN109789651A CN 109789651 A CN109789651 A CN 109789651A CN 201780058868 A CN201780058868 A CN 201780058868A CN 109789651 A CN109789651 A CN 109789651A
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Classifications
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- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种用于生产高强度透明高密度聚乙烯制品的方法,该方法包括以下步骤:(i)将高密度聚乙烯(HDPE)加热到高于HDPE熔融温度(Tm)的温度;(ii)模塑步骤(i)中得到的经加热的HDPE,形成热模塑HDPE制品;(iii)将热模塑HDPE制品冷却至低于Tm的温度,以形成熔融结晶的HDPE制品;(iv)将熔融结晶的HDPE制品拉伸至至少5的总拉伸比,其包括至少一个在低于熔融温度Tm的温度T1下将制品拉伸至至少2拉伸比(DR1)的步骤,以形成取向的HDPE制品,其中HDPE具有根据ASTM D1238在21.6kg和190℃下测量至多1.5g/10min的熔体流动指数(MFI)、根据ISO 1183‑1A测量至多0.955g/cm3的各向同性密度以及根据ISO 11357‑3测量大于130℃的Tm。本发明还涉及高强度透明HDPE制品和包含高强度透明HDPE制品的产品,例如防弹制品、遮阳板(visor)、汽车部件、火车部件、飞机部件、挡风玻璃、窗户和天线罩。
Description
本发明涉及包含至少部分取向的高密度聚乙烯(HDPE)的透明拉伸模塑制品,以及制备这种透明模塑制品的方法。
包含至少部分取向的高密度聚乙烯的拉伸模塑制品在行业中是公知的产品,通常它们以纤维、带或膜的形式存在。通常这种产品可以通过在熔融结晶和溶液结晶的聚合物的固态下拉伸而获得,导致高度的分子取向和链伸长。通常,取向的高密度聚合物制品表现出高模量和高强度,特别是当在聚合物取向的方向上测量时,例如在WO2007/122010和WO2013/087827中所呈现的。发明人观察到,在固态拉伸之前和/或之后,至少部分取向的聚合物制品在400-700nm波长范围内的光透射率(通常也称为透明度)通常相当低,这限制了它们在某些应用中的有用性。
据发明人所知,仅有少数研究描述了旨在改善光学透射率的固态拉伸聚合物的制备。在Jarecki等人,Polymer(Guildf).1979,20,1078中,可以通过在高温下处理具有宽分子量分布的低分子量聚合物来获得透明的超拉伸HDPE样品。这种方法不能广泛地应用于其他聚合物和制造工艺,因此难以获得透明取向的聚合物制品、尤其是在整个可见光谱中透明的取向的聚合物制品。此外,低分子量和宽分布将对透明超拉伸带的可获得的机械性能,例如拉伸强度产生负面影响。
最近,发明人在Appl.Mater.Interfaces,2016,8,17549中报告了通过高折射率添加剂的存在改善了超拉伸熔融结晶聚乙烯的透明度。结果表明,这些添加剂对重均分子量为约100kg/mol的高密度聚乙烯是有效的,可以生产出最大拉伸强度为约0.6GPa的拉伸透明薄膜。
因此,本发明的目的是提供包含至少部分取向的聚乙烯的具有改进的可见光透射率的制品,所述制品不受上述加工和性能限制的约束,例如通过添加剂的存在和低拉伸强度。
该目的通过在熔融结晶的HDPE制品上进行固态拉伸工艺来实现,其中HDPE具有根据ASTM D1238在21.6kg和190℃下测量的至多1.5g/10min的熔体流动指数(MFI)、根据ISO1183-1A测量的至多0.955g/cm3的各向同性密度以及根据ISO 11357-3测量的大于130℃的Tm。
与由不具有上述性能的熔融结晶HDPE制品制成的模塑制品相比,根据上述方法制备的拉伸模塑HDPE制品提供了改进的透光率。
特别地,制备高强度透明HDPE制品的方法包括以下步骤:(i)将高密度聚乙烯(HDPE)加热到高于HDPE熔融温度(Tm)的温度;(ii)模塑步骤(i)中得到的经加热的HDPE,形成热模塑HDPE制品;(iii)将热模塑HDPE制品冷却至低于Tm的温度,以形成熔融结晶的HDPE制品;(iv)将熔融结晶的HDPE制品拉伸至至少5的总拉伸比,其包括在低于熔融温度Tm的温度T1下至少一个将制品拉伸至至少2的拉伸比(DR1)的步骤,以形成取向的HDPE制品,所述方法的特征在于,HDPE具有根据ASTMD1238在21.6kg和190℃下测量的至多1.5g/10min的熔体流动指数(MFI)、根据ISO 1183-1A测量的至多0.955g/cm3的各向同性密度以及根据ISO11357-3测量的大于130℃的Tm。
在本发明的上下文中,拉伸的模塑制品可具有不同的形状,特别是拉伸的模塑制品可以是单丝、复丝纱线、带、条带和膜。拉伸的模塑制品优选是单丝、带或膜。在拉伸的模塑制品是带或膜的情况下,熔融结晶的制品是熔融结晶的片。本发明还涉及通过切分、搓捻、切割或拉断制品将拉伸的模塑制品分成较小的制品而获得的制品。因此,这种进一步分开的制品可以是切分带、纤维、长丝、短切纤维或原纤化带。
在本申请的上下文中,高密度聚乙烯(HDPE)是一类基于乙烯的聚合物,其密度大于0.92g/cm3,并且具有基本上线性的分子链结构,每1000个碳具有少于1个长链分支并且每1000个碳具有少于1个短链分支。本文中,长链分支被理解为具有多于20个碳原子的烃基侧链,例如连接至聚乙烯主链的低聚乙烯支链或聚乙烯支链,而短链支链被理解为具有至多20个碳原子的烃基侧链,例如通过共聚引入的甲基、乙基或丁基侧链。如本文所用,HDPE包括高分子量聚乙烯(HMWPE)和超高分子量聚乙烯(UHMWPE)或其混合物的各种变体。发明人观察到,对于HMWPE和UHMWPE,可以获得具有改善的机械性能的透明制品,同时可以基本上保持透明性。
在本发明的上下文中,模塑被理解为,熔融的HDPE通过模塑步骤成形。模塑步骤在HDPE的熔融温度以上并且不存在任何实质量溶剂或加工助剂的情况下进行。优选地,模塑步骤是低剪切速率模塑步骤,换句话说,模塑在施加低剪切速率的条件下进行,其中低剪切是指剪切速率小于10s-1,优选小于5s-1,更优选小于1s-1,最优选小于0.5s-1。优选的低剪切速率模塑步骤包括但不限于高于Tm的HDPE的压延、压缩模塑或连续带式压制。所述高于Tm的HDPE的低剪切模塑步骤与高强度拉伸聚乙烯制品领域中通常采用的模塑步骤形成对比,其中后者的模塑在被称为凝胶纺丝的溶液中进行(如EP 0205960中所述),或者通过以下方式进行:在聚乙烯的熔点以下将其压实,也被称为固态压缩模塑,如US 5,091,133中所述。
热模塑制品的冷却可以通过技术人员已知的任何方法进行,例如,通过以半连续或不连续的方法冷却模塑设备或通过将热模塑制品提供到以固体表面或流体形式的冷却介质,优选在低于HDPE熔融温度的温度下的液体。热HDPE的冷却可以在模塑步骤的同时进行,例如通过将熔融的HDPE提供给处于HDPE的熔融温度或低于HDPE的熔融温度下的模塑设备,由此在模塑时HDPE将冷却并在成型开始后不久之后达到低于其熔点的温度。
在本发明的上下文中,熔融结晶的聚乙烯被理解为聚乙烯已经保持在高于其熔融温度的温度下足够的时间以基本上除去聚乙烯链的结晶度和约束。通过使用液体添加剂(如溶剂)可以增强这种结晶性的去除和链的松弛,所述液体添加剂将在模塑步骤之前被除去。发明人发现,当在模塑之前或期间将HDPE加热至高于HDPE的Tm至少10℃、优选至少15℃,最优选至少比Tm高20℃的温度时,获得最佳的结晶度去除率。
在另一个优选的实施方式中,在本发明方法中制备的熔融结晶HDPE制品和/或取向HDPE制品包含至少80wt%、优选至少90wt%、更优选至少95wt%的HDPE,其中重量百分比表示为HDPE的重量与熔融结晶的HDPE制品的重量之比。最优选熔融结晶的HDPE制品和/或取向的HDPE制品基本上由HDPE组成。在本发明的上下文中,“基本上由……组成”表示小于2wt%、优选小于1wt%、最优选小于0.5wt%的其它组分存在于熔融结晶的HDPE制品中。可存在于制品中的其它组分可以是典型的添加剂,例如稳定剂、着色剂或上浆料以及溶剂的残余部分。
通过本文所述的熔融和压缩模塑方法,获得具有基本各向同性性质的熔融结晶聚乙烯制品,其中基本上各向同性(substantially isotropic)是指HDPE制品没有聚乙烯链或晶体的优选取向,例如可通过光散射或结晶方法观察。
将熔融结晶的HDPE制品在一个或多个步骤中伸长或拉伸至总拉伸比至少为5,由此至少一个拉伸步骤在低于HDPE的Tm的温度T1下进行至拉伸比(DR1)为至少2、优选至少4、更优选至少6、最优选至少8。
在另一个优选的实施方式中,T1和DR1是应用于熔融结晶的HDPE制品的第一拉伸步骤的条件。
在优选的实施方式中,温度T1为100至130℃,优选110℃至128℃,最优选115℃至125℃。发明人发现,特别是对于熔融结晶的HDPE制品的第一拉伸步骤,这样的温度提供了拉伸模塑制品的可达到的伸长速率和拉伸强度的最佳平衡。
拉伸通常也称为固态拉伸,因为它在低于熔点的温度下进行并且由模塑制品的伸长组成,导致伸长变形和聚乙烯链的取向增加,同时模塑制品是在拉伸条件下保持在低于聚乙烯熔融温度的温度下。考虑到本文提供的优选项,技术人员将能够优化生产方法以提供具有满足拉伸模塑制品应用于其中的领域要求的透射率和其它物理性能的拉伸模塑制品。
固态拉伸也可以通过受约束的单轴拉伸和/或其中制品(例如带)的宽度在很大程度上保留的拉伸来进行,这些方法在技术人员的术语下称为“短切割拉伸(kurz-spaltdrawing)”。
在本发明的上下文中,拉伸比理解为拉伸前的拉伸模塑制品的横截面积与拉伸后的制品的横截面积之比,其中横截面积是垂直于拉伸制品的至少一个拉伸方向的所述拉伸制品的相应交叉部分的表面。因此,拉伸比为1表示没有实际减小制品横截面积的方法,而拉伸比为2表示制品横截面积减半。该方法可包括一个以上的拉伸或伸长步骤,每个步骤具有其自己的拉伸比DRn和拉伸温度Tn。总拉伸比DR总是每个单独拉伸比的累积产物,并且可以通过将各个拉伸比相乘来计算。或者,可以通过比较制品的原始和最终横截面来测量总拉伸比。
在一个优选的实施方式中,本发明方法包括在至少T2的HDPE温度和拉伸速率DR2下进行的至少一个另外的拉伸步骤,由此在温度T1和拉伸速率DR1下拉伸之后进行进一步拉伸,并且其中温度T2大于T1(T2>T1),优选在大于Tm的温度T2(T2>Tm)下,但优选低于已经部分拉伸的制品的熔融温度。发明人观察到,在多个拉伸步骤中拉伸本发明的拉伸模塑制品提供了具有进一步改善的机械性能的制品。尽管在至少一个另外的拉伸步骤期间HDPE的温度可能超过未取向的HDPE的原始熔融温度Tm,但应该注意的是,由于随着聚乙烯链分子取向的增加,HDPE的熔融温度显著提高,因此这不会导致正在加工的制品熔化。
存在于熔融结晶制品中的HDPE以及存在于拉伸模塑制品中的HDPE具有根据ASTMD1238在21.6kg和190℃下测量的至多1.5g/10min的熔体流动指数(MFI)、根据ISO 1183-1A测量的至多0.955g/cm3的各向同性密度以及根据ISO 11357-3测量的大于130℃的Tm。
此外,熔融结晶的HDPE制品的HDPE以及存在于取向的HDPE制品中的HDPE具有至少200kg/mol的重均分子量(Mw)和/或具有介于2和10之间的分子量分布(MWD)。
本文所述的本发明方法提供了迄今为止不可获得的高强度透明HDPE拉伸模塑制品,因此在一个实施方式中,本发明涉及可通过本发明方法获得的高强度透明HDPE制品。此外,在另一个实施方式中,本发明涉及高强度透明HDPE制品,其中HDPE具有根据ASTM D1238在21.6kg和190℃下测量的至多1.5g/10min的熔体流动指数(MFI)、根据ISO 1183-1A测量的至多0.955g/cm3的各向同性密度以及根据ISO 11357-3测量的大于130℃的Tm,其中高强度透明HDPE制品具有至少0.5GPa的拉伸强度和在约0.1mm的膜厚度和550nm的波长下测量时至少为70%的透射率。拉伸的模塑制品的拉伸强度优选为至少0.7、更优选至少0.9、最优选至少1.0GPa。进一步优选的拉伸模塑制品在0.1mm的膜厚度和550nm的波长下测量时具有至少80%、更优选至少85%、最优选至少90%的透明度。
优选地,本发明的高强度HDPE制品包含至少80wt%、优选至少90wt%、更优选至少95wt%的HDPE,最优选高强度透明HDPE制品基本上由HDPE组成。
在一个优选的实施方式中,高强度透明HDPE制品的HDPE具有至多1.0g/10min、更优选至多0.8g/10min、最优选至多0.5g/10min的MFI(21.6kg,190℃)。对于高分子量聚乙烯和超高分子量聚乙烯,熔体流动指数将达到低于0.1g/10min的值,不能精确测量,因此本发明的优选实施方式涉及MFI小于0.1且特性粘度(IV)为至少3、优选至少4g/dl的HDPE。
在本发明的另一个优选实施方式中,高强度透明HDPE制品包含HDPE,其各向同性密度为至多0.953g/cm3,更优选至多0.952g/cm3,最优选至多0.950g/cm3。发明人发现,通过进一步降低的HDPE的各向同性密度,可以获得强度进一步提高的透明制品。
本发明还涉及高强度透明HDPE制品,其中HDPE的重均分子量(Mw)为至少200kg/mol,优选至少250kg/mol,最优选300kg/mol和/或分子量分布(MWD)为2至20,优选3至15,最优选4至10。
根据本发明的透明制品,尤其是透明带适合于组装成多层系统,从而提供大体透明或半透明以及具有良好的防弹或抗冲击性能的产品。因此,在另一个实施方式中,本发明涉及包含根据本发明的高强度透明HDPE制品的产品,优选该产品是防弹制品、遮阳板(visor)、汽车部件、火车部件、飞机部件、挡风玻璃、窗户或天线罩。
方法
·熔融温度(Tm)和熔化热(ΔHF)
根据ISO-11357-3通过差示扫描量热法在如下确定:在室温至200℃的间隔内以10℃/min的加热速率评估第二加热曲线。
结晶度(Xc)由下式计算:Xc=ΔHF/ΔHF0,其中ΔHF0是完全结晶的HDPE的熔化热,假设其等于280J/cm3。
·SEC-MALS
使用与多波段红外探测器(IR5PolymerChar)和来自Wyatt(DAWN EOS型)的多角度光散射(MALS)探测器(激光器波长为690nm)耦合的PL-210尺寸排阻色谱仪测量分子量分布(Mn、Mw、Mz、Mw/Mn)。使用两个PL-混合A柱。使用1,2,4-三氯苯作为溶剂,流速为0.5ml/min,测量温度为160℃。通过Wyatt(Astra)软件进行数据采集和计算。通过本领域技术人员已知的方法,在防止聚合物降解的条件下,HDPE应该完全溶解。
·透明度/雾度/透射率
在Shimadzu(日本)UV-3102PC分光光度计上在50%湿度和23℃下以1nm间隔在400-700nm范围内测量透射光谱。样品与检测器之间的距离约为150mm。在没有样品的情况下进行空白测量,并且将在每个波长下透射到检测器的光设定为100%。将记录的每个波长下的光透射率归一化为空白测量值,并获得透射率值。
·拉伸性能
在室温下在Zwick Z100拉伸试验机上以100mm/min的十字头速度测量拉伸样品的杨氏模量和拉伸强度。杨氏模量由应变低于0.1%的工程应力-应变曲线的切线计算。在所有情况下,测量至少三个条带并计算并报告杨氏模量和拉伸强度的平均值。为了计算拉伸强度,将测量的拉伸力除以横截面积(通过测量模塑拉伸带的厚度和宽度来确定);以模塑制品的密度为0.96g/cm3计算GPa值。
·各向同性密度根据ISO 1183-1方法A在各向同性样品上测定,所述各向同性样品通过在160℃下将样品退火1小时而获得。
·MFI根据ASTM D1238在21.6kg的重量和190℃的温度下测量。值通常以g/10min表示,其与SI单位dg/min相同。
·特性粘度(IV)
IV根据ASTM-D1601/2004在135℃下在十氢化萘中,溶解时间为4小时,DBPC作为抗氧化剂以2g/l溶液的量,通过外推在不同浓度下测量的粘度至零浓度来测定。
实验
选择具有不同物理性质的HDPE样品(表1)来生产HDPE片材。将聚乙烯1至4在同向旋转双螺杆挤出机中在160℃下均化10分钟。将挤出物在空气中冷却至室温,然后造粒。聚乙烯5通过从4wt%二甲苯溶液中浇铸而均化。
然后通过如下来制备给定厚度约1mm的基本上各向同性的熔融结晶HDPE片材:在160℃下压缩模塑10分钟,然后淬火至20℃。然后从压缩模塑片材上切下规格尺寸为12×2mm2、厚度为1mm的哑铃状样品。随后使用Zwick Z100拉伸试验机以100mm/min的十字头速度在不同温度下将这些哑铃状样品拉伸至各种拉伸比,以确定导致每种聚乙烯拉伸性能最高的拉伸温度和拉伸速率。这种最佳拉伸条件和性能列于表2中。假定取向PE的密度等于0.96g/cm3,通过称重计算拉伸样品的厚度。测量单轴拉伸后带的杨氏模量、强度和透射率,并记录在表2中。
表1:
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表2:
Claims (15)
1.一种用于生产高强度透明高密度聚乙烯制品的方法,所述方法包括以下步骤:
(i)将高密度聚乙烯(HDPE)加热到高于HDPE熔融温度(Tm)的温度;
(ii)模塑步骤(i)中得到的经加热的HDPE,形成热模塑HDPE制品;
(iii)将所述热模塑HDPE制品冷却至低于Tm的温度,以形成熔融结晶的HDPE制品;
(iv)将所述熔融结晶的HDPE制品拉伸至至少5的总拉伸比,其包括至少一个在低于所述熔融温度Tm的温度T1下将制品拉伸至至少2的拉伸比(DR1)的步骤,以形成取向的HDPE制品;
所述方法的特征在于,所述HDPE具有根据ASTM D1238在21.6kg和190℃下测量的至多1.5g/10min的熔体流动指数(MFI)、根据ISO1183-1A测量的至多0.955g/cm3的各向同性密度以及根据ISO11357-3测量的大于130℃的Tm。
2.根据权利要求1的方法,其中所述高强度制品是高强度的纤维、带或膜。
3.根据权利要求1的方法,其中在模塑之前或模塑期间,将所述HDPE加热至高于HDPE的Tm至少10℃的温度。
4.根据权利要求1或3的方法,其中在步骤(ii)期间,施加小于10s-1、优选小于5s-1、更优选小于1s-1、最优选小于0.5s-1的剪切速率。
5.根据前述权利要求中任一项的方法,其中T1为100至130℃,优选110℃至128℃,最优选115℃至125℃。
6.根据前述权利要求中任一项的方法,其中所述取向的HDPE制品包含至少80重量%、优选至少90重量%、更优选至少95重量的HDPE,最优选所述取向的HDPE制品基本上由HDPE构成。
7.根据前述权利要求中任一项的方法,其中HDPE具有至少200kg/mol的重均分子量(Mw)并且/或者具有2-10的分子量分布(MWD)。
8.根据前述权利要求中任一项的方法,其中所述熔融结晶的HDPE制品的拉伸包括在大于T1的温度T2下、优选在大于Tm的温度T2下的至少一个另外的拉伸步骤。
9.可通过权利要求1至8中任一项的方法获得的高强度透明HDPE制品。
10.一种高强度透明HDPE制品,其中HDPE具有根据ASTM D1238在21.6kg和190℃下测量的至多1.5dg/min的熔体流动指数(MFI)、根据ISO1183-1A测量的至多0.955g/cm3的各向同性密度以及根据ISO11357-3测量的大于130℃的Tm,其特征在于所述高强度透明HDPE制品具有至少0.5GPa的拉伸强度和至少70%的透射率,所述透射率是在0.1mm的膜厚度和550nm的波长下测量的。
11.根据权利要求9或10的高强度透明HDPE制品,其中所述制品包含至少80重量%、优选至少90重量%、更优选至少95重量的HDPE,最优选所述高强度透明HDPE制品基本上由HDPE制成。
12.根据权利要求9-11的高强度透明HDPE制品,其中HDPE具有在21.6kg和190℃下测量的至多1.0g/10min、更优选至多0.8g/10min、最优选至多0.5g/10min的MFI。
13.根据权利要求9-12的高强度透明HDPE制品,其中HDPE的各向同性密度为至多0.953g/cm3,更优选至多0.952g/cm3,最优选至多0.950g/cm3。
14.根据权利要求9-13的高强度透明HDPE制品,其中HDPE的重均分子量(Mw)为至少200kg/mol、优选至少250kg/mol、最优选300kg/mol和/或分子量分布(MWD)为2至20、优选3至15、最优选4至10。
15.一种产品,其包含根据权利要求9-14中任一项的高强度透明HDPE制品,优选所述产品是防弹制品、遮阳板、汽车部件、火车部件、飞机部件、挡风玻璃、窗户或天线罩。
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EP3519170A1 (en) | 2019-08-07 |
WO2018060224A1 (en) | 2018-04-05 |
KR20190062433A (ko) | 2019-06-05 |
US20200023567A1 (en) | 2020-01-23 |
EP3519170B1 (en) | 2023-08-16 |
CN109789651B (zh) | 2021-12-14 |
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