CN103003350A - 聚乙烯共混物和膜 - Google Patents
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Abstract
公开了聚乙烯共混物和膜。该共混物包含占共混物重量的1至99%的中密度聚乙烯(MDPE)和1至99%的选自高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)、聚丙烯、聚丁烯及其混合物的聚烯烃。该MDPE通过高压自由基聚合制造并具有在大于0.928至0.940g/cm3范围内的密度和在0.1至1dg/min范围内的MI2。由该共混物制成的收缩膜具有强收缩力和低蠕变。
Description
发明领域
本发明涉及聚乙烯共混物和膜。本发明更特别涉及包含通过高压自由基聚合制成的中密度聚乙烯(MDPE)的聚乙烯共混物和由其制成的整理收缩膜(collation shrink film)。
发明背景
聚乙烯被分成高密度(HDPE,密度0.941 g/cm3或更大)、中密度(MDPE,密度0.926至0.940 g/cm3)、低密度(LDPE,密度0.910至0.925 g/cm3)和线性低密度聚乙烯(LLDPE,密度0.910至0.925 g/cm3)。见ASTM D4976-98: Standard Specification for Polyethylene Plastic Molding and Extrusion Materials。线性聚乙烯,包括HDPE、MDPE和LLDPE通常通过配位催化剂,如齐格勒-纳塔和单位点催化剂制造,而支链聚乙烯LDPE通过在高压下的自由基聚合制造。对线性聚乙烯而言,密度随与乙烯一起使用的共聚单体的量而变。共聚单体沿乙烯骨架形成短链分支,由于分支造成乙烯骨架之间的分离,共聚单体的量越大,聚合物的密度越低。另一方面,支链聚乙烯的密度取决于长链分支的堆积紧密度和规则性,并通过反应器压力和热的改变而改变。因此,支链聚乙烯的密度无法宽范围改变,并且通常不通过高压自由基聚合制造HDPE和MDPE树脂。
与LLPDE相比,LDPE具有独特的性质组合,包括高收缩特性、可加工性和膜透明度。LDPE的这些独特属性基本来自于其长链支化结构。最近已通过高压自由基聚合制造MDPE树脂。参见美国专利申请公开No. 2004/0054097。不同于传统的MDPE——其是乙烯与α-烯烃共聚单体的共聚物,这些新型MDPE树脂是高度支化的乙烯均聚物。它们兼具传统MDPE和LDPE的属性。但是,这些新型MDPE树脂的制造更昂贵,因为它们需要独特的聚合条件且它们目前用于有限领域,如医疗和化妆品用途。通过高压自由基聚合制成的新型MDPE树脂具有许多独特的性质,它们为聚乙烯膜的改进提供新的可能性。
发明概述
本发明涉及聚乙烯共混物和膜。该共混物包含占共混物重量的1至99%的中密度聚乙烯(MDPE)和1至99%的选自高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)、聚丙烯、聚丁烯及其混合物的聚烯烃。该MDPE通过高压自由基聚合制造并具有在大于0.928至0.940 g/cm3范围内的密度和在0.1至1 dg/min范围内的MI2。本发明还包括由该共混物制成的整理收缩膜。该整理收缩膜具有清澈性与物理强度如模量、收缩力和抗蠕变性的组合。
发明详述
本发明的共混物包含占共混物重量的1至99重量%,优选50至95重量%,更优选75至95重量%的中密度聚乙烯(MDPE)。通过高压自由基聚合制造该MDPE。通过高压自由基聚合制备MDPE的方法是已知的。例如,美国专利申请公开No. 2004/0054097——其教导经此引用并入本文,教导了在具有至少两个聚合区的管式反应器中在150℃至350℃范围内的温度和500至5000巴范围内的压力下使用氧作为自由基引发剂制造乙烯均聚物和共聚物的方法。该方法使用脂族酮作为分子量调节剂。用于本发明的合适的MDPE的一个实例是来自Equistar Chemicals, LP的Petrothene L3035。
该MDPE优选是乙烯均聚物。该MDPE具有在0.928至0.940 g/cm3范围内,优选在0.929至0.939 g/cm3范围内,更优选在0.929至0.934 g/cm3范围内的密度。该MDPE具有在0.1至1 dg/min范围内,优选在0.2至0.7 dg/min范围内的熔体指数MI2。分别根据ASTM 1505和1238(条件190/2.16)测定密度和MI2。除非另行指明,使用这些方法测量本申请中使用的所有聚合物的密度和MI2。
本发明的共混物包含1至99重量%,优选5至50%,更优选5至25重量%的选自高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)、聚丙烯、聚丁烯等及其混合物的聚烯烃。合适的HDPE包括乙烯均聚物和乙烯与α-烯烃的共聚物。合适的α-烯烃包括1-丁烯、1-己烯和1-辛烯等及其混合物。HDPE中的α-烯烃含量优选小于2重量%。该HDPE具有优选在0.940至0.970 g/cm3范围内,更优选在0.945至0.965 g/cm3范围内的密度。该HDPE具有具有优选在0.001至100 dg/min范围内,更优选在0.05至50 dg/min范围内的熔体指数MI2。该HDPE可以是多峰的。“多峰”是指该HDPE包含至少两种组分,其中之一具有相对较低的分子量,另一种具有相对较高的分子量。许多HDPE树脂可购得,例如来自Equistar Chemicals, LP的L5885和M6020 HDPE树脂。
用在本发明的共混物中的合适的LLDPE可以用齐格勒-纳塔催化剂、单位点催化剂和任何其它合适的催化剂制备。它们包括乙烯和一种或多种C3至C10 α-烯烃的共聚物。合适的α-烯烃包括1-丁烯、1-己烯和1-辛烯等及其混合物。LLDPE的密度优选在0.865至0.940 g/cm3的范围内,更优选在0.910至0.940 g/cm3的范围内,最优选在0.915至0.935 g/cm3的范围内。该LLDPE优选具有在0.1至10 dg/min范围内,更优选在0.5至8 dg/min范围内的熔体指数MI2。特别优选的LLDPE树脂是具有在2至20重量%范围内的1-丁烯含量的乙烯和1-丁烯的共聚物。该乙烯-1-丁烯共聚物优选具有0.912至0.925 g/cm3,更优选0.915至0.920 g/cm3的密度。该乙烯-1-丁烯共聚物优选具有在0.5至15 dg/min范围内,更优选为1至10 dg/min的MI2。
用于本发明的合适的LDPE包括从工业中获知的那些。通常通过在高压下的自由基聚合制造LDPE。有两种用于制造LDPE的基本方法:高压釜和管式(tubular)。高压釜LDPE和管式LDPE适用于本发明。该LDPE具有优选在0.910至0.925 g/cm3范围内,更优选在0.915至0.925 g/cm3范围内的密度。该LDPE具有优选在0.1至100 dg/min范围内,更优选在0.5至50 dg/min范围内的熔体指数MI2。许多LDPE树脂可购得并适用在本发明的共混物中。合适的LDPE树脂的一个实例是来自Equistar Chemicals, LP的Petrothene NA940。合适的LDPE包括乙烯-乙酸乙烯酯共聚物(EVA)。通过乙烯和乙酸乙烯酯的自由基共聚制造EVA。合适的EVA包含优选2至30重量%乙酸乙烯酯,更优选5至18重量%乙酸乙烯酯。合适的EVA具有优选在2至500 dg/min范围内的熔体指数MI2。许多EVA树脂可购得,例如,EVA UE624可获自Equistar Chemicals, LP。
合适的聚丙烯包括非晶聚丙烯、半结晶聚丙烯等及其混合物。半结晶聚丙烯优选选自丙烯均聚物、丙烯与至少一种其它C2至C10 α-烯烃的共聚物等及其混合物。丙烯的共聚物包括无规共聚物和抗冲共聚物。用于这样的共聚物的优选α-烯烃包括乙烯、1-丁烯、1-戊烯、1-己烯、甲基-1-丁烯、甲基-1-戊烯、1-辛烯、1-癸烯等,及其混合物。本文所用的“半结晶”是指结晶度大于或等于40%,优选大于或等于55%,更优选大于或等于80%。半结晶聚丙烯优选具有在0.001 dg/min至500 dg/min范围内的溶体流动速率(通过ASTM D-1238-01在230℃的温度下和在2.16 kg的负荷下测得)。该半结晶聚丙烯优选具有在0.897 g/cm3至0.925 g/cm3范围内的密度和在85,000至900,000范围内的重均分子量(Mw)。
合适的聚丁烯包括1-丁烯的均聚物、1-丁烯与至少一种其它C2至C10 α-烯烃的共聚物等及其混合物。用于这样的共聚物的优选α-烯烃包括乙烯、丙烯、1-戊烯、1-己烯、甲基-1-丁烯、甲基-1-戊烯、1-辛烯、1-癸烯等及其混合物。该聚丁烯具有优选在0.01 dg/min至1000 dg/min范围内,更优选在0.1 dg/min至750 dg/min范围内的MI2。制造聚丁烯的方法是已知的。例如参见美国专利No. 6,306,996,其教导经此引用并入本文。
LLDPE和HDPE是用于制造本发明的共混物的优选聚烯烃。优选通过单位点催化剂(即sLLDPE)制造LLDPE。
任选地,该共混物还含有抗氧化剂、紫外线吸收剂、流动剂和其它添加剂。这些添加剂是本领域中公知的。例如,美国专利Nos. 4,086,204、4,331,586和4,812,500——其教导经此引用并入本文,教导了聚烯烃用的紫外线稳定剂。添加剂优选以小于总共混物的10重量%的量加入。
可以使用任何合适的共混技术。该聚合物和任选添加剂可以在溶液中或在热加工中共混。溶体螺杆挤出是优选的。
本发明包括包含本发明的共混物的制品,包括膜、片材、管道、容器、袋、衬垫等。本发明的一个特定用途是由该共混物制成的整理收缩膜。整理收缩膜用于粘合包装,如水瓶。本发明的整理收缩膜表现出高清澈度、强收缩力、低蠕变和高刚度的独特组合。本发明的收缩膜可以是单层膜或多层膜。对本发明的单层膜而言,该共混物优选包含50至90重量%,更优选75至90重量%的MDPE和优选10至50重量%,更优选10至25重量%的sLLDPE。优选的多层膜是包含两个外层和一个芯层的三层膜。外层由优选包含5至25重量%,更优选5至15重量% MDPE的MDPE和sLLDPE的共混物制成。芯层由优选包含75至95重量% MDPE的MDPE和HDPE的共混物制成。
制造整理收缩膜的方法是已知的。例如,吹膜法可用于制造本发明的双向拉伸整理收缩膜。在该方法中,聚乙烯溶体由挤出机通过环形模头中的模隙(0.025至0.100 英寸)进给以制造熔融管,其垂直向上推。将压缩空气送入管内部以提高管直径,以产生“气泡”。注入管中的空气体积控制管的尺寸或所得吹胀比,其通常为模头直径的1至3倍。在低颈挤出(low stalk extrusion)中,通过外表面上和任选在膜内表面上的冷却环快速冷却该管。霜线高度是指熔融挤出物固化的位置。这出现在模头直径的大约0.5-4倍的高度处。从模隙到最终膜厚度的拉伸(draw down)和管直径的膨胀造成膜的双向拉伸,这提供膜性质的所需平衡。气泡在一对轧辊(nip roll)之间坍塌并通过膜卷绕器卷绕到膜辊上。在最初冷却后在壁表面不会相互粘合的程度上进行管的坍塌。在两个方向——沿离开模头的聚合物流或纵向(MD)和垂直于离开模头的聚合物流或横向(TD)——上确定膜的物理性质。
下列实施例仅例示本发明。本领域技术人员会认识到在本发明的精神和权利要求的范围内的许多变动。
实施例1
本发明的共混物和单层整理收缩膜
通过高压自由基聚合制成的MDPE(乙烯均聚物)(80重量份)通过挤出与单位点sLLDPE(20重量份)共混。该MDPE具有0.930 g/cm3的密度和0.40 dg/min的MI2。该sLLDPE具有1.0 dg/min的MI2和0.918 g/cc的密度。在具有60密尔模隙的6’’模头上将该共混物转化成厚度2.0密尔的膜。以3:1的吹胀比(BUR)制造膜。该膜具有90 lb/in的刚度(刚度 = 模量x 膜厚度)、64的NAS(ASTM D1746,Zebedee窄角散射器)、9%的浊度(ASTM D1003)、5,000 psi的MD模量(ASTM E111)、4,100的TD模量(ASTM E111)、310 g的MD撕裂(ASTM D1922 Elmendorf Tear)、1,100 g的TD撕裂(ASTM D1922 Elmendorf Tear)、121 g的收缩力(ISO 14616)和80%的收缩率 135℃(ASTM D2732在炉中在135C下的无限制线性收缩(Unrestrained Linear Shrink in oven at 135C))。
对比例2
不含MDPE的共混物和单层整理收缩膜
通过挤出共混LDPE(乙烯均聚物,75重量份)、sLLDPE(20重量份)和HDPE(5重量份)。该LDPE具有0.924 g/cm3的密度和0.75 dg/min的MI2。该sLLDPE与实施例1中描述的相同。该HDPE具有0.960 g/ cm3的密度和2.9 dg/min的MI2。设计该共混物组合物以实现相当的膜性质,如整理收缩膜所需的收缩和收缩力(contraction force)。在这种共混物组合物中,HDPE是用于实现膜刚度,即模量和刚度的必要组分。除膜厚度外,使用如实施例1中描述的相同方法制造2.5密尔膜。要注意,对比例2中的2.5密尔的膜厚度是实现与实施例1的2.0密尔膜相当的膜性质,如收缩和收缩力所必须的。该膜具有90 lb/in的刚度、48的NAS(窄角散射)、11%的浊度、4,300 psi的MD模量、3,800的TD模量、420 g的MD撕裂、1,100 g的TD撕裂、116 g的收缩力和80%的收缩率 135℃。如这些结果所示,这种对比膜具有明显低于实施例1的膜的模量和透明度(通过NAS测得)。
实施例3
本发明的共混物和三层整理收缩膜
通过共挤出制造三层整理膜。该膜具有两个外层和一个芯层。外层由sLLDPE(90重量份)和MDPE(10重量份)的共混物制成,芯层由MDPE(80重量份)和HDPE(20重量份)的共混物制成。MDPE、LLDPE和HDPE与上述实施例1和对比例2中描述的相同。该膜具有2.5密尔的总厚度;芯层为总厚度的65%,各外层为总厚度的17.5%。该膜具有55的NAS、52,400 psi的1%割线MD模量(ASTM E111)、62,800的1%割线TD模量(ASTM E111)和76%的MD收缩率 135℃。
对比例4
三层整理收缩膜,其中芯层不含MDPE
遵循实施例3,但将芯层中的MDPE换成LDPE。LDPE与对比例2中描述的相同。该膜具有46的NAS、42,600 psi的1%割线MD模量、50,000的1%割线TD模量和76%的MD收缩率 135℃。
对比例5
遵循实施例1,但将通过高压自由基聚合制成的MDPE(乙烯均聚物)换成通过齐格勒-纳塔催化剂制成的MDPE(乙烯-α-烯烃共聚物)。该膜预计与实施例1的膜相比具有较低收缩率、低收缩力、较低光泽和较高浊度。其不适用于需要高收缩率、高收缩力和高清澈度的收缩膜。
Claims (15)
1.聚合物共混物,其包含:
(a) 占共混物重量的1%至99%的中密度聚乙烯(MDPE),其通过高压自由基聚合制造并具有在大于0.928至0.940 g/cm3范围内的密度、在0.1至1 dg/min范围内的MI2;和
(b) 占共混物重量的1%至99%的选自高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)、聚丙烯、聚丁烯及其混合物的聚烯烃。
2.权利要求1的共混物,其中所述MDPE具有在0.929至0.939 g/cm3范围内的密度。
3.权利要求2的共混物,其中所述MDPE具有在0.929至0.934 g/cm3范围内的密度。
4.权利要求2的共混物,其中所述MDPE具有在0.2至0.7 dg/min范围内的MI2。
5.权利要求1的共混物,其中所述聚烯烃选自LLDPE、HDPE及其混合物。
6.权利要求5的共混物,其中所述聚烯烃是单位点LLDPE(sLLDPE)。
7.权利要求5的共混物,其包含50%至95%的MDPE和5%至50%的聚烯烃。
8.权利要求7的共混物,其包含75%至95%的MDPE和5%至25%的聚烯烃。
9.权利要求8的共混物,其中所述聚烯烃是sLLDPE。
10.包含权利要求1的共混物的膜。
11.权利要求10的单层膜。
12.权利要求10的三层膜,其包含两个外层和一个芯层,其中所述外层包含5%至95% MDPE和5%至95% sLLDPE的共混物,所述芯层包含75%至95% MDPE和5%至25% HDPE或LLDPE。
13.权利要求12的膜,其中所述MDPE具有在0.929至0.934 g/cm3范围内的密度和在0.3至0.6 dg/min范围内的MI2。
14.包含权利要求10的膜的制品。
15.制备权利要求10的膜的方法,包括通过吹膜法将所述共混物转化成所述膜。
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