CN101432112A - 采用聚丙交酯树脂的注射拉伸吹塑方法 - Google Patents

采用聚丙交酯树脂的注射拉伸吹塑方法 Download PDF

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Publication number
CN101432112A
CN101432112A CNA2005800277009A CN200580027700A CN101432112A CN 101432112 A CN101432112 A CN 101432112A CN A2005800277009 A CNA2005800277009 A CN A2005800277009A CN 200580027700 A CN200580027700 A CN 200580027700A CN 101432112 A CN101432112 A CN 101432112A
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China
Prior art keywords
resin
precast body
container
lactic acid
pla resin
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CNA2005800277009A
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English (en)
Inventor
凯文·辛克
理查德·C·博普
凯文·D·赛克马
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NatureWorks LLC
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NatureWorks LLC
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Publication of CN101432112A publication Critical patent/CN101432112A/zh
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    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
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Abstract

使用具有特定乳酸立体异构体比例的PLA树脂和拉伸比以注射拉伸成型方法制造容器。该方法能以良好的生产率制造质量良好的容器。

Description

采用聚丙交酯树脂的注射拉伸吹塑方法
本发明在美国能源部资助的合同号为DE-FC36-00GO10598的美国政府资助下完成。美国政府对本发明拥有一定的权利。
本申请要求2004年6月23日提出的美国临时专利申请号60/582155的优先权。
本发明涉及制造容器的注射拉伸吹塑方法。
诸如瓶子的容器一般用注射拉伸吹塑方法由热塑性树脂成型。聚(对苯二甲酸乙二醇酯)(PET)瓶都以这种方式大批量制造。所述容器一般都有理想的透明度，常用于包装诸如水和碳酸饮料的饮品。PET非常适于此类应用，但缺点是它衍生自油基材料，不能被生物降解或不可堆肥化处理。开发衍生自每年可再生的资源的替代聚合物材料的兴趣日益增加。对可生物降解或可堆肥化处理的材料也很感兴趣，因为如果在合适条件下将其掩埋或堆肥化处理，它们会较快地分解。这种容器可以弃用并回收，从而提供较大范围的弃用/再利用选择。
聚丙交酯树脂(也称为聚乳酸或PLA)现在已可作为商品获得。这些树脂可用诸如玉米、稻谷或其他可制造糖或淀粉的植物的年度可再生资源制造。另外，PLA树脂是可堆肥化处理的。由于这些原因，在普遍采用油基热塑性材料的应用中用PLA进行代替有很大的兴趣。因此，已有人尝试将PLA树脂用于注射拉伸吹塑方法中以制造容器。参见例如美国专利5409751。然而，PLA树脂在注射拉伸吹塑方法中很难加工，因为和PET相比，PLA树脂往往具有明显不同的结晶性能和小得多的加工条件范围(processing windows)。迄今已证明很难以高运行率(operating rates)用PLA树脂制造高质量的瓶子。在某些情况中，该树脂根本不能吹塑。在其他情况下，该树脂在成型加工期间往往会应力致白，形成不透明而非透明的容器。在另外的情况下，PLA树脂会形成容器壁厚明显不均或冲击强度差的容器。结果，使得可用于由PLA树脂制造注射拉伸成型容器的加工条件范围很窄，以致于PLA树脂不能成功地用于注射拉伸吹塑加工。用于注射拉伸成型加工的其他类型树脂有时也会遇到类似问题。这些问题在某些情况下可通过改变聚合物结构，例如通过在聚合物骨架中结合共聚单体来克服。然而，诸如此类的改性也会改变诸如玻璃化转变温度、熔体粘度、溶解度、渗透性、耐化学性或毒性的其他聚合物性能。因此，通常优选的是避免改变聚合物的化学结构。
理想的是提供一种方法，通过所述方法可以将PLA树脂以良好的运行率以注射拉伸吹塑方法制造质量良好的容器。
本发明一方面是制造热塑性树脂容器的注射拉伸吹塑方法，其中，将热塑性树脂成型为预制体(preform)，将预制体机械拉伸并吹入容器模具中以从轴向和径向拉伸预制体形成容器，其中(1)热塑性树脂是聚乳酸(PLA)树脂，它是具有重复L和D乳酸单元的共聚物，其中L或D乳酸单元是主重复单元，且主重复单元构成了90-99.5％的乳酸重复单元，和(2)轴向和径向拉伸比的乘积为约3-约17.5。
本发明的注射拉伸吹塑方法可以是单步法或两步法，下面将更全面地描述。
选择具有所述对映体比值的PLA树脂给ISBM方法提供了明显的益处，使容器能以短循环时间、受控的结晶度、良好透明度、良好韧性和抗冲击性以及均匀的壁厚制备。采用具有所述异构体比值的PLA树脂增大了加工条件范围，使得更容易以高运行率制造高质量容器。
容器根据本发明用注射拉伸吹塑(ISBM)方法制造。ISBM方法是公知的，例如美国专利5409751中描述的。该方法涉及先形成中空的预制体或“管塞(plug)”，其尺寸为最终容器尺寸的一部分。通过将预制体插入模具中，并从轴向(即沿其长度方向)和径向拉伸，将预制体成型为容器。轴向拉伸通过机械手段进行，即在预制体中插入推杆棒，使预制体向模具底部机械地延伸。径向拉伸通过在管塞中注入压缩空气，从而迫使树脂向外以接触模具内表面来进行。一般来说，初级径向拉伸通过注入第一气体增量进行。这样为拉伸棒形成空间，然后才能插入拉伸棒。然后拉伸预制体并接着立即用更多气体吹塑，完成吹塑操作。
轴向应变(或轴向拉伸比)一般为约1.5-约3.5，特别是约2-约3。轴向应变被认为是容器长度与预制体长度之比。径向或“周向”应变(或周向拉伸比)一般为约2-约5，特别是3-约5，被认为是预制体周长与容器周长之比。周向应变对任何具体容器一般都不是恒定的，因为容器一般都没有恒定周长。除非另外说明，出于本发明的目的，周向比指容器侧壁的平均周向比。
面应变(或面拉伸比)是轴向应变乘以周向应变的积，一般在约3-约17.5，例如约3-约15、约5-约12或约8-约11范围内。
ISBM方法分成两种主要类型。一种是单步法，其中将预制体成型、调整，然后在预制体冷却到低于其软化温度前转移到拉伸吹塑操作中。ISBM方法的其他主要类型是提前制备预制体的两步法。在这种情况下，将预制体重新加热以进行拉伸吹塑步骤。两步法的优点是循环时间较快，因为拉伸吹塑步骤的完成不依赖于较慢的注射成型操作。然而，两步法的问题是要将预制体再次加热到拉伸吹塑温度。这一般通过红外加热给预制体外壁提供辐射能进行。用这种技术有时很难均匀加热预制体，除非小心地进行，在预制体外侧到中心之间可能存在很大的温度梯度。往往必须精心选择条件，以将预制体内部加热到合适成型温度而不使外壁过热。结果往往使两步法的操作范围比单步法更小。发现如上所述对PLA树脂的选择扩大了这种加工条件范围。
在两步法中，通常将预制体加热到使预制体变软到足以拉伸和吹塑的温度。该温度一般高于PLA树脂的玻璃化转变温度(Tg)。优选的温度为约70-约120℃，更优选的温度约80-约100℃。为了有助于获得整个预制体中更均匀的温度梯度，可将预制体短时间保持在上述温度使温度达到平衡。
两步法中的模具温度一般低于PLA树脂的玻璃化转变温度，例如约30-约60℃，特别是约35-约55℃。希望有较大壁厚的模具部分例如底部可保持在诸如约0-约35℃，特别是约5-约20℃的更低温度。
在单步法中，在预制体处于软化到足以拉伸和吹塑的温度的时候将注射成型加工得到的预制体转移到拉伸吹塑步骤，所述温度同样优选高于树脂的Tg，例如约80-约120℃，特别是约80-约110℃。成型前可使预制体短时间保持在该温度，以使其在该温度达到平衡。单步法中的模具温度可高于或低于PLA树脂的Tg。在所谓的“冷模具”工艺中，模具温度与两步法中所用温度类似。在“热模具”工艺中，模具温度保持高于树脂的Tg，例如约65-约100℃。在“热模具”工艺中，可使成型部件在成型完成后在模具中短时间保持受压状态，使树脂进一步结晶(热定形)。热定形往往能改善模塑容器的尺寸稳定性和耐热性，同时仍保持良好的透明度。热定形加工同样可用于两步法中，但很少采用，因为热定形加工往往会延长循环时间。
单步或两步法中的吹塑气体压力一般都在约5-约50巴(约0.5-约5MPa)范围内，例如约8-约45巴(约0.8-约4.5MPa)。初级径向拉伸中往往采用较低的气体注射压力，然后用较高压力注射完成吹塑加工。
对于本发明的目的，术语“聚丙交酯”、“聚乳酸”和“PLA”可互换使用，指具有-OC(O)CH(CH3)-结构的重复单元的聚合物，而不管这些重复单元如何形成聚合物。PLA树脂优选含有至少90％，例如至少95％或至少98％(重量)的这些重复单元。用于本发明的PLA树脂一般是同时含有D和L对映体重复单元的无规聚合物。当采用单步ISBM方法时，主要的对映体构成90-99.5％的聚合乳酸单元，而其他对映体构成0.5-10％的聚合乳酸单元。单步法的合适对映体比值包括例如92-98％主要对映体和2-8％其他对映体、94-98％主要对映体和2-6％其他对映体或95-97％主要对映体和3-5％其他对映体。最优选的是PLA树脂主要含有聚合的L乳酸单元，但在本发明范围内可等同地采用主要含有D乳酸单元的PLA树脂。
PLA树脂可以是平均对映体比值在上述范围内的PLA树脂的混合物。具体而言，可采用对映体比值为70:30-95:5，特别是80:20-90:10的一种树脂与对映体比值为95:5或更高，特别是97:3或更高的另一种树脂的混合物。成分树脂比例的选择应使混合物的总体平均对映体比值在上述范围内。在某些情况中，发现采用这种聚合物混合物可导致性能改善，例如收缩率降低且应力发白减少。
优选的PLA树脂是丙交酯的聚合物或共聚物。诸如乳酸的α-羟基酸作为两种旋光对映体存在，一般称为“D”和“L”对映体。D-或L-乳酸都可在合成方法中制备，而发酵方法常常(但不总是)有利于L对映体的制备。丙交酯类似地以各种对映体形式存在，即作为两个L-乳酸分子的二聚物的“L-丙交酯”、作为两个D-乳酸分子的二聚物的“D-丙交酯”，以及作为由一个L-乳酸分子与一个D-乳酸分子形成的二聚物的“内消旋丙交酯”。此外，熔化温度约126℃的L-丙交酯与D-丙交酯的50/50混合物常称为“D，L-丙交酯”。任何这些形式的丙交酯的聚合物或它们的混合物都可用于本发明，只要PLA树脂具有上述异构体比值即可。
优选的丙交酯通过聚合乳酸形成预聚物，然后解聚该预聚物并同时蒸馏出所产生的丙交酯来制备。这种方法描述在美国专利5274073(Gruber等)中，本说明书全文引参考用该专利。
PLA树脂还可含有衍生自可与丙交酯或乳酸共聚的其他单体的重复单元，所述其它单体例如烯化氧(包括环氧乙烷、氧化丙烯、环氧丁烷、四氢呋喃等)、环内酯或环碳酸酯。衍生自这些其他单体的重复单元可以以嵌段和/或无规排列存在。这种其他重复单元优选构成0-10％，特别是0-5％(重量)的PLA树脂。PLA树脂一般不含这种其它重复单元。
PLA树脂还可含有聚合期间常用于控制分子量的引发剂化合物残基。合适的这种引发剂包括例如水、醇、乙二醇醚、各种类型的多羟基化合物(例如乙二醇、丙二醇、聚乙二醇、聚丙二醇、甘油、三羟甲基丙烷、季戊四醇、羟基封端的丁二烯聚合物等)。
PLA树脂有益地具有约80,000-150,000，特别是约95,000-约120,000的数均分子量(通过GPC采用聚苯乙烯标准测量)。PLA树脂有益地表现出约3.4-约4.5，特别是3.6-约4.2的相对粘度(在30℃的二氯甲烷中测量)。
特别合适的通过聚合丙交酯制备PLA的方法描述在美国专利5,247,059、5,258,488和5,274,073中。这种优选的聚合方法一般包括脱挥发份步骤，在该步骤中，聚合物中游离的丙交酯含量减少，优选减少到1％(重量)以下，更优选减少到0.5％(重量)以下。为了制备熔融稳定的丙交酯聚合物，优选在聚合过程结束时除去或去活催化剂。这可通过沉淀催化剂或优选通过在聚合物中加入有效量的去活化剂进行。催化剂的去活化可通过在聚合容器中加入去活化剂，优选在脱挥发份步骤前加入来进行。合适的去活化剂包括羧酸，其中优选聚丙烯酸；受阻的烷基、芳基和酚酰肼；脂肪族和芳香族一元和二元羧酸的酰胺；环酰胺，脂肪族和芳香族醛的腙和双腙，脂肪族和芳香族一元和二元羧酸的酰肼，双酰化肼衍生物，亚磷酸盐化合物和杂环化合物。
PLA树脂可改性引入长链分支。已发现这种长链分支可改善聚合物的熔体流变学，尤其是改善熔体强度.已公开了引入长链分支的各种方法，包括美国专利53,59,026中描述的丙交酯与环氧化脂肪或油共聚，或WO 02/100,921A1中描述的丙交酯与双环环内酯共聚单体共聚；美国专利5,594,095和5,798,435中描述的用过氧化物处理PLA树脂，以及美国专利5,210,108和5,225,521(Spinu)、GB 2,277,324和EP632,081中描述的在其聚合反应中使用某些多官能引发剂。最近发现可使用含有多个环氧基团的丙烯酸类聚合物和共聚物作为PLA树脂的支化剂。这种聚合物和共聚物的实例可从Johnson Polymers，Inc.以商品名Joncryl
Figure A200580027567D0026113914QIETU
 4368和Joncryl
Figure A200580027567D0026113914QIETU
 4369商购。
PLA树脂可与各种添加剂混合，包括抗氧化剂、防腐剂、催化剂去活化剂、稳定剂、增塑剂、填料、成核剂、所有类型的着色剂和发泡剂。在制备透明瓶子的优选实施方案中，PLA树脂优选不含造成树脂发白(由于结晶)或变得不透明的添加剂。优选添加剂是诸如碳黑的颗粒材料，如果其用量非常少就不会引起发白或不透明，相反会通过吸收红外辐射并提高预制体加热速度而有助于ISBM(特别是两步法)加工。
PLA树脂可与具有阻挡性能的聚合物共注射，以形成具有阻挡聚合物层的预制体和最终容器，使容器更耐水和耐其他蒸汽透过。具有合适阻挡性能的聚合物的实例包括聚乙烯或乙烯共聚物、聚丙烯或丙烯共聚物、聚偏二氯乙烯或1，1-二氯乙烯的共聚物、乙烯-乙烯基醇共聚物、聚对苯二甲酸乙二醇酯、聚碳酸酯、聚酰胺以及类似的聚合物。
尤其关心用本发明制备透明瓶子。透明度通常用％浊度表达，其可根据ASTM D-1003测量。根据本发明制备的瓶子优选具有不大于20％，更优选不大于15％，甚至更优选不超过10％的浊度。
以下实施例用于说明本发明，但并不限制本发明的范围。所有份和百分比除另外指明外均指重量。分子量通过GPC在四氢呋喃中参照聚苯乙烯标准测定。
实施例1
通过以下两步ISBM方法由各种PLA树脂制备1.5L的瓶子。通过将树脂加热到200-210℃的温度并注入预制体模具中，注射成型长129mm、平均直径23mm、重量42-44g的预制体。优化成型条件，使部件应力最小，并制备无浊度的透明部件。在独立步骤中拉伸吹塑前将成型预制体冷却到室温。
拉伸吹塑在满负荷下每小时能制备约2400个瓶子的实验室规模设备上进行。用红外灯将预制体加热到约98-110℃的温度，插入模具中，在约10巴(1MPa)压力下预吹塑，然后拉伸和在38巴(3.8MPa)压力下吹塑。模具温度为100℉(38℃)，但模具底部急冷到40℉(4℃)。拉伸比为：轴向拉伸比＝2.1；周向拉伸比＝4.0；面拉伸比＝8.4。
所用PLA树脂是：
1.树脂1，数均分子量约105,000的96.5％的L-丙交酯和3.5％的D-丙交酯的共聚物；
2.树脂2，数均分子量约105,000的96％的L-丙交酯和4％的D-丙交酯的共聚物。
在这些条件下，以2,300-2,400个瓶子/小时的速率可以很好地加工树脂1和2，得到质量良好的透明瓶子。
实施例2
通过以下两步IBSN方法由各种PLA树脂制备16盎司的碳酸软饮料瓶子。通过将树脂加热到205-225℃的温度并注入预制体模具中，注射成型长68.2mm、参考内径15.7mm、参考外径22.4mm、重量约24g的预制体。
拉伸吹塑在满负荷下每小时能制备约1,200个瓶子的实验室规模设备上进行。用红外灯将预制体加热到约85-90℃的温度，插入模具中，在约20巴(2MPa)压力下预吹塑，然后拉伸和在38巴(3.8MPa)压力下吹塑。模具温度为120℉(49℃)，但模具底部急冷到40℉(4℃)。拉伸比为：轴向拉伸比＝2.2；周向拉伸比＝3.7；面拉伸比＝8.1。
然后改变预制体温度，以确定每种树脂能以所述生产率制备质量良好的瓶子的预制体温度范围。瓶子质量通过检查瓶子的应力发白外观、底部薄壁、薄侧壁和底部中心处树脂块(resin slug)的形成来评价。
树脂如下：
树脂3：数均分子量约102,000、相对粘度3.99的96.8％的L-丙交酯和3.2％的D-丙交酯的共聚物；
树脂4：数均分子量约103,500、相对粘度约4.00的95.9％的L-丙交酯和4.1％的D-丙交酯的共聚物；
树脂5：数均分子量约101,000、相对粘度3.6的95.1％的L-丙交酯和4.9％的D-丙交酯的共聚物；
树脂6：数均分子量约83,000、相对粘度3.29的95.7％的L-丙交酯和4.3％的D-丙交酯的共聚物；
树脂7：数均分子量约80,000、相对粘度3.23的95.3％的L-丙交酯和4.7％的D-丙交酯的共聚物；
用每种树脂3-7都制备出质量良好的瓶子。然而，加工条件范围有明显不同。树脂3和4表现出最宽的加工条件范围，它们在约88-95℃预制体温度下都制备了质量良好的瓶子。D-异构体含量较高且分子量和相对粘度略低的树脂5具有约87-91.5℃的加工条件范围，温度范围约4.5℃。D-异构体含量较低但分子量低于树脂5的树脂6和7也具有约4.5-5℃的加工条件范围。
实施例3
将82.5％的L-丙交酯和17.5％的D-丙交酯的粒状共聚物与98.6％的L-丙交酯和1.4％的D-丙交酯的粒状共聚物干混合。原材料比例的选择应使混合物的L-：D-对映体平均比值为96.8：3.2。
通过以下两步ISBM方法由各种PLA树脂制备1升的直壁瓶子。注射成型重量约29g的预制体。在独立步骤拉伸吹塑前中将成型预制体冷却到室温。
拉伸吹塑在每小时能制备约1,200个瓶子的速度下在实验室规模设备上进行。用红外灯将预制体加热到约83℃的温度，插入模具中，在约5巴(0.5MPa)压力下预吹塑，然后拉伸和在40巴(4MPa)压力下吹塑。模具温度为100℉(38℃)。拉伸比为：轴向拉伸比＝2.3；周向拉伸比＝4.35；面拉伸比＝10.0。
测量10个瓶子在环境条件下老化24小时后的瓶高、主直径和总容积。然后在100℉(38℃)和100％相对湿度下暴露瓶子24小时，测量其尺寸。表明瓶子的平均收缩率为1.03％。
以相同方式制备瓶子，但采用含96.8％的L-对映体和3.2％的D-对映体的单一PLA树脂，在相同试验中表现出1.19％的收缩率。
制备更多的瓶子，此时采用相同原材料树脂的混合物，其混合比使混合树脂中L-对映体与D-对映体的平均比值为96:4。这些瓶子都表现出1.16％的收缩率。采用L-对映体与D-对映体之比为96:4的单一PLA树脂制备的瓶子表现出1.32％的收缩率。
应该明白的是，可对以上描述的本发明进行许多修改而不脱离本发明的精神，本发明的范围由所附权利要求限定。

Claims (24)

1.一种制造热塑性树脂容器的注射拉伸吹塑方法，其中将热塑性树脂成型为预制体，将预制体在容器模具中机械拉伸并吹塑以从轴向和径向拉伸预制体形成容器，其中(1)所述热塑性树脂是聚乳酸(PLA)树脂，所述聚乳酸树脂是(a)具有重复L和D乳酸单元的共聚物，其中L或D乳酸单元是主重复单元，或(b)这些共聚物的混合物，其中共聚物或混合物中的主重复单元构成PLA树脂或混合物中90-99.5％的乳酸对映体重复单元，和(2)轴向拉伸比和径向拉伸比之积为约3-约17.5。
2.权利要求1的方法，在树脂成型为预制体后，在预制体成型后但在成型的预制体冷却到低于树脂软化温度之前在容器模具中机械拉伸预制体并吹塑预制体。
3.权利要求1的方法，其中所述容器是透明容器。
4.权利要求3的方法，其中PLA树脂的数均分子量为80,000-150,000，通过凝胶渗透色谱法用聚苯乙烯标准测量。
5.权利要求4的方法，其中PLA树脂在30℃在二氯甲烷中的相对粘度为3.4-4.5。
6.权利要求5的方法，其中PLA树脂中92-99.5％的乳酸对映体重复单元是主乳酸对映体。
7.权利要求6的方法，其中PLA树脂中94-99％的乳酸对映体重复单元是主乳酸对映体。
8.权利要求2的方法，其中容器模具的温度低于PLA树脂的玻璃化转变温度。
9.权利要求2的方法，其中容器模具的温度高于PLA树脂的玻璃化转变温度但低于其熔化温度。
10.权利要求9的方法，其中容器在容器模具中热定形。
11.权利要求2的方法，其中PLA树脂与阻挡聚合物共注射，以形成具有至少一层阻挡聚合物的预制体，并拉伸吹塑该预制体，形成具有至少一层阻挡聚合物的容器。
12.权利要求11的方法，其中阻挡聚合物是聚乙烯或乙烯共聚物、聚丙烯或丙烯共聚物、聚偏二氯乙烯或1，1-二氯乙烯的共聚物、乙烯-乙烯基醇共聚物、聚对苯二甲酸乙二醇酯、聚碳酸酯或聚酰胺。
13.权利要求1的方法，其中预制体从热塑性树脂的玻璃化转变温度以下加热到高于该温度，然后在容器模具中机械拉伸和吹塑。
14.权利要求13的方法，其中所述容器是透明容器。
15.权利要求14的方法，其中PLA树脂的数均分子量为80,000-150,000，通过凝胶渗透色谱法用聚苯乙烯标准测量。
16.权利要求15的方法，其中PLA树脂在30℃在二氯甲烷中的相对粘度为3.4-4.5。
17.权利要求16的方法，其中PLA树脂中92-99.5％的乳酸对映体重复单元是主乳酸对映体。
18.权利要求17的方法，其中PLA树脂中94-99％的乳酸对映体重复单元是主乳酸对映体。
19.权利要求13的方法，其中容器模具的温度低于PLA树脂的玻璃化转变温度。
20.权利要求13的方法，其中PLA树脂与阻挡聚合物共注射，以形成具有至少一层阻挡聚合物的预制体，并拉伸吹塑该预制体，以形成具有至少一层阻挡聚合物的容器。
21.权利要求20的方法，其中阻挡聚合物是聚乙烯或乙烯共聚物、聚丙烯或丙烯共聚物、聚偏二氯乙烯或1，1-二氯乙烯的共聚物、乙烯-乙烯基醇共聚物、聚对苯二甲酸乙二醇酯、聚碳酸酯或聚酰胺。
22.权利要求13的方法，其中容器模具的温度高于PLA树脂的玻璃化转变温度但低于其熔化温度。
23.权利要求2的方法，其中PLA树脂含有0-10％重量衍生自可与丙交酯或乳酸共聚的单体的重复单元。
24.权利要求13的方法，其中PLA树脂含有0-10％重量衍生自可与丙交酯或乳酸共聚的单体的重复单元。
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CN104086967A (zh) * 2014-06-27 2014-10-08 张雨生 一种塑料制品材料
CN104086967B (zh) * 2014-06-27 2016-06-22 张雨生 一种塑料制品材料
CN109153166A (zh) * 2016-05-17 2019-01-04 P.E.T.工程责任有限公司 用于制备聚合材料的瓶的方法
CN109153166B (zh) * 2016-05-17 2021-07-06 P.E.T.工程责任有限公司 用于制备聚合材料的瓶的方法

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US20070187876A1 (en) 2007-08-16
EP1778448A4 (en) 2009-08-19
BRPI0512366A (pt) 2008-03-11
EP1778448A2 (en) 2007-05-02
KR100844632B1 (ko) 2008-07-07
KR20070041524A (ko) 2007-04-18
JP2008504144A (ja) 2008-02-14
CA2571252A1 (en) 2006-01-05

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