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CN1072099C - 制备聚丙烯容器的拉伸吹塑－模塑方法及其制备的瓶子 - Google Patents

制备聚丙烯容器的拉伸吹塑－模塑方法及其制备的瓶子 Download PDF

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CN1072099C
CN1072099C CN96122456A CN96122456A CN1072099C CN 1072099 C CN1072099 C CN 1072099C CN 96122456 A CN96122456 A CN 96122456A CN 96122456 A CN96122456 A CN 96122456A CN 1072099 C CN1072099 C CN 1072099C
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crystalline propylene
propylene copolymer
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polypropylene material
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CN1159975A (zh
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C·莱斯卡
A·梅德里
A·佩里康尼
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Himont Inc
Basell North America Inc
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Abstract

用于制备聚丙烯容器的拉伸吹塑—模塑的方法，其中，使用含4%至12%重量的一种或几种C4-C8α-链烯烃类的结晶丙烯共聚物作为聚丙烯材料。

Description

制备聚丙烯容器的拉伸吹塑-模塑方法及其制备的瓶子
本发明涉及用于制备聚丙烯容器，特别是瓶子类的增强吹塑模塑的方法。
增强吹塑模塑的方法，不论一步还是二步法的，在该技术领域中被普遍使用来生产热塑性材料制的容器，特别是聚对苯二甲酸乙二醇酯(PET)。事实上，PET被证明特别适于用在上述方法中，因为它容许人们在宽的温度范围(加工性能范围(window of processability))内操作，并获得具有优良机械性能和高透明性的模塑制品。
然而，由于它的成本高，强烈的需要以其它热塑性材料代替PET。特别是，含少量的α-链烯烃共聚单体(例如乙烯或1-丁烯)的结晶聚丙烯共聚物，已知具有优良机械性能、高透明性，并且比PET价格低。
另一方面，上述丙烯共聚物的性质强烈的受到结晶聚合物组分含量的影响，后者在25℃不溶于二甲苯中，并且受上述组分的结晶在全部聚合物中的尺寸和分布的影响。因此用熔融法加工丙烯的结晶共聚物制取的产品的物理-机械性能大大取决于加工类型决定的热过程和后者进行时的具体条件。在增强吹塑模塑方法中，例如用含1-3％乙烯的结晶丙烯共聚物的操作，可加工范围在预成型的吹制期间，就上述预成型的温度而言，大约为+/-2℃，它是用熔融聚合物注射到适当的模具中而得到的。在上述吹制阶段大于+/-2℃的偏差导致最终制品物理-机械性能以及厚度均匀性的恶化。
在二步法的情形中，这个含1％至3％重量的乙烯的结晶丙烯共聚物问题变得特别关键，用注射聚合物到适当的模具中而获得的预制件，从室温开始(二次加热增强吹塑成型)，要经受不连续的吹制和拉伸，因此要求加热和热调整阶段(例如在130℃)。
因此，本发明的目的是解决现有技术中拉伸吹塑-模塑方法所存在的上述问题，从而得到具有良好性能的最终制品。
本申请人已经设计出一种增强吹塑成型方法，用于制备聚丙烯容器，其中使用含6％至10％重量的一种或几种C4-C8α-链烯烃类的结晶丙烯共聚物作为聚丙烯材料。
具体地说，本发明的方法包括把由上述结晶丙烯共聚物构成的或包含上述结晶丙烯共聚物的预制件吹制成型。
一般说来，上述预制件的获得，如先前所述是把熔融的聚合物注射到适当的模具中。
含6-10％重量的一种或几种C4-C8α-链烯烃类的结晶丙烯共聚物能够以纯的状态或以与其它链烯烃混合的状态使用，诸如丙烯均聚物或丙烯的结晶共聚物，其中含1％至3％重量的乙烯。当存在上述其它链烯烃聚合物时，存在的量相对聚丙烯材料的总重量而言，优选10％至40％重量，更优选10％至30％重量。
在二步法的情形中，上述结晶丙烯共聚物的熔融流速根据ASTMD 1238的条件L(M.F.R.L)测量，优选的范围为8至12g/10min.。
在一步法的情形中，预制件从模具中取出来，马上进行热调整，并且不经过冷却至室温步骤即行吹制，结晶丙烯共聚物的M.F.R.L可以更低，优选高于或等于1g/10min.。
上述结晶丙烯共聚物构成了本发明的基本特征，使用它能够使人们获得成品，尤其是具有优良的物理-机械性能的瓶子和细嘴瓶，在吹塑阶段约+/-4℃的加工范围内操作。
例如，如果人们想在130℃进行吹塑，预制件的温度围绕着上述值大约4℃的起伏(即从126至134℃)是能够允许的，因为上述起伏基本上不损害最终制品中物理-机械性能和厚度的均匀性。
我们指定的吹塑温度是125-135℃。
在本发明中使用的结晶丙烯共聚物，优选使熔融温度的范围为135℃至156℃，结晶点温度范围为105℃至120℃，二者都用DSC(差示扫描热量法)以每分钟20℃的温度变化测量。
再者，在25℃在二甲苯中不溶组分的含量，优选高于或等于93％重量，更优选高于或等于95％重量。
在上述结晶丙烯共聚物中所含的C4-C8α-链烯烃的具体的例子有：1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-辛烯。
优选丙烯/1-丁烯共聚物。
为获得更好透明度(浊度)在聚丙烯材料中加入0.05％至0.3％重量的成核剂是可行的。
成核剂的例子有：二亚苄基山梨醇(DBS)、甲基二亚苄基山梨醇(DMBS)、和二甲基二亚苄基山梨醇(DMD B S)、是以Millad 3988的商品牌号出售的。
使用在本发明的方法中的结晶丙烯共聚物是人所共知的，并且属于在配位催化剂参与的条件下能够用聚合的方法获得的共聚物族。上述方法和由它们得到的共聚物在本领域中有广泛的记述。例如，人们可以使用高产率和高立体有选择性的齐格勒一纳塔Ziegler-Natta催化剂和在欧洲专利第45977号中描述的聚合方法。
上述M.F.R.L值能够直接在聚合反应中通过充分调节分子量的调节剂(诸如氢)获得，或者用由结晶丙烯共聚物经减粘裂化的方法达到。
聚合物减粘裂化的过程用适当的技术进行。上述技术之一是以使用过氧化物为基础的，过氧化物按允许获得所要求的减粘裂化的重量加入到聚合物中。
减粘裂化过程中最宜于使用的过氧化物的分解温度优选的范围为150℃至250℃。上述过氧化物的例子有：过氧化二-叔-丁基、过氧化二枯基、2,5-二甲基-2,5-二(叔-丁基过氧)己炔、和2,5-二甲基-二(叔-丁基过氧)己烷，其市售的商标牌号是Luperox 101。
减粘裂化过程所需的过氧化物用量优选的范围为聚合物重量的0.05％至1％。
如前所述，本发明的方法可以使人们获得高物理-机械性能的聚丙烯容器。
例如，在有代表性的二步法的方法中，使用具有如下性能的一种丙烯/1-丁烯共聚物：
1-丁烯含量(％重量)：    8
MFRL(g/10min.)：        10
在25℃在二甲苯中
不溶的组分(％重量)：    96.5
熔点℃：                147
结晶温度(℃)：          113
DMDBS含量(％重量)：     0.22
并且在下列的加工条件下：
    预制件特征
预制件重量(g)           30
预制件最大厚度(mm)      5
预制件高度(mm)          102
预制件外径的最大值(mm)  31.5
预制件内径的最小值(mm)  21.5
    预制件模塑参数
聚合物熔融温度(℃)      220
模具的温度(℃)          20
注塑时间(秒)            6
注塑压力(Mpa)           50
总循环时间(秒)          35
    瓶子拉伸-吹塑参数
加热的类型              带有热风强制循环的红外灯
加热时间(秒)            90-120
预制件温度℃            127+/-4(用红外线电视摄像机)
拉伸和吹塑循环时间(秒)：    4.5
所得的瓶子具有下列的特征：
瓶子的几何特征
瓶子的重量                  30
瓶子的平均厚度(mm)          0.37+/-0.02
瓶子的高度(mm)              275
瓶子的横断面带圆角的方形
瓶子的横断面的对角线(mm)    30
瓶子横断面边长(mm)          65
平均径相拉伸比              2.3
平均轴向拉伸比              3.2
总拉伸比                    7.3
    瓶子的机械特性
23℃径向DMTA(MPa)           2320
最大负荷(N)                 165
浊度(％)                    3.1
注：
平均径向拉伸比=瓶子的最大内径/预制件在吹塑前最大内径；
平均轴向拉伸比=瓶子从轴向拉伸开始点至瓶子内底的长度/预制件从相应点至预制件的瓶内底的长度；
总拉伸比=上述二个比值的比；
径向DMT A：根据ASTMD 5026的标准测量
最大负荷：它是瓶壁塌陷(弯折)之前最大的挤压力；
浊度：根据ASTM 1003的标准测量。

Claims (7)

1．用于制备聚丙烯容器的拉伸吹塑-模塑的方法，该方法包括：
ⅰ)将聚丙烯材料模塑成预制件；
ⅱ)将所述的预制件拉伸成所需的制品；
其中所述的聚丙烯材料包括一种结晶丙烯共聚物，该共聚物含有大于6％最高达10％重量的一种或多种C4-C8α-烯烃，所述的结晶丙烯共聚物的熔融范围为135-156℃，结晶温度范围为105-120℃，并且所述的结晶丙烯共聚物包括在25℃二甲苯中的一种不溶组分，该组分的含量高于或等于93％重量。
2．权利要求1的方法，其中聚丙烯材料是一种丙烯/1-丁烯结晶共聚物。
3．权利要求1的方法，其中在拉伸步骤中所述预制件的温度为126-134℃。
4．权利要求1的方法，其中所述的预制件不必先冷却到室温就被拉伸成所需的制品，并且所述的结晶丙烯共聚物的熔融速率至少为1g/10分钟，该溶融速率根据ASTM D 1238条件L测定。
5．权利要求1的方法，其中所述的预制件被冷却至室温，随后在拉伸成所需的制品之前进行加热和热调整，所述的结晶丙烯共聚物的溶融速率为8-12g/10分钟，该溶融速率根据ASTM D 1238条件L测定。
6．权利要求1的方法，其中聚丙烯材料还包括0.05-0.30％重量的成核剂。
7．使用权利要求1的方法制备瓶子和细嘴瓶。
CN96122456A 1995-09-15 1996-09-14 制备聚丙烯容器的拉伸吹塑－模塑方法及其制备的瓶子 Expired - Fee Related CN1072099C (zh)

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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1012068A3 (fr) * 1998-07-10 2000-04-04 Solvay Corps creux biorientes a base de terpolymeres statistiques du propylene et procede pour la fabrication de ces corps creux.
DE60236166D1 (de) 2001-05-30 2010-06-10 Prysmian Spa Einen formstabilen polymer enthaltendes optisches faserkabel
BR0210069A (pt) * 2001-05-30 2004-08-10 Pirelli & C Spa Cabo de fibra ótica, componente de cabo de fibra ótica, e, uso do material polimérico
EP1870224A1 (en) * 2006-06-21 2007-12-26 Total Petrochemicals Research Feluy Low melt flow resins for medical applications in injection-stretch-blow-moulding
EP1870225A1 (en) * 2006-06-21 2007-12-26 Total Petrochemicals Research Feluy Stretching/blowing conditions in one-stage injection-stretch-blow-moulding
EP1870223A1 (en) 2006-06-21 2007-12-26 Total Petrochemicals Research Feluy Low melt flow index resins for injection-stretch-blow-moulding
BRPI0713834B1 (pt) * 2006-07-28 2018-12-26 Basell Poliolefine Italia Srl polímeros de propileno
EP2046845B1 (en) * 2006-07-28 2012-06-06 Basell Poliolefine Italia S.r.l. Propylene polymers
US9023446B2 (en) * 2009-09-22 2015-05-05 Graham Packaging Lc, L.P. PET containers with enhanced thermal properties and process for making same
CN102453283A (zh) * 2010-10-29 2012-05-16 中国石油化工股份有限公司 一种聚丙烯组合物及制备方法
CN102453282A (zh) * 2010-10-29 2012-05-16 中国石油化工股份有限公司 一种聚丙烯组合物及其制备方法
US9303108B2 (en) 2011-10-29 2016-04-05 China Petroleum & Chemical Corporation Propylene random copolymer, method for its preparation, and compositions and articles containing the same
CN103087420B (zh) * 2011-10-29 2015-02-11 中国石油化工股份有限公司 一种聚丙烯组合物及其制备方法
CN103087418B (zh) * 2011-10-29 2015-03-11 中国石油化工股份有限公司 一种食品包装容器及其制法
JP6511359B2 (ja) * 2014-10-30 2019-05-15 株式会社吉野工業所 容器の製造方法
US9725802B2 (en) 2014-11-11 2017-08-08 Graham Packaging Company, L.P. Method for making pet containers with enhanced silicon dioxide barrier coating
JP6878580B2 (ja) * 2017-05-30 2021-05-26 サントリーホールディングス株式会社 プリフォーム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56133138A (en) * 1980-03-24 1981-10-19 Dainippon Printing Co Ltd Manufacture of blow molded bottle by drawn polypropylene film
GB2139551A (en) * 1983-03-31 1984-11-14 Katashi Aoki Method of making a hollow article of polypropylene by biaxial stretch blow moulding
CN85101498A (zh) * 1985-04-01 1987-01-10 三井东压化学有限公司 注射拉伸吹塑容器及其树脂组合物
EP0417319A1 (en) * 1989-03-29 1991-03-20 Mitsubishi Chemical Corporation Blown polypropylene resin container

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0639554B2 (ja) * 1983-12-13 1994-05-25 三井東圧化学株式会社 透明なポリプロピレン樹脂製容器
DE3486446T2 (de) * 1983-12-13 1997-09-25 Mitsui Toatsu Chemicals Spritz-Blasformen
CA2029000C (en) * 1989-10-31 1996-12-24 Fred Chun-Chien Twu Process for the preparation of random copolymers
JP2814337B2 (ja) * 1993-03-15 1998-10-22 チッソ株式会社 高溶融張力を有するポリプロピレン、その製造方法および成形品
JPH06263133A (ja) * 1993-03-11 1994-09-20 Nissei Asb Mach Co Ltd 再充填可能な飲料水用ポリプロピレン系樹脂容器およびその製造方法
AU690907B2 (en) * 1994-05-12 1998-05-07 Showa Denko Kabushiki Kaisha Propylene polymer, process for producing the same, composition thereof, polymerization catalyst component, and process for producing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56133138A (en) * 1980-03-24 1981-10-19 Dainippon Printing Co Ltd Manufacture of blow molded bottle by drawn polypropylene film
GB2139551A (en) * 1983-03-31 1984-11-14 Katashi Aoki Method of making a hollow article of polypropylene by biaxial stretch blow moulding
CN85101498A (zh) * 1985-04-01 1987-01-10 三井东压化学有限公司 注射拉伸吹塑容器及其树脂组合物
EP0417319A1 (en) * 1989-03-29 1991-03-20 Mitsubishi Chemical Corporation Blown polypropylene resin container

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IL119161A0 (en) 1996-11-14
AR003577A1 (es) 1998-08-05
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