CN1159975A - 用于制备聚丙烯容器的拉伸吹塑—模塑的方法 - Google Patents
用于制备聚丙烯容器的拉伸吹塑—模塑的方法 Download PDFInfo
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- 238000000071 blow moulding Methods 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 32
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 1
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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
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℃)。
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4％至12％重量，优选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4-12％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ASTM D1238的条件L(M.F.R.L)测量，优选的范围为6至20，更优选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(DMDBS)、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DMTA：根据ASTMD5026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ASTM1003的标准测量。
Claims (9)
1.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。
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，其中结晶丙烯共聚物的熔融温度范围从135℃-156℃，结晶温度范围从105℃-120℃。
4.权利要求1的方法，其中结晶丙烯共聚物在25℃在二甲苯中不溶组分的含量，高于或等于93％重量。
5.权利要求1的方法，其中聚丙烯材料，除了包括结晶丙烯共聚物之外，还包括一种成核剂，含量范围为0.05-0.3％重量。
6.权利要求1的方法，其中在二步法操作中使用的结晶丙烯共聚物的M.F.R.L从6至20g/10min.。
7.权利要求1的方法，其中操作以一步法进行，而预制件经受热调整并且不经过冷却至室温阶段，使用的结晶丙烯共聚物的M.F.R.L大约等于1g/10min.。
8.使用权利要求1的方法制备瓶子和细嘴瓶。
9.用权利要求1的方法获得的聚丙烯瓶子和细嘴瓶。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT95MI001931A IT1282942B1 (it) | 1995-09-15 | 1995-09-15 | Processo di stretch blow molding per la preparazione di contenitori in polipropilene |
| ITMI95/A001931 | 1995-09-15 |
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| Publication Number | Publication Date |
|---|---|
| CN1159975A true CN1159975A (zh) | 1997-09-24 |
| CN1072099C CN1072099C (zh) | 2001-10-03 |
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| CN96122456A Expired - Fee Related CN1072099C (zh) | 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 |
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| EP (1) | EP0764514B1 (zh) |
| JP (1) | JPH09220757A (zh) |
| KR (1) | KR970014989A (zh) |
| CN (1) | CN1072099C (zh) |
| AR (1) | AR003577A1 (zh) |
| AU (1) | AU701662B2 (zh) |
| BR (1) | BR9603756A (zh) |
| CA (1) | CA2185475A1 (zh) |
| DE (1) | DE69619324T2 (zh) |
| IL (1) | IL119161A0 (zh) |
| IT (1) | IT1282942B1 (zh) |
| NO (1) | NO963847L (zh) |
| ZA (1) | ZA967450B (zh) |
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| 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 |
| 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 |
| CN101516929B (zh) * | 2006-07-28 | 2012-06-20 | 巴塞尔聚烯烃意大利有限责任公司 | 丙烯聚合物 |
| CN101472728B (zh) * | 2006-06-21 | 2012-08-29 | 道达尔石油化学产品研究弗吕公司 | 一步注射-拉伸-吹塑-成型中的拉伸/吹塑条件 |
| CN103087418A (zh) * | 2011-10-29 | 2013-05-08 | 中国石油化工股份有限公司 | 一种食品包装容器及其制法 |
| CN103087420A (zh) * | 2011-10-29 | 2013-05-08 | 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 |
| CN103648747A (zh) * | 2010-12-17 | 2014-03-19 | 格莱汉姆包装Lc公司 | 具有加强的热特性的pet容器及其制造工艺 |
| 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 |
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| 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. |
| US7466887B2 (en) | 2001-05-30 | 2008-12-16 | Prysmian Cavi E Sistemi Energia S.R.L. | Optical fiber cable with dimensionally stable polymeric component |
| 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 |
| EP1870223A1 (en) * | 2006-06-21 | 2007-12-26 | Total Petrochemicals Research Feluy | Low melt flow index resins for injection-stretch-blow-moulding |
| EP1870224A1 (en) * | 2006-06-21 | 2007-12-26 | Total Petrochemicals Research Feluy | Low melt flow resins for medical applications in injection-stretch-blow-moulding |
| US8178632B2 (en) | 2006-07-28 | 2012-05-15 | Basell Poliolefine Italia, s.r.l. | Propylene polymers |
| US20200282602A1 (en) * | 2017-05-30 | 2020-09-10 | Suntory Holdings Limited | Preform |
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| JPS56133138A (en) * | 1980-03-24 | 1981-10-19 | Dainippon Printing Co Ltd | Manufacture of blow molded bottle by drawn polypropylene film |
| JPS59179318A (ja) * | 1983-03-31 | 1984-10-11 | Katashi Aoki | ポリプロピレンの２軸延伸吹込成形方法 |
| EP0151741A3 (en) * | 1983-12-13 | 1985-09-25 | MITSUI TOATSU CHEMICALS, Inc. | Injection stretch-blow molded container and resin composition therefor |
| 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 |
| CN85101498B (zh) * | 1985-04-01 | 1988-03-16 | 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 |
| DE69028752T2 (de) * | 1989-03-29 | 1997-03-06 | Mitsubishi Chem Corp | Geblasener behälter aus polypropylenharz |
| MY104507A (en) * | 1989-10-31 | 1994-04-30 | Union Carbide Chemicals And Plastics Co Inc | Process for the preparation of random copolymers. |
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| 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 |
-
1995
- 1995-09-15 IT IT95MI001931A patent/IT1282942B1/it active IP Right Grant
-
1996
- 1996-08-30 IL IL11916196A patent/IL119161A0/xx unknown
- 1996-09-03 ZA ZA967450A patent/ZA967450B/xx unknown
- 1996-09-06 AU AU65511/96A patent/AU701662B2/en not_active Ceased
- 1996-09-12 JP JP24194796A patent/JPH09220757A/ja active Pending
- 1996-09-13 BR BR9603756A patent/BR9603756A/pt active Search and Examination
- 1996-09-13 CA CA002185475A patent/CA2185475A1/en not_active Abandoned
- 1996-09-13 KR KR1019960039900A patent/KR970014989A/ko not_active Application Discontinuation
- 1996-09-13 NO NO963847A patent/NO963847L/no not_active Application Discontinuation
- 1996-09-13 AR ARP960104343A patent/AR003577A1/es not_active Application Discontinuation
- 1996-09-13 EP EP96114723A patent/EP0764514B1/en not_active Expired - Lifetime
- 1996-09-13 DE DE69619324T patent/DE69619324T2/de not_active Expired - Lifetime
- 1996-09-14 CN CN96122456A patent/CN1072099C/zh not_active Expired - Fee Related
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| CN101472728B (zh) * | 2006-06-21 | 2012-08-29 | 道达尔石油化学产品研究弗吕公司 | 一步注射-拉伸-吹塑-成型中的拉伸/吹塑条件 |
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| 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 |
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| CN103087420A (zh) * | 2011-10-29 | 2013-05-08 | 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 |
| 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 |
| 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 |
| TWI567094B (zh) * | 2011-10-29 | 2017-01-21 | China Petro-Chemical Tech Dev Company Ltd | Propylene random copolymers, processes for their preparation, and compositions and articles comprising the same |
| CN103087418A (zh) * | 2011-10-29 | 2013-05-08 | 中国石油化工股份有限公司 | 一种食品包装容器及其制法 |
| CN107148333A (zh) * | 2014-10-30 | 2017-09-08 | 帝斯克玛股份有限公司 | 用于液体吹塑成型的预制件 |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU6551196A (en) | 1997-03-20 |
| CN1072099C (zh) | 2001-10-03 |
| DE69619324T2 (de) | 2002-08-29 |
| AU701662B2 (en) | 1999-02-04 |
| ITMI951931A0 (it) | 1995-09-15 |
| DE69619324D1 (de) | 2002-03-28 |
| IT1282942B1 (it) | 1998-04-02 |
| ITMI951931A1 (it) | 1997-03-15 |
| EP0764514A1 (en) | 1997-03-26 |
| AR003577A1 (es) | 1998-08-05 |
| NO963847D0 (no) | 1996-09-13 |
| IL119161A0 (en) | 1996-11-14 |
| EP0764514B1 (en) | 2002-02-20 |
| CA2185475A1 (en) | 1997-03-16 |
| NO963847L (no) | 1997-03-17 |
| KR970014989A (ko) | 1997-04-28 |
| JPH09220757A (ja) | 1997-08-26 |
| ZA967450B (en) | 1997-03-10 |
| MX9604049A (es) | 1997-07-31 |
| BR9603756A (pt) | 1998-06-02 |
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