CN1210547A - 聚对苯二甲酸乙二醇酯容器的尺寸稳定方法 - Google Patents

聚对苯二甲酸乙二醇酯容器的尺寸稳定方法 Download PDF

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CN1210547A
CN1210547A CN97192151A CN97192151A CN1210547A CN 1210547 A CN1210547 A CN 1210547A CN 97192151 A CN97192151 A CN 97192151A CN 97192151 A CN97192151 A CN 97192151A CN 1210547 A CN1210547 A CN 1210547A
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pet
preform
copet
dicarboxylic anhydride
acid
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H·阿尔哈塔
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Sinco Engineering SpA
Sinco Ricerche SpA
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/22—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at neck portion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/24—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at flange portion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/26—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at body portion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/28—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at bottom portion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3024—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
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    • B29C2949/3028—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components having three or more components
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3032—Preforms or parisons made of several components having components being injected
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C49/06—Injection blow-moulding
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    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

一种对于通过注坯吹塑获得的PET或COPET容器的尺寸稳定化处理方法,包括在吹塑阶段对预成型体进行热处理,由PET或COPET得到的预成型体在少量(0.01—0.2wt%)的芳族四羧酸的二酸酐,优选1,2,4,5－苯四酸二酸酐存在下固态改性。

Description

聚对苯二甲酸乙二醇酯容器的尺寸稳定方法
本发明涉及用于稳定通过注坯吹塑获得的聚对苯二甲酸乙二醇酯容器热形变的改进方法。
已经知道通过注坯吹塑获得的PET容器(瓶子)当在高温条件(如在热填充和消毒操作中出现的高温条件)下使用时，导致相当程度的形变。这些处理的温度可达到80-90℃，在此温度下材料趋于软化和在冷却后呈现收缩，体积减少可达15-25％。
为降低或消除这些不方便之处，将通过注塑获得的容器预成型体进行热稳定处理(热定型)，该处理在预成型体的吹塑阶段进行。热处理温度高于130℃，通常在130至180℃之间，时间为几秒。如此获得的预成型体使容器具有所需尺寸热定型性能。然而，在处理期间形成低聚物，这些低聚物会使模具变脏，因此必须清洁模具，这样生产循环经常被打断。
现在已发现，可以降低或消除低聚物在预成型吹塑模具中沉积，并且能够在不需要清洁模具的生产循环条件下操作。这可通过对由预先在少量芳族四羧酸的二酸酐存在下进行固态改性(upgrade)或缩聚(SSPA)的聚对苯二甲酸乙二醇酯(PET)或其共聚物(COPET)获得的预成型体进行热定型实现，所述共聚物中至多15mol％的衍生自对苯二甲酸的单元被衍生自邻苯二甲酸和/或萘二酸的单元取代。
1,2,4,5-苯四酸二酐是优选的化合物，二酸酐的用量为0.01至0.2wt％，优选0.04-0.1wt％。
固态缩聚处理通常在温度180至220℃下进行足够的时间以使聚合物的特性粘度升至所需值。
将二酸酐以熔融态加入PET或COPET中。可方便地将其溶于乙二醇中。
已发现，使用如上所述的改性PET和COPET，预成型体的热处理可在温度显著低于迄今已知的方法中使用温度的温度下进行。预成型体吹塑模具的加热温度为80至130℃，并足以使容器具有足够的尺寸稳定性。在这样的加热操作条件下进行不会出现模具弄污现象。
处理时间为几秒，通常低于10秒。
将如此获得的容器从模具中挤出后在空气中冷却。
将预成型体在温度100至140℃下放入预热的模具中。
按此方式获得的稳定容器适合诸如热填充应用。
提供如下实施例说明本发明，但并不限制本发明。实施例1
将20kg/hPET(IV=0.57dl/g)从PET生产试验装置的熔体缩聚部分连续加入装有脱气装置的反转非啮合双螺杆挤出机中。
向该挤出机中加入含20wt％PMDA的结晶PET的混合物(40g/h)(相当于0.04wt％PMDA在PET中的量)。试验条件为：
螺杆速度            =500rpm
螺杆的L/D比例       =48
料筒温度            =282℃
熔融产品温度        =298-302℃
平均停留时间        =35-50sec。
将产品以直径5mm和长度5mm切片形式挤出；IV为0.62dl/g。然后将这些粒料在连续试验装置中进行SSP，试验装置的在如下条件下操作：
切片流速                   =50kg/h
反应器中切片的平均温度     =203℃
反应器中气体/切片重量比    =1∶1
最终特性粘度               =0.828dl/g比较例1
将实施例1中获得的聚合物干燥后用注塑机BMB270通过如下工艺转化为预成型体：
模具          具有16个空腔
预成型体重量    =46.9g
循环时间        =21sec
螺杆温度        =273℃
加料时间       =10sec
注塑时间      =5sec
冷却水温度    =3℃
将如此获得的预成型体用Krupp Corpoplast吹塑机吹成瓶子形式。
条件如下：
瓶子生产率      =6,000个瓶子/h
加热元件温度    =100℃
吹塑压力        =35ba
瓶子体积        =1,500cm3实施例2
将由按照实施例1获得的粒料制备的预成型体在装有加热系统的具有模具的吹塑机中吹塑。模具温度为120℃，处理时间为5秒，然后将预成型体在空气中冷却。预成型体在模具中的起始温度为100℃。在整个生产循环中未观察到模具变脏。实施例3
将实施例2的瓶子和比较例1的瓶子置于如下温度条件下
50℃     6h
85℃     2min
90℃     2min
95℃     2min
95℃     10min
表1中给出瓶子的尺寸变化。
在85℃、90℃和95℃的试验对在50℃的水中老化6小时的瓶子进行。
                      表1
                    实施例2
    瓶子1         瓶子2                 瓶子3处理    前     在50℃ 前      在85℃ 在95℃   前     在90℃ 在95℃下
           下6h           下2min.下2min.         下2min. 10min.后
           后             后     后              后尽重(g) 46.8   46.8   46.8    46.8   46.8     47.1   47.1    47.1体积H2O1572.3 1570.9 1572.5  1571.7 1543     1574.2 1572.8  1550.2(cm3)瓶颈直径 27     27    27       27    27       27     27      27(mm)中心直径 80     80    80       80    80       80     80      80(mm)瓶底直径 92.5   92.5  92.5     92.5  90.5     92.5   92      90.5(mm)高度(mm) 308    308   309      309   31.05     308   308     310处理后的 0      -0.09 0        -0.05 -1.88     0     -0.09   -1.52变化％
               比较例1
      瓶子1              瓶子2处理      前       在85℃下  前     在85℃下
               2min.后          2min.后尽重(g)   47.1     47.1      47     47体积H2O  1574.8   1344      1574.1 1557.2(cm3)瓶颈直径  27       27        27     27(mm)中心直径  81       79        80     78.9(mm)瓶底直径  92.5     89        92.5   89(mm)高度(mm)    308    291    308    288处理后的变  0     -14.4   0      -15化％

Claims (3)

1．一种使通过注坯吹塑预成型体获得的聚对苯二甲酸乙二醇酯(PET)或其共聚物(COPET)的容器尺寸稳定的方法，所述共聚物中至多15mol％的衍生自对苯二甲酸的单元被衍生自邻苯二甲酸和/或萘二酸的单元取代，该方法包括在用于吹塑预成型体的加热至80-130℃的模具中进行热处理，对由PET或COPET获得的预成体在0.01至0.2wt％的芳族四羧酸的二酸酐存在下固态改性。
2．根据权利要求1的方法，其中二酸酐为1,2,4,5-苯四酸二酸酐，其用量为0.04-0.01wt％。
3．一种抗尺寸热变形的稳定容器，由在吹塑阶段热处理预成型体获得并由在0.01至0.2wt％的芳族四羧酸的二酸酐存在下固态改性的PET或COPET获得。
CN97192151A 1996-10-18 1997-10-15 聚对苯二甲酸乙二醇酯容器的尺寸稳定方法 Pending CN1210547A (zh)

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IT96MI002159A IT1285525B1 (it) 1996-10-18 1996-10-18 Procedimento perfezionato per la stabilizzazione dimensionale di manufatti in polietilentereftalato
ITMI96A002159 1996-10-18

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CN1089668C (zh) * 1999-07-08 2002-08-28 李缵缨 热灌装用p.e.t.容器瓶颈的制造方法
CN100418997C (zh) * 2003-06-18 2008-09-17 可口可乐公司 用于热填充应用的聚酯组合物、由它制备的容器、和方法
CN101863309A (zh) * 2009-03-06 2010-10-20 克罗内斯股份公司 用于制造和填充薄壁饮料容器的方法和设备

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KR20000072070A (ko) * 2000-07-21 2000-12-05 구광시 폴리에틸렌나프탈레이트계 유아용 수유병 및 그의 제조방법
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ITMI962159A1 (it) 1998-04-18
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US6458314B1 (en) 2002-10-01
DE69726261D1 (de) 2003-12-24
JP2000506799A (ja) 2000-06-06
KR19990072211A (ko) 1999-09-27
IT1285525B1 (it) 1998-06-08
CA2240837A1 (en) 1998-04-30
EP0877770B1 (en) 2003-11-19
DE69726261T2 (de) 2004-04-22
ES2208956T3 (es) 2004-06-16
WO1998017706A1 (en) 1998-04-30
EP0877770A1 (en) 1998-11-18
MX9805027A (es) 1998-09-30

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