CN1051100C - 一种瓶型坏及其制备方法 - Google Patents

一种瓶型坏及其制备方法 Download PDF

Info

Publication number
CN1051100C
CN1051100C CN95121331A CN95121331A CN1051100C CN 1051100 C CN1051100 C CN 1051100C CN 95121331 A CN95121331 A CN 95121331A CN 95121331 A CN95121331 A CN 95121331A CN 1051100 C CN1051100 C CN 1051100C
Authority
CN
China
Prior art keywords
polymkeric substance
parison
bottle
metal
oxyethyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN95121331A
Other languages
English (en)
Other versions
CN1130564A (zh
Inventor
N·廷代尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
Namur Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10666879&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1051100(C) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Namur Corp filed Critical Namur Corp
Publication of CN1130564A publication Critical patent/CN1130564A/zh
Application granted granted Critical
Publication of CN1051100C publication Critical patent/CN1051100C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3032—Preforms or parisons made of several components having components being injected
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1372—Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/258—Alkali metal or alkaline earth metal or compound thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

以热塑性聚合物组合物用挤出、拉坯吹塑法生产塑料瓶。热塑性聚合物组合物包括含金属颗粒的聚合物，优先选择的是聚酯，所含的金属(特别是锑)颗粒的特性吸收是在辐射波长为500nm至2000nm的区域内，其量应使聚合物的再热时间少于无此量金属颗粒的聚合物的再热时间。在合成聚合物的同时还原金属化合物以制取含金属的聚合物组合物的方法。

Description

一种瓶型坏及其制备方法
本发明涉及一种包装材料，特别涉及用聚合物组合物制成的塑料瓶，又特别是用聚酯组合物制成的塑料瓶。
利用聚酯组合物，特别是聚对苯二甲酸乙二醇酯或其共聚物(后通称“PET”)作为包装材料(例如以薄膜、瓶子或其他容器的形式)是已经为人们熟知的事。用塑料瓶或其他容器(后称塑料瓶)盛装如苏打饮料之类的加压液体时，以聚合物碎屑形式的组合物通常是以两道工序制成瓶状的：第一，注射模塑制成型坯，第二，立刻或在放置片刻后用压缩空气将型坯吹入模中成为最终的瓶形。吹塑步骤使组合物至少在瓶的选择区域内产生双轴定向作用，因此可使瓶子在使用时能抵抗由于内压力而产生的变形。在第二道工序中，型坯通常是处于环境温度下的，在吹塑步骤时须将其加热至100℃左右。此“再热”的步骤是第二道工序中的决定速率的步骤。
再热步骤所用的市售加热器多数是石英红外灯，其最强的辐射区域波长为500nm至2000nm。PET对该区域的电磁辐射的特性吸收较低。所观察到的此材料的任何吸收常常是悬浮的异物(例如催化剂残留物和杂质)所引起的，并且此吸收是悬浮物质引起的光散射和悬浮物质可显示的任何特性吸收的结合。因此，PET组合物的再热速率是非常取决于组合物的清洁与否的，脏的组合物由于污染物的存在而有相对高的雾度水平，其再热速率比清洁的组合物快。在某些应用中，组合物可含有颜料以使组合物着色(如绿色或褐色)，这些颜料对于减少组合物的再热时间起了作用，但是许多应用要求具有最小雾度的未着色(即不加颜料或染料)组合物，在这种情况下，使组合物的再热时间显著减少所要求的污染物的含量会导致组合物的雾度不合要求。
申请人发现，含有小量细微金属颗粒的聚合物组合物、特别是聚酯组合物的再热时间有惊人的和有效程度的减少，同时保持了可接受的雾度水平。
因此，本发明的目的是提供含金属颗粒的聚合物的包装材料，金属颗粒的特性吸收是在辐射波长为500nm至2000nm的区域内，含金属的量应使聚合物的再热时间小于无此量金属颗粒的聚合物的再热时间。
本发明的包装材料可特别采取瓶子的形式，如吹塑瓶、特别是注坯吹塑瓶，又特别是注射拉坯吹塑瓶。本发明包括可以用其生产此类塑料瓶的型坯、特别是注射模塑瓶型坯。
本发明也提供一种生产热塑性聚合物组合物的方法，该组合物由含金属颗粒的聚合物组成，金属颗粒的特性吸收是在辐射波长为500nm至2000nm区域内，其量应使聚合物的再热时间小于无此量金属颗粒的聚合物的再热时间，该方法包括将聚合物和可被还原的金属化合物与一种可以将该化合物还原成金属的还原剂相混合，使还原剂与金属化合物反应产生颗粒极细的金属。
本发明的方法可用来制造包装材料，特别是注坯吹塑包装材料，又特别是注射拉坯吹塑的包装材料、塑料瓶和可制造注塑瓶的型坯。在这些方法中，包装材料是由含金属颗粒的组合物制成的。用这些方法进行吹塑瓶的生产一般包括由含金属颗粒的聚合物组合物制成的注塑瓶型坯的预热步骤。
在本发明中使用的热塑性聚合物最常见的是聚酯、特别是至少主要由芳族二酸和脂肪(包括环状脂肪)二醇制得部分芳族聚酯、特别是聚酯衍生物。优先选择的部分芳族聚酯是含有至少50mol％、最好是至少70mol％的对苯二甲酸乙二醇酯残基的聚酯。在聚酯中也可含有由间苯二甲酸乙二醇酯、萘二甲酸乙二醇酯、对苯二甲酸乙氧基亚乙酯、间苯二甲酸乙氧基亚乙酯或萘二甲酸乙氧基亚乙酯衍生的残基。
适合的金属有锑、锡、铜、银、金、砷、镉、汞、铅、钯和铂或者它们之中二或二种以上的混合物。对于大多数的应用来说，银、金、砷、镉、汞、铅、钯和铂是比较昂贵的，或者是损害环境的，因此这些金属不是特别优先选择的金属。较满意的金属是锑、锡或铜中的一种或多钟，其中锑是特别有用的。
金属颗粒最好要有足够的细度，用肉眼观察不到，其粒度大小能在相对较宽的波长范围内而不是在一个特定波长或在较窄的区域内出现辐射吸收。
可以将金属颗粒以极细的颗粒状态加入到聚合物中，但我们发现以可还原形式的金属提供给聚合物是特别有利的，特别是以极细的金属化合物颗粒并在聚合物中加入一种适合的还原剂是特别有利的。金属化合物和还原剂之间的反应，例如在聚合物加工过程中进行反应，可导致形成遍布于聚合物中的金属。特别是当聚合物为聚对苯二甲酸乙二醇酯(或共聚物)时，将可被还原的金属化合物与还原剂在合成此聚合物时加入是有利的。如果金属为锑，此方法特别有利，将在下面叙述。
用于组合物中的金属颗粒的量是用以在所需减少的聚合物再热时间和一个给定的应用所能接受的雾度的量之间进行平衡。比较适合的金属颗粒的量为3ppm-300ppm(ppm为百万分之一重量份)，优先选择5ppm-150ppm，特别是10ppm-100ppm。如果需要，可制备含金属颗粒量十分高的聚合物组合物母料以备与基本无金属颗粒的聚合相混合，制成含有所需要的颗粒含量的聚合物。
使用可被还原的金属化合物时，能够很容易地由化学计算和其后的实验决定还原剂的用量。在某些聚合物体系中，还须加入超化学计量的还原剂以补尝损失和清洁作用(如还原剂与溶于聚合物中之氧之间的反应)等。适合的还原剂有磷(III)化合物，如亚磷酸或亚磷酸三苯酯。
在聚酯组合物中，锑是特别优先选择的金属，如以三氧化二锑(三价锑氧化物)形式存在的锑。在制备如聚对苯二甲酸乙二醇酯之类的聚酯时它是单体聚合的催化剂。由于聚酯单体熔融体是一微弱的还原环境，聚酯中自然会有一很小比例的金属锑存在，例如1ppm至2ppm。但是含量这么低的金属锑不会显著影响再热时间。所以有必要将聚合物中的金属锑的含量提高到高于此基本含量。
本发明的聚合物组合物还可含其他本技术领域中悉知的添加剂和/或润滑剂，如催化剂、加工助剂、抗氧剂、填充剂、增塑剂和核化剂。
通常，如聚对苯二甲酸乙二醇酯(PET)之类的聚酯是用二酸(作为游离酸)或其二甲酯与二醇反应，制得预聚物，然后再将其进行缩聚成为聚酯。需要时可用固态聚合进一步提高聚酯的分子量。
本发明包括由本发明的热塑性聚酯组合物制成的包装材料。
下面以实施例对本发明进行说明。所用的份或百分数均以重量计，除非另有指明。
试验方法
雾度：聚合物组合物的雾度测定是用标准尺寸的组合物块和加德纳雾度计(Gardener Haze meter)测定的。
亮度和黄度：聚合物组合物的亮度和黄度的测定是用数字色监测器测定的(数字色监测器是三色激励滤色片测色计，其设计能定量测定可见光谱的三个波长区域内的反射光强度)，由Instrnmental ColonrSystems(Newbury，Barkshire，GB)提供。
再热时间：聚合物组合物的再热时间的估计是将型坯暴露于环境温度(21℃)下加热45秒钟，再平衡20秒钟，然后测定型坯内表面的温度。型坯的加热是在Krupp Corpolast LB01拉坯吹塑机中进行的，该机装有红外石英电阻加热器。型坯是放在机内的旋转台上的，以确保均匀加热。型坯内表面的温度是用热电偶测定的，热电偶的末端与内表面接触。
实施例1
在装有加热夹套、搅拌机、冷凝器和压力/真空联接器的钢热压釜中于260±5℃的温度下加入熔融的聚对苯二甲酸乙二醇酯预聚物(70Kg)和磷酸(21.0g，300ppm)、亚磷酸(2.80g，40ppm)与乙二酵(500ml)的溶液。十分钟后在热压釜中加入三氧化二锑(17.5g，250ppm)于乙二醇(500ml)中的浆液。30分钟后热压釜中的压力降至1毫巴以下。聚合反应的进行伴随着乙二醇的消失。在达到所需求的融体粘度(相当于约0.6dl/g的特性粘度(IV)时，用氮将气体压力增至约2巴。然后将聚合物倾入水中骤冷，切成碎片。将所得到的非晶形聚合物碎片按上述方法进行亮度和测色试验。
在氮气流(预热至约215℃)中将碎片加热至约215℃使聚合物碎片进行固态聚合，氮气流速为30l/min，直至聚合物的IV增至接近0.8dl/g为止。
将一部分生成的聚合物组合物(样品6)模经干燥、然后注塑制成4mm厚的型坯，用于测定雾度和再热速率以与常规聚对苯二甲酸乙二醇酯(样品1)进行比较。预成型件是用55g预成型模和一Negri Bossi NB90注塑机制成的。试验结果和实施例2-5所制得的样品的试验结果总结于表1中。
实施例2
分别使用10、15、20、30和80ppm的亚磷酸将实施例1重量五次，制取样品2、3、4、5和7。
实施例3
在制取试验件以前将部分样品7按1∶1的重量比与常规聚对苯二甲酸乙二醇酯样品混合(样品8)。
实施例4
重复实施例1，但使用21g(最终产品的300ppm)亚磷酸和35g(最终产品的500ppm)三氧化锑(样品9)。
实施例5
在制取试验件以前将一部分样品9按1∶10的重量比与常规聚对苯二甲酸乙二醇酯样品混合(样品10)。
实施例6
重复实施例1，但以70g亚磷酸三苯酯(最终产品的1000ppm)代替亚磷酸(样品11)。
实施例7
将组合物1和4-7的型坯在Krupp机(恒定温度、不定时间)上吹塑，以测定成功吹塑成瓶所需要的最小暴置期，即由于冷吹，吹瓶时没有引发应力发白现象。结果列下表2。
从实施例和表1、2可以看出，由于相对小量的三氧化二锑被还原成金属锑，再热速率有了明显的改进，而聚合物不出现明显的雾度、黄度或亮度的增加。
实施例8
除了加酸后10分钟在热压釜中加入5.1g醋酸铜一水合物(最终产品的73ppm)于乙二醇(100ml)中的溶液，再过10分钟后加入三氧化二锑浆液外，重复实施例1。所得到的非晶形聚合物具有微橙色，说明有金属铜存在。经再热速率试验，测定由此聚合物制成的型坯内表面的温度为114℃。
实施例9
除以五氧化二锑代替三氧化二锑外，重复实施例1。经再热速率试验，由此聚合物制成的型坯的内表面的温度为113℃。
                          表1样品号Sb(o)  P(III)化合  P(III)  再热温度  黄度  亮度  雾度
  ppm    物含量ppm   化合物  ℃1     0      0           -       110       -5.2  36.5  2.22     9.9    10          H3PO3 110       -6.2  36.5  2.33     14.8   15          H3PO3 111       -6.3  36.0  -4     19.8   20          H3PO3 112       -6.6  35.0  3.65     29.7   30          H3PO3 114       -6.8  34.3  4.96     39.6   40          H3PO3 116       -7.4  33.0  5.57     79.2   80          H3PO3 120       -     -     -8     39.6   40          H3PO3 115.5     -     -     -9     296.9  300         H3PO3 140       -     -     -10    29.7   30          H3PO3 114       -     -     -11    261.8  1000        (PhO)3P135       -     -     -注：1 pH＝苯基2 Sb(O)含量由所用的P(III)化合物和Sb(III)化合物进行估计。
                       表2
P(III)化合物含量(ppm)          最小加工时间(秒)
0                              60
20                             52
30                             48
40                             45
80                             42

Claims (9)

1.一种瓶型坯，该瓶型坯具有由热塑性聚合物组成的壁，该聚合物含有金属颗粒，金属颗粒的细度足以使肉眼观察不到，其特性吸收是在辐射波长为500nm至2000nm的区域内，其量按聚合物重量计为10-300ppm，从而使聚合物的再热时间少于不含金属颗粒时聚合物的再热时间。
2.权利要求1所述的瓶型坯，其中热塑性聚合物是聚酯，该聚酯含有至少70mol％对苯二甲酸乙二醇酯残基，还可以进一步含有间苯二甲酸乙二醇酯、萘二甲酸乙二醇酯、对苯二甲酸乙氧基亚乙基酯、间苯二甲酸乙氧基亚乙基酯或萘二甲酸乙氧基亚乙基酯的残基。
3.权利要求1或2所述的瓶型坯，其中的金属是锑、锡、铜、银、金、砷、镉、汞、铅、钯和铂中的一种或多种。
4.权利要求3所述的瓶型坯，其中的金属是锑，其量按聚合物重量计为10ppm至100ppm。
5.一种制造如权利要求1所述的瓶型坯的方法，该方法包括：在热塑性聚合物中加入可被还原的金属化合物的细颗粒和能将金属化合物还原成金属的还原剂，并使金属化合物与还原剂反应生成金属细颗粒；由所得的聚合物制成瓶型坯。
6.权利要求5所述的方法，其中用注塑法由聚合物制成瓶型坯。
7.权利要求5或6所述的方法，其中聚合物是聚酯，该聚酯含有至少70mol％对苯二甲酸乙二醇酯残基，还可进一步含有间苯二甲酸乙二醇酯、萘二甲酸乙二醇酯、对苯二甲酸乙氧基亚乙基酯、间苯二甲酸乙氧基亚乙基酯或萘二甲酸乙氧基亚乙基酯的残基。
8.权利要求5所述的方法，其中可被还原的金属化合物颗粒和还原剂是作为聚合物合成的一部分加入聚合物的，并且形成金属颗粒的反应至少一部分是与聚合物的合成同时发生的。
9.权利要求5所述的方法，其中可被还原的金属化合物是三价锑氧化物，还原剂是三价磷化合物。
CN95121331A 1989-11-24 1995-12-15 一种瓶型坏及其制备方法 Expired - Fee Related CN1051100C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8926631.6 1989-11-24
GB898926631A GB8926631D0 (en) 1989-11-24 1989-11-24 Polymer compositions

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN90109656A Division CN1034871C (zh) 1989-11-24 1990-11-24 聚酯塑料瓶

Publications (2)

Publication Number Publication Date
CN1130564A CN1130564A (zh) 1996-09-11
CN1051100C true CN1051100C (zh) 2000-04-05

Family

ID=10666879

Family Applications (3)

Application Number Title Priority Date Filing Date
CN90109656A Expired - Fee Related CN1034871C (zh) 1989-11-24 1990-11-24 聚酯塑料瓶
CN95121329A Expired - Fee Related CN1051954C (zh) 1989-11-24 1995-12-15 制备热塑性聚合物的方法
CN95121331A Expired - Fee Related CN1051100C (zh) 1989-11-24 1995-12-15 一种瓶型坏及其制备方法

Family Applications Before (2)

Application Number Title Priority Date Filing Date
CN90109656A Expired - Fee Related CN1034871C (zh) 1989-11-24 1990-11-24 聚酯塑料瓶
CN95121329A Expired - Fee Related CN1051954C (zh) 1989-11-24 1995-12-15 制备热塑性聚合物的方法

Country Status (17)

Country Link
US (2) US5419936A (zh)
EP (1) EP0429311B1 (zh)
JP (1) JPH03230933A (zh)
KR (1) KR0170389B1 (zh)
CN (3) CN1034871C (zh)
AT (1) ATE162206T1 (zh)
CA (1) CA2030668C (zh)
DE (1) DE69031937T2 (zh)
DK (1) DK0429311T3 (zh)
ES (1) ES2111532T3 (zh)
GB (2) GB8926631D0 (zh)
GR (1) GR3025994T3 (zh)
IE (1) IE904192A1 (zh)
MW (1) MW8990A1 (zh)
ZA (1) ZA909312B (zh)
ZM (1) ZM5290A1 (zh)
ZW (1) ZW18390A1 (zh)

Families Citing this family (73)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994010242A1 (en) * 1992-10-26 1994-05-11 Allied-Signal Inc. Nucleating system for polyesters and articles formed therefrom
FR2716885B1 (fr) * 1994-03-01 1996-04-12 Solvay Matériau thermoplastique composite et procédé de fabrication d'articles à base de celui-ci.
US5830545A (en) * 1996-04-29 1998-11-03 Tetra Laval Holdings & Finance, S.A. Multilayer, high barrier laminate
US5795649A (en) * 1996-06-03 1998-08-18 Ici Americas Inc. Release film and method of making thereof
US6197851B1 (en) 1996-08-30 2001-03-06 Eastman Chemical Company Polyester compositions containing near infrared absorbing materials to improve reheat
US5925710A (en) * 1997-04-23 1999-07-20 Hoechst Celanese Corporation Infrared absorbing polyester packaging polymer
US5919848A (en) * 1997-10-03 1999-07-06 Eastman Chemical Company Magnetic polyester compositions
EP0921144B1 (en) * 1997-12-02 2005-03-23 Mitsubishi Chemical Corporation Polyester, stretch blow molded product formed thereof and method for producing polyester
US6022920A (en) * 1998-01-23 2000-02-08 Eastman Chemical Company Method for the production of clear bottles having improved reheat
US6503586B1 (en) 1998-02-25 2003-01-07 Arteva North America S.A.R.L. Title improved infrared absorbing polyester packaging polymer
CN1311807A (zh) * 1998-05-27 2001-09-05 伊斯曼化学公司 制备热塑性聚合物预制件的方法及由其制备的制品
DZ3093A1 (fr) * 1999-09-21 2004-06-20 Du Pont Procédé pour ajuster les propriétés de post-chauffage de résines de polyester.
US6660792B2 (en) 1999-12-21 2003-12-09 M & G Usa Corporation Process for fast heat-up polyesters
JP2001179810A (ja) * 1999-12-27 2001-07-03 Mitsui Chemicals Inc 多層中空成形体用プリフォーム、多層中空成形体およびその製造方法
US20020047262A1 (en) * 2000-09-14 2002-04-25 Steen Vesborg Holographic images
US20040030029A1 (en) * 2000-12-08 2004-02-12 Stephen Weinhold Polyester compositions for hot-fill containers
US7687124B2 (en) * 2001-07-26 2010-03-30 M&G Usa Corporation Oxygen-scavenging containers having low haze
US6780916B2 (en) * 2001-07-26 2004-08-24 M & G Usa Corporation Oxygen-scavenging resin compositions having low haze
US7740926B2 (en) 2001-07-26 2010-06-22 M&G Usa Corporation Oxygen-scavenging containers
US20040005419A1 (en) * 2002-07-02 2004-01-08 Mcgrath Thomas M. Container for product integrity and identification
US20040101642A1 (en) * 2002-11-26 2004-05-27 Quillen Donna Rice Glassy carbon thermoplastic compositions
DE10256084A1 (de) * 2002-11-29 2004-06-17 Crompton Gmbh Katalysatoren für die Herstellung von Polyestern, insbesondere Poly(alkylenterephthalaten), deren Verwendung und Verfahren zu deren Anwendung
US7303795B2 (en) 2003-03-13 2007-12-04 Invista North America S.A. R.L. Molding of polypropylene with enhanced reheat characteristics
US7189777B2 (en) * 2003-06-09 2007-03-13 Eastman Chemical Company Compositions and method for improving reheat rate of PET using activated carbon
US20050010017A1 (en) * 2003-07-11 2005-01-13 Blakely Dale Milton Addition of UV inhibitors to pet process for maximum yield
US20050054757A1 (en) * 2003-09-10 2005-03-10 Pearson Jason Clay Method for reducing the acetaldehyde level in polyesters
US7479517B2 (en) * 2003-11-28 2009-01-20 Futura Polyesters Ltd. Process for the preparation of fast reheat (FRH) bottle grade polyethyleneterephthalate (PET) resin
US20050147773A1 (en) * 2004-01-06 2005-07-07 Saliaris George P. Thermally conductive cap
US7368523B2 (en) 2004-11-12 2008-05-06 Eastman Chemical Company Polyester polymer and copolymer compositions containing titanium nitride particles
GB0407114D0 (en) * 2004-03-30 2004-05-05 Colormatrix Europe Ltd Polymer additives and methods of use thereof
US7282555B2 (en) * 2004-05-27 2007-10-16 Eastman Chemical Company Method for incorporating nitrogen containing methine light absorbers in pet and compositions thereof
US7541407B2 (en) 2004-05-27 2009-06-02 Eastman Chemical Company Process for adding methine UV light absorbers to PET prepared by direct esterification
US20050277716A1 (en) * 2004-05-27 2005-12-15 Pearson Jason C Furyl-2-methylidene UV absorbers and compositions incorporating the UV absorbers
US20050267283A1 (en) * 2004-05-27 2005-12-01 Weaver Max A Process for adding nitrogen containing methine light absorbers to poly(ethylene terephthalate)
US20050277759A1 (en) * 2004-05-27 2005-12-15 Pearson Jason C Process for adding furyl-2-methylidene UV light absorbers to poly(ethylene terephthalate)
US20060051542A1 (en) * 2004-09-03 2006-03-09 Zhiyong Xia Polyester polymer and copolymer compositions containing metallic molybdenum particles
US7662880B2 (en) 2004-09-03 2010-02-16 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic nickel particles
US20060110557A1 (en) * 2004-09-03 2006-05-25 Zhiyong Xia Polyester polymer and copolymer compositions containing metallic tungsten particles
BRPI0514777A (pt) * 2004-09-03 2008-06-24 Eastman Chem Co composição de poliéster e processos para produzir uma composição e uma preforma de poliéster
US7816436B2 (en) 2004-11-08 2010-10-19 INVISTA North America S.à.r.l. Carbon black with large primary particle size as reheat additive for polyester and polypropylene resins
US20060105129A1 (en) * 2004-11-12 2006-05-18 Zhiyong Xia Polyester polymer and copolymer compositions containing titanium carbide particles
US7300967B2 (en) 2004-11-12 2007-11-27 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic titanium particles
US20060122300A1 (en) * 2004-12-07 2006-06-08 Zhiyong Xia Polyester polymer and copolymer compositions containing steel particles
US20060177614A1 (en) * 2005-02-09 2006-08-10 Zhiyong Xia Polyester polymer and copolymer compositions containing metallic tantalum particles
US20060222795A1 (en) * 2005-03-31 2006-10-05 Howell Earl E Jr Polyester polymer and copolymer compositions containing particles of one or more transition metal compounds
US8557950B2 (en) 2005-06-16 2013-10-15 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
US20060287471A1 (en) * 2005-06-16 2006-12-21 Schreiber Benjamin R Accelerated acetaldehyde testing of polymers
DE102005038774A1 (de) * 2005-08-15 2007-02-22 Merck Patent Gmbh Polymere mit hoher IR-Absorption
US7655746B2 (en) * 2005-09-16 2010-02-02 Eastman Chemical Company Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers
US7932345B2 (en) 2005-09-16 2011-04-26 Grupo Petrotemex, S.A. De C.V. Aluminum containing polyester polymers having low acetaldehyde generation rates
US8431202B2 (en) 2005-09-16 2013-04-30 Grupo Petrotemex, S.A. De C.V. Aluminum/alkaline or alkali/titanium containing polyesters having improved reheat, color and clarity
US7776942B2 (en) 2005-09-16 2010-08-17 Eastman Chemical Company Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron
US7745512B2 (en) 2005-09-16 2010-06-29 Eastman Chemical Company Polyester polymer and copolymer compositions containing carbon-coated iron particles
US9267007B2 (en) * 2005-09-16 2016-02-23 Grupo Petrotemex, S.A. De C.V. Method for addition of additives into a polymer melt
US7838596B2 (en) * 2005-09-16 2010-11-23 Eastman Chemical Company Late addition to effect compositional modifications in condensation polymers
US20070260002A1 (en) * 2006-05-04 2007-11-08 Zhiyong Xia Titanium nitride particles, methods of making them, and their use in polyester compositions
US7709593B2 (en) * 2006-07-28 2010-05-04 Eastman Chemical Company Multiple feeds of catalyst metals to a polyester production process
US20080027207A1 (en) * 2006-07-28 2008-01-31 Jason Christopher Jenkins Non-precipitating alkali/alkaline earth metal and aluminum compositions made with mono-ol ether solvents
US7709595B2 (en) * 2006-07-28 2010-05-04 Eastman Chemical Company Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents
US7745368B2 (en) * 2006-07-28 2010-06-29 Eastman Chemical Company Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids
US20080058495A1 (en) * 2006-09-05 2008-03-06 Donna Rice Quillen Polyester polymer and copolymer compositions containing titanium and yellow colorants
US8563677B2 (en) * 2006-12-08 2013-10-22 Grupo Petrotemex, S.A. De C.V. Non-precipitating alkali/alkaline earth metal and aluminum solutions made with diols having at least two primary hydroxyl groups
US20080257883A1 (en) 2007-04-19 2008-10-23 Inbev S.A. Integrally blow-moulded bag-in-container having an inner layer and the outer layer made of the same material and preform for making it
US9475611B2 (en) 2007-04-19 2016-10-25 Anheuser-Busch Inbev S.A. Integrally blow-moulded bag-in-container having interface vents opening to the atmosphere at location adjacent to bag's mouth, preform for making it; and processes for producing the preform and bag-in-container
US20080258356A1 (en) 2007-04-19 2008-10-23 Inbev S.A. Integrally blow-moulded bag-in-container comprising an inner layer and an outer layer comprising energy absorbing additives, and preform for making it
CN104816877B (zh) 2009-07-09 2018-02-02 恩特格里斯公司 基于衬里的存储系统和输送材料的方法
CN102071412B (zh) * 2010-04-14 2012-03-07 比亚迪股份有限公司 一种塑料制品的制备方法及一种塑料制品
WO2012071370A2 (en) 2010-11-23 2012-05-31 Advanced Technology Materials, Inc. Liner-based dispenser
CN102173027B (zh) * 2011-01-08 2013-06-05 王�忠 注塑成型设备及使用该设备注塑金属感高光注塑件的工艺
BR112013022316A2 (pt) 2011-03-01 2017-05-30 Advanced Tech Materials sistema baseado em revestimento interno, e, método para prover um sistema baseado em revestimento interno
US10240021B2 (en) 2012-01-12 2019-03-26 Dak Americas Llc Polyester resins with particular carbon black as a reheat additive in the production of stretch blow molded bottles and containers
WO2014022226A1 (en) 2012-08-01 2014-02-06 Graham Packaging Company, L.P. In-situ polymerized polymer-platinum group metal nanoparticle blends and oxygen scavenging containers made therefrom
US11864943B2 (en) 2018-10-05 2024-01-09 3M Innovative Properties Company Metal injection molding for stethoscope chestpiece

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264255A (en) * 1961-05-01 1966-08-02 Ici Ltd Color stabilization of polyethylene terephthalate with finely divided metals

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB751751A (en) * 1952-12-05 1956-07-04 Du Pont Melt-extrusion of polyethylene
US3264225A (en) * 1962-10-15 1966-08-02 Standard Oil Co Mixed antimony oxide-thorium oxide oxidation catalyst
DE1495742A1 (de) * 1963-09-04 1969-04-03 Hoechst Ag Verfahren zur Herstellung von linearen film- und faserbildenden Polyestern
US3492151A (en) * 1966-04-06 1970-01-27 Du Pont Metallizing process
JPS5729496B2 (zh) * 1973-05-10 1982-06-23
US4250078A (en) * 1979-03-19 1981-02-10 Eastman Kodak Company Thermoplastic polyester molding compositions
US4545926A (en) * 1980-04-21 1985-10-08 Raychem Corporation Conductive polymer compositions and devices
FR2482971A1 (fr) * 1980-05-20 1981-11-27 Rhone Poulenc Ind Polyesters pour emballages a usage alimentaire et leur procede d'obtention
US4476272A (en) * 1982-02-24 1984-10-09 The Goodyear Tire & Rubber Company High clarity, low haze polyesters having reduced infrared heat-up times
US4643925A (en) * 1982-09-07 1987-02-17 The Goodyear Tire & Rubber Company Multi-layer polyisophthalate and polyterephthalate articles and process therefor
US4604257A (en) * 1982-09-07 1986-08-05 The Goodyear Tire & Rubber Company Multi-layer polyisophthalate and polyterephthalate articles and process therefor
US4447595A (en) * 1982-09-07 1984-05-08 The Goodyear Tire & Rubber Company Polyterephthalates and copolymers thereof having high clarity and process for making same
US4582872A (en) * 1983-07-26 1986-04-15 Princeton Polymer Laboratories Polymer-metal blend
IL72879A (en) * 1984-09-06 1988-12-30 Ginegar Kibbutz Plastic sheeting
US4684686A (en) * 1985-02-25 1987-08-04 General Electric Company Glass fiber reinforced polyester molding compositions containing metal powders
US4609721A (en) * 1985-06-21 1986-09-02 Celanese Corporation Process for making molding grade polyethylene terephthalate
US4772656A (en) * 1985-08-27 1988-09-20 Linwo Industries Limited Volatile aromatic barrier for polyolefin containers
DE3605574A1 (de) * 1986-02-21 1987-08-27 Basf Ag Metalldrahteinlagen enthaltende, photopolymerisierbare formmassen
JPS63142028A (ja) * 1986-12-05 1988-06-14 Toyo Seikan Kaisha Ltd ポリエステル製容器及び包装体
CA1302066C (en) * 1987-06-22 1992-06-02 David C. Strack Stitchbonded material including elastomeric nonwoven fibrous web
US4778820A (en) * 1987-08-19 1988-10-18 Eastman Kodak Company Polyester molding compositions
US4871790A (en) * 1987-11-25 1989-10-03 Minnesota Mining And Manufacturing Company Colloidal metals in monomers or polymers
GB9013481D0 (en) * 1990-06-15 1990-08-08 Ici Plc Polyester polymer products
US6567003B2 (en) * 2001-09-17 2003-05-20 B&G Plastics, Inc. Article identification and security tag

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264255A (en) * 1961-05-01 1966-08-02 Ici Ltd Color stabilization of polyethylene terephthalate with finely divided metals

Also Published As

Publication number Publication date
CN1051954C (zh) 2000-05-03
DE69031937T2 (de) 1998-04-30
ZM5290A1 (en) 1991-08-30
DK0429311T3 (da) 1998-09-07
KR0170389B1 (ko) 1999-03-30
KR910009804A (ko) 1991-06-28
MW8990A1 (en) 1992-01-08
GR3025994T3 (en) 1998-04-30
ES2111532T3 (es) 1998-03-16
JPH03230933A (ja) 1991-10-14
ATE162206T1 (de) 1998-01-15
IE904192A1 (en) 1991-06-05
CA2030668A1 (en) 1991-05-25
GB9025019D0 (en) 1991-01-02
EP0429311B1 (en) 1998-01-14
CN1051922A (zh) 1991-06-05
GB8926631D0 (en) 1990-01-17
EP0429311A3 (en) 1992-09-30
CN1131609A (zh) 1996-09-25
US5529744A (en) 1996-06-25
CN1034871C (zh) 1997-05-14
CA2030668C (en) 2001-07-31
US5419936A (en) 1995-05-30
CN1130564A (zh) 1996-09-11
ZW18390A1 (en) 1991-10-02
ZA909312B (en) 1992-04-29
EP0429311A2 (en) 1991-05-29
DE69031937D1 (de) 1998-02-19

Similar Documents

Publication Publication Date Title
CN1051100C (zh) 一种瓶型坏及其制备方法
TWI392700B (zh) 含氮化鈦顆粒之聚酯聚合物及共聚物組合物
US5340884A (en) Polyamide concentrate useful for producing blends having improved flavor retaining property and clarity
KR20070108359A (ko) 아연과 코발트를 함유하는 폴리에스테르와 산소 제거폴리아미드의 블렌드
JP2002226563A (ja) ポリエステル樹脂
MX2007002416A (es) Composiciones de polimero y copolimero de poliester que contienen particulas de tungsteno metalicas.
CA2135300A1 (en) Copolyester/polyamide blend having improved flavor retaining property and clarity
US7776942B2 (en) Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron
JP2006152315A (ja) 改質ポリエステル樹脂の製造方法
US20060051542A1 (en) Polyester polymer and copolymer compositions containing metallic molybdenum particles
JP2002226562A (ja) ポリエステル樹脂
JP2002020469A (ja) ポリエステル樹脂
MXPA06011692A (es) Metodos para elaborar resinas de tereftalato de polietileno catalizado por titanio.
JP2007002240A (ja) ポリエステル延伸中空成形体及びその製造方法
JP4296476B2 (ja) ポリエステル組成物及びそれからなる成形体
US20060177614A1 (en) Polyester polymer and copolymer compositions containing metallic tantalum particles
JP2002220443A (ja) 改質ポリエステル樹脂の製造方法
CN1094420A (zh) 高韧耐侯的改性聚丙烯材料
JP3465463B2 (ja) ポリエステル組成物
JP2004155994A (ja) ポリエステル組成物及びそれからなる成形体
JP3685303B2 (ja) ポリエステル樹脂
EP1794225A1 (en) Polyester polymer and copolymer compositions containing metallic molybdenum particles
JP2003082205A (ja) ポリエステル組成物及びそれからなる成形体
JPH11209593A (ja) ポリエステル樹脂組成物
JPH10251390A (ja) ポリエステルの製造法

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C53 Correction of patent of invention or patent application
COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: IMPERIAL CHEMICAL CORPORATION TO: E.I. DU PONT DE NEMOURS AND CO.

CP03 Change of name, title or address

Address after: Delaware

Applicant after: E.I. Du Pont de Nemours and Co.

Address before: London, England

Applicant before: Imperial Chemical Industries PLC

C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20000405

Termination date: 20091224