CN101175805B - 具有改进的耐热氧化降解性的聚烯烃模塑组合物及其在管道生产中的应用 - Google Patents
具有改进的耐热氧化降解性的聚烯烃模塑组合物及其在管道生产中的应用 Download PDFInfo
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Abstract
模塑组合物适合于生产当这些管道与包含具有氧化效果的消毒剂的液体长期接触时具有改进的耐热氧化降解性的管道。这样的模塑组合物包含，除了热塑性聚烯烃以外，数量为0.01～1.0重量％的多氧化合物和/或多羟基化合物作为添加剂。此外，该模塑组合物可以进一步包含数量最多为5重量％的不饱和脂肪烃。本发明也涉及通过使用这种模塑组合物提高水管长期耐受由水中的氧化消毒剂引起的损伤的方法。
Description
本发明涉及具有改进的耐热氧化降解性且尤其适用于生产长期接触包含具有氧化作用的消毒剂的液体的管道的聚烯烃模塑组合物。
多年来，包含聚乙烯(PE)、聚丙烯(PP)和聚-1-丁烯(PB-1)的模塑组合物被用于生产优选在建筑物中用于输送冷水和热水的塑料管道。
虽然包含所述塑料的管道具有十分良好的耐水性，但是发现当这些管道与因为卫生原因经常加入到水中的常用消毒剂接触时其寿命会被严重地限制。这很重要，因为少量的氧化性物质如氯气、次氯酸钠(漂白液)、次氯酸钙或二氧化氯通常作为消毒剂加入到市政自来水中。有时也使用过氧化氢(H2O2)或臭氧。
聚乙烯管道可以是未交联的或交联的。交联可以通过常规工业交联过程借助于有机过氧化物、接枝的乙烯基硅烷酯或借助于高能辐射(γ-或β-射线)来完成。
因此本发明的目的在于研发基于聚烯烃如聚乙烯(PE)、聚丙烯(PP)或聚-1-丁烯(PB-1)并保留优良的加工性能的新型的模塑组合物，来生产当其应用于包含具有氧化作用的消毒剂的自来水时具有改进的稳定性的管道。
这个目标可以通过开始提及的一般类别的模塑组合物实现，其区别特征在于其包含热塑性聚烯烃和基于模塑组合物总重量数量为0.01～1.0重量％的具有以下化学通式的有机多氧化合物(organicpolyoxy compound)：
R-[(CH2)n-O]m-H
其中n是从1到10的整数，m是从3到500的整数且R是氢原子或羟基基团或具有1到10个碳原子并且可以具有进一步的取代基如-OH、-COOH、-COOR、-OCH3或-OC2H5的烷基，或具有以下化学通式的有机多羟基化合物：
RO-CH2-C-(CH2-OR)3
其中R可以是氢原子或具有1～5个碳原子并且可以具有进一步的取代基如-OH、-COOH、-COOR、-OCH3或-OC2H5的烷基基团，或者两者的组合。
WO2001/90230公开了聚烯烃如PE或PP，其包含数量为5～50重量％的用作润滑剂的聚乙二醇并尤其是准备用于管道制造。但是，其中描述的聚乙二醇的高添加量会损害聚烯烃的机械性能并且因此不适合用于建筑物中的额定压力水管。
JP-A 09/143318(Nippon)公开了生产管道的方法，其中包含氟聚合物加聚氧化烯的添加剂组合的LLDPE通过挤出进行加工且据称借助于这种方式可以避免模头粉尘(die dust)。
本发明的模塑组合物不同于现有技术之处在于加入更少量的上述化学组成的多氧化合物或多羟基化合物，其虽然以如此少的数量存在但赋予包含所述模塑组合物的管道在长时间内对水中消毒剂的氧化作用的优良稳定性，这是尤其令人惊讶的。
已发现尤其有用的多氧化合物是聚乙二醇、甲氧基聚乙二醇和聚丙二醇。优选的是使用具有400～9000g/mol的平均摩尔质量的多氧化合物。使用这些多氧化合物的优选数量是0.01～0.5重量％，尤其优选0.1～0.3重量％。
已发现尤其有用的多羟基化合物是季戊四醇、三羟甲基丙烷、甘油、甘露糖醇和山梨醇。使用这些多羟基化合物的优选数量是0.01～0.5重量％，尤其优选0.1～0.3重量％。
在本发明的特定实施方案中，模塑聚合物可以包含具有以下化学通式的额外的不饱和脂肪烃化合物：
R1-[(CHR2)-CH＝CH-CHR3]n-R4
其中R1和R4彼此相互独立的是-H、-CH3、-OCH3或-CH2OH，且R2和R3彼此相互独立的是-H、-CH3、C2H5或C3H7。
在本发明的模塑组合物中所述额外的不饱和脂肪烃化合物可以存在的数量是可变的，且基于模塑组合物总重量为0.1～5重量％。
根据本发明，对于不饱和脂肪烃化合物，优选是聚异戊二烯，聚环辛烯(polyoctenamer)或聚环癸烯(polydecenamer)。
根据本发明尤其合适的热塑性聚烯烃是聚烯烃，例如PE、PP和PB-1，包括均聚物和它们与其它具有具有4～10个碳原子的烯属单体的共聚物，其可以容易地通过挤出技术加工来生产管道。这样的聚烯烃可以在合适的催化剂存在下通过单体的聚合来制备，所述合适的催化剂是例如Ziegler催化剂、Ziegler-Natta催化剂、含铬的Phillips催化剂或诸如茂金属的单侧催化剂(single side catalyst)等等。
聚合在0℃～200℃，优选25℃～150℃且更优选40℃～130℃的温度下和0.05～10Mpa且优选0.3～4MPa的压力下进行。聚合可以在单步或多步方法中非连续的实施或优选连续的实施。因此可以采用溶液聚合或悬浮聚合或搅拌气相聚合或气相流化床聚合。因为属于通用技术，所以本领域技术人员熟悉这种技术和这类方法。
本发明的模塑组合物可以包含PE，该PE可以是线型或非线型的且可以具有不同的密度，如高密度PE(HDPE)或中密度PE(MDPE)或低密度PE(LDPE)或线性低密度PE(LLDPE)。在优选的实施方案中，模塑组合物包含在23℃的温度下密度为0.93～0.965g/cm3和熔融指数MI190/5为0.1～2g/10min的PE。
本发明模塑组合物包含的PP可以是，例如，具有0.1～2g/10min的熔融指数MI230/5的高分子量全同或间同均聚物、无规共聚物或嵌段共聚物。
本发明模塑组合物包含的PB-1可以是，例如，具有0.1～1g/10min的熔融指数MI190/216和0.92～0.95g/cm3的在23℃温度下的密度的均聚物或共聚物。
本发明的模塑组合物除了所述热塑性聚烯烃之外可以进一步的包含其他的添加剂。此类添加剂优选是数量为0～10重量％，优选为0～5重量％的热稳定剂和加工稳定剂、抗氧化剂、UV吸收剂、光稳定剂、金属钝化剂、过氧化物破坏化合物、有机过氧化物、碱性共稳定剂，并且也可以是基于混合物总重量总数量为0～30重量％的碳黑、填料、颜料或这些的组合。
作为热稳定剂，本发明的模塑组合物可以包括酚类抗氧剂，尤其是购自德国Ciba Specialities的商品名为IRGANOX的季戊四醇(3，5-二叔丁基-4-羟苯基)丙酸酯。
尤其令人惊奇的是，根据本发明的模塑组合物可以加工制备具有显著改进的长期稳定性的管道，如果这些管道暴露于加氯水并且连续接触加氯水的话。另一个高度令人惊奇的发现是这类管道的高耐穿透性与其改进的感官感觉的结合。
增加下列的实施例是为了更好的说明新型模塑组合物的优点并且尤其是解释由它们制备的新型管道的优点。但是，这些实施例决不意味着对本发明的范围作出任何限制。
实施例1
将具有0.946g/cm3的密度和0.3g/10min的熔体流动指数MI190/5的高分子量中密度PE粉与0.1％的具有9000g/mol的摩尔质量的聚乙二醇，1％的Vestenamer 8012和0.35％的IRGANOX 1330混合并且在220℃的熔融温度下在Coperion Werner & Pfleiderer GmbH & CoKG的ZSK 53中造粒。颗粒在220℃的熔融温度下在Battenfeld的管材挤出单元中加工生产具有16×2mm直径的管道，且随后管道通过电子束交联。所施加的辐射剂量是120kGy。交联度根据DIN EN16892测定，为66％。
根据ASTM F2023进行的蠕变实验在115℃在4ppm的氯存在下在1.58MPa的载荷下，在交联的管道上进行。所实现的失败时间列于表1。
实施例2
将实施例1中的具有0.946g/cm3的密度和0.3g/10min的熔体流动指数MI190/5的高分子量MDPE粉与0.1％的具有400g/mol的摩尔质量的聚乙二醇和0.35％的IRGANOX 1330混合并造粒，挤出生产具有16×2mm直径的管道，且在120kGy下通过电子束交联。交联度根据DIN EN16892测定，为64％。
蠕变实验在115℃在4ppm的氯存在下在1.58MPa的载荷下在交联的管道上进行。该实验根据ASTM F2023进行。所实现的失败时间列于表1。
实施例3
将实施例1中的具有0.946g/cm3的密度和0.3g/10min的熔体流动指数MI190/5的高分子量MDPE粉与0.2％的具有400g/mol的摩尔质量的聚乙二醇和0.35％的IRGANOX 1330混合并造粒，挤出生产具有16×2mm直径的管道，且在120kGy下通过电子束交联。交联度根据DIN EN16892测定，为66％。
蠕变实验在115℃在4ppm的氯存在下在1.58MPa的载荷下在交联的管道上进行。该实验根据ASTM F2023进行。所实现的失败时间列于表1。
实施例4
将实施例1中的具有0.946g/cm3的密度和0.3g/10min的熔体流动指数MI190/5的高分子量MDPE粉与0.1％的具有400g/mol的摩尔质量的聚乙二醇，1％的Vestenamer 8012和0.35％的IRGANOX 1330混合并造粒，挤出生产具有16×2mm直径的管道，且在120kGy下通过电子束交联。交联度根据DIN EN16892测定，为65％。
蠕变实验在115℃在4ppm的氯存在下在1.58MPa的载荷下在交联的管道上进行。该实验根据ASTM F2023进行。所实现的失败时间列于表1。
对照实施例
为了对照，挤出来自Basell的商业化的PEXc材料Lupolen 4261 AQ416以生产具有16×2mm直径的管道并在120kGy下辐射交联。交联度经测量为63％。
蠕变实验在115℃在4ppm的氯存在下在1.58MPa的载荷下在交联的管道上进行。该实验根据ASTM F2023进行。
表1
| 实施例编号 | 在压力实验中破裂的时间，h |
| 实施例1 | 1186 |
| 实施例2 | 960 |
| 实施例3 | 1459 |
| 实施例4 | 1453 |
| 对照实施例 | 524 |
Claims (8)
1.有机多氧化合物用来改进与包含具有氧化作用的消毒剂的液体长期接触并包含热塑性聚烯烃的管道的耐氧化降解稳定性的用途，其中所述多氧化合物作为添加剂以基于聚烯烃和添加剂总重量为0.01～1.0重量％的量在管道生产之前加入到热塑性聚烯烃中，其中所述有机多氧化合物具有以下化学通式：
R-[(CH2)n-O]m-H
其中n是从1到10的整数，m是从3到500的整数，且R是氢原子或羟基基团或具有1到10个碳原子并且可以具有进一步的选自-OH、-COOH、-OCH3或-OC2H5的取代基的烷基，
其中抗氧化剂作为添加剂添加到所述热塑性聚烯烃中。
2.根据权利要求1的用途，其中不饱和脂肪烃化合物被添加到所述热塑性聚烯烃中，其中聚异戊二烯、聚环辛烯或聚环癸烯用作不饱和脂肪烃化合物。
3.根据权利要求1或2的用途，其中所述有机多氧化合物是聚乙二醇、甲氧基聚乙二醇或聚丙二醇。
4.根据权利要求1或2的用途，其中所述多氧化合物具有400～9000g/mol的平均摩尔质量。
5.根据权利要求1或2的用途，其中所述多氧化合物以0.01～0.5重量％的量使用。
6.根据权利要求1或2的用途，其中所述多氧化合物以0.1～0.3重量％的量使用。
7.根据权利要求2的用途，其中基于模塑组合物总重量所述不饱和脂肪烃化合物以0.1～5重量％的量使用。
8.根据权利要求1或2的用途，其中聚乙烯或聚丙烯或它们与具有4～10个碳原子的其它烯属不饱和单体的共聚物被用作热塑性聚烯烃。
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| DE102005023040.7 | 2005-05-13 | ||
| DE102005023040A DE102005023040A1 (de) | 2005-05-13 | 2005-05-13 | Polyolefinische Formmasse mit verbesserter Beständigkeit gegen thermo-oxidativen Abbau und ihre Verwendung für das Herstellen von Rohren |
| US68839705P | 2005-06-08 | 2005-06-08 | |
| US60/688,397 | 2005-06-08 | ||
| PCT/EP2006/004251 WO2006119935A1 (en) | 2005-05-13 | 2006-05-06 | Polyolefinic molding composition having improved resistance to thermooxidative degradation and its use for the production of pipes |
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| JP5481854B2 (ja) * | 2008-12-16 | 2014-04-23 | Ｔｄｋ株式会社 | 電子部品 |
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| JP2010180395A (ja) * | 2009-01-09 | 2010-08-19 | Sumitomo Chemical Co Ltd | ポリマー安定剤及び該安定剤を含有するポリマー組成物 |
| KR101329678B1 (ko) * | 2009-06-22 | 2013-11-14 | 보레알리스 아게 | 이산화염소 내성 폴리에틸렌 파이프, 그의 제조 및 용도 |
| JP2013158709A (ja) * | 2012-02-06 | 2013-08-19 | Nippon Rensui Co Ltd | 陰イオン交換樹脂および陰イオン交換樹脂の処理方法 |
| JP2013158708A (ja) * | 2012-02-06 | 2013-08-19 | Nippon Rensui Co Ltd | 水処理装置および水処理方法 |
| EP2746324A1 (en) * | 2012-12-21 | 2014-06-25 | Borealis AG | Use of pigments and additives for improving pipe stability against desinfectant containing water |
| EP3356467B1 (en) | 2015-10-01 | 2019-07-03 | SABIC Global Technologies B.V. | Pipe produced with a polymer composition comprising a polyolefin |
| CN105622922B (zh) * | 2016-04-06 | 2018-04-20 | 苏州博纳化学科技有限公司 | 一种亲水性双羟基化合物的制备方法 |
| EP3378890A1 (en) | 2017-03-22 | 2018-09-26 | Songwon Industrial Co., Ltd. | Polyolefin stabilizers with reduced fragmentation |
| EP3421529A1 (en) | 2017-06-29 | 2019-01-02 | Songwon Industrial Co., Ltd. | Polyolefin articles with improved resistance against chlorine dioxide |
| US20200308401A1 (en) * | 2017-11-14 | 2020-10-01 | Eos Gmbh Electro Optical Systems | Melt dispersed composition |
| DE102018105936A1 (de) | 2018-03-14 | 2019-09-19 | Fachhochschule Münster | Beschichtete Photokatalysatoren |
| US20220309653A1 (en) * | 2019-04-30 | 2022-09-29 | The Trustees Of Dartmouth College | System and method for attention-based classification of high-resolution microscopy images |
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| WO2023056250A1 (en) | 2021-09-30 | 2023-04-06 | Exxonmobil Chemical Patents Inc. | Fluoropolymer-free processing aids for ethylene-based polymers |
| WO2023149985A1 (en) | 2022-02-07 | 2023-08-10 | Exxonmobil Chemical Patents Inc. | Polyethylene glycol-based polymer processing aids |
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| RU2007145916A (ru) | 2009-06-20 |
| EP1879954A1 (en) | 2008-01-23 |
| CN101175805A (zh) | 2008-05-07 |
| CA2607223A1 (en) | 2006-11-16 |
| JP5721685B2 (ja) | 2015-05-20 |
| EP1879954B1 (en) | 2013-07-31 |
| AU2006246010A1 (en) | 2006-11-16 |
| KR20080007253A (ko) | 2008-01-17 |
| US8728370B2 (en) | 2014-05-20 |
| JP2008540746A (ja) | 2008-11-20 |
| KR101328412B1 (ko) | 2013-11-14 |
| CA2607223C (en) | 2013-07-09 |
| ES2429899T3 (es) | 2013-11-18 |
| RU2416622C2 (ru) | 2011-04-20 |
| DE102005023040A1 (de) | 2006-11-16 |
| BRPI0608803A2 (pt) | 2011-03-15 |
| WO2006119935A1 (en) | 2006-11-16 |
| JP2013057069A (ja) | 2013-03-28 |
| US20090069477A1 (en) | 2009-03-12 |
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