CN105705563A - 用于改性乙烯系聚合物和共聚物的方法 - Google Patents
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- C08F8/00—Chemical modification by after-treatment
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Abstract
用于官能化乙烯系(共)聚合物的方法，包括如下步骤：使乙烯系(共)聚合物在100-250℃的温度下与式(I)的叠氮化物接触，其中Y为(Ia)或(Ib)，m为0或1，n为0或1，n+m＝1或2，且X为具有1-12个碳原子的直链或支化脂族或芳族烃基，其任选包含杂原子。
Description
本发明涉及用于官能化和改性乙烯系(共)聚合物的方法、可由这些方法获得的官能化和改性的乙烯系(共)聚合物，及其用于生产电力电缆的用途。
典型的电缆和电缆芯线应用包括至少一个被一个或多个聚合物材料层包围的导体。
在一些电力电缆(包括中压(MV)、高压(HV)和特高压(EHV)电缆)中，导体被若干层(包括内部半导电层、绝缘层和外部半导电层)包围。电力电缆的外部半导电层可为不可剥离的(即结合的和不可剥落的)或可剥离的(即非结合的和可剥落的)。导体可被内部半导电层包围，该内部半导电层通常包含填充有导电碳黑的交联乙烯系共聚物。绝缘层通常由经交联以赋予其所需的长期性质的低密度聚乙烯(LDPE)制成。外部半导电层仍为交联的半导电乙烯系共聚物层，且其通常由金属配线增强或被薄片(金属屏蔽材料)覆盖。
电力电缆通常通过在导体上挤出层而生产。随后将一个或多个所述聚乙烯或乙烯系共聚物层交联，从而提高其在升高的温度下的抗变形性、机械强度和/或耐化学性。通常在挤出所述层之前或期间，将自由基引发剂如过氧化物掺入层材料中。在挤出和形成电缆之后，使电缆经历由自由基引发剂引发的交联步骤。
在自由基乙烯系(共)聚合物交联的常规方法中，源自过氧化物分解产物的残留挥发物如甲烷以孔隙形式保留在电缆中，或者作为高度可燃的气体物质形式释放。本发明的目的是提供用于交联聚乙烯的方法，其允许使用较低量的过氧化物，从而得到较低量的挥发物且仍具有良好的交联性能。
现已发现，如果首先用柠康酰亚胺型叠氮化物官能化乙烯系(共)聚合物，则自由基交联更快且更有效地发生，这意味着需要较低量的过氧化物。
此外，已发现所述使用柠康酰亚胺型叠氮化物的官能化可影响(共)聚合物的极性，从而导致例如与漆层更好的相容性。
此外，所述官能化可用于提高长链支链的数量，由此改变(共)聚合物的流变性，从而提高熔体强度。
因此，本发明涉及一种用于制备官能化的乙烯系(共)聚合物的方法，包括如下步骤：使乙烯系(共)聚合物在100-250℃的温度下与式(I)的叠氮化物接触：
其中Y为：
m为0或1，n为0或1，n+m＝1或2，且X为具有1-12个碳原子的直链或支化脂族或芳族烃结构部分，其任选包含杂原子。
本发明还涉及一种用于改性乙烯系(共)聚合物的方法，包括如下步骤：
-根据上述方法制备官能化的乙烯系(共)聚合物，
-使所述官能化的乙烯系(共)聚合物与有机过氧化物接触以形成聚合物/过氧化物混合物，和
-在140-300℃的温度下加热所述聚合物/过氧化物混合物。
该方法导致所述(共)聚合物的流变性发生改变。取决于精确的条件，结果为交联的(共)聚合物或具有提高的熔体强度的(共)聚合物。交联通过高过氧化物水平实现，提高的熔体强度在低过氧化物水平下实现。精确的水平取决于(共)聚合物的类型、过氧化物的类型和(共)聚合物的官能化水平。
术语“乙烯系(共)聚合物”包括乙烯均聚合物以及基于乙烯和一种或多种其他单体的共聚物。
乙烯系共聚物的实例为基于乙烯-丙烯的共聚物(EPM)、乙烯-丙烯-二烯三元共聚物(EPDM)、乙烯-乙酸乙烯酯(EVA)、乙烯-丙烯酸丁酯(EBA)、乙烯-丙烯酸乙酯(EEA)和聚烯烃弹性体(POE)；后者为乙烯与辛烯或丁烯的共聚物。
乙烯均聚物(即聚乙烯)通常根据其密度来分类。高密度聚乙烯(HDPE)由大于或等于0.941g/cm3的密度定义；中等密度聚乙烯(MDPE)由0.926-0.940g/cm3的密度定义；低线性密度聚乙烯(LLDPE)由0.915-0.925g/cm3的密度定义；低密度聚乙烯(LDPE)由0.910-0.940g/cm3的密度定义；极低密度聚乙烯(VLDPE)由0.880-0.915g/cm3的密度定义。
所有这些乙烯均聚物均可用于本发明的方法中。然而，LDPE是最优选的使用类型。由于其挠性和良好的机械强度，LDPE是优选的乙烯系(共)聚合物。
用于本发明方法中的叠氮化物具有下式：
其中Y为：
m为0或1，n为0或1，n+m＝1或2，优选为1，和
X为具有1-12个碳原子的直链或支化脂族或芳族烃结构部分，其任选包含杂原子。
式(I)的柠康酰叠氮化物(citraconazide)可以以纯形式使用，然而也可呈与相应衣康酰叠氮化物(itaconazide)的混合物的形式。
当X包含杂原子时，其优选具有如下结构之一：
其中Z、Q和P为1-6的整数，R选自H、烷基、芳基、苯基和取代的苯基。
然而，更优选X为具有1-12个，更优选1-6个，最优选2-4个碳原子的脂族烷二基。
最优选用于本发明方法中的叠氮化物为：
即，分别为4-(3-甲基-2,5-二氧代-2,5-二氢-1H-吡咯-1-基)苯磺酰基叠氮(也称为柠康酰亚胺苯磺酰基叠氮)和2-(3-甲基-2,5-二氧代-2,5-二氢-1H-吡咯-1-基)乙基羰酰叠氮酸酯(也称为柠康酰亚胺-C2-叠氮甲酸酯)。
存在若干种使叠氮化物与聚合物反应的机理，这取决于叠氮化物的类型和聚合物的类型。叠氮化物通常热分解成两种的氮宾：单重态(主要)和三重态(次要)。单重态氮宾与完全饱和的聚合物链的反应导致叠氮化物插入聚合物链中。单重态和三重态氮宾与不饱和键的反应导致在碳碳双键上发生加成反应，这也导致接枝。聚乙烯是仅具有少量不饱和键的饱和聚合物，所述不饱和键源自聚合期间的瑕疵。在EPDM中，通过使用第三种单体在聚合物主链中特意引入不饱和键。
与不饱和聚合物的反应也可通过在“点击(click)”反应中在相当低的温度下接枝，随后实施加热步骤(在此期间移除氮)而完成。
使乙烯系(共)聚合物和叠氮化物在100-250℃，优选140-230℃，最优选150-220℃的温度下接触。接触可以以不同方式实施，包括熔融掺合、在双辊研磨机中混合、挤出、由常规溶剂混合等。还可将叠氮化物混入经复合的乙烯系(共)聚合物(即已与油、填料和其他任选添加剂如抗降解剂、着色剂等混合的乙烯系(共)聚合物)中。
叠氮化物以0.1-5phr(重量份/100重量份(共)聚合物)的优选量，更优选0.2-4phr，最优选0.3-3phr与乙烯系(共)聚合物混合。
在交联乙烯系(共)聚合物的过程中，官能化的乙烯系(共)聚合物与有机过氧化物的最初接触在低于过氧化物的安全处理温度下实施。过氧化物的安全处理温度是焦化时间(ts2)长于20分钟时的温度。焦化时间使用移动模具在流变仪中根据ISO6502:1991测量。
以此方式测得的安全处理温度也可在AkzoNobel的手册“Crosslinkingelastomersandthermoplastics(2011)”中找到。
合适的有机过氧化物包括二烷基过氧化物和三氧杂环庚烷(trioxepane)。特别优选的过氧化物为3,3,5,7,7-五甲基-1,2,4-三氧杂环庚烷(安全处理温度：180℃)、2,5-二甲基-2,5-二(叔丁基过氧基)己炔-3(安全处理温度：145℃)、2,5-二甲基-2,5-二(叔丁基过氧基)己烷(安全处理温度：135℃)、二(叔丁基过氧异丙基)苯(安全处理温度：135℃)、过氧化二异丙苯(安全处理温度：170℃)和过氧化叔丁基异丙苯(安全处理温度：135℃)。
过氧化物可以以液体或熔融形式添加至官能化的乙烯系(共)聚合物的珠粒或颗粒中，并允许分散至所述珠粒或颗粒中。这优选在低于80℃，更优选低于60℃，最优选20-40℃的温度下完成。
或者，将过氧化物和官能化的乙烯系(共)聚合物在低于过氧化物的安全处理温度下挤出或熔融混合。另一种方法涉及在双辊研磨机上将过氧化物与接枝的乙烯系(共)聚合物混合。
有机过氧化物以0.1-5重量％的优选量，更优选0.2-4重量％，最优选0.3-3重量％用于本发明的方法中，基于含过氧化物的混合物(包括过氧化物、官能化的乙烯系(共)聚合物、填料和添加剂)的总重量。
可在该阶段添加其他组分，如抗氧化剂、阻燃剂、焦化阻滞剂、助剂、抗静电剂、颜料、着色剂、水树阻滞剂、润滑剂和/或滑爽剂。在聚乙烯的情况下，所有这些添加剂通常以较小量(通常小于总混合物的3重量％)使用。
水树阻滞剂的实例为聚乙二醇(PEG)，例如PEG-2000；分子量为2000Da的聚乙二醇。
焦化阻滞剂的实例为叔丁基氢醌和α-甲基苯乙烯二聚体(4,4-二甲基-2,4-二苯基-1-丁烯)。
助剂的实例为：TMAIC(异氰脲酸三甲基烯丙酯)、TAIC(异氰脲酸三烯丙酯)、TAC(氰脲酸三烯丙酯)、TRIM(三羟甲基丙烷三甲基丙烯酸酯)、二乙烯苯、HVA-2(N,N'-亚苯基双马来酰亚胺)和Perkalink900(1,3-双(柠康酰亚胺基甲基)苯)。
可以以较高量使用的其他添加剂为增强填料，如碳黑和硅石(尤其是对乙烯系共聚物而言)，或非增强型矿物填料。后者可以以至多60重量％的量添加。电子传导性碳黑可以以至多8重量％的量添加。
在过氧化物与官能化的乙烯系(共)聚合物接触之后且在任意其他热处理之前，过氧化物/(共)聚合物混合物可以以所需的形式成型。对成型而言，需要加热以熔融或软化乙烯系(共)聚合物。该成型可在模具(压缩、注射或传递模塑)、挤出机(其中成型模具可安装在挤出头处)或压延机(将聚合物熔体加工成薄片或薄膜)中实施，或者通过薄膜吹塑或热成型。
可使用任意方法来将混合物加热至所需的温度。实例为：在模具(压缩、注射或传递模塑)中加热；在(饱和蒸汽或氮气填充的)管式烘箱中加热；在盐浴中加热；和在热空气中使用烘箱或红外辐射加热。
温度优选为140-300℃，优选为150-250℃，最优选为160-230℃。
在一个优选的实施方案中，本发明的方法用于生产包括被一个或多个层包围的导电体(即一条或多条线)的电缆，其中至少一个层包含交联的乙烯系(共)聚合物。优选地，交联的乙烯系(共)聚合物为绝缘层的一部分和/或为所述电缆的外衣层。
该电缆生产包括优选通过(共)挤出在导体上施加一个或多个包含聚合物组合物的层的步骤，其中至少一个层包含交联的乙烯系(共)聚合物。如果电缆必须包含两个或更多个层，则各层可在独立的步骤中挤出，或者两个或更多个所述层可在同一挤出步骤中共挤出。
根据本实施方案，官能化的乙烯系(共)聚合物、有机过氧化物和任何其他任选组分可在引入挤出机之前在混合机中混合。或者，可将它们分别添加至挤出机中并在其中混合。在挤出机中，混合物经历升高的温度(通常高于聚合物的熔点)，并在导体上(共)挤出以形成电缆层。
在形成电缆层之后，使聚合物在140-300℃，优选150-250℃，最优选160-230℃的温度下交联。在交联步骤期间，压力优选为至多20巴，更优选为至多13巴，最优选为10-15巴。气氛优选为惰性的，例如为氮气或饱和蒸汽。然后，优选将交联的电缆在加压条件下在冷却介质如N2、油或水中冷却。
实施例
实施例1：LDPE的改性
将LDPE(BPD2000，获自Ineos)与0、1或2phr柠康苯磺酰基叠氮在ThermoScientificHaakePTW16，40L/D实验室挤出机上一起挤出。挤出机混合区域中的温度为180-230℃，螺杆速度为150rpm，产量为1kg/hr，在挤出机中的停留时间为约90秒。这些设置足以完全分解所述叠氮化物，如FT-IR光谱测定法所证实的那样。
在挤出后，将接枝的LDPE挤出物切断，并在60℃下以不同剂量水平将液体过氧化叔丁基异丙苯(T，获自AkzoNobel)添加至切断的聚合物珠粒中，从而允许过氧化物快速且均匀地掺入聚合物颗粒中。在LDPE上吸收过氧化物之后，在180℃下使用流变仪(Alfatechnologies流变仪MDR2000)评价固化速率和交联密度。
在独立的实验中，通过将特定量的交联LDPE浸入回流二甲苯(约为140℃)中以测定不溶物(＝凝胶)含量来测量交联LDPE的凝胶百分数。这是测定最终固化状态的工业方法。
结果示于下表中。记录的为固化速率的指标：t5、t50和t90，这些是达到最终最高交联密度的5％、50％和90％所需的时间。在流变仪中测得的Δ扭矩(ΔS)用作交联LDPE的交联密度的指标。
表1
| 对比 | 1 | 2 | 对比 | 3 | 4 | 对比 | 5 | 6 | 对比 | 7 | 8 | |
| 叠氮化物(phr) | 0 | 1 | 2 | 0 | 1 | 2 | 0 | 1 | 2 | 0 | 1 | 2 |
| 过氧化物(phr) | 0.5 | 0.5 | 0.5 | 1 | 1 | 1 | 1.6 | 1.6 | 1.6 | 2 | 2 | 2 |
| t5(分钟) | 0.9 | 0.5 | 0.5 | 0.8 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.8 | 0.5 | 0.4 |
| t50(分钟) | 3.3 | 1.8 | 1.7 | 3.0 | 1.3 | 1.3 | 2.9 | 2.1 | 1.5 | 2.9 | 2.1 | 1.6 |
| t90(分钟) | 10.2 | 7.3 | 7.5 | 8.8 | 6.1 | 6.0 | 8.6 | 7.2 | 6.1 | 8.5 | 7.0 | 6.1 |
| ΔS(Nm) | 0.15 | 0.26 | 0.24 | 0.26 | 0.53 | 0.54 | 0.44 | 0.62 | 0.74 | 0.57 | 0.68 | 0.84 |
| 凝胶％ | 69 | 81 | 81 | 80 | 90 | 91 | 89 | 92 | 93 | 91 | 94 | 96 |
从所述实验可以观察到，所述叠氮化物的接枝具有两个优点：提高固化速率(缩短t90)和提高固化水平(ΔS和凝胶％增大)。所述柠康酰叠氮化物含量的影响取决于过氧化物的剂量水平。在低过氧化物剂量水平下，柠康酰叠氮化物水平从1phr增加至2phr并不导致性质进一步提高。当提高过氧化物水平时，柠康酰叠氮化物的增加对交联密度的影响变得更明显。这表明可精细调整柠康酰叠氮化物的量和过氧化物的量以允许控制固化速率和交联密度。
实施例2：EPM的改性
用实施例1中所用的柠康酰叠氮化物改性无不饱和键的乙烯-丙烯共聚物(EPM)。为了实现该目的，将含有碳黑填料和油(组成参见表2)的EPM基化合物与2份/100份橡胶(phr)的柠康苯磺酰基叠氮混合，并在150-180℃下在班伯里型密闭式混合机中热处理，以允许所述叠氮化物接枝至EPM上。
在用所述叠氮化物改性EPM化合物之后，使用双辊研磨机将3phr的14-40B-pd(获自AkzoNobel，＝于碳酸钙上的40重量％双(叔丁基过氧化异丙基)苯，对应于0.4重量％的纯过氧化物)与EPM混合。
通过在170℃加热而固化EPM。
使用流变测定法(Alfatechnologies流变仪MDR2000)评价固化速率和交联密度。结果示于表2中。
作为对比实验，将未改性的EPM与过氧化物混合并以相同方式交联。
表2
在流变仪中测得的Δ扭矩(ΔS)为交联EPM的交联密度的指标。可观察到所述叠氮化物的接枝具有两个优点：提高固化速率(较短的t90)和提高固化水平(提高ΔS)。
Claims (15)
1.用于官能化乙烯系(共)聚合物的方法，包括如下步骤：使乙烯系(共)聚合物在100-250℃的温度下与式(I)的叠氮化物接触：
其中Y为：
m为0或1，n为0或1，n+m＝1或2，且X为具有1-12个碳原子的直链或支化脂族或芳族烃结构部分，其任选包含杂原子。
2.如权利要求1或2的方法，其中所述乙烯系(共)聚合物为LDPE。
3.如权利要求1或2的方法，其中所述乙烯系(共)聚合物为EPM。
4.如前述权利要求中任一项的方法，其中所述叠氮化物选自4-(3-甲基-2,5-二氧代-2,5-二氢-1H-吡咯-1-基)苯磺酰基叠氮(也称为柠康酰亚胺苯磺酰基叠氮)和2-(3-甲基-2,5-二氧代-2,5-二氢-1H-吡咯-1-基)乙基羰酰叠氮酸酯(也称为柠康酰亚胺-C2-叠氮甲酸酯)。
5.如前述权利要求中任一项的方法，其中所述乙烯系(共)聚合物与所述叠氮化物在140-230℃的温度下接触。
6.如前述权利要求中任一项的方法，其中所述叠氮化物以0.1-5phr的量与所述乙烯系(共)聚合物混合。
7.用于改性乙烯系(共)聚合物的方法，包括如下步骤：
-根据权利要求1-6中任一项的方法制备官能化的乙烯系(共)聚合物，
-使所述官能化的乙烯系(共)聚合物与有机过氧化物接触以形成聚合物/过氧化物混合物，和
-在140-300℃的温度下加热所述聚合物/过氧化物混合物。
8.如权利要求7的方法，其中在加热之前，将所述聚合物/过氧化物混合物成型。
9.如权利要求8的方法，其中所述聚合物/过氧化物混合物通过挤出成型。
10.如权利要求7或8的方法，其中所述有机过氧化物为二烷基过氧化物或三氧杂环庚烷。
11.如权利要求10的方法，其中所述过氧化物选自3,3,5,7,7-五甲基-1,2,4-三氧杂环庚烷、2,5-二甲基-2,5-二(叔丁基过氧基)己炔-3、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、二(叔丁基过氧异丙基)苯、过氧化二异丙苯和过氧化叔丁基异丙苯。
12.可通过权利要求1-6中任一项的方法获得的官能化的乙烯系(共)聚合物。
13.可通过权利要求7-11中任一项的方法获得的改性的乙烯系(共)聚合物。
14.如权利要求12的官能化的乙烯系(共)聚合物用于制造电力电缆的用途。
15.电力电缆，其包括一个或多个如权利要求13的改性的乙烯系(共)聚合物的层。
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| EP13191976.3 | 2013-11-07 | ||
| EP13191976 | 2013-11-07 | ||
| PCT/EP2014/073418 WO2015067533A1 (en) | 2013-11-07 | 2014-10-31 | Process for modifying ethylene-based polymers and copolymers |
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| CN105705563A true CN105705563A (zh) | 2016-06-22 |
| CN105705563B CN105705563B (zh) | 2018-03-23 |
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| EP (1) | EP3066151A1 (zh) |
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| TW (1) | TWI627197B (zh) |
| WO (1) | WO2015067533A1 (zh) |
| ZA (1) | ZA201602832B (zh) |
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| ES2660495T3 (es) * | 2013-11-07 | 2018-03-22 | Akzo Nobel Chemicals International B.V. | Proceso para modificar polímeros |
| US10471690B2 (en) * | 2014-12-30 | 2019-11-12 | Dow Global Technologies Llc | Sulfonylazide derivative for tie layer |
| KR20170134719A (ko) | 2015-04-24 | 2017-12-06 | 아크조 노벨 케미칼즈 인터내셔널 비.브이. | 중합체의 관능화 방법 |
| MX2017013392A (es) | 2015-04-24 | 2018-01-30 | Akzo Nobel Chemicals Int Bv | Proceso para modificar polimeros. |
| EP3728441B1 (en) * | 2017-12-18 | 2023-03-01 | Borealis AG | Crosslinkable composition without antioxidant and beneficial methane formation with reduced crosslinking |
| US11555083B2 (en) | 2017-12-18 | 2023-01-17 | Borealis Ag | Cable made from crosslinkable composition without antioxidant and with beneficial methane formation |
| KR20200091442A (ko) | 2017-12-18 | 2020-07-30 | 보레알리스 아게 | 폴리에틸렌을 포함하는 중합체 조성물 |
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- 2014-10-31 CA CA2928332A patent/CA2928332A1/en not_active Abandoned
- 2014-10-31 WO PCT/EP2014/073418 patent/WO2015067533A1/en active Application Filing
- 2014-10-31 KR KR1020167014339A patent/KR20160084842A/ko not_active Application Discontinuation
- 2014-10-31 MX MX2016005599A patent/MX2016005599A/es unknown
- 2014-10-31 US US15/034,720 patent/US9688783B2/en not_active Expired - Fee Related
- 2014-10-31 CN CN201480058504.7A patent/CN105705563B/zh not_active Expired - Fee Related
- 2014-10-31 RU RU2016121181A patent/RU2671352C2/ru not_active IP Right Cessation
- 2014-10-31 JP JP2016527298A patent/JP6306176B2/ja not_active Expired - Fee Related
- 2014-11-06 TW TW103138589A patent/TWI627197B/zh not_active IP Right Cessation
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2016
- 2016-04-25 ZA ZA2016/02832A patent/ZA201602832B/en unknown
- 2016-04-28 SA SA516371025A patent/SA516371025B1/ar unknown
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| US4329556A (en) * | 1979-05-16 | 1982-05-11 | Siemens Aktiengesellschaft | N-Azidosulfonylaryl-maleinimides |
| US6313314B1 (en) * | 2000-04-18 | 2001-11-06 | Industrial Technology Research Institute | Method for preparing azide photo-initiators |
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| Publication number | Publication date |
|---|---|
| JP6306176B2 (ja) | 2018-04-04 |
| WO2015067533A1 (en) | 2015-05-14 |
| ZA201602832B (en) | 2017-04-26 |
| JP2017500379A (ja) | 2017-01-05 |
| KR20160084842A (ko) | 2016-07-14 |
| SA516371025B1 (ar) | 2017-10-24 |
| US9688783B2 (en) | 2017-06-27 |
| US20160347876A1 (en) | 2016-12-01 |
| TW201522401A (zh) | 2015-06-16 |
| RU2016121181A3 (zh) | 2018-06-06 |
| CN105705563B (zh) | 2018-03-23 |
| RU2016121181A (ru) | 2017-12-08 |
| RU2671352C2 (ru) | 2018-10-30 |
| TWI627197B (zh) | 2018-06-21 |
| CA2928332A1 (en) | 2015-05-14 |
| MX2016005599A (es) | 2016-07-21 |
| EP3066151A1 (en) | 2016-09-14 |
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