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CN109996834B - 过氧化物母料 - Google Patents

过氧化物母料 Download PDF

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CN109996834B
CN109996834B CN201780071881.8A CN201780071881A CN109996834B CN 109996834 B CN109996834 B CN 109996834B CN 201780071881 A CN201780071881 A CN 201780071881A CN 109996834 B CN109996834 B CN 109996834B
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peroxide
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ethylene
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CN109996834A (zh
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W·J·E·贝克
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Nouryon Chemicals International BV
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Abstract

本发明涉及一种过氧化物母料，其包含：‑15‑55重量％的一种或多种有机过氧化物，‑15‑45重量％的一种或多种至少两种不同单体的共聚物，其中第一单体为乙烯或丙烯，第二单体为包含至少四个碳原子和任选地杂原子的乙烯基单体，‑6‑70重量％的至少两种类型的填料‑1型填料和2型填料‑各自具有不同BET表面积：(i)1型填料以3‑30重量％的浓度存在于该母料中且具有大于100m2/g的BET表面积；(ii)2型填料以3‑40重量％的浓度存在于该母料中且具有100m2/g或更小的BET表面积；其中该母料具有挤出物形式。

Description

过氧化物母料
技术领域
本发明涉及一种过氧化物母料、其制备和在聚合物的交联和改性中的用途。
背景技术
弹性体，包括热塑体、弹性热塑体、聚烯烃，和橡胶，例如聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯共聚物(EPM)、乙烯-辛烯共聚物(POE)、乙烯-丙烯二烯橡胶(EPDM)和丁二烯-丙烯腈共聚物通常均低价、广泛使用，且具有允许宽范围用途的优异物理性能。在用有机过氧化物处理时，弹性体可经交联或其熔体性能可经改性，例如通过降解或通过形成长链分支。
出于安全考虑，在交联或改性过程中通常不允许纯有机过氧化物。此外，考虑到有效交联所需的少量过氧化物，在弹性体中非常难以获得纯过氧化物的均匀分布。非均匀分布导致非均匀产物，其明显是不希望的。
代替纯过氧化物，通常使用有机过氧化物的稀释形式。该类稀释形式的实例为过氧化物在惰性填料中的粉末混合物和所谓的母料(其中过氧化物分散于聚合基质)。
与粉末配制剂相比，使母料在弹性体中均匀分散需要较少时间且母料可在不产生灰尘下处理。
常规母料基于乙烯丙烯共聚物(EPM)或乙烯丙烯二烯共聚物(EPDM)，且使用密闭混合器或开口的双辊研机来制备，然后使用成粒机将母料压延并成型。这为劳动密集且并非非常成本有效的两步或三步程序。
挤出为制备母料的少得多的劳动密集且更成本有效的方式。然而，不幸地，由于合适的EPM和EPDM树脂仅为成包的，而不是呈颗粒或丸粒形式，因此挤出不用于商业实践。无法将包加入挤出机且研磨EP(D)M包至适于供入挤出机的大小不具有经济吸引力，因为经重设大小/经研磨的EP(D)M易于结块，从而限制其用于短时间范围。且尽管该问题可在一定程度上受限于加入防结块剂，但这不仅增加母料成本，而且其使母料不适用于某些应用。
发明内容
因此，本发明的目的为提供一种制备过氧化物母料的挤出方法和提供一种呈挤出物形式的过氧化物母料。
另一目的为提供适用于分散在弹性体，特别是EPM和EPDM中的母料。
该目的通过提供母料实现，所述母料包含：
-15-55重量％的一种或多种有机过氧化物，
-15-45重量％的一种或多种至少两种不同单体的共聚物，其中第一单体为乙烯或丙烯，第二单体为包含至少四个碳原子和任选地杂原子的乙烯基单体，
-6-70重量％的至少两种类型的填料-1型填料和2型填料-各自具有不同BET表面积：
(i)1型填料以3-30重量％的浓度存在于该母料中且具有大于100m2/g的BET表面积；
(ii)2型填料以3-40重量％的浓度存在于该母料中且具有100m2/g或更小的BET表面积；
其中该母料具有挤出物形式。
具体实施方式
可通过将一种或多种过氧化物、一种或多种共聚物的颗粒或丸粒和至少两种填料供入挤出机中且挤出该组合以产生组分的均匀混合物制备这些母料。
母料具有挤出物的形式，这是指其已通过挤出制备，通常然后切割或粒化出自挤出机模的条或带。
存在于母料中的有机过氧化物的总量基于母料总重量为15-55重量％，优选地30-52重量％，更优选地35-50重量％，最优选地35-45重量％。
合适的有机过氧化物的实例为过氧化二异丙苯、二(叔丁基过氧异丙基)苯、1,1-二(叔丁基过氧基)-3,3,5-三甲基-环己烷、4,4-二(叔丁基过氧基)戊酸丁基酯、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己炔-3、过苯甲酸叔丁基酯、叔丁基过氧化2-乙基己基碳酸酯、3,6,9-三乙基-3,6,9-三甲基-1,4,7-三过氧壬烷、叔丁基过氧化3,5,5-三甲基己酸酯及其混合物。
优选过氧化物为过氧化二异丙苯、二(叔丁基过氧异丙基)苯、1,1-二(叔丁基过氧基)-3,3,5-三甲基环己烷、4,4-二(叔丁基-过氧基)戊酸丁基酯、2,5-二甲基-2,5-二(叔丁基过氧基)己烷和叔丁基过氧化3,5,5-三甲基己酸酯。
母料中存在的共聚物的总量基于母料总重量为15-45重量％，更优选地20-40重量％，最优选地25-35重量％。
共聚物优选地具有1g/10min或更少的熔融流动指数(MFI；在190℃下测量，2.16kg；ASTM D1238)。这允许强挤出物条的生产，其在水浴中冷却之后可容易地切碎。
适用于本发明母料的共聚物的实例为乙烯-乙酸乙烯酯共聚物，(i)乙烯或丙烯与(ii)1-丁烯、1-己烯和/或1-辛烯的共聚物，乙烯与丙烯酸酯的共聚物，苯乙烯乙烯丁烯氢化共聚物，苯乙烯乙烯丙烯氢化共聚物。
在一个优选实施方案中，共聚物为乙烯乙酸乙烯酯共聚物或(i)乙烯或丙烯与(ii)1-丁烯或1-辛烯的共聚物。甚至更优选(i)乙烯或丙烯与(ii)1-丁烯或1-辛烯的共聚物。该类共聚物通常称为聚烯烃弹性体(POE)。其通常通过茂金属催化制备。这些共聚物为半结晶的，含有无定形相和结晶相，各相可无规分布或呈嵌段构象。
POE可作为自由流动丸粒形式市购。合适POE的实例为EngageTM聚烯烃弹性体(购自Dow)、TAFMERTM系列DF、A和XM(购自Mitsui)、QueoTM塑性体(购自Borealis)和ExactTM塑性体(购自ExxonMobil)。
母料含有6-70重量％，优选地13-45重量％，最优选地22-37重量％的至少两种具有不同BET表面积的填料：1型填料和2型填料。
1型填料表示所谓的补强填料，其用于吸收过氧化物，协助过氧化物分散于弹性体中，并防止过氧化物渗出母料。这些填料还影响挤出物的硬度、其抗结块性及其分散于聚合物中的容易性。
1型填料具有大于100m2/g，优选地大于110m2/g，最优选地大于120m2/g的BET表面积。BET表面积是指根据熟知的Brunauer-Emmett-Teller方法通过氮吸附测量的表面积。
可用作1型填料的合适材料的实例为二氧化硅、炭黑及其组合。二氧化硅为优选的材料。
母料中存在的1型填料的量基于母料总重量为3-30重量％，更优选地3-15重量％，最优选地7-12重量％。
具有其有限表面积的2型填料包括所谓的非补强填料和半补强填料。2型填料用于提高产量、降低成本和增强热导率，从而允许较低操作温度。后者对安全地加工有机过氧化物是重要的。
这些低表面积填料通常比1型补强填料便宜。其还较少磨蚀的且因此减小挤出机内部的摩擦和磨损。其还比高表面积填料致密，其有助于易于加料和低能量压缩。此外，其热膨胀较低，这降低聚合物熔体的体积。在恒定加工条件下，这导致较低熔体压力以及较低螺杆驱动扭矩。因此，可增加螺杆速度，且从而可增加输出。
此外，其热导率高，这导致热能通过聚合物熔体快速分布，从而加速在挤出期间聚合物的熔融及其后的冷却。这还有助于更均匀的熔体，具有较少局部热点，导致更均匀的熔融粘度。
2型填料具有小于100m2/g，优选地小于50m2/g，最优选地小于10m2/g的BET表面积。
可用作2型填料的合适的材料的实例包括碳酸钙、粘土、硫酸钡及其组合。优选的材料为碳酸钙。
母料中存在的2型填料的量基于母料总重量为3-40重量％，更优选地10-30重量％，最优选地15-25重量％。
本发明的母料可进一步含有选自以下的组的一种或多种助剂：抗氧化剂、防焦剂、UV稳定剂、阻燃剂、颜料、染料、加工油、润滑剂、发泡剂(例如偶氮二甲酰胺或充气热塑性微球体，例如
Figure GDA0003336773710000051
)和通常用于弹性体中的其他添加剂。这些产物以常规量使用，条件为其不会不利影响母料的性能和储存稳定性。通常，其占总母料的5重量％或更少。
通过挤出制备本发明母料。在一个优选实施方案中，使用双螺杆挤出机。
将呈颗粒或丸粒形式的共聚物加入挤出机。优选地，加入共聚物作为自由流动丸粒或颗粒。
挤出机的温度控制在50-95℃，更优选地60-90℃，最优选地70-85℃范围内。若有机过氧化物在室温下为固体，则挤出温度优选在过氧化物的熔融温度以上，从而允许过氧化物吸收于填料上。若将挤出机加热至95℃以上的温度，则过氧化物的安全挤出成为问题。
在一个实施方案中，经由主挤出机进料同时加入母料的所有成分。若所有成分具有类似大小和形状，则可使用单个进料器。在另一实施方案中，经由相同进料区中的单独进料器加入共聚物丸粒或颗粒。在再一实施方案中，经由第一进料器加入共聚物，经由第二进料器加入过氧化物，并经由第三和任选地第四进料器加入填料，所有进料器处于相同进料区中或处于单独进料区中。
可将过氧化物如此或以稀释形式加入挤出机。其可在溶剂中稀释或混合或吸附于固体稀释剂上。若在加入挤出机时过氧化物或其稀释物处于液态，则可使用液体加料系统(例如泵)将其加入挤出机。可将过氧化物加入与其他成分中的一种或多种相同的进料区，或可将其加入更下游进料区。
可通过简单地混合过氧化物和稀释剂使用固体稀释剂稀释过氧化物，条件为过氧化物在室温下为固体。若过氧化物在室温下为液体，则可将过氧化物喷于固体稀释剂上。还可首先使固体过氧化物熔融且然后将其喷于固体稀释剂上。作为固体稀释剂，可使用1型和/或2型填料。
挤出机的螺杆速度通常在50至250rpm范围内变化。优选地将成分以导致螺杆的进料不足的速率供入挤出机。这防止机筒内部的成分累积。
挤出之后，优选地尽可能快地冷却离开挤出机模的条或带；这将防止过氧化物“出汗”且将辅助挤出的条/带的切割或粒化。
可在水浴中进行挤出物的冷却，但优选通过使用(经冷却)气流进行。若使用水浴，则需要使用干或冷空气干燥切碎的挤出物，从而防止所得颗粒在该干燥过程中结块。
挤出物优选地具有圆柱形尺寸，其中直径为1-10mm且长度为3-20mm，更优选地直径为1-5mm且长度为3-5mm，最优选地直径为1-3mm且长度为3-5mm。挤出物还可具有其他形状如立方体形状。
本发明的母料适用于涉及使用有机过氧化物处理聚合物的各种应用。
一个尤其优选的应用为如下弹性体的交联-包括热塑体、弹性热塑体、聚烯烃和橡胶-例如EPM、EPDM、乙烯-乙酸乙烯酯共聚物、天然橡胶、聚丁二烯、聚异戊二烯、聚丁烯、聚异丁烯、聚丙烯酸酯、苯乙烯-丁二烯共聚物、丙烯腈-丁二烯共聚物、氢化丙烯腈-丁二烯共聚物、丙烯腈-丁二烯-苯乙烯三元共聚物、氟化橡胶、硅氧橡胶、氨基甲酸酯橡胶、聚乙烯、乙烯-α-烯烃共聚物和氯化聚乙烯。
尤其优选其在EPM和EPDM的交联中的用途。本发明母料可在非常短时间范围内均匀地分散于EPM和EPDM中，从而允许快速加工时间。
本发明的母料相对于待交联的弹性体的重量通常以0.2-20重量％，更优选地1-10重量％的量使用。
可使用任何常规方法进行弹性体的交联。在该类方法中，待交联的弹性体通常首先均匀地与惰性填料如滑石和碳酸钙和/或炭黑和加工油混合，且然后与所需量的母料混合或捏合。合适的混合设备包括Banburry类型密闭混合器。由于弹性体粘度和由填料引起的摩擦，混合器内部的温度将快速上升。为了避免提前交联，在接近混合循环结束时加入过氧化物母料。其不利的一面为仅存在过氧化物母料可用的有限混合时间。这说明快速和均匀分散于弹性体中的母料的重要性。
在后续交联步骤中，通常将混合物在模具中加热至140-200℃并保持5-30分钟。
本发明母料的其他应用包括聚乙烯的交联，聚乙烯或聚丙烯的官能化，改性聚乙烯以增加长链支化，聚丙烯的降解和热塑性硫化物(TPV)的生产。后者涉及EPDM的组合交联和聚丙烯的有限降解。本发明母料快速分散至EPDM中允许交联与降解之间的更好平衡。
实施例
实施例1
制备两种本发明母料。第一母料包含过氧化二异丙苯(
Figure GDA0003336773710000071
购自AkzoNobel)；第二母料包含二(叔丁基过氧异丙基)苯(
Figure GDA0003336773710000072
购自AkzoNobel)。
所用共聚物为乙烯与1-辛烯的POE共聚物(EngageTM 8180，购自Dow)。1型填料为具有125m2/g的BET表面积的二氧化硅。2型填料为具有5m2/g的BET表面积的CaCO3。
这些母料通过挤出使用75℃的机筒温度和100rpm的螺杆速度制备。挤出之后，将所产生的带冷却且切碎成颗粒。
在双辊磨机上制备类似但相当的母料。前辊的温度范围为开始时的60℃至生产期间的50℃。后辊的温度范围为开始时的75℃至生产期间的70℃。夹持点设定为1mm，冷却后产生4mm厚的片。在冷却和静置一周之后，将片切割成10×8×4mm片段。
测试所得母料在EPDM中的分散行为。将该行为与含有相同过氧化物但基于EPM且使用双辊磨机
Figure GDA0003336773710000073
BC-40MB-GR和
Figure GDA0003336773710000074
14-40MB-GR-S代替挤出机制备的两种商业AkzoNobel母料的行为相比较。
通过在双辊磨机上在60℃下混合100重量份的EPDM(
Figure GDA0003336773710000081
购自Versalis)、70重量份的炭黑N-550和70重量份的炭黑N-772(均购自Cabot)、70重量份的加工油(Catanex D 579，购自Shell)和10重量份的母料来测试分散行为。
碳/EPDM系统为黑色；母料为白色。因此，可通过目视检验观测母料在橡胶中的分散。要求实现母料在EPDM基料中的视觉全分散的混合时间列于表1中，且显示本发明母料比在双辊磨机上制备的母料在EPDM中分散快得多。
表1
Figure GDA0003336773710000082
使用表2中所列的材料、量和条件在流变仪中测试母料的交联行为。其显示通过使用本发明母料所获得的交联密度和机械性能与使用商业母料所获得的那些相当。
表2
Figure GDA0003336773710000091
实施例2
重复实施例1，不同的是使用不同共聚物：
-EngageTM HM7387，购自Dow(乙烯与1-丁烯的POE共聚物)
Figure GDA0003336773710000101
购自DuPont(乙烯乙酸乙烯酯共聚物)
该实施例的所有母料在挤出机中制备。
结果显示于表3中。
表3
Figure GDA0003336773710000102
实验本发明3和对比2和3和实验本发明4和对比4显示填料，尤其是类型1填料优选用于获得合适的挤出物。

Claims (16)

1.过氧化物母料，包含：
-15-55重量％的一种或多种有机过氧化物，
-15-45重量％的一种或多种至少两种不同单体的共聚物，其中第一单体为乙烯或丙烯，第二单体为包含至少四个碳原子和任选地杂原子的乙烯基单体，
-6-70重量％的至少两种类型的填料-1型填料和2型填料-各自具有不同BET表面积：
(i)1型填料以3-30重量％的浓度存在于所述母料中且具有大于100m2/g的BET表面积；
(ii)2型填料以3-40重量％的浓度存在于所述母料中且具有100m2/g或更小的BET表面积；
其中所述母料具有挤出物的形式。
2.根据权利要求1的过氧化物母料，其包含30-52重量％的一种或多种过氧化物。
3.根据权利要求1或2的过氧化物母料，其中所述有机过氧化物选自由如下组成的组：过氧化二异丙苯、二(叔丁基过氧异丙基)苯、1,1-二(叔丁基过氧基)-3,3,5-三甲基环己烷、4,4-二(叔丁基过氧基)戊酸丁基酯、2,5-二甲基-2,5-二(叔丁基过氧基)己烷和叔丁基过氧化3,5,5-三甲基己酸酯。
4.根据权利要求1或2的过氧化物母料，其中所述共聚物选自乙烯-乙酸乙烯酯共聚物，(i)乙烯或丙烯与(ii)1-丁烯、1-己烯和/或1-辛烯的共聚物，乙烯与丙烯酸酯的共聚物，苯乙烯乙烯丁烯氢化共聚物，苯乙烯乙烯丙烯氢化共聚物。
5.根据权利要求4的过氧化物母料，其中所述共聚物为(i)乙烯或丙烯与(ii)1-丁烯和/或1-辛烯的共聚物。
6.根据权利要求4的过氧化物母料，其中所述共聚物为乙烯-乙酸乙烯酯共聚物。
7.根据权利要求1或2的过氧化物母料，其包含3-15重量％的1型填料和10-30重量％的2型填料。
8.根据权利要求1或2的过氧化物母料，其中1型填料具有大于150m2/g的BET表面积。
9.根据权利要求1或2的过氧化物母料，其中1型填料选自炭黑、二氧化硅及其组合。
10.根据权利要求1或2的过氧化物母料，其中2型填料具有小于10m2/g的BET表面积。
11.根据权利要求1或2的过氧化物母料，其中2型填料选自碳酸钙、硫酸钡、粘土及其组合。
12.一种制备根据权利要求1-11中任一项的过氧化物母料的方法，其中将所述一种或多种有机过氧化物、所述一种或多种共聚物的颗粒或丸粒和所述至少两种类型的填料加入挤出机且在50-95℃的温度下挤出。
13.根据权利要求12的方法，其中在70-85℃的温度下进行挤出。
14.一种使弹性体交联的方法，包括以下步骤：将根据权利要求1-11中任一项的过氧化物母料分散于待交联的弹性体中。
15.根据权利要求14的方法，其中所述弹性体为EPM或EPDM。
16.根据权利要求1-11中任一项的过氧化物母料在聚乙烯的交联、改性或官能化，聚丙烯的降解或官能化或热塑性硫化物的生产中的用途。
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