CN107108999A - 含有不存在乙烯基的线性超高分子量聚二甲基硅氧烷的聚合物母料 - Google Patents
含有不存在乙烯基的线性超高分子量聚二甲基硅氧烷的聚合物母料 Download PDFInfo
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Abstract
本发明涉及包括线性超高分子量不含乙烯基的聚二甲基硅氧烷的聚合物母料及其作为添加剂在制备配混物中的用途。
Description
本发明涉及包括线性超高分子量不含乙烯基的聚二甲基硅氧烷的聚合物母料及其作为添加剂在制备配混物中的用途。
由聚烯烃和有机聚硅氧烷组成的混合物或聚合物组合物在现有技术中长期以来被称为术语“母料”或“共混物”，并在制备热塑性有机聚合物混合物(即所谓的“配混物”)中被用作添加剂或加工助剂。
举例而言，WO2014/044759A1描述了聚烯烃和有机聚硅氧烷的共混物的制备，所述有机聚硅氧烷的聚合度大于4000并带有至少2个诸如乙烯基的官能团。
EP1153975B1描述了热塑性树脂的制备，其中使用了两种共混物。第一共混物由热塑性树脂和有机聚硅氧烷组成，第二共混物是与包含乙烯基或其它烯基的有机聚硅氧烷化学键连的热塑性树脂。
EP0710692A2描述了将聚有机硅氧烷键接到聚丙烯上的方法。为此，使用了具有至少一个硅氧烷键接的乙烯基或其它烯基的聚有机基硅氧烷。
EP0826737B2描述了具有相互作用性的二有机聚硅氧烷的有机聚合物的改性。这些聚硅氧烷的平均分子量Mn至少为10.000g/mol，并包括相互作用的基团，例如羟基、氨基或乙烯基。
EP0826727A1描述了用相互作用性的二有机聚硅氧烷改性的低密度聚乙烯；这些聚硅氧烷的平均分子量Mn至少为38.000g/mol，并包含羟基、氨基或乙烯基。
EP0722981A2描述了一种包含平均分子量至少为10.000g/mol的羟基官能的二有机聚硅氧烷的聚烯烃制剂。
US3865897描述了一种制备聚烯烃和聚二有机硅氧烷共混物的方法，其中使用了具有乙烯基的高分子量聚二甲基硅氧烷。
现有技术的母料在配混物中被用作添加剂，以便通过其中的聚硅氧烷对所述配混物的性能特性产生影响，例如降低摩擦系数或增加疏水性、耐磨损性、耐磨性、或耐划痕性。然而，这些效果并不是总能够达到预期。因此，需要进一步改善这些配混物的性能特征。
因此，本发明的目的是提供用于配混物的母料，其可以改善配混物的诸如上述的性能特征。
令人惊奇的是，该目的通过根据本发明的聚合物母料得以实现。
根据本发明的聚合物母料包含
A)至少一种热塑性聚丙烯均聚物和
B)至少一种具有三甲基硅基端基的线性聚二甲基硅氧烷特征在于
A)熔体流动指数为5-20g/10min，根据DIN ISO 1133在230℃/2.16kg下测定，和
B)平均分子量Mw为至少200 000g/mol，且不含乙烯基。
根据本发明的聚合物母料优选包含40-70重量％的A)和30-60重量％的B)，特别优选45-55重量％的A)和45-55重量％的B)。
所述热塑性聚丙烯均聚物A)的熔体流动指数(MFI)为5-20g/10min。这是根据DINISO 1133在230℃/2.16kg下测定的。
组分A)很早就具有商业产品。取决于制备方法或目的应用，A)以已经包含下述添加剂，例如用于稳定其的添加剂。这些添加剂包括加工和长期稳定剂，如酚类抗氧化剂，亚磷酸酯，亚膦酸酯，任选的增效剂如硫醚和酸受体如Ca或Zn的硬脂酸酯。这些添加剂是本领域技术人员长期以来已知的，并例如描述在教科书中：Taschenbuch derKunststoff-Additive第三版，Hanser Verlag 1989；ISBN 3-4446-15627-5第50页及之后。
A)可以单独使用或作为至少2种热塑性聚丙烯均聚物的混合物使用。优选单独使用A)。
组分B)是本领域技术人员已知的，并且可以市购得到。B)是线性甲基官能的超高分子量聚二甲基硅氧烷，其平均分子量Mw为至少200000g/mol；优选至少300 000g/mol，且粘度优选至少是10 000 000mPas，特别优选至少是20 000 000mPas。
B)可以单独使用或作为至少2种线性甲基官能的超高分子量聚二甲基硅氧烷的混合物使用。优选单独使用B)。
根据本发明的聚合物母料的制备是通过在A)和B)都是液相的温度下混合二者而实现的。这可以在，例如，如本领域技术人员已知的，市售的共旋转双螺杆挤出机中进行。这些螺杆的长径比(L/D比)优选至少为30，特别优选至少为35。
优选在150-250℃的温度下将组分B)掺入组分A)的熔体，特别优选170-230℃。混合后，将该聚合物母料在例如水浴中冷却。然后可将其造粒以便进一步加工。
根据本发明的聚合物母料作为添加剂或加工助剂被用于热塑性配混物的制备中。显而易见，令人惊奇的是，与使用包含相互作用性有机聚硅氧烷的母料的现有技术所制备的模制品相比，由聚丙烯配混物制成并使用根据本发明的聚合物母料作为添加剂的汽车内部用的模制品的表面具有显著更好的耐划痕性。
实施例
下述实施例用于阐明本发明而不限制所述发明。除非另有说明，主要的压力为1013mbar的标准压力。
制备聚合物母料的实施例
实施例1(发明的)
将熔体流动指数为12g/10min(根据DIN ISO 1133在230℃/2.16kg下测定)的粒状聚丙烯均聚物(例如，可从捷克共和国布拉格的Unipetrol得到，商品名为NB1112)在进料区域中以重量法在12kg/h的进料速率下加入到ZSE 27HP双螺杆挤出机(德国纽伦堡的Leistritz)中，其长/径比为40，螺杆直径为27mm。平均螺杆温度为170-210℃。将具有三甲基硅基端基和平均分子量为533.000g/mol的不含乙烯基的线性超高分子量聚二甲基硅氧烷(可从德国慕尼黑的Wacker Chemie AG市购，商品名为Gum)以相同的重量份，类似地在12kg/h的进料速率下计量加入到聚丙烯中。将挤出物在水浴中冷却并造粒。通过Wurtzschmidt分解的元素分析硅测定间接测定了超高分子量聚二甲基硅氧烷的含量，得到了48.2％的含量。
实施例2(发明的)
将熔体流动指数为7g/10min(在230℃/2.16kg下测定)粒状聚丙烯均聚物(例如，可从捷克共和国布拉格的Unipetrol得到，商品名为GB107)在进料区域中以重量法在12kg/h的进料速率下加入到ZSE 27HP双螺杆挤出机(德国纽伦堡的Leistritz)中，其长/径比为40，螺杆直径为27mm。平均螺杆温度为170-210℃。将具有三甲基硅基端基和平均分子量为533.000g/mol的不含乙烯基的线性超高分子量聚二甲基硅氧烷(可从德国慕尼黑的Wacker Chemie AG市购，商品名为Gum)以相同的重量份，类似地在12kg/h的进料速率下计量加入到聚丙烯中。将挤出物在水浴中冷却并造粒。通过Wurtzschmidt分解的元素分析硅测定间接测定了超高分子量聚二甲基硅氧烷的含量，得到了47.9％的含量。
实施例3(非发明的)
使用可市购的母料作为比较性母料：法国Saint Laurent du Pont的Multibase(Dow Corning Company)的DOWMB50-001。该母料由50％的MFI为12的PP均聚物和50％的二甲基乙烯基封端的超高分子量PDMS组成(根据生产商的说明书)。
制备聚丙烯配混物
将四种配混物(表1的组合物)在长/径比为47且螺杆直径为25mm、温度为185-190℃的KraussMaffei Berstorff(德国Hannover)ZE 25双螺杆挤出机上配混，螺杆转速为400rpm，生产量为10kg/h。为此，将所有粒料组分混合得到干混物，并将该干混物重量法计量到挤出机的进料区。同样地，将所有粉末组分混合得到干混物，并将该干混物同样地按重量法计量到挤出机的进料区。将所得挤出物在水浴中冷却并造粒。
下述简称对应于下述反应物：
1.PP MIC＝聚丙烯中度耐冲击共聚物，熔体流动指数为33g/10min(230℃/2.16kg)，根据DIN ISO 1133；由SABIC Europe,Sittard,Netherlands获得。
2.POE＝聚烯烃弹性体；密度0.87g/cm3，熔体流动指数为5g/10min(190℃/2.16kg)，根据DIN ISO 1133；由Dow Chemical Company,Midland,MI,USA获得。
3.Talc＝滑石，由Imerys,Paris,France的3CA获得。
4.LL2590，由Cabot Corporation,Boston,MA,USA获得。
5.MB Ex.1＝实施例1的母料
6.MB Ex.2＝实施例2的母料
7.MB Ex.3＝实施例3的母料(非本发明的)
表1
由配混物A至D制备注塑成型的片材
在Engel ES 600/125注塑成型机上，在190-250℃、注射速率40mm/s、反压力5bar和保持压力25bar下，将这样制备的聚丙烯配混物A-D用于生产具有纹理表面(代表汽车内部应用)且尺寸为8cm x 12cm、厚度为2mm的注塑成型片材。
片材A由配混物A生产。
片材B由配混物B生产。
片材C由配混物C生产。
片材D由配混物D生产。
评估注塑成型片材A-D的表面耐划痕性：短期研究
将所述注塑成型的片材A-D在23℃和50％的相对湿度的标准环境条件下储存2天。储存后，使用来自Erichsen，Hemer，Germany(型号430P-I)的刮痕硬度计，以1000mm/min的速率用10N的力向所述纹理表面施加划痕。这里使用的工具有一个直径为1mm的圆头。在每种情况下，以2mm间隔施加20个平行线，然后在其垂直方向90°的角度上以2mm间隔施加另外20个平行线，从而形成网格状的划痕图案。在每种情况下，通过测量同一片材上的划伤表面和未划伤表面之间的亮度差来量化耐划痕性。所述亮度之间的差异(ΔL)是用Erichsen,Hemer,Germany(型号spectromaster 565-45)的颜色和光泽测量仪测定。结果总结在表2中。
评估注塑成型片材A-D的表面的耐划痕性：长期研究
将所述由A-D制备的注塑成型的片材在80℃存储7天以加速老化。在存储后，根据短期研究方法来评估所述片材。结果总结在表2中。
表2
| 注塑成型的片材 | A | B | C | D |
| ΔL短期研究 | 6.0 | 0.4 | 0.3 | 0.6 |
| ΔL长期研究 | 4.6 | 0.1 | 0.0 | 0.6 |
ΔL值越小，施加的划痕图案就越不明显。因此，ΔL值越小，耐划痕性就越好。
表1的结果表明，由根据实施例1和2的本发明聚合物母料制备的配混物制备的注塑成型片材B和C具有较低的ΔL值，因此实现了更好的耐划痕性。
Claims (5)
1.聚合物母料，其包括：
A)至少一种热塑性聚丙烯均聚物，和
B)至少一种具有三甲基硅基端基的线性聚二甲基硅氧烷，特征在于
A)的熔体流动指数为5-20g/10min，根据DIN ISO 1133在230℃/2.16kg下测定，和
B)的平均分子量Mw至少为200 000g/mol，且不含乙烯基。
2.权利要求1所述的聚合物母料，特征在于其包含40-70重量％的A)和30-60重量％的B)。
3.权利要求1所述的聚合物母料，特征在于其包含45-55重量％的A)和45-55重量％的B)。
4.制备权利要求1-3中任何一项所述的聚合物母料的方法，其在A)和B)都以液相存在的温度下将二者混合。
5.权利要求1-3中任何一项所述的聚合物母料作为添加剂或加工助剂在制备热塑性配混物中的用途。
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| DE102014225685.2A DE102014225685A1 (de) | 2014-12-12 | 2014-12-12 | Polymer-Masterbatch enthaltend lineares, ultrahochmolekulares, vinylgruppenfreies Polydimethylsiloxan |
| DE102014225685.2 | 2014-12-12 | ||
| PCT/EP2015/078000 WO2016091626A1 (de) | 2014-12-12 | 2015-11-30 | Polymer-masterbatch enthaltend lineares, ultrahochmolekulares, vinylgruppenfreies polydimethylsiloxan |
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| CN107108999A true CN107108999A (zh) | 2017-08-29 |
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| US (1) | US20170342221A1 (zh) |
| EP (1) | EP3230366B1 (zh) |
| JP (1) | JP2017534733A (zh) |
| KR (1) | KR20170083118A (zh) |
| CN (1) | CN107108999A (zh) |
| DE (1) | DE102014225685A1 (zh) |
| WO (1) | WO2016091626A1 (zh) |
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| EP3275918A1 (en) * | 2016-07-27 | 2018-01-31 | Clariant Plastics & Coatings Ltd | Compositions comprising polyacrylate-polysilane block copolymers |
| PL243805B1 (pl) * | 2018-01-03 | 2023-10-16 | Albert Groenwald | Koncentrat polisiloksanu w osnowie polimeru termoplastycznego i nieorganicznego napełniacza i sposób wytwarzania koncentratu polisiloksanu |
| JP7346407B2 (ja) | 2018-02-01 | 2023-09-19 | ダウ シリコーンズ コーポレーション | 組成物、それを用いて形成されるポリマー複合体物品、およびその調製方法 |
| ES2887052T3 (es) * | 2018-05-03 | 2021-12-21 | Dow Global Technologies Llc | Hilo de césped artificial con capacidad de procesado y gestión de la fricción mejoradas |
| US11312862B2 (en) | 2019-08-07 | 2022-04-26 | Dow Silicones Corporation | Solid carrier component including a liquid polydiorganosiloxane and methods for preparation and use of the solid carrier component |
| CN112654679B (zh) | 2019-08-07 | 2023-02-03 | 美国陶氏有机硅公司 | 烯基官能化聚二有机硅氧烷组合物及其在形成木塑复合材料中的使用方法 |
| KR102326113B1 (ko) | 2019-08-07 | 2021-11-16 | 다우 실리콘즈 코포레이션 | 액체 폴리오가노실록산을 포함하는 고체 담체 성분, 및 고체 담체 성분의 제조 및 사용 방법 |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE102014225685A1 (de) | 2016-06-16 |
| JP2017534733A (ja) | 2017-11-24 |
| KR20170083118A (ko) | 2017-07-17 |
| EP3230366A1 (de) | 2017-10-18 |
| US20170342221A1 (en) | 2017-11-30 |
| EP3230366B1 (de) | 2018-03-14 |
| WO2016091626A1 (de) | 2016-06-16 |
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