CN1195799C - 积附形成减少的接枝聚合物模塑料 - Google Patents
积附形成减少的接枝聚合物模塑料 Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0053—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping
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Abstract
本发明涉及用于高光泽应用的热塑性接枝聚合物模塑料，它在加工过程中表现出能够减少添加剂从热塑性模塑料中渗出的趋势，并且能减少在模具中积附的累积。
Description
本发明涉及用于高光泽应用的热塑性接枝聚合物模塑料，它在加工过程中表现出能够减少添加剂从热塑性模塑料中渗出的趋势，并且能减少在模具中积附的累积。
接枝聚合物，特别是ABS模塑料，是由下述物质组成的两相塑料：
I.苯乙烯和丙烯腈的热塑性共聚物，其中苯乙烯可以用其它单体例如α-甲基苯乙烯或甲基丙烯酸甲酯部分地或完全地替代；该共聚物有时也称为SAN树脂或基体树脂，它形成了连续相；
II.至少一种ABS型接枝聚合物，它是通过一种或多种I项中所述单体在丁二烯均聚物或共聚物(“接枝基底”)上的接枝反应制备的。该接枝聚合物(“弹性体相”或“接枝橡胶”)形成了在基体树脂中的分散相。
从这些模塑料生产高光泽模制品时重要的一点是市场越来越要求不在模具中(例如全自动塑料加工，注塑制备模制品)产生积附，和可靠地避免由于液体或低粘度成分的渗出而对玷污模制品，这对于高光泽应用是必须的。类似地，在花纹模具上也必须没有积附物粘附，否则便会转移到模制品中。另一方面，ABS模塑料必须表现出优化的性能，特别是其热塑性可加工性和粘度，这常常仅能通过加入往往是液体的特定添加剂来保证。
因此，本发明的目的是提供高光泽应用的接枝聚合物模塑料(优选ABS模塑料)，它具有非常好的加工技术性能，在热塑性加工过程中不出现积附形成。
业已发现，如果从特别制成的成分合成模塑料并且如果满足一定的相容性条件便可实现上述目的。
本发明涉及ABS型热塑性模塑料，它含有
A)5-95％(重量)、优选10-90％(重量)、最优选20-75％(重量)的苯乙烯、α-甲基苯乙烯、丙烯腈、N-取代的马来酰亚胺或其混合物至少一种的热塑性均聚物、共聚物或三元共聚物，
B)5-95％(重量)、优选10-90％(重量)、最优选25-80％(重量)至少一种接枝聚合物，它是
B.1)5-90重量份、优选30-80重量份苯乙烯、α-甲基苯乙烯、丙烯腈、N-取代的马来酰亚胺或其混合物在
B.2)95-10重量份、优选70-20重量份玻璃化转变温度不超过0℃的橡胶上的接枝聚合物，和
C)1-10重量份、优选2-7.5重量份、最优选3-5重量份(每100重量份A+B)至少一种选自内润滑剂、抗静电剂、脱模剂或其混合物的添加剂，
其特征在于，成分A)是通过本体聚合、溶液聚合或悬浮聚合制备的，其低聚物含量不超过1％(重量)、优选不超过0.75％(重量)、最优选不超过0.5％(重量)，成分B)是通过乳液聚合制备的，模塑料中低聚物的总含量(二聚体、三聚体、四聚体)不超过0.8％(重量)、优选不超过0.7％(重量)、最优选不超过0.6％(重量)，在模塑料中添加剂分子量与添加剂量之比(重量百分数)不低于150、优选不低于200、最优选不低于250。
适用于本发明的聚合物A)是用本体聚合、溶液聚合或悬浮聚合(非乳液聚合)生产的苯乙烯、α-甲基苯乙烯、丙烯腈、N-取代的马来酰亚胺或其混合物的树脂状热塑性无橡胶产物，其低聚物含量不超过1％(重量)、优选不超过0.75％(重量)、最优选不超过0.5％(重量)。
优选的聚合物是从苯乙烯/丙烯腈混合物、α-甲基苯乙烯/丙烯腈混合物、苯乙烯/α-甲基苯乙烯/丙烯腈混合物、苯乙烯/N-苯基甲基马来酰亚胺混合物和苯乙烯/丙烯腈/N-苯基马来酰亚胺混合物生产的聚合物。
苯乙烯/丙烯腈共聚物和α-甲基苯乙烯/丙烯腈共聚物是特别优选的聚合物。
这类聚合物是已知的。生产的这些树脂中低聚物含量必须不超过所需的值。在工业上最为常用的热溶液聚合法或本体聚合法，低聚物最好是具有2-4个单体单元的低聚物(关于这方面，可参见K.Kirchner和H.Schlapkohl在Makromol.Chem.177(1976)，第2031-2042页：TheFormation of Oligomers in the Thermal Copolymerisation of theStyrene/Acrylonitrile System)。为了避免这样的低聚物的形成，必须使用特别的反应条件，包括某些引发剂的使用，例如过氧化二叔丁基、1，1-二(叔丁基过氧)环己烷、过氧化苯甲酰或偶氮二异丁腈。象这样的方法是已知的(例如，参见US-PS 4 068 064)。
因此，适用于本发明的聚合物A)最好是采用本体、溶液或悬浮聚合，用有机自由基引发剂并在保持获得低含量低聚物所必须的其它反应条件(例如美国专利4068064所述的条件)下生产的。
一般来说，生产适用于本发明的聚合物A)的进一步方法包括通过脱气步骤(例如在熔体中)使含低聚物树脂达到所需的低聚物含量；然而该方法相当昂贵。
低聚物可以用常规方法测定，它们通常是用气相色谱或凝胶渗透色谱测定的。
树脂成分A)的平均分子量
Mw最好为20,000-200,000，极限粘度[η]为20-110毫升/克(在二甲基甲酰胺中于25℃测定)。
特别适用于生产接枝聚合物B)的橡胶是聚丁二烯、丁二烯/苯乙烯共聚物、丁二烯/丙烯腈共聚物、聚异戊二烯或基于丙烯酸C1-C18烷基酯、特别是丙烯酸乙酯、丁酯和乙基己酯的丙烯酸烷基酯橡胶。
丙烯酸烷基酯橡胶还可选地含有至多30％(重量)(相对于橡胶的重量计)的通过共聚混入的单体，例如乙酸乙烯酯、丙烯腈、苯乙烯、甲基丙烯酸甲酯和/或乙烯基醚。它们还可以含有少量，最好不超过5％(重量)(相对于橡胶的重量计)具有交联效应的、通过共聚混入的烯不饱和单体。交联剂的例子包括亚烷基二醇二丙烯酸酯，亚烷基二醇二甲基丙烯酸酯、聚酯二丙烯酸酯和聚酯二甲基丙烯酸酯、二乙烯基苯、三乙烯基苯、三烯丙基氰尿酸酯、丙烯酸烯丙酯和甲基丙烯酸烯丙酯、丁二烯或异戊二烯。
用作接枝基底的丙烯酸酯橡胶还可以含有从一种或多种共轭二烯例如丁二烯生产的交联二烯橡胶核，或共轭二烯与烯不饱和单体例如苯乙烯和/或丙烯腈的共聚物核。
生产接枝聚合物B)所优选的橡胶是二烯和丙烯酸烷基酯橡胶。特别优选聚丁二烯和丁二烯与苯乙烯的共聚物和丁二烯与丙烯腈的共聚物。
在接枝聚合物B)中的橡胶是至少部分交联的颗粒的形式，平均粒径(d50)为0.05-0.60μm，优选0.08-0.50μm，最优选0.1-0.45μm。
平均粒径d50是按照W.Scholtan等人，Kolloid-Z.u.z.Polymere250(1972)，782-796所述的方法通过超离心测定的。
接枝聚合物B)是通过单体B.1)在待接枝的橡胶B.2)存在下(以乳液的形式存在)自由基引发的乳液接枝聚合制备的。
本发明适宜的添加剂C)包括内润滑剂、抗静电剂和脱模剂；这些添加剂对于获得良好的表面质量起着重要的作用。在这方面，这些添加剂的用量为1-10重量份，优选2-7.5重量份，最优选3-5重量份(均相对于100重量份A+B计)。
内润滑剂的例子包括碳氢化合物(例如石蜡油、聚乙烯蜡)、醇类(例如硬脂醇)、羧酸(例如月桂酸、棕榈酸、硬脂酸)、羧酰胺(硬脂酰胺、乙二胺-硬脂酰胺)、羧酸酯(例如硬脂酸正丁酯、硬脂酸硬脂酯、丙三醇一硬脂酸酯、丙三醇三硬脂酸酯、季戊四醇四硬脂酸酯)；优选的内润滑剂是羧酰胺和羧酸酯。
抗静电剂的例子包括阳离子活性化合物(例如季铵盐、鏻盐或锍盐)、阴离子活性化合物(例如烷基磺酸盐、烷基硫酸盐、碱金属盐或碱土金属盐形式的羧酸盐)、非离子生成化合物(例如聚乙烯二醇酯、聚乙烯二醇醚、脂肪酸的酯、乙氧基化脂肪胺)；优选的抗静电剂是非离子生成化合物。
脱模剂的例子包括硬脂酸钙、硬脂酸锌和硬脂酸镁；优选的脱模剂是硬脂酸镁。
在这方面，为了确保积附形成的满意减少，(所加添加剂的分子量)∶(模塑料中所加添加剂的重量百分数)的比值不应低于150，优选200，最优选250。
除了上述添加剂外，本发明的模塑料还可以含有稳定剂、颜料和填充剂。
本发明的混合物是通过已知的方式，同时或依次在室温或在高温下将各成分混合，然后在150-300℃下在常规加工设备例如密炼机、挤出机或双螺杆装置中将其混合而制备的。
本发明的模塑料可以用来生产任何形式的模制品，其中可以采用常规生产方法。特别可以通过注塑技术生产模制品。
加工本发明的模塑料的另一种方法是由用已知方法预先生产的片材或板材热成型来生产模制品。
实施例
所用成分
A1：苯乙烯/丙烯腈＝平均分子量
Mw为88,000的72∶28共聚物，用过氧化二叔丁基在140℃下通过悬浮聚合生产。
低聚物含量：0.35％(重量)。
A2：苯乙烯/丙烯腈＝平均分子量
Mw为81,000的72∶28共聚物，用过氧化二叔丁基在150℃下通过周期本体聚合生产。
低聚物含量：0.60％(重量)。
AV：(比较例)
苯乙烯/丙烯腈＝平均分子量
Mw为85,000的72∶28共聚物，通过在165℃下热本体聚合生产。
低聚物含量：1.83％(重量)。
B1：通过过硫酸钾引发的乳液聚合获得的接枝聚合物，将45重量份苯乙烯和丙烯腈的单体混合物(重量比73∶27)在55重量份(以固体计)平均粒度(d50)为大约400nm的聚丁二烯胶乳存在下聚合，用硫酸镁/乙酸混合物聚沉，将聚合物粉末干燥。
B2：通过过硫酸钾引发的乳液聚合获得的接枝聚合物，将45重量份苯乙烯和丙烯腈的单体混合物(重量比73∶27)在55重量份(以固体计)平均粒度(d50)为大约130nm的聚丁二烯胶乳存在下聚合，用硫酸镁/乙酸混合物絮凝，将聚合物粉末干燥。
C1：乙二胺二硬脂酰胺(Henkel KG，Düsseldorf，Germany)
C2：硬脂酸正丁酯(Merk AG，Darmstadt，Germany)
C3：硬脂酸镁(Brlocher，Munich，Germany)
将上述成分按照表1给出的量在大约190-200℃下、在密炼机中均匀混合，随后转化为粒状。
用图1所示的热流道型模具按照下面给出的条件将物料加工。
350次注射操作后，取出圆片，测定积附的量(参见别1，最后一栏)。
从结果可以看出，只有本发明的模塑料产生非常轻微的积附。
加工条件
注塑机： Klocker-Ferromatik-FM 60，全控制
蜗杆直径 ：25mm
合模力 ：600kN
最大填充重量 ：45g
最大注塑压力 ：3000bar
模具： 圆片，直径118mm，厚度2-4mm，
优选2mm，带有热流道(图1)，
6个可相互交换终端圆片，
双针尖型浇口(直径均为0.1-2mm，最好直径均为0.8
mm)，带有合并接缝和气力顶销，
壁厚1.5mm(可改变)，
加料重量20克(圆片15克，注道残料5克)
注塑参数： 物料温度 ：240℃
模具温度 ：28℃
蜗杆前进速率 ：100mm/s
注塑时间 ：0.5s
平均停留时间 ：143s
总周期 ：35.5s
(压力持续时间12s，冷却时间18s，中断时间1s)
采用了特定的模具来测定在注塑这些ABS模塑料时在模具中形成的积附(图1)。按照给出的加工条件，经由两个浇口1(直径0.8毫米)在该模具中注塑制成圆片7(118mm外径，厚度2毫米)。当热物料(240℃)流入腔体2时，在环流线上形成挥发性成分积附4，环流线在腔体的中部相交。在这些流线接触后，终止注塑操作，从而留出一个大致上为三角形的区域6，用来评定积附(图2)。该方法对应于总计量距离的80％。每经过350次注塑操作后，从模具中取出可相互交换的终端圆片3，测定积附的量，并测定其总量(图2)。用剃刀除去积附，再检测重量。
表1：模塑组合物的组成和形成的积附(重量百分数)
| 实施例 A1 A2 AV B1 B2 C1 C2 C3(SAN) (SAN) (SAN) (接枝聚合物) (接枝聚合物) (添加剂) (添加剂) (添加剂) | 积附量(mg) |
| 1 70 -- -- 15 15 3.5 -- --2 -- 70 -- 15 15 3.5 -- --3(比较例) -- -- 70 15 15 3.5 -- --4(比较例) 70 -- -- 15 15 -- 3.5 --5(比较例) 70 -- -- 15 15 5 -- --6 65 -- -- 35 -- 3.3 -- 0.57(比较例) -- -- 65 35 -- 3.3 -- 0.5 | 68281615631 |
Claims (5)
1.ABS型热塑性模塑料，它含有
A)5-95％(重量)的至少一种苯乙烯、α-甲基苯乙烯、丙烯腈、N-取代的马来酰亚胺或其混合物的热塑性均聚物、共聚物或三元共聚物，
B)5-95％(重量)至少一种接枝聚合物，它是
B.1)5-90重量份苯乙烯、α-甲基苯乙烯、丙烯腈、N-取代的马来酰亚胺或其混合物在
B.2)95-10重量份玻璃化转变温度不超过0℃的橡胶上的接枝聚合物，和
C)1-10重量份(每100重量份A+B)至少一种选自内润滑剂、抗静电剂、脱模剂或其混合物的添加剂，
其特征在于，成分A)是通过本体聚合、溶液聚合或悬浮聚合制备的，其低聚物含量不超过1％(重量)，成分B)是通过乳液聚合制备的，模塑料中低聚物的总含量不超过0.8％(重量)，在模塑料中添加剂分子量与添加剂量之比(重量百分数)不低于150。
2.根据权利要求1的ABS型热塑性模塑料，它含有
A)10-90％(重量)的至少一种苯乙烯、α-甲基苯乙烯、丙烯腈、N-取代的马来酰亚胺或其混合物的热塑性均聚物、共聚物或三元共聚物，
B)10-90％(重量)至少一种接枝聚合物，它是
B.1)30-80重量份苯乙烯、α-甲基苯乙烯、丙烯腈、N-取代的马来酰亚胺或其混合物在
B.2)70-20重量份玻璃化转变温度不超过0℃的橡胶上的接枝聚合物，和
C)2-7.5重量份(每100重量份A+B)至少一种选自内润滑剂、抗静电剂、脱模剂或其混合物的添加剂，
其特征在于，成分A)是通过本体聚合、溶液聚合或悬浮聚合制备的，其低聚物含量不超过0.75％(重量)，成分B)是通过乳液聚合制备的，模塑料中低聚物的总含量不超过0.7％(重量)，在模塑料中添加剂分子量与添加剂量之比(重量百分数)不低于200。
3.根据权利要求1或2的热塑性模塑料，其特征在于苯乙烯/丙烯腈共聚物和/或α-甲基苯乙烯/丙烯腈共聚物被用作热塑性树脂成分A)。
4.根据权利要求1-3中任何一项的热塑性模塑料在通过注塑生产模制品中的用途。
5.根据权利要求1-3的中任何一项热塑性模塑料在高光泽模制品生产中的用途。
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| DE19713509A DE19713509A1 (de) | 1997-04-01 | 1997-04-01 | Pfropfpolymerisat-Formmassen mit reduzierter Belagsbildung |
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| KR102436712B1 (ko) | 2017-04-24 | 2022-08-25 | 이네오스 스티롤루션 그룹 게엠베하 | Ａｂｓ 그래프트 공중합체를 제조하기 위한 개선된 방법 |
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| KR102514316B1 (ko) | 2017-07-05 | 2023-03-24 | 이네오스 스티롤루션 그룹 게엠베하 | 개선된 uv 내성을 갖는 열가소성 수지 조성물 |
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| ES2886928T3 (es) | 2017-12-11 | 2021-12-21 | Ineos Styrolution Group Gmbh | Procedimiento para la producción de una composición de moldeo termoplástica modificada al impacto con procesamiento y resistencia al impacto mejorados |
| US11807752B2 (en) | 2018-07-24 | 2023-11-07 | Ineos Styrolution Group Gmbh | Process for preparing graft rubber compositions with improved dewatering |
| EP3844195A1 (en) | 2018-08-29 | 2021-07-07 | INEOS Styrolution Group GmbH | Process for the production of graft copolymer powder compositions and thermoplastic resin compositions |
| KR102311952B1 (ko) * | 2018-09-21 | 2021-10-14 | 주식회사 엘지화학 | 열가소성 수지 조성물 |
| EP3750929A1 (en) * | 2019-06-12 | 2020-12-16 | Trinseo Europe GmbH | Styrenic polymers having reduced trimer content |
| WO2021110550A1 (en) * | 2019-12-04 | 2021-06-10 | Covestro Intellectual Property Gmbh & Co. Kg | Flame retardant impact-modified polycarbonate composition |
| KR20230145587A (ko) | 2021-02-16 | 2023-10-17 | 이네오스 스티롤루션 그룹 게엠베하 | 열가소성 코폴리머 a 및 그라프트 코폴리머 b를 포함하는 열가소성 몰딩 컴파운드를 제조하기 위한 방법 |
| WO2023209004A1 (en) | 2022-04-29 | 2023-11-02 | Ineos Styrolution Group Gmbh | Acrylonitrile styrene acrylate copolymer composition with improved uv resistance |
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| WO2024028309A1 (de) | 2022-08-04 | 2024-02-08 | Ineos Styrolution Group Gmbh | Thermoplastische abs-formmassen mit einer guten eigenschaftskombination von verarbeitbarkeit und oberflächenqualität |
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| US4068064A (en) * | 1975-12-22 | 1978-01-10 | The Dow Chemical Company | Method for preparing monovinyl aromatic monomer-acrylonitrile copolymer |
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| DE2842005A1 (de) * | 1978-09-27 | 1980-04-10 | Bayer Ag | Polycarbonate mit alkylphenyl-endgruppen, ihre herstellung und ihre verwendung |
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| DE3506472A1 (de) * | 1985-02-23 | 1986-08-28 | Bayer Ag, 5090 Leverkusen | Neue polydiorganosiloxan-polycarbonat-blockcopolymere |
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| US5975936A (en) * | 1997-09-03 | 1999-11-02 | Lucent Technologies Inc. | Blade carrier for use in a communication plug |
-
1997
- 1997-04-01 DE DE19713509A patent/DE19713509A1/de not_active Withdrawn
-
1998
- 1998-03-11 TW TW087103524A patent/TW496886B/zh not_active IP Right Cessation
- 1998-03-18 AU AU59378/98A patent/AU726342B2/en not_active Ceased
- 1998-03-19 DE DE59807349T patent/DE59807349D1/de not_active Expired - Lifetime
- 1998-03-19 ES ES98104998T patent/ES2193430T3/es not_active Expired - Lifetime
- 1998-03-19 EP EP98104998A patent/EP0869147B1/de not_active Expired - Lifetime
- 1998-03-24 US US09/047,254 patent/US6140426A/en not_active Expired - Lifetime
- 1998-03-25 US US09/047,598 patent/US5994463A/en not_active Expired - Lifetime
- 1998-03-26 JP JP10096933A patent/JPH10279754A/ja active Pending
- 1998-03-27 CA CA002233431A patent/CA2233431C/en not_active Expired - Fee Related
- 1998-03-30 AR ARP980101439A patent/AR012204A1/es unknown
- 1998-03-31 BR BR9801146-4A patent/BR9801146A/pt not_active IP Right Cessation
- 1998-03-31 KR KR1019980011256A patent/KR100543493B1/ko not_active IP Right Cessation
- 1998-04-01 CN CNB981063160A patent/CN1195799C/zh not_active Expired - Lifetime
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2009
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0869147A1 (de) | 1998-10-07 |
| US6140426A (en) | 2000-10-31 |
| JP2009114464A (ja) | 2009-05-28 |
| CN1195000A (zh) | 1998-10-07 |
| BR9801146A (pt) | 2000-10-31 |
| CA2233431A1 (en) | 1998-10-01 |
| EP0869147B1 (de) | 2003-03-05 |
| US5994463A (en) | 1999-11-30 |
| TW496886B (en) | 2002-08-01 |
| DE19713509A1 (de) | 1998-10-08 |
| KR19980080948A (ko) | 1998-11-25 |
| JPH10279754A (ja) | 1998-10-20 |
| ES2193430T3 (es) | 2003-11-01 |
| AU5937898A (en) | 1998-10-15 |
| CA2233431C (en) | 2006-06-06 |
| AU726342B2 (en) | 2000-11-02 |
| DE59807349D1 (de) | 2003-04-10 |
| AR012204A1 (es) | 2000-09-27 |
| KR100543493B1 (ko) | 2006-03-23 |
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