CN101469101B - 一种无卤低烟阻燃abs树脂及其制备方法 - Google Patents
一种无卤低烟阻燃abs树脂及其制备方法 Download PDFInfo
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
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- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
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- 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
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Abstract
本发明涉及一种无卤低烟阻燃ABS树脂及其制备方法，首先将ABS类树脂100重量份，无机磷系阻燃剂6-45重量份、多羟基化合物2-15重量份、水合金属化合物0.05-2.5重量份和晶体硅铝酸盐0.1-3重量份，受阻酚类主抗氧剂0.1-1重量份和亚磷酸酯类辅抗氧剂0.1-1重量份，在高速搅拌机中充分混合均匀，混合完全后，通过精密计量的送料装置，将物料送入双螺杆挤出机中，各区温度在180-210℃，物料再螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料。与现有技术相比，本发明提供了一种燃烧时发烟量低，毒性小，有利于环保的无卤阻燃ABS类树脂，且流程简单、连续、高效、产品质量稳定。
Description
技术领域
本发明涉及一种阻燃树脂，尤其涉及一种无卤低烟阻燃ABS树脂及其制备方法。
背景技术
ABS树脂是一种综合性能良好，易加工成型的热塑性树脂，因此被广泛的应用于机电、化工、军工、电子电器等领域。随着社会的发展，人们对越来越多的材料提出了耐热防火的要求，但由于ABS树脂本身的阻燃性很低，其氧指数为18.3-20.0，垂直燃烧也无法达到UL94V-2标准，燃烧时还会释放出大量的烟雾及有害气体，其发烟量用最大烟密度(Dm)表示在720左右，这使得ABS的应用受到了限制。由于阻燃ABS的许多性能，比如光稳定性，力学性能、热性能等会因阻燃剂的加入而受到严重的影响。所以，虽然有文献报道的用于ABS的阻燃体系很多，但溴系阻燃剂仍是工业生产阻燃ABS的首选。
目前，改善ABS类树脂阻燃性能最常用的方法是添加含卤阻燃剂与三氧化二锑的复合阻燃体系。但由于卤的存在，使其阻燃时释放的气体具有高腐蚀性，在特定的条件下，还能分解出致癌物质，因此限制了ABS在特定场合的应用。随着人们环保意识的增强和相关的环保法规的日趋完善，无卤阻燃材料的研制与开发已经成为阻燃领域的一个重要的发展方向。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种燃烧时发烟量低，毒性小，有利于环保的无卤低烟阻燃ABS树脂及其制备方法。
本发明的目的可以通过以下技术方案来实现：
一种无卤低烟阻燃ABS树脂，其特征在于，该组合物包括以下成分和含量(重量份)：
ABS类树脂 100；
无机磷系阻燃剂 6-45；
多羟基化合物 2-15；
金属化合物 0.05-2.5；
晶体硅铝酸盐 0.1-3；
受阻酚类主抗氧剂 0.1-1；
亚磷酸酯类辅抗氧剂 0.1-1。
所述的ABS类树脂包括丙烯腈-丁二烯-苯乙烯接枝共聚物(ABS)、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物(MBS)、丙烯腈-苯乙烯-丙烯酸酯三元共聚物(ASA)、丙烯腈-乙丙二烯-苯乙烯三元共聚物(AEA)、马来酸酐接枝丙烯腈-丁二烯-苯乙烯三元共聚物(ABS-g-MAH)、马来酸酐接枝苯乙烯(SMA)。
所述的无机磷系阻燃剂包括聚磷酸铵及其衍生物。
所述的多羟基化合物包括季戊四醇，季戊四醇的二聚物、三聚物以及含有羟基的有机树脂。
所述的金属化合物包括二价或多价金属化合物。
所述的晶体硅铝酸盐(Zeolites)结构式为Mx/n[(AlO2)x，(SiO2)y]zH2O。
还包括稳定剂、润滑剂、脱模剂、成核剂、抗静电剂、填料、增强材料以及颜料中的一种或是几种。
一种无卤低烟阻燃ABS树脂的制备方法，其特征在于，首先将ABS类树脂100重量份，无机磷系阻燃剂6-45重量份、多羟基化合物2-15重量份、金属化合物0.05-2.5重量份和晶体硅铝酸盐0.1-3重量份，受阻酚类主抗氧剂0.1-1重量份和亚磷酸酯类辅抗氧剂0.1-1重量份，在高速搅拌机中充分混合均匀，混合完全后，通过精密计量的送料装置，将物料送入双螺杆挤出机中，各区温度在180-210℃，物料再螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料。
所述的双螺杆挤出机的长径比20-50，带有精确的温度控制和真空排气设备，螺杆各区的温度在160-220℃之间。
所述的双螺杆挤出机的长径比为35；所述的螺杆各区的温度为180-210℃。
与现有技术相比，本发明以聚磷酸酯为主的无卤阻燃体系对ABS类树脂进行阻燃改性，运用本发明所述配方制得的材料不仅具有优异的阻燃性能，而且还具有燃烧时发烟量低，毒性小，有利于环保的优点。
具体实施方式
以下结合具体实施例对本发明作进一步说明。
实施例1
一种无卤低烟阻燃ABS树脂，该组合物包括以下成分和含量(重量份)
| 原料 | 重量份数 |
| ABS | 60 |
| SMA | 10 |
| 聚磷酸铵APP | 22.5 |
| 季戊四醇PER | 7.5 |
| 晶体硅铝酸盐Zeolites | 1 |
| MnSO4·H2O | 1 |
| Irganox 1076 | 0.2 |
| Irgafos 168 | 0.5 |
| N，N′-乙撑双脂肪酰胺 | 0.5 |
注：Irganox 1076、Irgafos 168均为Ciba精化公司。
所得共混物材料的测试结果如下(ASTM)：
| 弯曲强度(MPa) | 52 |
| 弯曲模量(MPa) | 2810 |
| Charpy缺口冲击强度(KJ/m2) | 5.4 |
| 烟密度(Dm) | 200 |
| 阻燃性UL94(1.6mm) | FV-0 |
| 燃烧后卤化氢气体(mg/g) | 0 |
从实施例1可以看出，本发明的阻燃体系与ABS树脂共混得到的材料，其阻燃性得到改进的同时，燃烧后的烟密度和毒性也得到了良好的抑制。
实施例2、3
| 原料 | 重量份数 | |
| ABS | 70 | 50 |
| SMA | 10 | 10 |
| 聚磷酸铵APP | 15 | 30 |
| 季戊四醇PER | 5 | 10 |
| 晶体硅铝酸盐Zeolites | 1 | |
| MnSO4·H2O | 1 | |
| Irganox 1076 | 0.2 | 0.2 |
| Irgafos 168 | 0.5 | 0.5 |
| N，N′-乙撑双脂肪酰胺 | 0.5 | 0.5 |
所得共混物材料的测试结果如下(ASTM)：
| 弯曲强度(MPa) | 50 | 55 |
| 弯曲模量(MPa) | 2760 | 2790 |
| Charpy缺口冲击强度(KJ/m2) | 6.0 | 4.5 |
| 烟密度(Dm) | 400 | 180 |
| 阻燃性UL94(1.6mm) | FV-1 | FV-0 |
| 燃烧后卤化氢气体(mg/g) | 0 | 0 |
实施例4
一种无卤低烟阻燃ABS树脂，该组合物包括以下成分和含量(重量份)丙烯腈-丁二烯-苯乙烯接枝共聚物(ABS)100重量份，聚磷酸铵6重量份、季戊四醇2重量份、多价金属Mn化合物0.05重量份和晶体硅铝酸盐0.1重量份，受阻酚类主抗氧剂0.1重量份和亚磷酸酯类辅抗氧剂0.1重量份，首先将上述原料在高速搅拌机中充分混合均匀，混合完全后，通过精密计量的送料装置，将物料送入长径比20的双螺杆挤出机中，各区温度在160℃，物料再螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料。
实施例5
一种无卤低烟阻燃ABS树脂，该组合物包括以下成分和含量(重量份)甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物(MBS)100重量份，聚磷酸铵45重量份、季戊四醇的二聚物15重量份、二价金属Zn化合物2.5重量份和晶体硅铝酸盐3重量份，受阻酚类主抗氧剂1重量份和亚磷酸酯类辅抗氧剂1重量份，首先将上述原料在高速搅拌机中充分混合均匀，混合完全后，通过精密计量的送料装置，将物料送入长径比50的双螺杆挤出机中，各区温度在220℃，物料再螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料。
实施例6
一种无卤低烟阻燃ABS树脂，该组合物包括以下成分和含量(重量份)甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物(MBS)100重量份，聚磷酸铵45重量份、季戊四醇的二聚物15重量份、二价金属Zn化合物2.5重量份和晶体硅铝酸盐3重量份，受阻酚类主抗氧剂1重量份和亚磷酸酯类辅抗氧剂1重量份，首先将上述原料在高速搅拌机中充分混合均匀，混合完全后，通过精密计量的送料装置，将物料送入长径比35的双螺杆挤出机中，各区温度在180℃，物料再螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料。
所述的无机磷系阻燃剂还包括聚磷酸铵衍生物，所述的晶体硅铝酸盐(Zeolites)结构式为Mx/n[(AlO2)x，(SiO2)y]z·H2O。还包括稳定剂、润滑剂、脱模剂、成核剂、抗静电剂、填料、增强材料以及颜料中的一种或是几种。
Claims (8)
1.一种无卤低烟阻燃ABS树脂，其特征在于，该组合物包括以下成分和含量(重量份)：
ABS类树脂 100；
无机磷系阻燃剂 6-45；
多羟基化合物 2-15；
金属化合物 0.05-2.5；
晶体硅铝酸盐 0.1-3；
受阻酚类主抗氧剂 0.1-1；
亚磷酸酯类辅抗氧剂 0.1-1；
所述的ABS类树脂包括丙烯腈-丁二烯-苯乙烯接枝共聚物(ABS)、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物(MBS)、丙烯腈-苯乙烯-丙烯酸酯三元共聚物(ASA)、丙烯腈-乙丙二烯-苯乙烯三元共聚物(AEA)、马来酸酐接枝丙烯腈-丁二烯-苯乙烯三元共聚物(ABS-g-MAH)、马来酸酐接枝苯乙烯(SMA)；
该无卤低烟阻燃ABS树脂采用以下步骤制备：首先将ABS类树脂100重量份，无机磷系阻燃剂6-45重量份、多羟基化合物2-15重量份、金属化合物0.05-2.5重量份和晶体硅铝酸盐0.1-3重量份，受阻酚类主抗氧剂0.1-1重量份和亚磷酸酯类辅抗氧剂0.1-1重量份，在高速搅拌机中充分混合均匀，混合完全后，通过精密计量的送料装置，将物料送入双螺杆挤出机中，各区温度在180-210℃，物料再螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料；所述的双螺杆挤出机的长径比20-50，带有精确的温度控制和真空排气设备。
2.根据权利要求1所述的一种无卤低烟阻燃ABS树脂，其特征在于，所述的无机磷系阻燃剂包括聚磷酸铵及其衍生物。
3.根据权利要求1所述的一种无卤低烟阻燃ABS树脂，其特征在于，所述的多羟基化合物包括季戊四醇，季戊四醇的二聚物、三聚物以及含有羟基的有机树脂。
4.根据权利要求1所述的一种无卤低烟阻燃ABS树脂，其特征在于，所述的金属化合物包括二价或多价金属化合物。
5.根据权利要求1所述的一种无卤低烟阻燃ABS树脂，其特征在于，所述的晶体硅铝酸盐结构式为Mx/n[(AlO2)x，(SiO2)y]z·H2O。
6.根据权利要求1所述的一种无卤低烟阻燃ABS树脂，其特征在于，还包括稳定剂、润滑剂、脱模剂、成核剂、抗静电剂、填料、增强材料以及颜料中的一种或是几种。
7.一种如权利要求1所述的无卤低烟阻燃ABS树脂的制备方法，其特征在于，首先将ABS类树脂100重量份，无机磷系阻燃剂6-45重量份、多羟基化合物2-15重量份、金属化合物0.05-2.5重量份和晶体硅铝酸盐0.1-3重量份，受阻酚类主抗氧剂0.1-1重量份和亚磷酸酯类辅抗氧剂0.1-1重量份，在高速搅拌机中充分混合均匀，混合完全后，通过精密计量的送料装置，将物料送入双螺杆挤出机中，各区温度在180-210℃，物料再螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料。
8.根据权利要求7所述的一种无卤低烟阻燃ABS树脂的制备方法，其特征在于，所述的双螺杆挤出机的长径比为35。
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