CN102850793A - 一种玻璃纤维增强尼龙66复合材料及其制备方法 - Google Patents
一种玻璃纤维增强尼龙66复合材料及其制备方法 Download PDFInfo
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- 230000003078 antioxidant effect Effects 0.000 claims description 12
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
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- CDZXKKXSZAMHFU-UHFFFAOYSA-J lead(2+);phosphonato phosphate Chemical compound [Pb+2].[Pb+2].[O-]P([O-])(=O)OP([O-])([O-])=O CDZXKKXSZAMHFU-UHFFFAOYSA-J 0.000 description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
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- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
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- 229920002530 polyetherether ketone Polymers 0.000 description 1
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- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
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- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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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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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种玻璃纤维增强尼龙66复合材料及其制备方法。该复合材料包含下列组分：尼龙66 29.8-58.5份，玻璃纤维40份，磷酸盐玻璃1-30份，抗氧剂0.2-0.5份。其制备方法是将粉末化的尼龙66和磷酸盐玻璃粉末与玻纤熔融共混后挤出、造粒。本发明制备的玻璃纤维增强尼龙66复合材料具有较高玻纤填充量和较高熔体流动速率，并具有优良的力学性能。可用于大型薄壁制件的制备，具有良好的发展前景。
Description
技术领域
本发明属于玻纤增强聚酰胺及其制备领域，具体涉及由尼龙66、玻璃纤维和磷酸盐玻璃制成的高填充、高流动性复合材料及其制备方法。
背景技术
尼龙是五大工程塑料中产量最大、品种最多、应用领域最广的一种高分子材料，主要涉及机械制造业，电子电器和交通运输等领域。其中，尼龙6和尼龙66的产量最大，约占尼龙总产量的90%。这主要是因为尼龙树脂具有较高的机械强度、耐热性、自润滑性、优良的阻隔性能和耐化学腐蚀等优异的综合性能。但是纯尼龙也存在明显的缺陷：如吸水率大，制品尺寸稳定性差，阻燃性能一般。随着汽车工业、电子工业的发展，人们对尼龙制品的强度和稳定性提出了更高的要求。尤其要求提高尼龙制品的机械强度，以取代工业应用中金属材料作为结构制件，增强尼龙的研究层出不穷。
目前，以玻璃纤维增强尼龙66复合材料最具代表性。使用玻璃纤维填充尼龙66可以大幅提高材料的强度、模量、耐热性，但由于填充量很大，造成熔体流动性差，增加功耗和设备损耗，降低生产效率，增加制品成型难度。人们开始关注提高玻璃纤维的填充含量的同时增强尼龙66复合材料的加工流动性能。中国授权专利公告号为CN101230192B，公开了一种提高玻璃纤维增强聚酰胺复合材料流动性的方法：通过处理可膨胀石墨，降低膨胀石墨的温度，使得在加工过程中膨胀石墨进行连续膨胀，促进纤维在基质树脂中的分散和熔融效果，使得材料熔体流动速率提高了1-2.5倍。但是，此发明提高玻纤增强尼龙66体系的流动性主要体现在造粒阶段，对二次成型时熔体流动性的改善有限。虽然玻纤的最高填充量达到了50%，但材料的流动性会明显降低，并且处理膨胀石墨使用了有毒的小分子物质，不适于当前对环保材料的要求。
1983年美国专利US4379070通过一步熔融法制得了一系列的磷酸盐玻璃。近些年来Otaigbe等研究者开始了关于锌碱金属磷酸盐玻璃（zinc alkali phosphate glasses，Tg：270-330℃），铅磷酸盐玻璃（lead pyrophosphate glasses，Tg：390℃左右），锡氟磷酸盐玻璃（tin fluorophosphates glasses，Tg：55-150℃）与聚合物（LDPE、PP、PS、PEI、PEEK、PPS等）形成的杂化材料的研究，并发现许多优异的性能。而目前尤其以锡氟磷酸盐玻璃/聚合物杂化材料的研究最为突出，这类特殊的磷酸盐玻璃的具有较低的玻璃化转变温度，且在很宽广的频率和温度范围内表现近似牛顿流体,它的粘度有强烈的温度依赖性。由于低Tg的特点，使得它们在许多聚合物的加工温度范围内呈流体状态，避免了高填充量带来的加工问题。因此，可以通过将磷酸盐玻璃加入到玻纤填充尼龙66的体系中，制备一种具有高玻纤填充量、高流动性的尼龙66复合材料。
发明内容
本发明的目的在于提供一种高填充、高流动性的玻璃纤维增强尼龙66复合材料及其制备方法。
本发明提供的玻璃纤维增强尼龙66复合材料的组成和重量份数如下：
其中，磷酸盐玻璃参照了美国专利US4379070以氟化亚锡53份，氧化亚锡18份，五氧化二磷29份为主要原料并通过一步熔融法制得的锡氟磷酸盐玻璃粉末。
所述尼龙66是选自己二胺和己二酸通过直接或间接法缩聚生成的熔体流动速率大于10.0g/10min的共聚物。
所述玻璃纤维是经过偶联剂表面处理的玻璃纤维。所使用的偶联剂是硅烷类偶联剂，如：γ-氨丙基三乙氧基硅烷或γ-缩水甘油醚丙基三甲氧基硅烷。
所述抗氧剂是针对于聚酰胺的氧化降解的抗氧剂，可采用酚类抗氧剂或亚磷酸酯类抗氧剂，其中酚类抗氧剂是抗氧剂1010、抗氧剂1076、抗氧剂330、抗氧剂300中的一种或两种；亚磷酸酯类抗氧剂是抗氧剂168。
一种玻璃纤维增强尼龙66复合材料的制备方法，包括如下制备步骤：
A、尼龙66粉末的制备：
将15-20重量份尼龙66溶解于50-100重量份60-100℃81-88wt%的甲酸溶液重，将尼龙66溶液边倾倒、边搅拌加入到60-100份乙醇的水溶液，抽滤。
将抽滤后得到的产品继续在60-100℃蒸馏水中水洗、抽滤，如此重复3-7次，于80-120℃干燥3-24h，得到尼龙66粉末；
B、玻璃纤维增强尼龙66复合材料的制备：
按上述重量份配比将粉末原料混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-290℃，螺杆转速为50rap/min，从而制得玻璃纤维增强尼龙66复合材料。
本发明的优点：
1.本发明制备的玻璃纤维增强尼龙66复合材料具有较高玻纤填充量和较高熔体流动速率并赋予复合材料优良的力学性能。
2.本发明制备工艺简单，易于操作，无需复杂设备。
具体实施方式
下面通过实施例对本发明给予进一步说明：
实施例1
A、尼龙66粉末的制备：
将20份尼龙66溶解于100份100℃的81wt%甲酸溶液，将尼龙66溶液边倾倒边搅拌加入到60份乙醇的水溶液，抽滤。将抽滤产品继续在60℃蒸馏水中水洗、抽滤，如此重复7次，80℃干燥24h，得到尼龙66粉末；
B、磷酸盐玻璃/尼龙66复合材料的制备：
将尼龙66粉58.5份、玻璃纤维40份、磷酸盐玻璃1份、抗氧剂1010 0.5份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，从而制得玻璃纤维增强尼龙66复合材料。
实施例2
将实施例1中制备的尼龙66粉49.6份、磷酸盐玻璃10份与玻璃纤维40份、抗氧剂3300.4份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，从而制得玻璃纤维增强尼龙66复合材料。
实施例3
将实施例1中制备的尼龙66粉39.7份、磷酸盐玻璃20份与玻璃纤维40份、抗氧剂3000.3份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，从而制得玻璃纤维增强尼龙66复合材料。
实施例4
将实施例1中制备的尼龙66粉29.8份、磷酸盐玻璃30份与玻璃纤维40份、抗氧剂1680.2份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，从而制得玻璃纤维增强尼龙66复合材料。
实施例5
A、尼龙66粉末的制备：
将15份尼龙66溶解于50份60℃的88wt%甲酸溶液，将尼龙66溶液边倾倒边搅拌加入到100份乙醇的水溶液，抽滤。将抽滤产品继续在100℃蒸馏水中水洗、抽滤，如此重复3次，120℃干燥3h，得到尼龙66粉末；
B、磷酸盐玻璃/尼龙66复合材料的制备：
将尼龙66粉29.8份、玻璃纤维40份、磷酸盐玻璃30份、抗氧剂168 0.2份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，从而制得玻璃纤维增强尼龙66复合材料。
对比例1
将实施例1中制备的尼龙66粉59.5份与玻璃纤维40份、抗氧剂1010 0.5份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，从而制得玻璃纤维增强尼龙66复合材料。
将所有样品注塑成ISO标准样条进行测试，其中熔体流动速率按照ISO1133进行测试，测试条件275℃，2.16Kg；拉伸性能按ISO527进行测试，拉伸速度为50mm/min，弯曲性能按ISO178进行测试，弯曲速度为2mm/min，跨距为64mm。悬臂梁无缺口冲击强度按照ISO180进行测试，测试结果见表1。
表1实施例和对比例的配方及材料性能对照表
表1中，磷酸盐玻璃的玻璃化转变温度为91±2℃，密度3.7g/cm3。结果表明本发明制备的玻璃纤维增强尼龙66复合材料具有高的玻纤填充量、熔体流动速率提高了1-3倍，拉伸强度提高了6-16%，弯曲模量提高了10-41%，并无缺口冲击强度提高了3-16%。
Claims (10)
1.一种玻璃纤维增强尼龙66复合材料，其包括：
2.根据权利要求1所述的玻璃纤维增强尼龙66复合材料，其特征在于：所述尼龙66是由己二胺和己二酸通过直接或间接法缩聚生成的共聚物，且其熔体流动速率大于10g/10min。
3.根据权利要求2所述的玻璃纤维增强尼龙66复合材料，其特征在于：玻璃纤维是经过偶联剂表面处理的玻璃纤维，所述偶联剂是硅烷类偶联剂，其中硅烷类偶联剂是γ-氨丙基三乙氧基硅烷或γ-缩水甘油醚丙基三甲氧基硅烷。
4.根据权利要求3所述的玻璃纤维增强尼龙66复合材料，其特征在于，所述抗氧剂为酚类抗氧剂或亚磷酸酯类抗氧剂；酚类抗氧剂是抗氧剂1010、抗氧剂1076、抗氧剂330、抗氧剂300中的一种或两种；亚磷酸酯类抗氧剂是抗氧剂168。
5.一种玻璃纤维增强尼龙66复合材料的制备方法：
尼龙66粉末的制备：
将15-20重量份尼龙66溶解于50-100重量份60-100℃81-88wt%的甲酸溶液重，将尼龙66溶液边倾倒、边搅拌，加入到60-100重量份乙醇的水溶液，抽滤；
将抽滤后获得的产品继续在60-100℃蒸馏水中水洗、抽滤，如此重复3-7次，于80-120℃干燥3-24h，得到尼龙66粉末；
玻璃纤维增强尼龙66复合材料的制备：
按重量份配比
将粉末原料混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-290℃，螺杆转速为50rap/min，制得玻璃纤维增强尼龙66复合材料。
6.根据权利要求5所述的玻璃纤维增强尼龙66复合材料的制备方法，其特征在于：
将20份尼龙66溶解于100份100℃的81wt%甲酸溶液，将尼龙66溶液边倾倒、边搅拌加入到60份乙醇的水溶液中，抽滤；将抽滤后获得的产品继续在60℃蒸馏水中水洗、抽滤，如此重复7次，80℃干燥24h，得到尼龙66粉末；
磷酸盐玻璃/尼龙66复合材料的制备：
将尼龙66粉58.5份、玻璃纤维40份、磷酸盐玻璃1份、抗氧剂10100.5份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，制得玻璃纤维增强尼龙66复合材料。
7.根据权利要求5所述的玻璃纤维增强尼龙66复合材料的制备方法，其特征在于：
将制备的尼龙66粉49.6份、磷酸盐玻璃10份与玻璃纤维40份、抗氧剂330 0.4份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，制得玻璃纤维增强尼龙66复合材料。
8.根据权利要求5所述的玻璃纤维增强尼龙66复合材料的制备方法，其特征在于：
将制备的尼龙66粉39.7份、磷酸盐玻璃20份与玻璃纤维40份、抗氧剂300 0.3份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，制得玻璃纤维增强尼龙66复合材料。
9.根据权利要求5所述的玻璃纤维增强尼龙66复合材料的制备方法，其特征在于：将制备的尼龙66粉29.8份、磷酸盐玻璃30份与玻璃纤维40份、抗氧剂1680.2份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数：熔体温度为260-280℃，螺杆转速为50rap/min，从而制得玻璃纤维增强尼龙66复合材料。
10.根据权利要求5所述的玻璃纤维增强尼龙66复合材料的制备方法，其特征在于：
尼龙66粉末的制备：
将15份尼龙66溶解于50份60℃的88wt%甲酸溶液，将尼龙66溶液边倾倒、边搅拌加入到100份乙醇的水溶液，抽滤；将抽滤产品继续在100℃蒸馏水中水洗、抽滤，如此重复3次，120℃干燥3h，得到尼龙66粉末；
磷酸盐玻璃/尼龙66复合材料的制备：
将尼龙66粉29.8份、玻璃纤维40份、磷酸盐玻璃30份、抗氧剂168 0.2份混合均匀，经过双螺杆挤出机熔融共混，挤出造粒，工艺参数为：熔体温度为260-280℃，螺杆转速为50rap/min，制得玻璃纤维增强尼龙66复合材料。
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| CN104140632A (zh) * | 2014-08-03 | 2014-11-12 | 湘潭大学 | 改性锡氟磷酸盐玻璃/聚丙烯杂化材料及其制备方法 |
| CN104140632B (zh) * | 2014-08-03 | 2017-02-15 | 湘潭大学 | 改性锡氟磷酸盐玻璃/聚丙烯杂化材料及其制备方法 |
| CN106832896A (zh) * | 2017-02-17 | 2017-06-13 | 四川大学 | 一种可原位成纤增强聚合物的低粘高模聚合物复合材料 |
| CN115011114A (zh) * | 2022-07-02 | 2022-09-06 | 厦门市嘉能科技有限公司 | 一种高流动性的尼龙及其制备方法 |
| CN115011114B (zh) * | 2022-07-02 | 2023-05-26 | 厦门市嘉能科技有限公司 | 一种高流动性的尼龙及其制备方法 |
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