CN100549095C - 一种无卤无磷环保阻燃的聚酰胺树脂及其制备方法 - Google Patents
一种无卤无磷环保阻燃的聚酰胺树脂及其制备方法 Download PDFInfo
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- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 4
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- 239000010949 copper Substances 0.000 claims description 3
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- 239000003063 flame retardant Substances 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 19
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- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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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
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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
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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
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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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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Abstract
本发明公开了一种无卤无磷环保阻燃的聚酰胺树脂及其制备方法。聚酰胺树脂由以下配比的原料配制成：聚酰胺68-92%；氰尿酸三聚氰胺5-25%；增韧剂2-15%；抗氧剂0.1-1%；热稳定剂0.1-2%；结晶促进剂0.1-2%。本发明制得的聚酰胺材料的物理力学性能好、阻燃性能优异；本发明所采用的助剂，如氰尿酸三聚氰胺、结晶促进剂、热稳定剂、增韧剂和抗氧剂等组分，均为价格低廉的市售产品，材料的生产成本较低；本发明所提出的无卤阻燃聚酰胺复合材料的制备工艺简单、成本低廉。
Description
[技术领域]
本发明涉及聚酰胺树脂材料，尤其涉及一种无卤无磷环保阻燃的聚酰胺树脂及其制备方法。
[背景技术]
聚酰胺树脂(polyamide简称PA)，作为五大工程塑料之首，其性能特点是：机械强度高，软化点高，耐热性好，耐磨损，自润滑性，吸震性和消音性，耐油，耐弱酸，耐碱，电绝缘性好，因而聚酰胺是电子、电器元件方面的首选材料，而这类产品对于材料的阻燃性能的要求很高，聚酰胺的氧指数大约为25％，只可以达到UL94-V2级，显然无法满足要求。因此对聚酰胺进行阻燃处理十分必要。目前阻燃尼龙常采用的阻燃体系大约有三种：1)溴锑系阻燃剂2)磷系阻燃剂，3)无机氢氧化物阻燃剂。由于欧盟公布的ROHS指令(TheRestriction of the use of certain Hazardous substances inElectnical and Electronic Equipment在电子电气设备中限制使用某些有害物质指令)和WEEE指令(Waste from Electrical andElectronic Equipment报废电子电气设备指令)使得溴系阻燃剂正在逐步退出市场；磷类阻燃剂对于模具的强腐蚀性极大限制了其广泛应用；无机氢氧化物阻燃剂的添加量极大，与聚酰胺相容性差、对材料的物理力学性能影响和破坏较大，使得材料丧失了很多使用价值。而目前，此领域正处于开发初期阶段，迄今为止尚未有成熟产品问世，因此无卤无磷阻燃聚酰胺材料具有极大的市场开发价值。
[发明内容]
本发明要解决的技术问题是提供一种无卤无磷环保阻燃，物理力学性能较好的聚酰胺树脂及其制备方法。本发明还要提供一种该种聚酰胺树脂的制备方法。
为了解决上述技术问题，本发明采用的技术方案是，一种无卤无磷环保阻燃的聚酰胺树脂，由以下配比的原料配制成：
聚酰胺 68-92％；
氰尿酸三聚氰胺 5-25％；
增韧剂 2-15％；
抗氧剂 0.1-1％；
热稳定剂 0.1-2％；
结晶促进剂 0.1-2％。
以上所述的无卤无磷环保阻燃的聚酰胺树脂，最好由以下配比的原料配制成：
聚酰胺 68-76％；
氰尿酸三聚氰胺 8-18％；
增韧剂 4-5％；
抗氧剂 0.1-0.3％；
热稳定剂 0.2-0.4％；
结晶促进剂 0.1-0.5％。
其中，所述聚酰胺为聚己二酰己二胺和聚己内酰胺的混合物，相对密度为1.12-1.15g/cm3，熔点为255-265℃，熔体粘度为0.3-3。所述热稳定剂为一类铜复合物的抗氧剂和增效剂的混合物。所述增韧剂为热塑性弹性体。所述热塑性弹性体为乙丙橡胶接枝物或热塑性聚聚烯烃。所述的结晶促进剂为一种有机成分和无机成分的细致粉末混合物。
上述无卤无磷环保阻燃的聚酰胺树脂的制备方法，包括以下步骤：
按重量比称取原料：聚酰胺(PA)58-92％，氰尿酸三聚氰胺5-25％，增韧剂2-15％，抗氧剂0.1-1％，热稳定剂0.1-2％，结晶促进剂0.1-2％；
将聚酰胺、增韧剂、抗氧化剂、热稳定剂、结晶促进剂在中速混合器中预混2-3分钟，然后再加入氰尿酸三聚氰胺混合5-10分钟；
将混合的原料置于特定螺杆组合的双螺杆机中，经熔融挤出，造粒，其工艺为：双螺杆一区温度210-230℃，二区温度230-250℃，三区温度250-270，四区温度260-280；在料筒中停留时间1-2分钟，熔体压力为10-20MPa。
本发明的有益效果是：通过添加氰尿酸三聚氰胺、结晶促进剂、热稳定剂三组分复合阻燃剂，能够有效地提高聚酰胺的氧指数，同时由于其均为有机高分子材料，与聚酰胺的相容性好，所以对其综合性能的影响小，所以所制得的阻燃材料综合性能好，并且符合环保要求，应用前景广阔；本发明在无卤无磷阻燃聚酰胺材料中由氰尿酸三聚氰胺、结晶促进剂、热稳定剂构成的无卤无磷环保阻燃体系，使得聚酰胺材料的物理力学性能好、阻燃性能优异，而且有良好的热稳定性；本发明所采用的助剂，如氰尿酸三聚氰胺、结晶促进剂、热稳定剂、增韧剂和抗氧剂等组分，均为价格低廉的市售产品，材料的生产成本较低；本发明所提出的无卤阻燃PA复合材料的制备工艺简单、成本低。
[具体实施方式]
下面通过实施例对本发明进行进一步阐述：
在实施复合材料配方中，聚酰胺为聚己二酰己二胺(PA66)和聚己内酰胺(PA6)的混合物，相对密度为1.12-1.15g/cm3，熔点为255-265℃，熔体粘度为0.3-3；增韧剂为一种接枝的乙烯共聚物，为Dupont公司生产，商品牌号为493D的接枝共聚物；热稳定剂为铜复合物的抗氧剂和增效剂的混合物，为BRUGGOLEN公司生产，商品牌号为H3373；结晶促进剂为德国科莱恩公司生产，商品牌号为CAV102，抗氧剂化学名称为四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯，如Ciba公司生产，商品牌号为Irganox 1010。
实施例1
将重量比为PA66---79.7％、PA6---10％、493D---4.5％、MCA---5％、CAV102---0.3％、1010---0.2％、H3373---0.3％在中速混合器中在室温状态下预混3分钟，然后再加入阻燃剂混合5分钟，然后经熔融挤出、造粒制成复合材料。双螺杆一区温度220℃，二区温度240℃，三区温度260，四区温度270；在料筒中停留时间1.5分钟，熔体压力为16MPa。
实施例2
将重量比为PA66---74.7％、PA6---10％、493D---4.5％、MCA---10％、CAV102---0.3％、1010---0.2％、H3373---0.3％在中速混合器中在室温状态下预混3分钟，然后再加入阻燃剂混合5分钟，然后经熔融挤出、造粒制成复合材料。双螺杆一区温度220℃，二区温度240℃，三区温度260，四区温度270；在料筒中停留时间1.5分钟，熔体压力为16MPa。
实施例3
将重量比为PA66---69.7％、PA6---10％、493D---4.5％、MCA---15％、CAV102---0.3％、1010---0.2％、H3373---0.3％在中速混合器中在室温状态下预混3分钟，然后再加入阻燃剂混合5分钟，然后经熔融挤出、造粒制成复合材料。双螺杆一区温度220℃，二区温度240℃，三区温度260，四区温度270；在料筒中停留时间1.5分钟，熔体压力为16MPa。
实施例4
将重量比为PA66---64.7％、PA6---10％、493D---4.5％、MCA---20％、CAV102---0.3％、1010---0.2％、H3373---0.3％在中速混合器中在室温状态下预混3分钟，然后再加入阻燃剂混合5分钟，然后经熔融挤出、造粒制成复合材料。双螺杆一区温度220℃，二区温度240℃，三区温度260，四区温度270；在料筒中停留时间1.5分钟，熔体压力为16MPa。
实施例5
将重量比为PA66---59.7％、PA6---10％、493D---4.5％、MCA---25％、CAV102---0.3％、1010---0.2％、H3373---0.3％在中速混合器中在室温状态下预混3分钟，然后再加入阻燃剂混合5分钟，然后经熔融挤出、造粒制成复合材料。双螺杆一区温度220℃，二区温度240℃，三区温度260，四区温度270；在料筒中停留时间1.5分钟，熔体压力为16MPa。
对比例1
将重量比为PA66---70％、PA6---10％、493D---4.5％、MCA---15％、1010---0.2％、H3373---0.3％在中速混合器中在室温状态下预混3分钟，然后再加入阻燃剂混合5分钟，然后经熔融挤出、造粒制成复合材料。双螺杆一区温度220℃，二区温度240℃，三区温度260，四区温度270；在料筒中停留时间1.5分钟，熔体压力为16MPa。
性能评价方式及实行标准：
将按上述方法完成造粒的粒子材料预先在100℃的鼓风烘箱中干燥3-6小时，然后再将干燥好的粒子材料在注射成形机上进行注射成型制样，注射成型模温控制在100℃左右。
拉伸强度测试按ISO527-2进行，试样尺寸为150×10×4mm，拉伸速度为50mm/min；弯曲性能测试按ISO 178进行，试样尺寸为80×10×4，弯曲速度为2mm/min，跨距为64mm；简支梁冲击强度按ISO179进行，试样尺寸为55×6×4mm，缺口尺寸为试样厚度的三分之一；阻燃性能按UL94方法进行，样条厚度大约为1.5mm。
综合力学性能通过测试所得的拉伸强度、断裂伸长率、弯曲模量以及冲击强度的数值进行评判；材料的阻燃性能按UL94的标准进行评判。
实施例1-5以及对比例1-2的配方及力学性能测试结果见表1及表2；
表1实施例1-5的配方及材料性能表
| 组成 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
| PA66(％) | 79.7 | 74.7 | 69.7 | 64.7 | 59.7 |
| PA6(％) | 10 | 10 | 10 | 10 | 10 |
| MCA(％) | 5 | 10 | 15 | 20 | 25 |
| 493D(％) | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 |
| CAV102(％) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| H3373(％) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| 1010(％) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| 缺口冲击强度(KJ/M2) | 18 | 17.3 | 16.8 | 16.2 | 15.5 |
| 拉伸强度(Mpa) | 80 | 82 | 78 | 80 | 76 |
| 断裂伸长率(％) | 15 | 13 | 16 | 15 | 16 |
| 弯曲模量(Mpa) | 2300 | 2450 | 2400 | 2460 | 2430 |
| 长期热稳定性(h) | 5 | 5.5 | 5 | 4.5 | 5 |
| 阻燃性(UL94) | V0 | V0 | V0 | V0 | V0 |
表2对比例1-2的配方及材料性能表
| 组成 | 对比例1 | 对比例2 |
| PA66(％) | 70 | 29.7 |
| PA6(％) | 10 | 10 |
| MCA(％) | 15 | / |
| 氢氧化镁 | / | 55 |
| 493D(％) | 4.5 | 4.5 |
| CAV102(％) | 0.3 | 0.3 |
| H3373(％) | 0.3 | |
| 1010(％) | 0.2 | 0.2 |
| 缺口冲击强度(KJ/M2) | 15 | 6 |
| 拉伸强度(Mpa) | 80 | 76 |
| 断裂伸长率(％) | 15 | 3 |
| 弯曲模量(Mpa) | 2500 | 1500 |
| 长期热稳定性(h) | 0.5 | 3.5 |
| 阻燃性(UL94) | V0 | V0 |
通过表1实施例1-5及表2对比例1-2的各项性能分析可知，无卤无磷阻燃聚酰胺复合材料的综合力学性能较好，其阻燃性能达到了UL94V0的标准。并且从表1实施例1-5的各项性能数据来看，无卤无磷复合阻燃体系三种组分缺其中那一种都无法达到阻燃V0级，而且结晶促进剂的加入加速了树脂的结晶速度，所形成的晶粒细小均匀，使得整体材料的强度高，不易滴落。而阻燃剂添加量过多会影响材料的综合物理力学性能，还会导致燃烧过程中出现滴落现象，阻燃性能无法达到UL94-V0级。MCA添加量为15％，CAV102含量为0.3％，热稳定剂为0.3％时材料的综合力学性能、阻燃性以及性价比均较好，经过以上改性处理的复合材料综合性能优异。
本发明的聚酰材料的氧指数得到有效提高，其具有制备工艺简单、成本适中、各项物理化学性能优异、阻燃性能优良等特点，可用于电子、电器元件、汽车配件等技术领域。
Claims (4)
1.一种无卤无磷环保阻燃的聚酰胺树脂，其特征在于，由以下配比的原料配制成：
聚酰胺 68-92％；
氰尿酸三聚氰胺 5-25％；
增韧剂 2-15％；
抗氧剂 0.1-1％；
热稳定剂 0.1-2％；
结晶促进剂 0.1-2％；
所述增韧剂为热塑性弹性体；所述热稳定剂为一类铜复合物的抗氧剂和增效剂的混合物；所述的结晶促进剂为一种有机成分和无机成分的细致粉末混合物。
2.根据权利要求1所述的无卤无磷环保阻燃的聚酰胺树脂，
其特征在于，由以下配比的原料配制成：
聚酰胺 68-76％；
氰尿酸三聚氰胺 8-18％；
增韧剂 4-5％；
抗氧剂 0.1-0.3％；
热稳定剂 0.2-0.4％；
结晶促进剂 0.1-0.5％；
上述各组分的配比百分数之和为100％。
3.根据权利要求1所述的无卤无磷环保阻燃的聚酰胺树脂，其特征在于：所述聚酰胺为聚己二酰己二胺和聚己内酰胺的混合物，相对密度为1.12-1.15g/cm3，熔点为255-265℃，熔体粘度为0.3-3。
4.根据权利要求4所述的无卤无磷环保阻燃的聚酰胺树脂，其特征在于：所述热塑性弹性体为乙丙橡胶接枝物或热塑性聚烯烃。
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| CN103242655B (zh) * | 2013-05-31 | 2015-08-19 | 广东国立科技股份有限公司 | 无卤阻燃pa66塑胶改性材料及其制备方法 |
| CN104774457A (zh) * | 2015-04-21 | 2015-07-15 | 广东顺德顺炎新材料有限公司 | 一种高冲击环保无卤阻燃增强尼龙材料及制备方法和应用 |
| CN105062062A (zh) * | 2015-09-16 | 2015-11-18 | 东莞市沃府工程塑料科技有限公司 | 一种无卤阻燃尼龙复合材料及其制备方法 |
| CN105924956A (zh) * | 2016-05-24 | 2016-09-07 | 桐城市中汇塑业有限公司 | 一种无卤阻燃的尼龙复合材料 |
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