CN102850648A - 无卤阻燃聚丙烯复合材料及其制备方法 - Google Patents

无卤阻燃聚丙烯复合材料及其制备方法 Download PDF

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CN102850648A
CN102850648A CN201210111466XA CN201210111466A CN102850648A CN 102850648 A CN102850648 A CN 102850648A CN 201210111466X A CN201210111466X A CN 201210111466XA CN 201210111466 A CN201210111466 A CN 201210111466A CN 102850648 A CN102850648 A CN 102850648A
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polypropylene
glasscloth
composite material
flame retardant
halogen
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CN102850648B (zh
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孟波
李艳涛
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Changzhou Weimao New Material Technology Co., Ltd.
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JIANGSU AGT TECHNOLOGY DEVELOPMENT CO LTD
JIANGSU AGT NEW MATERIAL TECHNOLOGY CO LTD
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    • 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
    • B29C48/07—Flat, e.g. panels
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • 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
    • B29C48/397—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 a single screw
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    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • 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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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
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    • B29C2948/92—Measuring, controlling or regulating
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    • B29C2948/92647—Thickness
    • 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
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
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    • 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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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
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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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    • B29C2948/92923—Calibration, after-treatment or cooling zone

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Abstract

本发明涉及复合材料制备技术领域，尤其是一种无卤阻燃聚丙烯复合材料及其制备方法，复合材料组分包括聚丙烯浸渍液、阻燃聚丙烯流延层和玻璃纤维布，制备方法包括玻璃纤维布经过聚丙烯浸渍液预浸渍和阻燃聚丙烯流延层的挤压复合。本发明采用先预浸渍和后压延的制备流程，所得无卤阻燃聚丙烯复合材料氧指数较高，阻燃性能较强，制备方法简单环保，可显著提高现有劳动生产效率。

Description

无卤阻燃聚丙烯复合材料及其制备方法
技术领域
本发明涉及复合材料制备技术领域，尤其是一种无卤阻燃聚丙烯复合材料及其制备方法。
背景技术
复合材料对于现代科学技术的发展有着十分重要的作用，其特点在于高强度、低密度、容易成型及加工方便等，主要分为热固性和热塑性复合材料，热固性复合材料有较好的力学强度，但是存在加工工艺复杂及不能回收的缺点；连续纤维增强热塑性复合材料是热塑性复合材料中的一种，其强度高于一般短纤维增强复合材料。CN201010148904.0公开了一种经纬交叠无织造复合材料的加工设备，描述了一种生产连续纤维增强复合材料的生产设备，此篇专利所用技术不能满足一些应用领域对于阻燃产品的需求；CN200610023796.8公开了一种膨胀型阻燃玻璃纤维增强聚丙烯复合材料及其制备方法，其描述了一种玻璃纤维毡和聚丙烯复合的方法，这种方法是先制备聚丙烯片材，然后和玻璃纤维毡复合压制，这种做法选用低流动性聚丙烯，玻璃纤维毡含量少于50％，连续生产效率低，产品尺寸有一定限制。
发明内容
本发明要解决的技术问题是：提供一种阻燃性能较强和生产效率较高的无卤阻燃聚丙烯复合材料及其制备方法。
本发明解决其技术问题所采用的技术方案是：一种无卤阻燃聚丙烯复合材料，其组分包括聚丙烯浸渍液、阻燃聚丙烯流延层和玻璃纤维布，按质量百分数计，其中的聚丙烯浸渍液配方为：49-80％聚丙烯、19-50％相容剂及1-3％抗氧化剂；阻燃聚丙烯流延层配方为：51-90％聚丙烯、1-30％复合膨胀型阻燃剂、6-16％相容剂及1-3％抗氧化剂。
所述聚丙烯为均聚聚丙烯或丙烯与乙烯共聚物，熔指范围60-150g/10min；相容剂为马来酸酐接枝聚丙烯或环氧乙烷接枝聚丙烯，其可提高树脂和玻纤相容性，降低加工温度；抗氧化剂为1076汽巴抗氧剂和168汽巴抗氧剂按质量比2∶1组成的配方。
所述复合膨胀型阻燃剂为按聚戊四醇和聚磷酸铵质量比1∶2组成的配方。
所述玻璃纤维布的经向和纬向交角为70-90°，可保证复合材料在各个方向有均匀强度。
一种无卤阻燃聚丙烯复合材料的制备方法，包括玻璃纤维布经过聚丙烯浸渍液预浸渍和阻燃聚丙烯流延层的挤压复合，其具体步骤为：
1)按照49-80％聚丙烯、19-50％相容剂及1-3％抗氧化剂称量聚丙烯浸渍液配方；按照51-90％聚丙烯、1-30％复合膨胀型阻燃剂、6-16％相容剂及1-3％抗氧化剂称量阻燃聚丙烯流延层配方，将其放入100℃的烘箱中干燥3小时；
2)将上述步骤1)的两类聚丙烯树脂分别均匀地从双螺杆机加料口加入，熔融温度设置为200℃，螺杆转速400r/min，通过混炼、水下切粒和干燥完成造粒；
3)首先将玻璃纤维布通过浸渍池内使玻璃纤维布处于松弛和紧张交替状态的牵引辊，再将聚丙烯浸渍液配方粒子通过单螺杆挤出机在25 0℃形成的聚丙烯浸渍液引入浸渍池，使聚丙烯浸渍液渗透入玻璃纤维布间隙；
4)将玻璃纤维布从浸渍池中拉出，并保持180℃进入下步骤；
5)使用双模头挤出机，将阻燃聚丙烯流延层配方粒子挤出成双层熔体涂敷于浸渍了聚丙烯浸渍液的玻璃纤维布两侧，温度控制在220℃，玻璃纤维布走布速度5m/min，采用1-3对圆辊控制厚度并压实。
有益效果：本发明的无卤阻燃聚丙烯复合材料聚丙烯浸渍液与玻璃纤维布相容性好，在玻璃纤维布内部流动性好；阻燃聚丙烯流延层对复合材料的整体阻燃性能具有较大贡献，所得复合材料氧指数较高，阻燃性能较强，本发明采用先预浸渍和后压延的制备流程，制备方法简单环保，可显著提高现有劳动生产效率。
具体实施方式
以下结合优选实施例叙述技术方案，但本发明不仅限于下述实施例。对照例，实施例一到五
一种无卤阻燃聚丙烯复合材料的制备方法，具体步骤为：
1)按质量百分数计，其中的聚丙烯浸渍液配方如表1所示，阻燃聚丙烯流延层配方和玻璃纤维布如表2所示，将其放入100℃的烘箱中干燥3小时；
表1聚丙烯浸渍液配方
Figure BDA0000153742490000031
表2阻燃聚丙烯流延层配方和玻璃布选择
Figure BDA0000153742490000032
2)将上述步骤1)的两类聚丙烯树脂分别均匀地从双螺杆机加料口加入，熔融温度设置为200℃，螺杆转速400r/min，通过混炼、水下切粒和干燥完成造粒；
3)首先将玻璃纤维布通过浸渍池内使玻璃纤维布处于松弛和紧张交替状态的牵引辊，再将聚丙烯浸渍液配方粒子通过单螺杆挤出机在250℃形成的聚丙烯浸渍液引入浸渍池，使聚丙烯浸渍液渗透入玻璃纤维布间隙；
4)将玻璃纤维布从浸渍池中拉出，并保持180℃进入下步骤；
5)使用双模头挤出机，将阻燃聚丙烯流延层配方粒子挤出成双层薄膜涂敷于浸渍了聚丙烯浸渍液的玻璃纤维布两侧，温度控制在220℃，玻璃纤维布走布速度5m/min，采用3对圆辊控制涂敷厚度0.75mm。
上述实施例一到五所得产品性能参数见表3
表3产品主要技术指标
Figure BDA0000153742490000042
结合上述实施例配方和产品技术指标可知，比较对照例一和实施例一，阻燃剂的加入提高了氧指数；由实施例二和三可知，复合膨胀型阻燃剂添加量较高时，产品的氧指数较高；实施例五产品发黄是必然现象，现场有严重氨气气味，提示阻燃剂分解，氧指数严重下降。

Claims (3)

1.一种无卤阻燃聚丙烯复合材料，其组分包括聚丙烯浸渍液、阻燃聚丙烯流延层和玻璃纤维布，其特征是：按质量百分数计，其中的聚丙烯浸渍液配方为：49-80％聚丙烯、19-50％相容剂及1-3％抗氧化剂；阻燃聚丙烯流延层配方为：51-90％聚丙烯、1-30％复合膨胀型阻燃剂、6-16％相容剂及1-3％抗氧化剂；
所述聚丙烯为均聚聚丙烯或丙烯与乙烯共聚物，熔指范围60-150g/10min；相容剂为马来酸酐接枝聚丙烯或环氧乙烷接枝聚丙烯；复合膨胀型阻燃剂为按聚戊四醇和聚磷酸铵质量比1∶2组成的配方。
2.如权利要求1所述的无卤阻燃聚丙烯复合材料，其特征是：所述玻璃纤维布的经向和纬向交角为70-90°。
3.如权利要求1所述的无卤阻燃聚丙烯复合材料的制备方法，其特征是：具体步骤为：
1)按照49-80％聚丙烯、19-50％相容剂及1-3％抗氧化剂称量聚丙烯浸渍液配方；按照51-90％聚丙烯、1-30％复合膨胀型阻燃剂、6-16％相容剂及1-3％抗氧化剂称量阻燃聚丙烯流延层配方，将其放入100℃的烘箱中干燥3小时；
2)将上述步骤1)的两类聚丙烯树脂分别均匀地从双螺杆机加料口加入，熔融温度设置为200℃，螺杆转速400r/min，通过混炼、水下切粒和干燥完成造粒；
3)首先将玻璃纤维布通过浸渍池内使玻璃纤维布处于松弛和紧张交替状态的牵引辊，再将聚丙烯浸渍液配方粒子通过单螺杆挤出机在250℃形成的聚丙烯浸渍液引入浸渍池，使聚丙烯浸渍液渗透入玻璃纤维布间隙；
4)将玻璃纤维布从浸渍池中拉出，并保持180℃进入下步骤；
5)使用双模头挤出机，将阻燃聚丙烯流延层配方粒子挤出成双层薄膜涂敷于浸渍了聚丙烯浸渍液的玻璃纤维布两侧，温度控制在220℃，玻璃纤维布走布速度5m/min，采用1-3对圆辊控制厚度并压实。
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