CN113527783A - 发泡喷丝材料和糙面土工膜及各自的制备方法 - Google Patents

发泡喷丝材料和糙面土工膜及各自的制备方法 Download PDF

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CN113527783A
CN113527783A CN202010291215.9A CN202010291215A CN113527783A CN 113527783 A CN113527783 A CN 113527783A CN 202010291215 A CN202010291215 A CN 202010291215A CN 113527783 A CN113527783 A CN 113527783A
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foaming
geomembrane
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CN113527783B (zh
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摆音娜
李蕾
徐毅辉
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Beijing Yanshan Petrochemical Hi Tech Co ltd
China Petroleum and Chemical Corp
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Abstract

本发明涉及高分子材料领域，公开了一种发泡喷丝材料和糙面土工膜及各自的制备方法。该发泡喷丝材料包含组分I、组分II、组分III、组分IV和组分V，其中，所述组分I为低密度聚乙烯，所述组分II选自聚苯乙烯、聚碳酸酯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯和聚酰胺中的至少一种；组分III选自聚丙烯和/或高密度聚乙烯；所述组分IV为无机填料；组分V由发泡剂和发泡促进剂组成。该发泡喷丝材料经过喷丝工艺喷涂于聚乙烯光面土工膜上，喷丝稳定，喷后不脱落，可以达到对聚乙烯光面土工膜加糙及减震降噪的目的。

Description

发泡喷丝材料和糙面土工膜及各自的制备方法
技术领域
本发明涉及高分子材料领域，具体涉及一种发泡喷丝材料和糙面土工膜及各自的制备方法。
背景技术
聚乙烯土工膜是以聚乙烯(PE)为基本原料生产的防水阻隔性材料，具有极低的渗透性，是理想的防渗材料。与传统的防水材料比，PE土工膜具有柔性好、变形适用性强、强度高、渗透系数低、整体连接性好、施工方便等优点。PE土工膜按产品外形可分为光滑面土工膜和糙面土工膜。糙面土工膜表面由凹凸状结构组成，摩擦系数高。与光滑面土工膜相比，糙面土工膜不仅能应用于屋顶防漏、园林绿化、农田水渠的防渗和水土保持、滩涂围垦造田、环境工程中垃圾填埋等工程，还能应用于陡坡或边坡膜体表面需要覆土等要求有较大摩擦系数的工程项目中，是陡坡施工、山区施工等工程项目的首选材料。因此，水利、水电、交通、环保、建筑等各个领域都为糙面土工膜的应用发展提供了广阔的前景。
PE土工膜糙面成型方法主要包括喷丝加糙法、轧花成糙法、化学发泡成糙法和氮气(N2)加糙法等。其中，喷丝加糙法是将PE光滑面土工膜预热，使所需加糙土工膜面层达到热变形温度以上，通过特殊的喷塑设备喷丝，将熔融状塑料丝喷涂在所需加糙的土工膜表面，经过冷却制得粗糙面层的方法。喷丝加糙法属于二次成型，即,将光滑面土工膜再一次加工成型，可将压延成型和吹塑成型工艺生产的光滑面土工膜进行预热喷丝，得到PE糙面土工膜，也可将预热和喷丝工序直接添加到土工膜生产线中，以实现PE糙面土工膜的连续化生产。
但是，喷丝加糙法工艺复杂，糙面质量不稳定，喷丝工艺难度大，塑料丝在土工膜表面容易脱落，降低其防滑性能。现有的喷丝过程通常需要对长达数米甚至数十米的光面土工膜进行二次加热，喷丝材料与光面土工膜结合不好，容易脱落，也就失去了防滑功能，加糙效果不持久。
发明内容
为了克服现有的喷丝加糙工艺存在的上述缺陷，本发明的目的在于提供一种发泡喷丝材料和糙面土工膜及各自的制备方法。该发泡喷丝材料经过喷丝工艺喷涂于聚乙烯光面土工膜上，喷丝稳定，喷后不脱落，可以达到对PE光面土工膜加糙及减震降噪的目的。
本发明的第一方面提供一种发泡喷丝材料，该喷丝发泡材料包含组分I、组分II、组分III、组分IV和组分V，其中，所述组分I为低密度聚乙烯，所述组分II选自聚甲基丙烯酸甲酯、聚碳酸酯、聚对苯二甲酸乙二醇酯、聚苯乙烯、聚对苯二甲酸丁二醇酯和聚酰胺中的至少一种；所述组分III选自聚丙烯和/或高密度聚乙烯；所述组分IV选自无机填料；所述组分V由发泡剂和发泡促进剂组成；
以所述发泡喷丝材料的总重量为基准，所述组分I的含量为32-65重量％，所述组分II的含量为15-26重量％，所述组分III的含量为3-16重量％，所述组分IV的含量为10-30重量％，所述组分V的含量为3-5重量％。
本发明的第二方面提供一种制备本发明第一方面所述发泡喷丝材料的方法，该方法包括：将所述发泡喷丝材料中的各组分进行熔融共混并挤出造粒。
本发明的第三方面提供一种糙面土工膜，所述糙面土工膜包括PE光面土工膜和形成在该光面土工膜至少一个表面上的糙面，其中，所述糙面由本发明第一方面所述的发泡喷丝材料制成。
本发明的第四方面提供所述糙面土工膜的制备方法，该制备方法包括：通过喷丝工艺将所述发泡喷丝材料喷涂于所述PE光面土工膜的至少一个表面上，形成所述糙面。
本发明的发泡喷丝材料组成简单，成本低，以该发泡喷丝材料对PE光面土工膜的表面进行喷丝加糙，能够省去传统工艺中对土工膜二次加热的过程，从而节能减耗，喷丝后表面粗糙部分不脱落，加糙持久，并且减震降噪，有效降低施工过程中的噪音污染。
附图说明
图1是表示应用实施例1制备的糙面土工膜的糙面形貌的照片。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
第一方面，本发明提供了一种发泡喷丝材料，该发泡喷丝材料包含组分I、组分II、组分III、组分IV和组分V。
在本发明中，所述组分I为低密度聚乙烯(LDPE)，能够提高喷丝材料与光面土工膜的结合强度。优选地，所述低密度聚乙烯在190℃、2.16kg下的熔体流动质量速率(MFR)为35-50g/10min。
在本发明中，所述组分II能够降低复合材料的熔体拉伸强度。所述组分II具体聚甲基丙烯酸甲酯、聚碳酸酯、聚对苯二甲酸乙二醇酯、聚苯乙烯、聚对苯二甲酸丁二醇酯和聚酰胺中的一种或两种以上。
优选地，所述聚甲基丙烯酸甲酯在230℃、3.8kg的熔体流动质量速率为为1.7-2.0g/10min，密度为1.16-1.20g/cm3。
优选地，所述聚碳酸酯在300℃、1.2kg的熔体流动质量速率为3-4g/10min，密度为1.18-1.22g/cm3。
优选地，所述聚苯乙烯的在200℃、5kg下的熔体流动质量速率为1.5-8g/10min，密度为1.02-1.07g/cm3。
优选地，所述聚对苯二甲酸丁二醇酯的密度为1.2-1.5g/cm3。
优选地，所述聚对苯二甲酸乙二醇酯的密度为1.62-1.70g/cm3。
所述聚酰胺可以选自尼龙6、尼龙66、尼龙1010和尼龙1212中的一种或两种以上。优选地，所述聚酰胺的密度1-1.6g/cm3。
在本发明中，所述组分III选自聚丙烯(PP)和高密度聚乙烯(HDPE)引入组分III能够增加喷丝材料的喷丝挺度。
优选地，所述聚丙烯在230℃、2.16kg下熔体流动质量速率为1-5g/10min。
优选地，所述高密度聚乙烯在190℃、2.16kg下的熔体流动质量速率为0.5-5g/10min。
在本发明中，熔体流动质量速率(MFR)根据GB/T 3682-2000测得，密度通过GB/T1033.2-2008测得。
在本发明中，所述组分IV为无机填料，能为喷丝材料提供喷丝断点。所述无机填料可参照现有聚丙烯材料中的进行选择，只要能起到前述作用即可。但为了在保证所述喷丝材料性能的同时进一步降低原料成本，优选情况下，所述无机填料选自碳酸钙、滑石粉、蒙脱土、二氧化硅和高岭土中的至少一种。制备所述发泡喷丝材料时，所述无机填料可以为粉末状，也可以是以其填料母粒形式引入到所述复合材料中。其中，以粉末状使用的所述无机填料的粒径范围可以为80-180μm。所述填料母粒中，无机填料的含量一般为30-80重量％，作为成型母粒时的其它组分，其具体种类和含量均为本领域所熟知，在此不再赘述。
在本发明中，所述组分V由发泡剂和发泡促进剂组成。本发明对发泡剂和发泡促进剂没有特别限定，只要能起到发泡作用即可。所述发泡剂和发泡促进剂的质量之比可以为1:0.2-1。
优选地，所述发泡剂选自4,4’-氧代双苯磺酰肼、偶氮二甲酰胺、偶氮二异丁腈和二亚硝基五次甲基四胺中的至少一种。
优选地，所述发泡促进剂选自氧化锌和/或硬脂酸锌。更优选地，所述发泡促进剂为氧化锌和/或硬脂酸锌的组合，两者的质量比为1:0.5-1。
在本发明中，以所述发泡喷丝材料的总重量为基准，所述组分I的含量为32-65重量％，所述组分II的含量为15-26重量％，所述组分III的含量为3-16重量％，所述组分IV的含量为10-30重量％，所述组分V的含量为3-5重量％。所述含量均根据各组分的投料量计算得到。
在本发明中，根据应用需要，所述发泡喷丝材料中还可以含有其它加工助剂，例如本领域技术人员所知的色母粒、抗氧剂等。所述其它加工助剂的具体种类和用量均为本领域所熟知，本发明不再赘述。
在本发明中，所述发泡喷丝材料中的各种组分均可通过本领域熟知的方法制得，也可通过商购获得。
第二方面，本发明提供了一种制备所述发泡喷丝材料的方法，该方法包括：将所述发泡喷丝材料中的各组分在挤出发泡设备上进行熔融共混并发泡。
按照一种实施方式，所述挤出发泡设备包括依次串联的双螺杆挤出机和单螺杆挤出机，其中，所述发泡阶段在单螺杆挤出机中进行。优选地，所述组分I、组分II、组分III、组分IV在所述双螺杆挤出机中熔融共混并挤出，然后将挤出产物送入所述单螺杆挤出机，同时加入所述组分V进行发泡。
所述双螺杆挤出机的长径比通常大于等于30，转速可以为50-100r/min。优选地，所述熔融共混的温度为170-250℃，所述发泡的温度为160-240℃。螺杆的挤出速度可以为5-30rpm，熔体压力为3-35bar。
优选地，所述双螺杆挤出机中的挤出产物在190℃、2.16kg下的熔体质量流动速率为17-25g/10min，密度为0.988-1.182g/10cm3，熔体拉伸断裂速度为76-90m/min，熔体拉伸张力为0.004-0.006N。
在本发明中，熔体拉伸断裂速度、熔体拉伸张力均按照熔体强度测试仪法，采用毛细管流变仪测得。
在本发明中，所述发泡喷丝材料通过喷丝工艺能够在PE光滑土工膜表面形成糙面，且与光面土工膜具有较高的结合强度。
第三方面，本发明提供了一种糙面土工膜，所述糙面土工膜包括PE光面土工膜和形成在该光面土工膜至少一个表面上的糙面，其中，所述糙面是由所述发泡喷丝材料制成。采用本发明的发泡喷丝材料在所述光面土工膜上形成糙面，喷丝内部产生气孔，可以起到减震降噪的作用。
第四方面，本发明提供了所述糙面土工膜的制备方法，该方法包括：通过喷丝工艺将所述发泡喷丝材料喷涂于所述PE光面土工膜的至少一个表面上，形成所述糙面。
本发明的第三、第四方面旨在说明所述发泡喷丝材料在糙面土工膜上的应用，因此对所述PE光面土工膜以及喷丝工艺的具体操作没有特别限定，均可参照现有技术选择。所述发泡喷丝材料通过喷涂法在所述PE光面土工膜形成糙面，可利用现有的土工膜糙面喷涂机制备所述糙面土工膜。一般地，土工膜糙面喷涂机由数个单螺杆挤出机并联而成，并联后整体进行左右移动，所述复合材料由出料口喷射而出，经过热风送至光面土工膜表面，光面土工膜延喷射方向传送卷曲，使表面充分粘结所述复合材料。优选地，喷丝料温为130-150℃，熔体压力为3-35bar，挤出速度为6-80rpm，风温为300-370℃。
所述糙面土工膜的表面喷涂率可以为5-20％，喷丝直径可以为0.2-0.5mm。其中，喷涂率＝糙丝面积/光面土工膜面积。
根据本发明，在喷丝过程中，所述PE光面土工膜的温度可保持在其热变形温度以下，即所述制备方法无需对PE光面土工膜进行预热的步骤，从而节省能耗。
以下将通过实施例对本发明进行详细描述。
实施例1-7用于说明本发明的发泡喷丝材料及其制备方法。
实施例和对比例中，
LDPE购自燕山石化，牌号为YG220P，MFR(190℃、2.16kg)为40g/10min，密度0.922±0.005g/cm3；
PC购自GE塑料公司，牌号为131R，MFR(300℃、1.2kg)为3.5g/10min，密度为1.21g/cm3；
PS购自扬子石化，牌号为158K，MFR(200℃、5kg)为3g/10min，密度1.05g/cm3；
PMMA购自台湾奇美，牌号CM-205，MFR(230℃、3.8kg)为1.8g/10min，密度为1.19g/cm3；
PBT购自美国杜邦，牌号S600F10，密度为1.30g/cm3；
PET购自美国杜邦，牌号FR330，密度为1.67g/cm3；
PA6购自日本三菱，牌号1030，密度为1.14g/cm3；
PP购自燕山石化公司，牌号K8303，MFR(1230℃、2.16kg)为2.0g/10min；
HDPE购自燕山石化公司，牌号3000J，MFR(190℃、2.16kg)为2.3g/10min；
无机填料均为粉末状，粒径范围为80-180μm。
实施例1-7和对比例1-5
按照表1的配方将物料在挤出发泡设备上熔融共混并挤出造粒，其中，双螺杆挤出机的挤出温度为180-230℃，挤出速度为15-20rpm，熔体压力为20-30bar，双螺杆挤出机的长径比为32，转速为70-90r/min；单螺杆挤出机的发泡温度为170-220℃，由此制备得到发泡喷丝材料母粒。
实施例1-7制备的发泡喷丝材料分别记为A1-A7，对比例1-5制备的发泡喷丝材料分别记为D1-D5。
表1
Figure BDA0002450461870000081
*：“×/×”是表示发泡剂与发泡促进剂的质量比，实施例和对比例中，发泡促进剂为氧化锌和硬脂酸锌的组合时，两者的质量比为1:1。
测试例1
在不添加组分V的情况下，即对双螺杆挤出机的挤出产物进行熔体质量流动速率、密度、熔体拉伸断裂速度、熔体拉伸张力的测试。
熔体质量流动速率(MFR)(190℃、2.16kg)根据GB/T 3682-2000测得；
按照熔体强度测试仪法，采用毛细管流变仪测量熔体拉伸断裂速度(haul off)、熔体拉伸张力(haul off)；
密度根据GB/T 1033.1-2008测得。
测试结果如表2所示。
表2
Figure BDA0002450461870000091
以下应用实施例1-7用于说明本发明的糙面土工膜及其制备方法。
应用实施例1-7和应用对比例1-5
采用喷丝工艺分别将复合材料A1-A7和D1-D5喷涂在PE光面土工膜的一个表面上，形成加糙土工膜。
PE光面土工膜的厚度为2mm。
糙面土工膜采用山东大三层塑料机械厂的土工膜糙面喷涂机来制备。其中，喷丝料温为140-145℃，熔体压力为25-30bar，挤出速度为65-70rpm，风温为310-340℃。糙面土工膜表面的喷涂率为5％，喷丝直径为0.4mm。
结果显示，发泡喷丝材料A1-A7在光面土工膜表面的喷丝均匀(实施例1的复合材料A1喷丝效果如图1所示)；
对比例1的喷丝材料D1无法同光面土工膜进行粘结；
对比例2-3的喷丝材料D2、D3形成的是连续喷丝；
对比例4的喷丝材料D4喷丝垮塌；
对比例5的喷丝材料D5无法形成喷丝。
测试例2
(1)摩擦系数
采用摆式摩擦系数仪对糙面土工膜进行摩擦系数测定，滑移速度为10km/h。
(2)质量损失百分率
依据GB/T 17636-1998对糙面土工膜进行磨损试验，以每分钟90周期的频率进行工作，测试磨100个周期的质量损失百分率。
(3)拉伸断裂后糙点距离
采用万能拉力机对糙面土工膜进行拉伸，拉伸速度为50mm/min，根据GB/T1040.2-2006，采用五根样条，测试前每根样条上选选取有效拉伸区域内间隔1mm的3对糙点，待样条断裂后测量两点间距离，每根样条上选取断裂后在同一侧的点为有效值，测试5次，选取中间值为最终测试结果。
糙面土工膜的性质如表3所示。
表3
Figure BDA0002450461870000101
Figure BDA0002450461870000111
结合表3的数据可知，与对比例1-5相比，实施例1-7的发泡喷丝材料形成的糙面与光滑土工膜具有较高的结合强度且结合稳定性高。对比例2和3形成连续喷丝，导致光面土工膜加糙后表面纹理构造过大，失去摩擦抗滑力。对比例4喷丝垮塌，降低了摩擦效果；对比例5形成连续喷丝且喷丝垮塌，摩擦效果差。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (11)

1.一种发泡喷丝材料，其特征在于，该发泡喷丝材料包含组分I、组分II、组分III、组分IV和组分V，其中，
所述组分I为低密度聚乙烯，所述组分II选自聚甲基丙烯酸甲酯、聚碳酸酯、聚对苯二甲酸乙二醇酯、聚苯乙烯、聚对苯二甲酸丁二醇酯和聚酰胺中的至少一种；所述组分III选自聚丙烯和/或高密度聚乙烯；所述组分IV为无机填料；所述组分V由发泡剂和发泡促进剂组成；
以所述发泡喷丝材料的总重量为基准，所述组分I的含量为32-65重量％，所述组分II的含量为15-26重量％，所述组分III的含量为3-16重量％，所述组分IV的含量为10-30重量％，所述组分V的含量为3-5重量％。
2.根据权利要求1所述的发泡喷丝材料，其中，所述无机填料选自碳酸钙、滑石粉、蒙脱土、二氧化硅和高岭土中的至少一种。
3.根据权利要求1所述的发泡喷丝材料，其中，所述低密度聚乙烯在190℃、2.16kg下的熔体流动质量速率为35-50g/10min。
4.根据权利要求1所述的发泡喷丝材料，其中，所述聚碳酸酯在300℃、1.2kg的熔体流动质量速率为3-4g/10min，密度为1.18-1.22g/cm3；
优选地，所述聚甲基丙烯酸甲酯在230℃、3.8kg的熔体流动质量速率为为1.7-2.0g/10min，密度为1.16-1.20g/cm3；
优选地，所述聚苯乙烯在200℃、5kg下的熔体流动质量速率为1.5-8g/10min，密度为1.02-1.07g/cm3。
5.根据权利要求1所述的发泡喷丝材料，其中，所述聚酰胺选自尼龙6、尼龙66、尼龙1010和尼龙1212中的至少一种；
优选地，所述聚酰胺的密度1-1.6g/cm3。
6.根据权利要求1所述的发泡喷丝材料，其中，所述聚丙烯在230℃、2.16kg下熔体流动质量速率1-5g/10min；
优选地，所述高密度聚乙烯在190℃、2.16kg下的熔体流动质量速率为0.5-5g/10min。
7.根据权利要求1所述的发泡喷丝材料，其中，所述发泡剂选自4,4’-氧代双苯磺酰肼、偶氮二甲酰胺、偶氮二异丁腈和二亚硝基五次甲基四胺中的至少一种；所述发泡促进剂选自氧化锌和/或硬脂酸锌；
优选地，所述发泡剂与所述发泡促进剂的质量比为1:0.2-1；
优选地，所述发泡促进剂为氧化锌和硬脂酸锌的组合，且两者的质量比为1:0.5-1。
8.一种制备权利要求1-7中任意一项所述发泡喷丝材料的方法，该方法包括：将所述发泡喷丝材料中的各组分在挤出发泡设备上进行熔融共混并发泡。
9.根据权利要求8所述的方法，其中，所述熔融共混的温度为170-250℃，所述发泡的温度为160-240℃。
10.一种糙面土工膜，该糙面土工膜包括PE光面土工膜和形成在该光面土工膜至少一个表面上的糙面，其特征在于，所述糙面是由权利要求1-7中任意一项所述的发泡喷丝材料制成。
11.权利要求10所述糙面土工膜的制备方法，该制备方法包括：通过喷丝工艺将所述发泡喷丝材料喷涂于所述PE光面土工膜的至少一个表面上，形成所述糙面。
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