CN111363251A - 一种ppr管专用着色母料及其制备方法与应用 - Google Patents
一种ppr管专用着色母料及其制备方法与应用 Download PDFInfo
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- CN111363251A CN111363251A CN202010086272.3A CN202010086272A CN111363251A CN 111363251 A CN111363251 A CN 111363251A CN 202010086272 A CN202010086272 A CN 202010086272A CN 111363251 A CN111363251 A CN 111363251A
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- Prior art keywords
- pigment
- ppr pipe
- master batch
- yellow
- antioxidant
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- C08J2423/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种PPR管专用着色母料，由以下按重量百分比计的组分组成：颜料15～70％，载体树脂20～81.4％，分散剂3～6％，N,N’‑二环己基对本二甲酰胺0.1～5％，抗氧剂0～5％，纳米氧化锌0.5～10％。本发明还提供所述PPR管专用着色母料的制备方法以及应用。所述PPR管专用着色母料在PPR管中的添加量为PPR管重量的1％‑4％。本发明的PPR管专用着色母料具有优异的分散性能和易稀释性能，可以使制品PPR管具有优异的耐热、耐候性能，能够显著提高制品PPR管的低温冲击性能，改善PPR管管材的低温跌落性能，增强PPR管管材的耐静液压强度和耐慢速开裂增长性能。
Description
技术领域
本发明属于塑料着色技术领域，特别涉及一种PPR管专用着色母料及其制备方法与应用。
背景技术
色母料是把塑料助剂超常量地载附于树脂中而制成的浓缩体，制造塑料制品时，不必再加入该种塑料助剂，而只需加入相应的母料即可。色母料的基本组成为载体树脂、颜料以及分散剂，上述材料通过混料、熔融挤出、造粒，形成与树脂颗粒大小相当的颗粒状母料。色母料是当今世界塑料助剂应用的最主要形式之一，其工艺简单，使用方便，便于实现生产自动化，提高劳动生产率，又避免环境污染，有利于工人健康的清洁文明生产。
PPR管材与传统的铸铁管、镀锌钢管、水泥管等管道相比，具有节省材料、环保、轻质高强、耐腐蚀、内壁光滑不结垢、施工和维修简便、使用寿命长等优点，广泛应用于建筑给排水、城乡给排水、城市燃气、电力和光缆护套、工业流体输送、农业灌溉等建筑业、市政、工业、和农业领域。近几年，随着建筑业、市政工程、水利工程、农业和工业等行业市场需求的不断加大，中国PPR 管材行业呈现出了高速发展态势。我国塑料管道在产量增加的同时，消费者对产品环保、健康、耐用等方面的品质要求也不断在提高。PPR给水管对着色母料有特殊的要求：1、一定的遮盖力；2、颜料耐高温性能好；3、具有一定的耐候性。
专利申请CN102850658A公开了一种新型高效PPR管材耐寒增韧色母粒，所述色母粒的原料组成及其重量份数为：聚丙烯5～25份，颜料5～50份，耐寒改性剂35～65份，增强改性剂1～15份；其中，所述耐寒改性剂为苯乙烯- 丁二烯-苯乙烯三元嵌段共聚物、乙烯-醋酸乙烯共聚物和乙烯-辛烯共聚物中的一种或几种的混合物，所述增强改性剂为纳米碳酸钙、纳米硅和纳米硫酸钡中的一种或几种的混合物。但是，国标GB18742-2017规定PPR管中不应含有碳酸钙、硫酸钡等成分，该色母粒已经无法满足新国标的技术要求。
专利申请CN104059299A公开了一种PPR管专用着色母料及其制备方法，该色母料由以下重量份的原材料组成：载体树脂40～60份，颜料35～55份，分散剂0.5～5份，抗氧剂0.1～3份，抗菌剂0.1～3份。该发明所优选的颜料为钛白粉、炭黑和永固黄，永固黄的着色力虽然强，但耐高温不好，加工过程中容易产生色变，影响管材的正常颜色；另外，该发明中加入的分散剂优选为聚乙二醇200，聚乙二醇400，一般条件下，聚乙二醇是很稳定的，但在120℃或更高的温度下它能与空气中的氧发生作用，从而导致其失去分散的作用，故该发明的着色母料仍然不能解决现有问题如：遮光性不好、分散性不好、易色变以及内表面不平而藏污纳垢的技术问题。
专利申请CN104497424A公开了一种PPR管用着色母料及其制备方法，该色母料包括以下按质量百分比计的原材料：金红石钛白粉50～65％，PPR树脂 28～40％，铁红3.9～9％，钛黄1.0～1.5％，炭黑0.1～0.5％，聚有机硅氧烷0.5～ 1.5％；所述的金红石钛白粉的平均粒径0.2～0.25μm之间，折射率为2.7的金红石钛白粉，其遮盖力强，紫外线吸收能力强，可耐300℃的温度；所述的炭黑为用槽法生产的平均粒径为10～27nm的色素炭黑。该发明的着色母料采用 PPR4220或PPR2400作载体，熔指低，低温跌落性能较差。
发明内容
本发明的目的旨在解决现有技术中PPR管用色母料的低温跌落、耐候性、耐热性、分散性差的问题，提供一种PPR管专用着色母料。该着色母料具有良好的加工性能和耐候性，能够满足PPR管生产厂家的要求。
本发明的另一目的在于提供所述PPR管专用着色母料的制备方法。
本发明的再一目的在于提供所述PPR管专用着色母料的应用。
本发明的目的通过下述技术方案实现：一种PPR管专用着色母料，由以下按重量百分比计的组分组成：颜料15～70％，载体树脂20～81.4％，分散剂3～6％，N,N’-二环己基对本二甲酰胺0.1～5％，抗氧剂0～5％，纳米氧化锌0.5～10％。
进一步地，所述颜料为无机颜料或/和有机颜料。
进一步地，所述无机颜料为金红石钛白粉、炭黑、铝粉、铜粉、珠光粉、铁红、铁黑、铁棕及金属复合无机颜料中的一种或至少两种的混合物。
进一步地，所述金属复合无机颜料为颜料黄53、颜料黄119、颜料黄161、颜料黄164、颜料黄189、颜料棕24、颜料棕29、颜料棕48、颜料蓝28、颜料绿 50、颜料紫47和颜料黑26中的一种或至少两种的混合物。
进一步地，所述有机颜料为颜料黄62、颜料黄93、颜料黄95、颜料黄109、颜料黄110、颜料黄138、颜料黄151、颜料黄155、颜料黄168、颜料黄180、颜料黄181、颜料黄183、颜料黄191:1、颜料黄214、颜料黄215、颜料橙43、颜料橙61、颜料橙64、颜料橙68、颜料橙72、颜料橙73、颜料橙79、颜料红122、颜料红149、颜料红166、颜料红170、颜料红175、颜料红176、颜料红177、颜料红178、颜料红179、颜料红185、颜料红187、颜料红202、颜料红220、颜料红254、颜料红264、颜料紫19、颜料紫23、颜料紫29、颜料蓝15:1、颜料蓝15:3、颜料蓝15:4、颜料绿7和颜料绿36中的一种或至少两种的混合物。
本申请使用的颜料具有优异的耐热、耐光耐候以及耐化学性。
进一步地，所述载体树脂为聚丙烯、聚乙烯、乙烯丙烯共聚物和聚异丁烯中的一种或至少两种的混合物。
进一步地，所述聚丙烯为嵌段共聚聚丙烯、无规共聚聚丙烯或均聚聚丙烯。
进一步地，所述分散剂为硬脂酸钙、硬脂酸庚二酸钙、硬脂酸季戊四醇钙、硬脂酸镧和硬脂酸季戊四醇镧中的一种或至少两种的混合物。这类分散剂在提供颜料分散性能的同时，还可以提高PPR管的抗冲击性能和韧性，特别是该类分散剂与N,N’-二环己基对本二甲酰胺复配时，协同效果更显著。
进一步地，所述抗氧剂为抗氧剂P-EPQ(四(2,4-二叔丁基酚)-4,4'-联苯基二亚磷酸酯)、抗氧剂3114(三(3,5-二叔丁基-4-羟基苄基)异氰酸酯)、抗氧剂CPL (对甲酚和双环戊二烯共聚物)、抗氧剂1330(1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯)、抗氧剂1790(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1, 3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、抗氧剂4120(季戊四醇四(3-月桂基硫代丙酸酯))中的一种或至少两种的混合物。这类抗氧剂不仅抗氧化效果优异，还具有极佳的耐水萃取性能，在保证PPR制品优异抗老化效果的同时，可以减少抗氧剂对水的污染。
另一方面，所述PPR管专用着色母料的制备方法，包括以下步骤：
A、将颜料15～70％，载体树脂20～81.4％，分散剂3～6％，N,N’-二环己基对本二甲酰胺0.1～5％，抗氧剂0～5％及纳米氧化锌0.5～10％加入混料机中混合，得到混合物，待混合物的温度为100-120℃时，出料；所述百分比为重量百分比；
B、将步骤A的混合物转移至双螺杆挤出机，熔融挤出，冷却，造粒，得到 PPR管专用着色母料；所述双螺杆挤出机的挤出温度为150-230℃、螺杆转速为 400-900rpm。
所述PPR管专用着色母料主要应用于建筑给排水、城乡给排水、城市燃气、电力和光缆护套、工业流体输送、农业灌溉等建筑业、市政、工业和农业领域。
所述PPR管专用着色母料在PPR管中的添加量为PPR管重量的1％-4％，优选的添加量为PPR管重量的1.5％-2％。
本发明相对于现有技术具有如下的优点及效果：
1)本发明所述的PPR管专用着色母料具有优异的分散性能和易稀释性能。
2)本发明所述的PPR管专用着色母料使制品PPR管具有优异的耐热、耐候性能。
3)本发明所述的PPR管专用着色母料能够显著提高制品PPR管的低温冲击性能，改善PPR管管材的低温跌落性能，增强PPR管管材的耐静液压强度和耐慢速开裂增长性能。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
除非另有定义，本文所使用的所有的技术和科学术语属于本申请的技术领域的技术人员通常理解的含义相同。本文在说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。
本申请中，除有特殊说明外，所有原料均为市售。除非另有说明，否则本申请中所用的“百分比”或“％”是指所有组分的重量百分比。
本申请中，词语“约”或“大约”是指在由所属领域的技术人员确定的指定具体参数的可接受范围内，其部分地取决于测量或测定所述值的方式，即测量***的限值。例如，“约”可指至多给定值的10％的范围。
本发明提供一种PPR管专用着色母料，由以下按重量百分比计的组分组成：颜料15～70％，载体树脂20～81.4％，分散剂3～6％，N,N’-二环己基对本二甲酰胺0.1～5％，抗氧剂0～5％，纳米氧化锌0.5～10％。
进一步地，所述颜料为无机颜料或/和有机颜料。
进一步地，所述无机颜料为金红石钛白粉、炭黑、铝粉、铜粉、珠光粉、铁红、铁黑、铁棕及金属复合无机颜料中的一种或至少两种的混合物。
进一步地，所述金属复合无机颜料为颜料黄53、颜料黄119、颜料黄161、颜料黄164、颜料黄189、颜料棕24、颜料棕29、颜料棕48、颜料蓝28、颜料绿 50、颜料紫47和颜料黑26中的一种或至少两种的混合物。
进一步地，所述有机颜料为颜料黄62、颜料黄93、颜料黄95、颜料黄109、颜料黄110、颜料黄138、颜料黄151、颜料黄155、颜料黄168、颜料黄180、颜料黄181、颜料黄183、颜料黄191:1、颜料黄214、颜料黄215、颜料橙43、颜料橙61、颜料橙64、颜料橙68、颜料橙72、颜料橙73、颜料橙79、颜料红122、颜料红149、颜料红166、颜料红170、颜料红175、颜料红176、颜料红177、颜料红178、颜料红179、颜料红185、颜料红187、颜料红202、颜料红220、颜料红254、颜料红264、颜料紫19、颜料紫23、颜料紫29、颜料蓝15:1、颜料蓝15:3、颜料蓝15:4、颜料绿7和颜料绿36中的一种或至少两种的混合物。
本申请使用的颜料具有优异的耐热、耐光耐候以及耐化学性。
进一步地，所述载体树脂为聚丙烯、聚乙烯、乙烯丙烯共聚物和聚异丁烯中的一种或至少两种的混合物。
进一步地，所述聚丙烯为嵌段共聚聚丙烯、无规共聚聚丙烯或均聚聚丙烯。
进一步地，所述分散剂为硬脂酸钙、硬脂酸庚二酸钙、硬脂酸季戊四醇钙、硬脂酸镧和硬脂酸季戊四醇镧中的一种或至少两种的混合物。这类分散剂在提供颜料分散性能的同时，还可以提高PPR管的抗冲击性能和韧性，特别是该类分散剂与N,N’-二环己基对本二甲酰胺复配时，协同效果更显著。
进一步地，所述抗氧剂为抗氧剂P-EPQ(四(2,4-二叔丁基酚)-4,4'-联苯基二亚磷酸酯)、抗氧剂3114(三(3,5-二叔丁基-4-羟基苄基)异氰酸酯)、抗氧剂CPL (对甲酚和双环戊二烯共聚物)、抗氧剂1330(1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯)、抗氧剂1790(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1, 3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、抗氧剂4120(季戊四醇四(3-月桂基硫代丙酸酯))中的一种或至少两种的混合物。这类抗氧剂不仅抗氧化效果优异，还具有极佳的耐水萃取性能，在保证PPR制品优异抗老化效果的同时，可以减少抗氧剂对水的污染。
另一方面，所述PPR管专用着色母料的制备方法，包括以下步骤：
A、将颜料15～70％，载体树脂20～81.4％，分散剂3～6％，N,N’-二环己基对本二甲酰胺0.1～5％，抗氧剂0～5％及纳米氧化锌0.5～10％加入混料机中混合，得到混合物，待混合物的温度为100-120℃时，出料；所述百分比为重量百分比；
B、将步骤A的混合物转移至双螺杆挤出机，熔融挤出，冷却，造粒，得到 PPR管专用着色母料；所述双螺杆挤出机的挤出温度为150-230℃、螺杆转速为 400-900rpm。
所述PPR管专用着色母料主要应用于建筑给排水、城乡给排水、城市燃气、电力和光缆护套、工业流体输送、农业灌溉等建筑业、市政、工业和农业领域。
所述PPR管专用着色母料在PPR管中的添加量为PPR管重量的1％-4％，优选的添加量为PPR管重量的1.5％-2％。
本发明所述的PPR管专用着色母料具有优异的分散性能和易稀释性能，可以使制品PPR管具有优异的耐热、耐候性能，能够显著提高制品PPR管的低温冲击性能，改善PPR管管材的低温跌落性能，增强PPR管管材的耐静液压强度和耐慢速开裂增长性能。
实施例1
金红石型钛白粉40％，酞菁蓝5％，颜料黄183 5％，炭黑1％，硬脂酸庚二酸钙3％，硬脂酸季戊四醇酸镧3％，聚乙烯23％，N,N’-二环己基对本二甲酰胺 5％，抗氧剂13301％，抗氧剂P-EPQ 1％，抗氧剂3114 1％，抗氧剂1790 1％，抗氧剂4120 1％，纳米氧化锌10％。将上述原材料加入高速混料机中高速混合，待物料温度达到100℃后，将混好的料转移至双螺杆挤出机(挤出温度：150℃，螺杆转速400rpm)中，熔融造粒，干燥、包装，得色母粒。
实施例2
碳黑15％，硬脂酸庚二酸钙3％，嵌段共聚聚丙烯载体树脂40％，无规共聚聚丙烯载体树脂41.4％，N,N’-二环己基对本二甲酰胺0.1％，纳米氧化锌0.5％。将上述原材料加入高速混料机中高速混合，待物料温度达到120℃后，将混好的料转移至双螺杆挤出机(挤出温度：200℃，螺杆转速900rpm)中，熔融造粒，干燥、包装，得色母粒。
实施例3
金红石型钛白粉15％、金色珠光粉10％，颜料橙64 10％、硬脂酸镧2％，硬脂酸庚二酸镧3％，均聚聚丙烯载体树脂27％，乙烯丙烯共聚物8％，聚异丁烯13％，抗氧剂13302％，抗氧剂P-EPQ 3％，N,N’-二环己基对本二甲酰胺2％，纳米氧化锌5％。将上述原材料加入高速混料机中高速混合，待物料温度达到110℃后，将混好的料转移至双螺杆挤出机(挤出温度：210℃，螺杆转速600rpm)中，熔融造粒，干燥、包装，得色母粒。
对比实施例
金红石型钛白粉40％，酞菁蓝5％，颜料黄183 5％，炭黑1％，聚乙烯蜡 6％，聚乙烯38％，抗氧剂1330 1％，抗氧剂P-EPQ 1％，抗氧剂3114 1％，抗氧剂1790 1％，抗氧剂4120 1％。将上述原材料加入高速混料机中高速混合，待物料温度达到100℃后，将混好的料转移至双螺杆挤出机(挤出温度：150℃，螺杆转速400rpm)中，熔融造粒，干燥、包装，得色母粒。
将实施例和对比例按照如下方法进行测试，测试时母料与PPR的添加量为 2％。测试结果见表1。
(1)分散性能
按照标准《GB/T 18251-2000聚烯烃管材、管件和混配料中颜料或炭黑分散的测定方法》方法测定。
(2)耐热色差评价
将所制得着色母料与PPR树脂混合均匀；于230℃、连续注射20块色板。测定其平均L、a、b值(标记L0，a0，b0)作为标准，然后于200℃、停留 5min连续注塑3块板测其平均L、a、b值(标记L1，a1，b1)。耐热色差＝[(L1-L0)2+(a1-a0)2+(b1-b0)2]1/2。
(3)耐候色差评价
按照标准《GB/T 16422.2-2014塑料实验室光源暴露试验方法第2部分：氙弧灯》测试。
(4)冲击性能
按照标准《GB/T 1043.1-2008塑料简支梁冲击性能的测定第1部分：非仪器化冲击试验》测试。
(5)抗菌性能
按照标准《JIS Z 2801-2010抗菌产品.抗菌活性和效果的试验》测试。
表1
| 检测项目 | 实施例1 | 实施例2 | 实施例3 | 对比例1 |
| 分散性 | 1级 | 2级 | 1级 | 3级 |
| 耐热色差 | 0.51 | 0.3 | 0.4 | 0.6 |
| 耐候色差 | 1.01 | 0.47 | 1.23 | 1.87 |
| 缺口冲击(23℃) | 65.4 | 43.9 | 58.6 | 39.3 |
| 缺口冲击(-20℃) | 9.41 | 5.54 | 7.92 | 4.58 |
| 抗菌性能 | 99.9％ | 93.4％ | 99.0％ | 0％ |
从实验结果看，本发明方法制备的着色母料，在分散性能、耐候耐热性能以及低温冲击性能方面明显优于对比例，此外本发明制备的着色母料还提供了优异的抗菌性能。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种PPR管专用着色母料，其特征在于，由以下按重量百分比计的组分组成：颜料15～70％，载体树脂20～81.4％，分散剂3～6％，N,N’-二环己基对本二甲酰胺0.1～5％，抗氧剂0～5％，纳米氧化锌0.5～10％。
2.根据权利要求1所述的PPR管专用着色母料，其特征在于，所述颜料为无机颜料或/和有机颜料。
3.根据权利要求2所述的PPR管专用着色母料，其特征在于，所述无机颜料为金红石钛白粉、炭黑、铝粉、铜粉、珠光粉、铁红、铁黑、铁棕及金属复合无机颜料中的一种或至少两种的混合物。
4.根据权利要求3所述的PPR管专用着色母料，其特征在于，所述金属复合无机颜料为颜料黄53、颜料黄119、颜料黄161、颜料黄164、颜料黄189、颜料棕24、颜料棕29、颜料棕48、颜料蓝28、颜料绿50、颜料紫47和颜料黑26中的一种或至少两种的混合物。
5.根据权利要求2所述的PPR管专用着色母料，其特征在于，所述有机颜料为颜料黄62、颜料黄93、颜料黄95、颜料黄109、颜料黄110、颜料黄138、颜料黄151、颜料黄155、颜料黄168、颜料黄180、颜料黄181、颜料黄183、颜料黄191:1、颜料黄214、颜料黄215、颜料橙43、颜料橙61、颜料橙64、颜料橙68、颜料橙72、颜料橙73、颜料橙79、颜料红122、颜料红149、颜料红166、颜料红170、颜料红175、颜料红176、颜料红177、颜料红178、颜料红179、颜料红185、颜料红187、颜料红202、颜料红220、颜料红254、颜料红264、颜料紫19、颜料紫23、颜料紫29、颜料蓝15:1、颜料蓝15:3、颜料蓝15:4、颜料绿7和颜料绿36中的一种或至少两种的混合物。
6.根据权利要求1所述的PPR管专用着色母料，其特征在于，所述载体树脂为聚丙烯、聚乙烯、乙烯丙烯共聚物和聚异丁烯中的一种或至少两种的混合物。
7.根据权利要求6所述的PPR管专用着色母料，其特征在于，所述聚丙烯为嵌段共聚聚丙烯、无规共聚聚丙烯或均聚聚丙烯。
8.根据权利要求1所述的PPR管专用着色母料，其特征在于，所述分散剂为硬脂酸钙、硬脂酸庚二酸钙、硬脂酸季戊四醇钙、硬脂酸镧和硬脂酸季戊四醇镧中的一种或至少两种的混合物；所述抗氧剂为抗氧剂P-EPQ、抗氧剂3114、抗氧剂CPL、抗氧剂1330、抗氧剂1790、抗氧剂4120中的一种或至少两种的混合物。
9.权利要求1-8任一项所述的PPR管专用着色母料的制备方法，其特征在于，包括以下步骤：
A、将颜料15～70％，载体树脂20～81.4％，分散剂3～6％，N,N’-二环己基对本二甲酰胺0.1～5％，抗氧剂0～5％及纳米氧化锌0.5～10％加入混料机中混合，得到混合物，待混合物的温度为100-120℃时，出料；所述百分比为重量百分比；
B、将步骤A的混合物转移至双螺杆挤出机，熔融挤出，冷却，造粒，得到PPR管专用着色母料；所述双螺杆挤出机的挤出温度为150-230℃、螺杆转速为400-900rpm。
10.权利要求1-8任一项所述的PPR管专用着色母料应用于建筑给排水、城乡给排水、城市燃气、电力和光缆护套、工业流体输送以及农业灌溉领域；所述PPR管专用着色母料在PPR管中的添加量为PPR管重量的1％-4％。
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