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CN109679057B - 抗菌耐黄变型tpu材料及其制备方法 - Google Patents

抗菌耐黄变型tpu材料及其制备方法 Download PDF

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CN109679057B
CN109679057B CN201811425842.6A CN201811425842A CN109679057B CN 109679057 B CN109679057 B CN 109679057B CN 201811425842 A CN201811425842 A CN 201811425842A CN 109679057 B CN109679057 B CN 109679057B
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nano
percent
diisocyanate
tpu material
yellowing
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CN109679057A (zh
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陈海良
刘永成
陈淑海
管永
贺宽宽
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Shandong Dongda Inov Polyurethane Co Ltd
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Shandong Dongda Inov Polyurethane Co Ltd
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Abstract

本发明属于热塑性聚氨酯弹性体技术领域，具体涉及一种抗菌耐黄变型TPU材料及其制备方法。所述材料，由以下原料外加催化剂制成，聚酯多元醇：45.5‑70％；二异氰酸酯：23‑42％；扩链剂：5.5‑12％；无机抗菌剂：0.3‑0.6％；其中，催化剂的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.02‑0.06％；所述的无机抗菌剂为纳米Ag3PO4与纳米MgO混合物，纳米Ag3PO4与纳米MgO的质量比为2‑5：1。本发明制备的TPU材料，抗菌性能好，并且具有安全、稳定的特点，同时能够提高材料的拉伸性能，促进了抗菌型TPU材料的广泛使用；其制备方法，科学合理、简单易行，适合工业化生产。

Description

抗菌耐黄变型TPU材料及其制备方法
技术领域
本发明属于热塑性聚氨酯弹性体技术领域，具体涉及一种抗菌耐黄变型TPU材料及其制备方法。
背景技术
热塑性聚氨酯弹性体(thermoplastic polyurethane elastomer,TPU)是一种加热可熔融、溶剂可溶解的聚氨酯高分子材料。TPU是一种典型的(AB)n型嵌段线性聚合物，由软段和硬段交替排列，从而形成重复结构单元。由于其特殊的分子结构，使其具有高模量、高强度、高伸长、高弹性和高耐磨等优良的物理机械特性，同时，也具有耐油、耐腐蚀等优点。TPU由于同时兼具橡胶和塑料的优异性能，并且加工方便、价格便宜、废料可再生利用，被公认为是一种绿色环保、性能优异的新型高分子材料。随着TPU行业的高速发展，新技术、新产品、新用途不断涌现，TPU的用途几乎延伸到各个行业。目前已被广泛应用于片材、鞋材、汽车、电缆、医疗、薄膜等多个领域。但是，TPU材料本身不具备抑菌杀菌性能，这使得其在一些特殊领域，如医疗、食用包装等对抗菌要求高的领域得不到广泛应用。因此，具有抑菌杀菌性能的TPU材料成为人们研究的热点。
目前，抗菌型TPU材料的制备方法主要是在TPU合成过程中添加抗菌剂。较为常用的抗菌剂多为有机类抗菌剂，如季铵盐、季鏻盐、吡啶盐类等。例如，中国专利CN104961874A公开了一种防水透气抗菌型TPU薄膜及其制备方法，利用环氧氯烷、环氧酸和卤代烷与叔胺基发生季铵化反应，生成双链季铵盐和单链季铵盐的混合物作为抗菌剂。在TPU材料中添加该类有机物质，虽然在一定条件下初始杀菌力强，但总体而言，其化学稳定性差，并且其杀菌原理是通过其毒性杀死微生物，使用安全性较差。
发明内容
针对现有技术的不足，本发明的目的是提供一种抗菌耐黄变型TPU材料，抗菌性能好，并且具有安全、稳定的特点，同时能够提高材料的拉伸性能，促进抗菌型TPU材料的广泛使用；本发明还提供其制备方法，科学合理、简单易行，适合工业化生产。
本发明所述的抗菌耐黄变型TPU材料，由以下重量百分数的原料外加催化剂制成，
聚酯多元醇：45.5-70％；
二异氰酸酯：23-42％；
扩链剂：5.5-12％；
无机抗菌剂：0.3-0.6％；
其中，催化剂的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.02-0.06％；
所述的无机抗菌剂为纳米Ag3PO4与纳米MgO混合物，纳米Ag3PO4与纳米MgO的质量比为2-5：1，纳米Ag3PO4的粒径为20-80nm，纳米MgO的粒径为20-50nm。
所述的聚酯多元醇是聚酯型二醇，具体为聚己二酸乙二醇酯二醇、聚己二酸乙二醇-1,2-丙二醇酯二醇、聚己二酸乙二醇-1,4-丁二醇酯二醇或聚己二酸-1,4-丁二醇酯二醇中的一种或几种，数均分子量为1000-4000。
所述的二异氰酸酯是脂肪族异氰酸酯，具体为六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、环己烷二亚甲基二异氰酸酯(H6XDI)、4,4’-二环己基甲烷二异氰酸酯(H12MDI)中的一种，优选为六亚甲基二异氰酸酯(HDI)。
所述的扩链剂为1,3-丙二醇、2-甲基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇或1,6-己二醇中的一种或几种，优选为1,4-丁二醇。
所述的催化剂为有机铋、有机锡或钛酸酯类催化剂中的一种，优选为辛酸亚锡(T-9)。
本发明所述的抗菌耐黄变型TPU材料的制备方法，先将聚酯多元醇与扩链剂混合均匀，加入二异氰酸酯，采用一步法合成，经水下切造粒系统制备TPU颗粒。
所述的抗菌耐黄变型TPU材料的制备方法，具体包括以下步骤：
1)将聚酯多元醇、无机抗菌剂加入到A反应釜中，设置温度为95-110℃，搅拌均匀；
2)将二异氰酸酯加入到B反应釜中，设置温度为65-75℃；
3)将扩链剂加入到C反应釜中，设置温度为45-65℃；
4)通过灌注系统先将A、C反应釜中的原料经高速旋转混合头混合，再经混合器注入双螺杆挤出机喂料口，同时，将B反应釜中二异氰酸酯经灌注系统，催化剂经微量注射泵注入双螺杆挤出机喂料口进行反应；
5)反应完毕，经水下切粒机切粒，得抗菌耐黄变型TPU材料。
其中，双螺杆挤出机温度为150-200℃，转速为180-240r/min。
与现有技术相比，本发明的有益效果如下：
1、本发明制备的抗菌耐黄变型TPU材料具有较好的耐黄变性能，黄变等级4.5。
2、本发明将无机纳米Ag3PO4/纳米MgO混合物作为抗菌剂，添加到TPU材料体系中，提高了TPU材料的抗菌性能，特别是对常见大肠杆菌的抗菌率能达93％，并且具有安全、稳定的特点，促进了抗菌型TPU材料的广泛使用。
3、本发明采用的纳米MgO和纳米Ag3PO4的极性较强，表面容易吸附水分子极化成表面羟基，与TPU具有较好的相容性，能均匀分散在材料体系中，提高了材料的拉伸性能。
4、本申请采用的纳米MgO和纳米Ag3PO4之间存在协同作用，纳米MgO能够吸附并且抑制细菌，细菌被吸附后，在纳米Ag3PO4的强杀菌作用下，进一步增强了材料的抗菌性能。
具体实施方式
下面结合实施例对本发明做进一步说明，但不限定本发明。
实施例中用到的所有原料除特殊说明外，均为市购。
实施例1
一种抗菌耐黄变型TPU材料，由以下重量百分数的原料外加催化剂制成，
聚己二酸乙二醇-1,4-丁二醇酯二醇(M＝2000)：69.79％
六亚甲基二异氰酸酯(HDI)：24.20％
1,4-丁二醇(BDO)：5.71％
纳米MgO(尺寸为20-50nm)：0.1％
纳米Ag3PO4(尺寸为20-80nm)：0.2％
其中，辛酸亚锡(T-9)的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.03％。
其制备方法如下：
将697.9g聚己二酸乙二醇-1,4-丁二醇酯二醇(M＝2000)、1g尺寸为20-50nm纳米MgO、2g尺寸为20-80nm的纳米Ag3PO4加入到具有机械搅拌及温控系统的A反应釜中，设置温度为110℃，并进行搅拌；将242g六亚甲基二异氰酸酯(HDI)放置于B反应釜中，设置温度为75℃；将57.1g BDO放置于C反应釜中，设置温度为65℃。
待各反应釜物料搅拌均匀、温度稳定，通过带有精确计量的灌注系统，先将A/C反应釜中的原料按比例经高速旋转混合头混合，再经混合器注入双螺杆挤出机喂料口，同时将B反应釜中HDI经灌注系统、0.3gT-9经微量注射泵精确计量注入双螺杆挤出机喂料口，使其与A、B、C料充分混合反应。双螺杆挤出机温度为150-200℃，双螺杆挤出机转速为180r/min，使混合物料在双螺杆筒体内均匀反应塑化，经水下切粒机切成粒径均匀的椭圆形粒子。
实施例2
一种抗菌耐黄变型TPU材料，由以下重量百分数的原料外加催化剂制成，
聚己二酸乙二醇-1,2-丙二醇酯二醇(M＝3000)：64.39％
六亚甲基二异氰酸酯(HDI)：27.34％
1,3-丙二醇(PDO)：7.87％
纳米MgO(尺寸为20-50nm)：0.1％
纳米Ag3PO4(尺寸为20-80nm)：0.3％
其中，辛酸亚锡(T-9)的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.02％。
其制备方法如下：
将643.9g聚己二酸乙二醇-1,2-丙二醇酯二醇(M＝3000)、1g尺寸为20-50nm纳米MgO以及3g尺寸为20-80nm的纳米Ag3PO4加入到A反应釜中，设置温度为95℃。将273.4g六亚甲基二异氰酸酯(HDI)放置于B反应釜中，设置温度为65℃。将78.7g PDO放置于C反应釜中，设置温度为45℃。
待各反应釜物料搅拌均匀、温度稳定，通过带有精确计量的灌注系统，先将A/C反应釜中的原料按比例经高速旋转混合头混合，再经混合器注入双螺杆挤出机喂料口，同时将B反应釜中HDI经灌注系统、0.2gT-9经微量注射泵精确计量注入双螺杆挤出机喂料口，使其与A、B、C料充分混合反应。双螺杆挤出机温度为150-200℃，双螺杆挤出机转速为240r/min，使混合物料在双螺杆筒体内均匀反应塑化，经水下切粒机切成粒径均匀的椭圆形粒子。
实施例3
一种抗菌耐黄变型TPU材料，由以下重量百分数的原料外加催化剂制成，
聚己二酸-1,4-丁二醇酯二醇(M＝4000)：55.87％
六亚甲基二异氰酸酯(HDI)：33.17％
1,4-丁二醇(BDO)：10.46％
纳米MgO(尺寸为20-50nm)：0.1％
纳米Ag3PO4(尺寸为20-80nm)：0.4％
其中，有机铋(新癸酸铋)催化剂的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.04％。
将558.7g聚己二酸-1,4-丁二醇酯二醇(M＝4000)、1g尺寸为20-50nm纳米MgO以及4g尺寸为20-80nm的纳米Ag3PO4加入A反应釜中，设置温度为100℃。将331.7g六亚甲基二异氰酸酯(HDI)放置于B反应釜中，设置温度为70℃。将104.6gBDO放置于C反应釜中设置温度为50℃。
待各反应釜物料搅拌均匀、温度稳定，通过带有精确计量的灌注系统，先将A/C反应釜中的原料按比例经高速旋转混合头混合，再经混合器注入双螺杆挤出机喂料口，同时将B反应釜中HDI经灌注系统、0.4g新癸酸铋经微量注射泵精确计量注入双螺杆挤出机喂料口，使其与A、B、C料充分混合反应。双螺杆挤出机温度为150-200℃，双螺杆挤出机转速为200r/min，使混合物料在双螺杆筒体内均匀反应塑化，经水下切粒机切成粒径均匀的椭圆形粒子。
实施例4
一种抗菌耐黄变型TPU材料，由以下重量百分数的原料外加催化剂制成，
聚己二酸乙二醇-1,4-丁二醇酯二醇(M＝1000)：48.83％
4,4’-二苯基甲烷二异氰酸酯(MDI-100)：40.00％
1,6-己二醇(HDO)：10.57％
纳米MgO(尺寸为20-50nm)：0.1％
纳米Ag3PO4(尺寸为20-80nm)：0.5％
其中，辛酸亚锡(T-9)的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.04％。
将488.3g聚己二酸乙二醇-1,4-丁二醇酯二醇(M＝1000)、1g尺寸为20-50nm纳米MgO以及5g尺寸为20-80nm的纳米Ag3PO4加入到A反应釜中，设置温度为105℃。将400g六亚甲基二异氰酸酯(HDI)放置于B反应釜中，设置温度为70℃。将105.7g HDO放置于C反应釜中，设置温度为60℃。
待各反应釜物料搅拌均匀、温度稳定，通过带有精确计量的灌注系统，先将A/C反应釜中的原料按比例经高速旋转混合头混合，再经混合器注入双螺杆挤出机喂料口，同时将B反应釜中HDI经灌注系统、0.4gT-9经微量注射泵精确计量注入双螺杆挤出机喂料口，使其与A、B、C料充分混合反应。双螺杆挤出机温度为150-200℃，双螺杆挤出机转速为220r/min，使混合物料在双螺杆筒体内均匀反应塑化，经水下切粒机切成粒径均匀的椭圆形粒子。
对比例1
一种抗菌耐黄变型TPU材料，由以下重量百分数的原料外加催化剂制成，
聚己二酸乙二醇-1,4-丁二醇酯二醇(M＝2000)：69.97％
六亚甲基二异氰酸酯(HDI)：24.31％
1,4-丁二醇(BDO)：5.72％
其中，辛酸亚锡(T-9)的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.03％。
制备方法为与实施例1相同。
对比例2
一种抗菌耐黄变型TPU材料，由以下重量百分数的原料外加催化剂制成，
聚己二酸乙二醇-1,4-丁二醇酯二醇(M＝2000)：69.79％
六亚甲基二异氰酸酯(HDI)：24.20％
1,4-丁二醇(BDO)：5.71％
纳米Ag3PO4(尺寸为20-80nm)：0.3％
其中，辛酸亚锡(T-9)的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.03％。
制备方法为与实施例1相同。
对比例3
一种抗菌耐黄变型TPU材料，由以下重量百分数的原料外加催化剂制成，
聚己二酸乙二醇-1,4-丁二醇酯二醇(M＝2000)：69.79％
六亚甲基二异氰酸酯(HDI)：24.20％
1,4-丁二醇(BDO)：5.71％
纳米MgO(尺寸为20-50nm)：0.3％
其中，辛酸亚锡(T-9)的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.03％。
制备方法为与实施例1相同。
TPU材料性能检测：
对实施例1-4及对比例1-3所制备的TPU材料进行性能测试，即热塑性聚氨酯弹性体邵氏硬度测试执行GB/T531-2009标准；拉伸强度测试执行GB/T528-2009标准；抗菌性检测执行QB/T 4341-2012《抗菌聚氨酯合成革抗菌性能试验方法和抗菌效果》，检测用菌为大肠杆菌(E.coli)。耐黄变性能检测执行HG/T 3689-2014标准。检测结果见表1。
表1实施例1-4及对比例1-3所制备TPU材料性能检测结果
Figure BDA0001881590690000061
由上述检测结果可看出，本发明中将无机纳米Ag3PO4/纳米MgO混合物作为抗菌剂引入TPU材料中，二者协同作用，可使TPU材料具有较好的抗菌性，抑菌率达93％，具有安全、稳定的特点，同时能够显著提高材料的拉伸性能。

Claims (10)

1.一种抗菌耐黄变型TPU材料，其特征在于：由以下重量百分数的原料外加催化剂制成，
聚酯多元醇：45.5-70％；
二异氰酸酯：23-42％；
扩链剂：5.5-12％；
无机抗菌剂：0.3-0.6％；
其中，催化剂的用量为聚酯多元醇、二异氰酸酯、扩链剂和无机抗菌剂总质量的0.02-0.06％；
所述的无机抗菌剂为纳米Ag3PO4与纳米MgO混合物，纳米Ag3PO4与纳米MgO的质量比为2-5：1，纳米Ag3PO4的粒径为20-80nm，纳米MgO的粒径为20-50nm。
2.根据权利要求1所述的抗菌耐黄变型TPU材料，其特征在于：所述的聚酯多元醇为聚己二酸乙二醇酯二醇、聚己二酸乙二醇-1,2-丙二醇酯二醇、聚己二酸乙二醇-1,4-丁二醇酯二醇或聚己二酸-1,4-丁二醇酯二醇中的一种或几种，数均分子量为1000-4000。
3.根据权利要求1所述的抗菌耐黄变型TPU材料，其特征在于：所述的二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、环己烷二亚甲基二异氰酸酯或4,4’-二环己基甲烷二异氰酸酯中的一种。
4.根据权利要求3所述的抗菌耐黄变型TPU材料，其特征在于：所述的二异氰酸酯为六亚甲基二异氰酸酯。
5.根据权利要求1所述的抗菌耐黄变型TPU材料，其特征在于：所述的扩链剂为1,3-丙二醇、2-甲基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇或1,6-己二醇中的一种或几种。
6.根据权利要求5所述的抗菌耐黄变型TPU材料，其特征在于：所述的扩链剂为1,4-丁二醇。
7.根据权利要求1所述的抗菌耐黄变型TPU材料，其特征在于：所述的催化剂为有机铋、有机锡或钛酸酯类催化剂中的一种。
8.根据权利要求7所述的抗菌耐黄变型TPU材料，其特征在于：所述的催化剂为辛酸亚锡。
9.一种权利要求1-8任一所述的抗菌耐黄变型TPU材料的制备方法，其特征在于：包括以下步骤：
1)将聚酯多元醇、无机抗菌剂加入到A反应釜中，设置温度为95-110℃，搅拌均匀；
2)将二异氰酸酯加入到B反应釜中，设置温度为65-75℃；
3)将扩链剂加入到C反应釜中，设置温度为45-65℃；
4)通过灌注系统先将A、C反应釜中的原料经高速旋转混合头混合，再经混合器注入双螺杆挤出机喂料口，同时，将B反应釜中二异氰酸酯经灌注系统，催化剂经微量注射泵注入双螺杆挤出机喂料口进行反应；
5)反应完毕，经水下切粒机切粒，得抗菌耐黄变型TPU材料。
10.根据权利要求9所述的制备方法，其特征在于：双螺杆挤出机温度为150-200℃，转速为180-240r/min。
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