CN107467787A - 一种碳基纳米材料复合安全鞋头及其制备方法 - Google Patents

一种碳基纳米材料复合安全鞋头及其制备方法 Download PDF

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CN107467787A
CN107467787A CN201710810899.7A CN201710810899A CN107467787A CN 107467787 A CN107467787 A CN 107467787A CN 201710810899 A CN201710810899 A CN 201710810899A CN 107467787 A CN107467787 A CN 107467787A
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马延文
陈剑宇
蒋旭
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Nanjing Suzhan Intelligent Technology Co Ltd
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    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08Heel stiffeners; Toe stiffeners
    • A43B23/081Toe stiffeners
    • A43B23/086Toe stiffeners made of impregnated fabrics, plastics or the like
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10Epoxy resins modified by unsaturated compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02Synthetic macromolecular fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/714Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145Rot proof, resistant to bacteria, mildew, mould, fungi
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

本发明公开了一种碳基纳米材料复合安全鞋头及其制备方法,碳基纳米材料复合安全鞋头,其原料组分包括:热固性树脂浆料40‑50份,纤维布30‑35份,碳基纳米材料0.1‑10份,溶剂5‑10份,丁腈橡胶5‑10份,固化剂1‑2份,脱模剂0.9‑1.1份,增稠剂0.9‑1.1份和促进剂0.9‑1.1份,所述份数为质量份数。本发明碳基纳米材料复合安全鞋头,具有质量轻、均匀性好、强度高、耐腐蚀、抗菌效果好、光泽度高和透气性能好的特点,且具有受冲击形变后立即复原的能力。

Description

一种碳基纳米材料复合安全鞋头及其制备方法
技术领域
本发明涉及一种碳基纳米材料复合安全鞋头及其制备方法,属于安全鞋头领域。
背景技术
随着我国工业化技术的不断进步以及全球鞋用材料的日益更新,安全防护已成为工业企业切实关心的一个问题,因此各方面的安全防护设施及可穿戴设备也相应需要配套,用于工人脚部安全防护的安全鞋头就是其中一个重要部分。
安全鞋头是一种具有很高机械强度的防护用具,用以防止工人在施工环境中碰到尖锐物及高空坠落重物砸伤脚趾。采用金属制品生产的安全鞋头安全性能较高,也一直被国内外工厂使用,但因钢制的金属鞋头较重,极大的减缓了工人的行动能力及灵活性,并且金属制品的鞋头存在着不透气、易受潮湿空气及脚汗的影响而腐蚀的问题,且一旦碰到尖锐物及高空坠落重物,因金属制品的形变及不能复原性还是会导致脚趾容易受到一定程度的砸伤。另外,金属制品的安全鞋头在重要安检闸口,会因为金属探测器的探测而引发警报,给使用者造成极大的时间延误及多方面的不便,因此,国内外对非金属安全防护制品的需求与日俱增。
发明内容
本发明提供一种碳基纳米材料复合安全鞋头及其制备方法,碳基纳米材料复合安全鞋头具有质量轻,强度高,耐腐蚀,透气性能好,形变后的复原能力强、抗菌效果优异的特点。
为解决上述技术问题,本发明所采用的技术方案如下:
一种碳基纳米材料复合安全鞋头,其原料组分包括:热固性树脂浆料40-50份,纤维布30-35份,碳基纳米材料0.1-10份,溶剂5-10份,丁腈橡胶5-10份,固化剂1-2份,脱模剂0.9-1.1份,增稠剂0.9-1.1份和促进剂0.9-1.1份,所述份数为质量份数。
脱模剂、增稠剂和促进剂均优选为1份。
申请人经研究发现,用上述原料制备得到的碳基纳米材料复合安全鞋头具有质量轻,强度高,耐腐蚀,透气性能好,形变后的复原能力强、抗菌效果优异的特点,且耐磨性好,使用寿命长。
为了进一步促进各组分之间的协同效应,同时进一步提高抗菌效果和耐冲击性能,碳基纳米材料为:石墨烯、氧化石墨烯、石墨稀纳米片、碳纳米管、炭黑、石墨或石墨炔中的至少一种。
石墨烯是单层石墨烯、双层石墨烯和多层石墨烯的统称。
进一步优选,碳基纳米材料为单层石墨烯,片径大小为0.5-2μm,厚度为0.8-1.2nm。
为了进一步提高与其他组分的相容性,避免分层、开裂,同时提高产品的耐磨性,纤维布为玻璃纤维布或者碳纤维布。
为了进一步促进各组分之间的协同效应,同时避免分层、开裂,提高耐冲击性,热固性树脂为环氧乙烯基树脂;固化剂为过氧化二苯甲酰或者过氧化甲乙酮。
为了进一步促进各组分之间的协同效应,提高反应效率,提升产品质量,促进剂为过氧化苯甲酸叔丁酯(TBPB),脱模剂为硬脂酸锌;增稠剂为硅藻土。
为了使各组分之间的协同效应发挥到最佳,溶剂为苯乙烯、N-甲基吡咯烷酮(NMP)、甲苯或甲甲酯中的至少一种。
甲甲酯就是甲基丙烯酸甲酯。
上述碳基纳米材料复合安全鞋头的制备方法,包括以下步骤:
(1)将热固性树脂在温度为25±5℃,转速为800±50rpm的条件下,搅拌10±2min;
(2)将丁腈橡胶、溶剂及步骤(1)所得物料混合,在温度为50-70℃,转速为800±50rpm的条件下,搅拌20±3min;
(3)将碳基纳米材料与步骤(2)所得物料混合,在温度为25±5℃,转速为800±50rpm的条件下搅拌直至碳基纳米材料均匀分散在溶液中;
(4)将固化剂、增稠剂、促进剂和脱模剂依次加入步骤(3)所得物料中,在温度为60±5℃,转速为800±50rpm的条件下搅拌30min,得树脂浆料;
(5)将步骤(4)所得树脂浆料涂布在透明塑料隔离薄膜上;
(6)将纤维布置于步骤(5)所得涂覆有树脂浆料的透明塑料隔离薄膜上,通过辊压机实现树脂浆料对纤维布的浸渍,浸渍温度为60±5℃;
(7)将步骤(6)所得物料自然冷却,根据鞋模的规格进行裁剪得到树脂纤维布薄片;
(8)将步骤(7)中得到的树脂纤维布薄片背面的透明塑料隔离薄膜揭掉,并依次将5-8片揭掉透明塑料隔离薄膜的树脂纤维布薄片进行叠加、压实,得到多层树脂纤维布毡片;
(9)将步骤(8)中得到的多层树脂纤维布毡片放置在安全鞋头模压机中,在温度为150±10℃,压力为30±3Mpa的条件下,反应时间为5-60s;
(10)待反应结束后,降温冷却至室温,打开安全鞋头模压机,即得碳基纳米材料复合安全鞋头。
上述透明塑料隔离薄膜优选为聚酯薄膜。
本发明未提及的技术均参照现有技术。
本发明碳基纳米材料复合安全鞋头,解决了钢制鞋强度低,质量大,透气性差,防腐能力差等问题,同时解决了石墨烯等碳纳米材料分散性差的问题;具有质量轻、均匀性好、强度高、耐腐蚀、抗菌效果好、光泽度高和透气性能好的特点,且具有受冲击形变后立即复原的能力;进一步,石墨烯等碳纳米材料与环氧乙烯基树脂的复合极大的提高了安全鞋头的强度等特点;丁腈橡胶与环氧乙烯基树脂的复合,使得受到一定程度的冲击力时具有很高的复原能力。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
表1各实施例原料用量表
表2各实施例原料表
以上环氧乙烯基树脂采购自南京苏展智能科技有限公司,牌号:SZIP001,苯乙烯、甲甲酯、甲苯、NMP采购自国药集团化学试剂有限公司,玻璃纤维布采购自正大玻璃钢原料有限公司,碳纤维布及单层石墨烯(高分散性单层石墨烯粉末,片径大小为0.5-2μm,厚度为0.8-1.2nm)采购自南京先丰纳米材料科技有限公司,碳纳米管(锂离子电池特种涂料专用)采购自东莞市华悦科明贸易有限公司,丁腈橡胶采购自南京苏展智能科技有限公司,牌号:SZIP002,固化剂、促进剂和脱模剂采购自江阴奇达化工有限公司,硅藻土细度为1000目采购自灵寿县永鑫矿物粉体厂。
各实施例中,碳基纳米材料复合安全鞋头的制备方法,包括以下步骤:
(1)将热固性树脂在温度为25℃、转速为800rpm的条件下,搅拌10min;
(2)将丁腈橡胶、溶剂及步骤(1)所得物料混合,在温度为60℃,转速为800rpm的条件下,搅拌20min;
(3)将碳基纳米材料与步骤(2)所得物料混合,在温度为25℃、转速为800rpm的条件下搅拌直至碳基纳米材料均匀分散在溶液中;
(4)将固化剂、增稠剂、促进剂和脱模剂依次加入步骤(3)所得物料中,在温度为60℃、转速为800rpm的条件下搅拌30min,得树脂浆料;
(5)将步骤(4)所得树脂浆料涂布在聚酯薄膜(高透明PET薄膜,厚度0.02mm,东莞市众联电子材料有限公司)上;
(6)将纤维布置于步骤(5)所得涂覆有树脂浆料的聚酯薄膜上,通过辊压机实现树脂浆料对纤维布的浸渍,浸渍温度为60℃;
(7)将步骤(6)所得物料自然冷却,根据鞋模的规格进行裁剪得到树脂纤维布薄片;
(8)将步骤(7)中得到的树脂纤维布薄片背面的聚酯薄膜揭掉,并依次将6片揭掉透明塑料隔离薄膜的树脂纤维布薄片进行叠加、压实,得到多层树脂纤维布毡片;
(9)将步骤(8)中得到的多层树脂纤维布毡片放置在安全鞋头模压机中,在温度为150℃,压力为30Mpa的条件下,反应时间为20s;
(10)待反应结束后,降温冷却至室温,打开安全鞋头模压机,即得碳基纳米材料复合安全鞋头。
抗冲击力测试说明:将安全鞋头和圆柱状橡皮泥(橡皮泥在安全鞋头下面)放在冲击机下,固定好被检鞋头,提升冲击锤到要求的高度然后自由落体冲击鞋头。取出橡皮泥用卡尺测量,测试方向垂直向下,冲击锤高度1.4m,冲击锤重量20kg。各实施例性能如表3所示:
各例所得碳基纳米材料复合安全鞋头,质量轻、均匀性好、强度高、耐腐蚀、抗菌效果好、光泽度高、透气性能好,且具有受冲击形变后立即复原的能力。

Claims (10)

1.一种碳基纳米材料复合安全鞋头,其特征在于:其原料组分包括:热固性树脂40-50份,纤维布30-35份,碳基纳米材料0.1-10份,溶剂5-10份,丁腈橡胶5-10份,固化剂1-2份,脱模剂0.9-1.1份,增稠剂0.9-1.1份和促进剂0.9-1.1份,所述份数为质量份数。
2.根据权利要求1所述碳基纳米材料复合安全鞋头,其特征在于:碳基纳米材料为:石墨烯、氧化石墨烯、石墨稀纳米片、碳纳米管、炭黑、石墨或石墨炔中的至少一种。
3.根据权利要求2所述碳基纳米材料复合安全鞋头,其特征在于:碳基纳米材料为单层石墨烯,片径大小为0.5-2μm,厚度为0.8-1.2nm。
4.根据权利要求1-3任意一项所述碳基纳米材料复合安全鞋头,其特征在于:纤维布为玻璃纤维布或者碳纤维布。
5.根据权利要求1-3任意一项所述碳基纳米材料复合安全鞋头,其特征在于:热固性树脂为环氧乙烯基树脂;固化剂为过氧化二苯甲酰或者过氧化甲乙酮。
6.根据权利要求1-3任意一项所述碳基纳米材料复合安全鞋头,其特征在于:促进剂为过氧化苯甲酸叔丁酯,脱模剂为硬脂酸锌。
7.根据权利要求1-3任意一项所述碳基纳米材料复合安全鞋头,其特征在于:增稠剂为硅藻土。
8.根据权利要求1-3任意一项所述碳基纳米材料复合安全鞋头,其特征在于:溶剂为苯乙烯、N-甲基吡咯烷酮、甲苯或甲甲酯中的至少一种。
9.权利要求1-8任意一项所述的碳基纳米材料复合安全鞋头的制备方法,其特征在于:包括以下步骤:
(1)将热固性树脂在温度为25±5℃,转速为800±50rpm的条件下,搅拌10±2min;
(2)将丁腈橡胶、溶剂及步骤(1)所得物料混合,在温度为50-70℃,转速为800±50rpm的条件下,搅拌20±3min;
(3)将碳基纳米材料与步骤(2)所得物料混合,在温度为25±5℃,转速为800±50rpm的条件下搅拌直至碳基纳米材料均匀分散在溶液中;
(4)将固化剂、增稠剂、促进剂和脱模剂依次加入步骤(3)所得物料中,在温度为60±5℃,转速为800±50rpm的条件下搅拌30min,得树脂浆料;
(5)将步骤(4)所得树脂浆料涂布在透明塑料隔离薄膜上;
(6)将纤维布置于步骤(5)所得涂覆有树脂浆料的透明塑料隔离薄膜上,通过辊压机实现树脂浆料对纤维布的浸渍,浸渍温度为60±5℃;
(7)将步骤(6)所得物料自然冷却,根据鞋模的规格进行裁剪得到树脂纤维布薄片;
(8)将步骤(7)中得到的树脂纤维布薄片背面的透明塑料隔离薄膜揭掉,并依次将5-8片揭掉透明塑料隔离薄膜的树脂纤维布薄片进行叠加、压实,得到多层树脂纤维布毡片;
(9)将步骤(8)中得到的多层树脂纤维布毡片放置在安全鞋头模压机中,在温度为150±10℃,压力为30±3Mpa的条件下,反应时间为5-60s;
(10)待反应结束后,降温冷却至室温,打开安全鞋头模压机,即得碳基纳米材料复合安全鞋头。
10.如权利要求9所述的方法,其特征在于:透明塑料隔离薄膜为聚酯薄膜。
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