CN116922894A - 一种高阻燃性隔热防护面料及其制备方法 - Google Patents

一种高阻燃性隔热防护面料及其制备方法 Download PDF

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CN116922894A
CN116922894A CN202310851891.0A CN202310851891A CN116922894A CN 116922894 A CN116922894 A CN 116922894A CN 202310851891 A CN202310851891 A CN 202310851891A CN 116922894 A CN116922894 A CN 116922894A
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flame
retardant
heat
mass ratio
silicon dioxide
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韩志强
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Shenzhen Wanqi Clothing Co ltd
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    • 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
    • B32B5/262Layered 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 characterised by one fibrous or filamentary layer being a woven fabric layer
    • B32B5/263Layered 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 characterised by one fibrous or filamentary layer being a woven fabric layer next to one or more woven fabric layers
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F292/00Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
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    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06BTREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B15/00Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
    • DTEXTILES; PAPER
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    • D06B3/18Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics combined with squeezing, e.g. in padding machines
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    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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Abstract

本发明涉及功能性面料技术领域,具体公开了一种高阻燃性隔热防护面料及其制备方法。所述方法包括以下步骤:将芳纶纤维和涤纶纤维混纺织造得到基布,将基布浸渍到二氧化硅‑石墨烯接枝共聚物分散液中,二浸二轧,干燥,得到阻燃隔热层,其中无机阻燃剂纳米二氧化硅和氧化石墨烯具有很好的隔热阻燃效果,和有机阻燃剂N,N‑双(2‑羟乙基)氨基亚甲基膦酸二乙酯协效作用在基体上,具有很高的阻燃隔热性,将棉纤维和蛋白纤维混纺织造得到舒适层,阻燃隔热层和舒适层通过缝合,得到高阻燃性隔热防护面料,得到的面料柔软舒爽,且透气性优良,舒适度好,是一种优良的阻燃隔热防护面料。

Description

一种高阻燃性隔热防护面料及其制备方法
技术领域
本发明涉及功能性面料技术领域,具体为一种高阻燃性隔热防护面料及其制备方法。
背景技术
消防、冶金铸造、电力电气等行业的工作人员常常会在高温环境中作业,可能受到高温飞溅物、强辐射热、烫伤等的危害。为保障这些特殊从业人员的人身安全,需要穿着特定的阻燃隔热防护服。制备这类防护服的面料需具备优良的阻燃性能和隔热性能,同时在遇火和高温条件下不会发生熔滴,面料尺寸稳定,同时具有优良的耐磨损和抗撕裂特性,能够有效提高阻燃隔热防护服的使用寿命。
中国专利申请CN110387740A提供了一种基于石墨烯散热的电焊防护服面料制备方法及制得的电焊防护服面料,采用氧化石墨烯溶液对阻燃基布进行正面施加,干燥,再进行还原处理,干燥,制得基于石墨烯散热的电焊防护服面料。制得的电焊防护服面料具有良好的表面散热性能、阻燃性能和防熔融金属滴落升温功能。但该防护服面料在多次洗涤后,石墨烯容易脱落,影响防护服面料的性能。中国专利CN201640555U公开了一种耐高温复合防护服面料,防护服面料由复合阻燃纱线织造而成,复合阻燃纱线由芳纶纤维和阻燃粘胶纤维混纺并包覆于玻璃纤维芯纱的外表面构成,但该面料吸湿性较差,在高温环境中使用时,不能吸走人体产生的汗水,给人带来严重的不适感,同时加入的玻璃纤维对人体有一定的伤害。
因此,开发出一款吸湿性好的高阻燃性隔热防护面料具有重要的意义和价值。
发明内容
为了解决上述技术问题,本发明提供了一种高阻燃性隔热防护面料及其制备方法,制备了一种吸湿性好的高阻燃性隔热防护面料。
为了实现上述目的,本发明公开了一种高阻燃性隔热防护面料的制备方法,包括以下步骤:
步骤一、将纳米二氧化硅(SiO2)超声分散到甲苯中,再加入3-氯丙基三乙氧基硅烷,搅拌混合,在惰性气体氛围中反应,反应后,离心,洗涤,干燥,得到氯硅烷改性二氧化硅;
步骤二、将N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和甲基丙烯酸缩水甘油酯混合,在惰性气体氛围中反应,反应后,旋蒸,得到含有不饱和双键的阻燃中间体;
将氧化石墨烯(GO)超声分散到乙醇水溶液中,加入γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,反应,反应后,离心,洗涤,干燥,得到烯基改性氧化石墨烯;
将氯硅烷改性二氧化硅分散到有机溶剂中,再加入氯化亚铜(CuCl),搅拌混合后,加入烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体,在惰性气体氛围中,反应,反应后,沉淀,过滤,干燥,得到二氧化硅-石墨烯接枝共聚物;
步骤三、将芳纶纤维和涤纶纤维混纺得到经纱和纬纱,织造得到基布;将二氧化硅-石墨烯接枝共聚物分散到去离子水中,得到二氧化硅-石墨烯接枝共聚物分散液;将基布置于二氧化硅-石墨烯接枝共聚物分散液中浸渍,二浸二轧,干燥,得到阻燃隔热层;
将棉纤维和蛋白纤维混纺得到经纱和纬纱,织造得到舒适层;
以阻燃隔热层作为外层,舒适层作为内层,将阻燃隔热层和舒适层对齐层叠后,缝合,得到高阻燃性隔热防护面料。
优选地,所述步骤一中:纳米二氧化硅、甲苯和3-氯丙基三乙氧基硅烷的质量比为100:8000-12000:85-105,反应条件为100-110℃温度下反应18-24h,离心条件为6000-8000r/min速度下离心12-15min,干燥条件为60℃温度下干燥12-18h。
优选地,所述步骤二中:N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、甲基丙烯酸缩水甘油酯的质量比为1500-1800:100:50-60,反应条件为65-75℃温度下反应36-42h。
优选地,所述步骤二中:氧化石墨烯、乙醇水溶液和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷的质量比为100:9000-9500:75-105,反应条件为60-65℃温度下反应24-30h。
优选地,所述步骤二中:氯硅烷改性二氧化硅、有机溶剂、氯化亚铜、烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体的质量比为100:3500-6000:1-2:1-1.5:5-9,反应条件为90-95℃温度下反应2-3h。
优选地,所述步骤四中有机溶剂包括二甲苯、N,N-二甲基甲酰胺和甲苯中的至少一种。
优选地,所述步骤三中:芳纶纤维和涤纶纤维的质量比为100:60-70,基布的克重为190-240g/m2,基布中经纱和纬纱的质量比为100:78-85,二氧化硅-石墨烯接枝共聚物和去离子水的质量比为3-8:100。
优选地,所述步骤三中:所述步骤三中:浸渍条件为60-75℃温度下浸渍35-45min,干燥条件为90-95℃干燥15-18min。
优选地,所述步骤三中:棉纤维和蛋白纤维的质量比为100:35-55,舒适层的克重为102-150g/m2,舒适层中经纱和纬纱的质量比为100:65-72。
优选地,一种采用上述的高阻燃性隔热防护面料的制备方法制备得到的高阻燃性隔热防护面料。
与现有技术相比,本发明的有益效果为:
本发明中使用3-氯丙基三乙氧基硅烷对纳米二氧化硅进行改性,在纳米二氧化硅表面引入氯硅烷改性二氧化硅,得到氯硅烷改性二氧化硅,N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯上的羟基和甲基丙烯酸缩水甘油酯上的环氧基团发生反应,得到含有不饱和双键的阻燃中间体,引入了羟基和双键,使用γ-(甲基丙烯酰氧)丙基三甲氧基硅烷对氧化石墨烯进行改性,得到烯基改性氧化石墨烯,烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体在引发剂氯硅烷改性二氧化硅和催化剂氯化亚铜作用下,发生聚合反应,得到二氧化硅-石墨烯接枝共聚物。将芳纶纤维和涤纶纤维混纺织造得到基布,将基布浸渍到二氧化硅-石墨烯接枝共聚物分散液中,二浸二轧,干燥,得到阻燃隔热层,分散液中的二氧化硅-石墨烯接枝共聚物含有大量的活性基团,能够和基布上的基团间形成作用力,提高二氧化硅-石墨烯接枝共聚物的附着力,洗涤后不易脱落,将棉纤维和蛋白纤维混纺织造得到舒适层,阻燃隔热层和舒适层通过缝合,得到高阻燃性隔热防护面料。
本发明中阻燃隔热层中芳纶纤维和涤纶纤维具有超高强度,且化学结构稳定、不易损坏,芳纶纤维在燃烧过程中无熔滴,且柔软性好,收缩性低,涤纶纤维具有很好的韧性,不易损坏,且弹性好、耐热性好,两种纤维混纺得到纱线,再织造得到基布,浸渍到二氧化硅-石墨烯接枝共聚物分散液中,二浸二轧,干燥,得到阻燃隔热层具有优良的阻燃隔热性能。纳米二氧化硅是一种常见的增强无机填料,能够有效的提高基体的力学性能和热稳定性,同时是一种效果优良的阻燃协效剂,纳米二氧化硅和石墨烯分散在基布表面,在燃烧过程中,能够有效提高碳层的热稳定性、抗高温的能力和致密度,阻隔基体内外热量的传递,同时减缓热解产物的释放,二者协同作用,能够在很大程度上提高基体的阻燃能力。在纳米二氧化硅表面引入3-氯丙基三乙氧基硅烷,氯原子不仅能作为后续反应的引发剂,同时在燃烧过程中可以和基体分解的自由基HO·反应生成卤素自由基Cl·,再与高分子链反应,生产HCl,从而切断HO·和氧的反应,且含量较低,对人体基本无伤害,同时还含有硅元素。在氧化石墨烯表面也引入了硅元素,均能进一步提高燃烧过程中炭层的致密度,且改性后有效避免了纳米二氧化硅和氧化石墨烯的团聚,且无机阻燃剂具有很好的隔热效果。有机阻燃剂N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯中的磷元素在燃烧过程中产生的PO·自由基,能够捕获火焰中的·OH和H·自由基,中断燃烧链式反应,降低燃烧释放的热量,同时生成含磷酸性物质,促进基体表面成炭,形成的炭层更加致密,防止热量的传导,进一步阻止燃烧反应的继续;含有的氮元素在燃烧过程中生成不可燃的气体,有效稀释燃烧所需的氧气浓度,减少了燃烧反应所需的要素。
本发明中舒适层中棉纤维上含有大量的羟基亲水基团,接触到皮肤让人感觉柔软不僵硬且具有优良的耐热性,蛋白纤维具有很好的亲肤性、透气、导湿功能,两种纤维混纺得到纱线,再织造得到的舒适层作为内层,面料柔软舒爽,且透气性优良,避免了工作人员在穿着过程中闷热,舒适度好,热压后得到的面料具有很高的阻燃隔热性,是一种优良的防护面料。
附图说明
图1是本发明中制备高阻燃性隔热防护面料的流程图;
图2是本发明中制备二氧化硅-石墨烯接枝共聚物的流程图;
图3是本发明中制备氯硅烷改性二氧化硅的结构示意图;
图4是本发明中制备含有不饱和双键的阻燃中间体的结构示意图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例,基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种高阻燃性隔热防护面料的制备方法,包括以下步骤:
(1)将纳米二氧化硅超声分散到甲苯中,再加入3-氯丙基三乙氧基硅烷,搅拌混合,在氩气氛围中,加热回流发生反应,加热回流的温度为100℃,加热回流的时间为24h,其中纳米二氧化硅、甲苯和3-氯丙基三乙氧基硅烷的质量比为100:8000:85,反应结束后,离心分离,离心的速率为6000r/min,离心的时间为15min,使用无水乙醇洗涤,在60℃真空干燥12h,得到氯硅烷改性二氧化硅;
(2)将质量比为1500:100:50的N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、甲基丙烯酸缩水甘油酯混合均匀,加热,在65℃氮气氛围中发生反应,反应的时间为42h,反应结束后,旋蒸,得到含有不饱和双键的阻燃中间体;
(3)将氧化石墨烯超声分散到95wt%乙醇水溶液中,分散均匀后,加入γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,搅拌混合,在60℃发生反应30h,其中氧化石墨烯、95wt%乙醇水溶液和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷的质量比为100:9000:75,反应结束后,离心分离,离心的速率为6000r/min,离心的时间为10min,再使用无水乙醇和去离子水洗涤,洗涤至中性,在60℃真空干燥12h,得到烯基改性氧化石墨烯;
(4)将氯硅烷改性二氧化硅分散到有机溶剂N,N-二甲基甲酰胺中,再加入氯化亚铜,搅拌混合均匀后,加入烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体,在氩气氛围中,搅拌混合,在90℃发生反应3h,加入的氯硅烷改性二氧化硅、有机溶剂N,N-二甲基甲酰胺、氯化亚铜、烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体的质量比为100:3500:1:1:5,反应结束后,在甲醇中沉淀,在60℃干燥12h,得到二氧化硅-石墨烯接枝共聚物;
(5)S1、将质量比为100:60的芳纶纤维和涤纶纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到基布,其中经纱和纬纱的质量比为100:78,基布的克重为190g/m2
S2、将二氧化硅-石墨烯接枝共聚物分散到去离子水中,其中二氧化硅-石墨烯接枝共聚物和去离子水的质量比为3:100,得到二氧化硅-石墨烯接枝共聚物分散液;
S3、将基布置于二氧化硅-石墨烯接枝共聚物分散液中浸渍35min,浸渍的温度为75℃,其中基布和二氧化硅-石墨烯接枝共聚物分散液的质量比为100:600,二浸二轧,90℃干燥18min,得到阻燃隔热层,将阻燃隔热层作为外层;
(6)舒适层由质量比为100:35的棉纤维和蛋白纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到舒适层,其中经纱和纬纱的质量比为100:65,舒适层的克重为102g/m2,将舒适层作为内层;
(7)将阻燃隔热层和舒适层对齐层叠后,采用涤纶缝纫线缝合,得到高阻燃性隔热防护面料。
实施例2
一种高阻燃性隔热防护面料的制备方法,包括以下步骤:
(1)将纳米二氧化硅超声分散到甲苯中,再加入3-氯丙基三乙氧基硅烷,搅拌混合,在氩气氛围中,加热回流发生反应,加热回流的温度为105℃,加热回流的时间为20h,其中纳米二氧化硅、甲苯和3-氯丙基三乙氧基硅烷的质量比为100:9500:92,反应结束后,离心分离,离心的速率为7000r/min,离心的时间为14min,使用无水乙醇洗涤,在60℃真空干燥15h,得到氯硅烷改性二氧化硅;
(2)将质量比为1600:100:54的N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、甲基丙烯酸缩水甘油酯混合均匀,加热,在70℃氮气氛围中发生反应,反应的时间为38h,反应结束后,旋蒸,得到含有不饱和双键的阻燃中间体;
(3)将氧化石墨烯超声分散到95wt%乙醇水溶液中,分散均匀后,加入γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,搅拌混合,在62℃发生反应26h,其中氧化石墨烯、95wt%乙醇水溶液和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷的质量比为100:9200:85,反应结束后,离心分离,离心的速率为6000r/min,离心的时间为10min,再使用无水乙醇和去离子水洗涤,洗涤至中性,在60℃真空干燥12h,得到烯基改性氧化石墨烯;
(4)将氯硅烷改性二氧化硅分散到有机溶剂N,N-二甲基甲酰胺中,再加入氯化亚铜,搅拌混合均匀后,加入烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体,在氩气氛围中,搅拌混合,在92℃发生反应2.5h,加入的氯硅烷改性二氧化硅、有机溶剂N,N-二甲基甲酰胺、氯化亚铜、烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体的质量比为100:4500:1.4:1.2:6.5,反应结束后,在甲醇中沉淀,在65℃干燥10h,得到二氧化硅-石墨烯接枝共聚物;
(5)S1、将质量比为100:62的芳纶纤维和涤纶纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到基布,其中经纱和纬纱的质量比为100:80,基布的克重为205g/m2
S2、将二氧化硅-石墨烯接枝共聚物分散到去离子水中,其中二氧化硅-石墨烯接枝共聚物和去离子水的质量比为5:100,得到二氧化硅-石墨烯接枝共聚物分散液;
S3、将基布置于二氧化硅-石墨烯接枝共聚物分散液中浸渍38min,浸渍的温度为70℃,其中基布和二氧化硅-石墨烯接枝共聚物分散液的质量比为100:680,二浸二轧,92℃干燥16min,得到阻燃隔热层,将阻燃隔热层作为外层;
(6)舒适层由质量比为100:42的棉纤维和蛋白纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到舒适层,其中经纱和纬纱的质量比为100:68,舒适层的克重为120g/m2,将舒适层作为内层;
(7)将阻燃隔热层和舒适层对齐层叠后,采用涤纶缝纫线缝合,得到高阻燃性隔热防护面料。
实施例3
一种高阻燃性隔热防护面料的制备方法,包括以下步骤:
(1)将纳米二氧化硅超声分散到甲苯中,再加入3-氯丙基三乙氧基硅烷,搅拌混合,在氩气氛围中,加热回流发生反应,加热回流的温度为105℃,加热回流的时间为22h,其中纳米二氧化硅、甲苯和3-氯丙基三乙氧基硅烷的质量比为100:11000:100,反应结束后,离心分离,离心的速率为7000r/min,离心的时间为14min,使用无水乙醇洗涤,在60℃真空干燥16h,得到氯硅烷改性二氧化硅;
(2)将质量比为1700:100:58的N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、甲基丙烯酸缩水甘油酯混合均匀,加热,在70℃氮气氛围中发生反应,反应的时间为40h,反应结束后,旋蒸,得到含有不饱和双键的阻燃中间体;
(3)将氧化石墨烯超声分散到95wt%乙醇水溶液中,分散均匀后,加入γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,搅拌混合,在62℃发生反应28h,其中氧化石墨烯、95wt%乙醇水溶液和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷的质量比为100:9400:95,反应结束后,离心分离,离心的速率为6000r/min,离心的时间为10min,再使用无水乙醇和去离子水洗涤,洗涤至中性,在60℃真空干燥12h,得到烯基改性氧化石墨烯;
(4)将氯硅烷改性二氧化硅分散到有机溶剂N,N-二甲基甲酰胺中,再加入氯化亚铜,搅拌混合均匀后,加入烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体,在氩气氛围中,搅拌混合,在92℃发生反应2.5h,加入的氯硅烷改性二氧化硅、有机溶剂N,N-二甲基甲酰胺、氯化亚铜、烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体的质量比为100:5500:1.8:1.4:8,反应结束后,在甲醇中沉淀,在75℃干燥11h,得到二氧化硅-石墨烯接枝共聚物;
(5)S1、将质量比为100:68的芳纶纤维和涤纶纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到基布,其中经纱和纬纱的质量比为100:82,基布的克重为225g/m2
S2、将二氧化硅-石墨烯接枝共聚物分散到去离子水中,其中二氧化硅-石墨烯接枝共聚物和去离子水的质量比为7:100,得到二氧化硅-石墨烯接枝共聚物分散液;
S3、将基布置于二氧化硅-石墨烯接枝共聚物分散液中浸渍42min,浸渍的温度为65℃,其中基布和二氧化硅-石墨烯接枝共聚物分散液的质量比为100:750,二浸二轧,92℃干燥17min,得到阻燃隔热层,将阻燃隔热层作为外层;
(6)舒适层由质量比为100:50的棉纤维和蛋白纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到舒适层,其中经纱和纬纱的质量比为100:70,舒适层的克重为135g/m2,将舒适层作为内层;
(7)将阻燃隔热层和舒适层对齐层叠后,采用涤纶缝纫线缝合,得到高阻燃性隔热防护面料。
实施例4
一种高阻燃性隔热防护面料的制备方法,包括以下步骤:
(1)将纳米二氧化硅超声分散到甲苯中,再加入3-氯丙基三乙氧基硅烷,搅拌混合,在氩气氛围中,加热回流发生反应,加热回流的温度为110℃,加热回流的时间为18h,其中纳米二氧化硅、甲苯和3-氯丙基三乙氧基硅烷的质量比为100:12000:105,反应结束后,离心分离,离心的速率为8000r/min,离心的时间为12min,使用无水乙醇洗涤,在60℃真空干燥18h,得到氯硅烷改性二氧化硅;
(2)将质量比为1800:100:60的N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、甲基丙烯酸缩水甘油酯混合均匀,加热,在75℃氮气氛围中发生反应,反应的时间为36h,反应结束后,旋蒸,得到含有不饱和双键的阻燃中间体;
(3)将氧化石墨烯超声分散到95wt%乙醇水溶液中,分散均匀后,加入γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,搅拌混合,在65℃发生反应24h,其中氧化石墨烯、95wt%乙醇水溶液和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷的质量比为100:9500:105,反应结束后,离心分离,离心的速率为6000r/min,离心的时间为10min,再使用无水乙醇和去离子水洗涤,洗涤至中性,在60℃真空干燥12h,得到烯基改性氧化石墨烯;
(4)将氯硅烷改性二氧化硅分散到有机溶剂N,N-二甲基甲酰胺中,再加入氯化亚铜,搅拌混合均匀后,加入烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体,在氩气氛围中,搅拌混合,在95℃发生反应2h,加入的氯硅烷改性二氧化硅、有机溶剂N,N-二甲基甲酰胺、氯化亚铜、烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体的质量比为100:6000:2:1.5:9,反应结束后,在甲醇中沉淀,在80℃干燥9h,得到二氧化硅-石墨烯接枝共聚物;
(5)S1、将质量比为100:70的芳纶纤维和涤纶纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到基布,其中经纱和纬纱的质量比为100:85,基布的克重为240g/m2
S2、将二氧化硅-石墨烯接枝共聚物分散到去离子水中,其中二氧化硅-石墨烯接枝共聚物和去离子水的质量比为8:100,得到二氧化硅-石墨烯接枝共聚物分散液;
S3、将基布置于二氧化硅-石墨烯接枝共聚物分散液中浸渍45min,浸渍的温度为60℃,其中基布和二氧化硅-石墨烯接枝共聚物分散液的质量比为100:800,二浸二轧,95℃干燥15min,得到阻燃隔热层,将阻燃隔热层作为外层;
(6)舒适层由质量比为100:55的棉纤维和蛋白纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到舒适层,其中经纱和纬纱的质量比为100:72,舒适层的克重为150g/m2,将舒适层作为内层;
(7)将阻燃隔热层和舒适层对齐层叠后,采用涤纶缝纫线缝合,得到高阻燃性隔热防护面料。
对比例1
一种高阻燃性隔热防护面料的制备方法,包括以下步骤:
(1)将纳米二氧化硅超声分散到甲苯中,再加入3-氯丙基三乙氧基硅烷,搅拌混合,在氩气氛围中,加热回流发生反应,加热回流的温度为110℃,加热回流的时间为18h,其中纳米二氧化硅、甲苯和3-氯丙基三乙氧基硅烷的质量比为100:12000:105,反应结束后,离心分离,离心的速率为8000r/min,离心的时间为12min,使用无水乙醇洗涤,在60℃真空干燥18h,得到氯硅烷改性二氧化硅;
(2)将质量比为1800:100:60的N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、甲基丙烯酸缩水甘油酯混合均匀,加热,在75℃氮气氛围中发生反应,反应的时间为36h,反应结束后,旋蒸,得到含有不饱和双键的阻燃中间体;
(3)将氯硅烷改性二氧化硅分散到有机溶剂N,N-二甲基甲酰胺中,再加入氯化亚铜,搅拌混合均匀后,加入含有不饱和双键的阻燃中间体,在氩气氛围中,搅拌混合,在95℃发生反应2h,加入的氯硅烷改性二氧化硅、有机溶剂N,N-二甲基甲酰胺、氯化亚铜和含有不饱和双键的阻燃中间体的质量比为100:6000:2:10.5,反应结束后,在甲醇中沉淀,在80℃干燥9h,得到二氧化硅接枝共聚物;
(4)S1、将质量比为100:70的芳纶纤维和涤纶纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到基布,其中经纱和纬纱的质量比为100:85,基布的克重为240g/m2
S2、将二氧化硅接枝共聚物分散到去离子水中,其中二氧化硅接枝共聚物和去离子水的质量比为8:100,得到二氧化硅接枝共聚物分散液;
S3、将基布置于二氧化硅接枝共聚物分散液中浸渍45min,浸渍的温度为60℃,其中基布和二氧化硅接枝共聚物分散液的质量比为100:800,二浸二轧,95℃干燥15min,得到阻燃隔热层,将阻燃隔热层作为外层;
(5)舒适层由质量比为100:55的棉纤维和蛋白纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到舒适层,其中经纱和纬纱的质量比为100:72,舒适层的克重为150g/m2,将舒适层作为内层;
(6)将阻燃隔热层和舒适层对齐层叠后,采用涤纶缝纫线缝合,得到高阻燃性隔热防护面料。
对比例2
一种高阻燃性隔热防护面料的制备方法,包括以下步骤:
(1)将纳米二氧化硅超声分散到甲苯中,再加入3-氯丙基三乙氧基硅烷,搅拌混合,在氩气氛围中,加热回流发生反应,加热回流的温度为110℃,加热回流的时间为18h,其中纳米二氧化硅、甲苯和3-氯丙基三乙氧基硅烷的质量比为100:12000:105,反应结束后,离心分离,离心的速率为8000r/min,离心的时间为12min,使用无水乙醇洗涤,在60℃真空干燥18h,得到氯硅烷改性二氧化硅;
(2)将氧化石墨烯超声分散到95wt%乙醇水溶液中,分散均匀后,加入γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,搅拌混合,在65℃发生反应24h,其中氧化石墨烯、95wt%乙醇水溶液和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷的质量比为100:9500:105,反应结束后,离心分离,离心的速率为6000r/min,离心的时间为10min,再使用无水乙醇和去离子水洗涤,洗涤至中性,在60℃真空干燥12h,得到烯基改性氧化石墨烯;
(3)S1、将质量比为100:70的芳纶纤维和涤纶纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到基布,其中经纱和纬纱的质量比为100:85,基布的克重为240g/m2
S2、将氯硅烷改性二氧化硅、烯基改性氧化石墨烯、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯分散到去离子水中,其中氯硅烷改性二氧化硅、烯基改性氧化石墨烯、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和去离子水的质量比为7.2:0.1:0.7:100,得到阻燃分散液;
S3、将基布置于阻燃分散液中浸渍45min,浸渍的温度为60℃,其中基布和阻燃分散液的质量比为100:800,二浸二轧,95℃干燥15min,得到阻燃隔热层,将阻燃隔热层作为外层;
(4)舒适层由质量比为100:55的棉纤维和蛋白纤维混纺得到纱线,将纱线分别作为经纱和纬纱,采用梭织工艺织造得到舒适层,其中经纱和纬纱的质量比为100:72,舒适层的克重为150g/m2,将舒适层作为内层;
(5)将阻燃隔热层和舒适层对齐层叠后,采用涤纶缝纫线缝合,得到高阻燃性隔热防护面料。
本发明中实施例和对比例中使用的纳米二氧化硅购自南京保克特新材料有限公司,产品型号为PST-Q02,一次粒径为20nm,比表面积为200m2/g;氧化石墨烯购自杭州智钛净化科技有限公司,氧化石墨烯为单层氧化石墨烯,平均厚度为0.5-1.2nm,直径为4-7μm;芳纶纤维(AF)购自美国杜邦公司,为1500D,1670detx;涤纶纤维购自江苏三联新材料股份有限公司,细度为50D/144F;蚕丝纤维购自嵊州市协和丝绸有限公司;涤纶缝纫线购自东莞大昌线厂有限公司,规格:20S/2;其它试剂均为市售。
对实施例1-4和对比例1-2中制得的高阻燃性隔热防护面料作为样品进行性能测试,测试如下:
(1)阻燃性能测试:采用GB/T 5454-1997《纺织品燃烧性能试样氧指数法》的测试标准,将试样夹在试样夹上垂直于燃烧筒内,在向上流动的氧氮气流中,点燃试样上端,观察其燃烧特性,并与规定的极限值比较续燃时间或损毁长度。通过在不同氧浓度中的一系列试验,可以测得维持燃烧时氧气体积分数表示的最低氧浓度值;将实施例1-4和对比例1-2中对应的样品洗涤50次,洗涤后,再进行阻燃性能测试,测试方法和洗涤前保持一致;
(2)透气度测试:使用ISO9237的费雷泽方法测量试样的透气度,测量气压为125Pa;
(3)吸湿性能测试:依据国家标准GB/T 21655.1-2008《纺织品吸湿速干性的评定第1部分:单项组合试验法》对样品进行测试;
以上性能测试结果如表1所示:
表1
根据表1的测试结果可知,实施例1-4对应的面料具有优良的阻燃性能,在经过50次洗涤后,仍保持着较好的阻燃功效,同时透气度好,吸水率好。防护面料的阻燃隔热层中,含有的无机阻燃剂纳米二氧化硅和氧化石墨烯具有优良的隔热阻燃功效,有机阻燃剂N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯中含有的磷元素和氮元素,均能在基体燃烧过程中起到阻燃的功效。舒适层中棉纤维上含有大量的羟基亲水基团,接触到皮肤让人感觉柔软不僵硬且具有优良的耐热性,蛋白纤维具有很好的亲肤性、透气、导湿功能,使得防护面料柔软舒爽,且透气性优良。对比例1中未加入烯基改性氧化石墨烯,阻燃性能有一定的降低,对透气性和吸湿性影响较小;对比例2中未进行聚合反应,直接混合得到阻燃分散液,对基布进行处理,分散性较差,对透气性和吸湿性有一定的影响,且多次洗涤后,阻燃剂容易发生脱落,阻燃效果大大降低。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,凡依本发明申请范围所作的均等变化与改进等,均应仍归属于本发明的专利涵盖范围之内。

Claims (10)

1.一种高阻燃性隔热防护面料的制备方法,其特征在于,包括以下步骤:
步骤一、将纳米二氧化硅超声分散到甲苯中,再加入3-氯丙基三乙氧基硅烷,搅拌混合,在惰性气体氛围中反应,反应后,离心,洗涤,干燥,得到氯硅烷改性二氧化硅;
步骤二、将N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和甲基丙烯酸缩水甘油酯混合,在惰性气体氛围中反应,反应后,旋蒸,得到含有不饱和双键的阻燃中间体;
将氧化石墨烯超声分散到乙醇水溶液中,加入γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,反应,反应后,离心,洗涤,干燥,得到烯基改性氧化石墨烯;
将氯硅烷改性二氧化硅分散到有机溶剂中,再加入氯化亚铜,搅拌混合后,加入烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体,在惰性气体氛围中,反应,反应后,沉淀,过滤,干燥,得到二氧化硅-石墨烯接枝共聚物;
步骤三、将芳纶纤维和涤纶纤维混纺得到经纱和纬纱,织造得到基布;将二氧化硅-石墨烯接枝共聚物分散到去离子水中,得到二氧化硅-石墨烯接枝共聚物分散液;将基布置于二氧化硅-石墨烯接枝共聚物分散液中浸渍,二浸二轧,干燥,得到阻燃隔热层;
将棉纤维和蛋白纤维混纺得到经纱和纬纱,织造得到舒适层;
以阻燃隔热层作为外层,舒适层作为内层,将阻燃隔热层和舒适层对齐层叠后,缝合,得到高阻燃性隔热防护面料。
2.根据权利要求1所述的一种高阻燃性隔热防护面料的制备方法,其特征在于,所述步骤一中:纳米二氧化硅、甲苯和3-氯丙基三乙氧基硅烷的质量比为100:8000-12000:85-105,反应条件为100-110℃温度下反应18-24h。
3.根据权利要求1所述的一种高阻燃性隔热防护面料的制备方法,其特征在于,所述步骤二中:N,N-二甲基甲酰胺、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、甲基丙烯酸缩水甘油酯的质量比为1500-1800:100:50-60,反应条件为65-75℃温度下反应36-42h。
4.根据权利要求1所述的一种高阻燃性隔热防护面料的制备方法,其特征在于,所述步骤二中:氧化石墨烯、乙醇水溶液和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷的质量比为100:9000-9500:75-105,反应条件为60-65℃温度下反应24-30h。
5.根据权利要求1所述的一种高阻燃性隔热防护面料的制备方法,其特征在于,所述步骤二中:氯硅烷改性二氧化硅、有机溶剂、氯化亚铜、烯基改性氧化石墨烯和含有不饱和双键的阻燃中间体的质量比为100:3500-6000:1-2:1-1.5:5-9,反应条件为90-95℃温度下反应2-3h。
6.根据权利要求5所述的一种高阻燃性隔热防护面料的制备方法,其特征在于,所述有机溶剂包括二甲苯、N,N-二甲基甲酰胺和甲苯中的至少一种。
7.根据权利要求1所述的一种高阻燃性隔热防护面料的制备方法,其特征在于,所述步骤三中:芳纶纤维和涤纶纤维的质量比为100:60-70,基布的克重为190-240g/m2,基布中经纱和纬纱的质量比为100:78-85,二氧化硅-石墨烯接枝共聚物和去离子水的质量比为3-8:100。
8.根据权利要求1所述的一种高阻燃性隔热防护面料的制备方法,其特征在于,所述步骤三中:浸渍条件为60-75℃温度下浸渍35-45min,干燥条件为90-95℃干燥15-18min。
9.根据权利要求1所述的一种高阻燃性隔热防护面料的制备方法,其特征在于,所述步骤三中:棉纤维和蛋白纤维的质量比为100:35-55,舒适层的克重为102-150g/m2,舒适层中经纱和纬纱的质量比为100:65-72。
10.一种采用权利要求1-9任一项所述的高阻燃性隔热防护面料的制备方法制备得到的高阻燃性隔热防护面料。
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CN117944337A (zh) * 2024-03-27 2024-04-30 成都鲲鹏云智科技有限公司 一种阻燃隔热复合纤维面料及其制备方法、在防火服中的应用

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* Cited by examiner, † Cited by third party
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CN117944337A (zh) * 2024-03-27 2024-04-30 成都鲲鹏云智科技有限公司 一种阻燃隔热复合纤维面料及其制备方法、在防火服中的应用

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