CN110358141A - 一种难燃高分子材料的制备方法 - Google Patents
一种难燃高分子材料的制备方法 Download PDFInfo
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- CN110358141A CN110358141A CN201910615059.4A CN201910615059A CN110358141A CN 110358141 A CN110358141 A CN 110358141A CN 201910615059 A CN201910615059 A CN 201910615059A CN 110358141 A CN110358141 A CN 110358141A
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- Prior art keywords
- fire retardant
- high molecular
- molecular material
- graphene
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating 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
- D06M11/07—Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
-
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Abstract
本发明涉及一种难燃高分子材料的制备方法，将质量浓度为5~8%的石墨烯水溶液或石墨烯醇溶液与质量浓度为2~4%的无机盐水溶液按1：0.5~1：2的体积比混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按所述复配体系的阻燃剂质量的0.2~1.0%加入粘结剂，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将所述复配体系的阻燃剂整理液与高分子材料缔合在一起，即得难燃高分子材料。本发明方法简单、成本低廉，所得的难燃高分子材料具有较高的极限氧指数，阻燃效果较好，极限氧指数在38%~52%之间，远远优于目前商用阻燃剂的性能。
Description
技术领域
本发明涉及高分子材料领域，尤其涉及一种难燃高分子材料的制备方法。
背景技术
随着高分子材料广泛应用于交通、建筑、室内外装饰、保温、隔音、家电等诸多领域，人们对高分子材料性能的要求越来越高，绝大多数高分子材料本身极限氧指数均低于21%，属于易燃材料。2015年，全国公安消防部门共接报火灾34.7万起，死亡1899人，受伤1213人，直接损失财产43.6亿元（公安部消防局.中国消防年鉴.2016[M].昆明：云南出版集团，2016，03-04.），其中很多涉及到高分子材料。高分子材料易燃，燃烧时热释放速率大，热值高，易传播，不易熄灭，并且燃烧会产生有毒有害气体，危害环境，危害人们身体健康，对人们的生命财产安全构成了极大的威胁。
高分子阻燃材料可分为无机和有机、含卤和无卤等多种类型。无机阻燃材料主要指氢氧化铝、氢氧化镁、硅系、三氧化二锑等。有机阻燃材料主要以卤系、氮系和磷系为主，他们通过复配或者反应得到添加型或者反应型复合高分子材料，进而起到阻燃作用。如专利CN 107936341 A中将膨胀型阻燃剂、硅系阻燃剂和无机阻燃剂组合添加于高分子基材中，经过双螺杆熔融挤出，在注塑机中压制成型得到高分子阻燃材料。虽然无机阻燃材料具有成本低、热学性能好，燃烧时有毒气体少等优点，但是它们也具有机械性能差、填充量大且与基体相容性差等缺陷。如专利CN 109517279 A中，将无卤磷系协同阻燃剂添加于高分子复合材料中得到阻燃高分子材料，由于无机阻燃剂添加量较多，高分子材料的强度较差。虽然有机型阻燃材料具有阻燃性能好，与基材相容性好，填充量小等优点，但是具有燃烧时发烟量大且产生有毒气体等缺陷。因此发展低烟、低毒、无卤、机械性能优越等环保型阻燃高分子材料成为该领域的重要研究课题。二维碳纳米材料的出现和发展为解决上述阻燃高分子材料的现有缺陷提供了可能。
石墨烯由于独特的单原子二维片层结构，比表面积高达2630m2/g可在高分子材料中平面覆盖和层层叠加，形成致密的物理隔热层，起到突出的物理隔绝作用，提高阻燃性能；石墨烯还可以与树脂进行交联复合，在高分子表面进一步形成一层致密的保护膜，起到隔绝空气的作用，从而发挥阻燃的效果；并且在高温下，石墨烯涂层会生成CO2和水，并生成更致密连续的碳层，起到进一步的阻隔作用，从而提高了高分子材料的阻燃性能。与传统的阻燃材料相比，添加少量的石墨烯就可以改善聚合物基体的热稳定性和阻燃性能，而且这一新型阻燃材料具有环保、低毒、综合性能优异的特点，但阻燃级别较低则限制了石墨烯阻燃剂的适用范围，于是复配体系的石墨烯阻燃剂作为膨胀型阻燃剂由于其多重阻燃机制以及分子组装的组分间的协同作用，将成为制备难燃或不燃高分子材料的新途径和新方法。
发明内容
本发明所要解决的技术问题是提供一种方法简单、成本低廉的难燃高分子材料的制备方法。
为解决上述问题，本发明所述的一种难燃高分子材料的制备方法，其特征在于：将质量浓度为5~8%的石墨烯水溶液或石墨烯醇溶液与质量浓度为2~4%的无机盐水溶液按1：0.5~1：2的体积比混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按所述复配体系的阻燃剂质量的0.2~1.0%加入粘结剂，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将所述复配体系的阻燃剂整理液与高分子材料缔合在一起，即得难燃高分子材料。
所述质量浓度为5~8%的石墨烯水溶液或石墨烯醇溶液是指在1L去离子水或无水乙醇中加入50~80g石墨烯，搅拌均匀即得；所述石墨烯是指普通石墨烯、氧化石墨烯、还原氧化石墨烯、改性石墨烯、改性氧化石墨烯中的一种或几种复配。
所述质量浓度为2~4%的无机盐水溶液是指在1L去离子水中加入20~40g无机盐，搅拌均匀即得；所述无机盐是指氯化钠、氯化钾、氯化铵、硝酸钠、硝酸钾、磷酸钠、磷酸二氢钠、磷酸钾、磷酸铵、磷酸二氢铵、硫酸钠、硫酸钾、硫酸铵、硫酸氢铵、碳酸铵、碳酸钠、碳酸钾、碳酸氢铵中的一种或几种。
所述高分子材料是指一维纤维材料、二维材料、三维材料、织物、涂料中的一种。
所述一维纤维材料是指聚乙烯醇纤维、聚丙烯腈纤维、粘胶纤维、聚酯纤维、尼龙纤维、棉纤维、醋酯纤维、纤维素纤维中的一种或几种。
所述二维材料是指聚乙烯薄膜、聚丙烯薄膜、聚酯薄膜、环氧树脂薄膜、聚酰亚胺薄膜、纤维素薄膜、聚酰胺薄膜、聚乙烯醇薄膜、聚对苯二甲酸乙二酯薄膜中的一种或几种。
所述三维材料是指聚氨酯泡沫塑料、聚乙烯泡沫塑料、聚丙烯泡沫塑料及聚苯乙烯泡沫塑料中的一种或几种。
所述织物是指纯棉、丙纶、涤纶、锦纶及腈纶中的一种或几种混纺。
所述涂料是指水性、油性或粉末涂料中的一种。
所述缔合方式是指涂覆、浸渍、沉积、添加、复合、键合、交联、印刷中的任意一种。
本发明与现有技术相比具有以下优点：
1、本发明中石墨烯与无机盐通过分子组装形成复配体系的阻燃剂或整理液具有无卤、低烟、无毒、稳定性好、分解温度高、不腐蚀设备等多种优异性能。
2、传统的卤系、有机或无机阻燃剂在基体材料中需要高填充量，对阻燃材料的物理机械性能影响较大，而本发明所得的复配体系阻燃剂添加量小，保证了基材的机械强度。
3、本发明利用化学交联法，借助分子间作用力（主要包括静电作用力、氢键和配位键等）为驱动力，使石墨烯、氧化石墨烯、表面改性和修饰石墨烯与无机盐离子及高分子基体之间层层缔合，形成具有酯膜结构的分子聚集体和超分子结构的“砌体结构”，构筑成致密的结构完整、性能稳定的物理隔热层，起到突出的物理隔绝作用，提高阻燃性能。
4、本发明将石墨烯与无机盐离子通过分子组装复配制备出阻燃剂或整理液。该复配体系体现出膨胀型阻燃剂和抑烟协效剂的作用，使用后明显增强高分子材料的阻燃和抑烟性能，杜绝熔滴现象，且不影响高分子基体材料的机械强度，为制备高性能高分子阻燃材料提供了新途径。
5、与目前商用的阻燃剂相比，本发明所得的难燃高分子材料具有较高的极限氧指数，阻燃效果较好，极限氧指数在38%~52%之间，远远优于目前商用阻燃剂的性能（参见表1）。
表1极限氧指数与UL94燃烧等级测试结果
6、本发明通过调控组装分子的结构、化学性质和组成，可以便捷地将多种组装体系结合在一起。
7、本发明在常温常压下即可完成难燃高分子材料的制备，工艺条件温和。
8、本发明石墨烯分子组装的复配体系的阻燃剂或整理液可重复利用，具有环境友好等特点。
9、本发明方法简单，原材料易获取，制备成本低廉，适合工业化大规模应用。
具体实施方式
实施例1 一种难燃高分子材料的制备方法，将质量浓度为5%的氧化石墨烯水溶液与质量浓度为3%的硫酸铵水溶液按1：0.5的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.2%加入聚氨酯，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将聚氨酯泡沫塑料浸渍于复配体系的阻燃剂整理液中，5min后取出，在室温下干燥，即可得到聚氨酯难燃或不燃泡沫塑料。
其中：质量浓度为5%的氧化石墨烯水溶液是指在1L去离子水中加入50g氧化石墨烯，搅拌均匀即得。
质量浓度为3%的硫酸铵水溶液是指在1L去离子水中加入30g硫酸铵，搅拌均匀即得。
实施例2 一种难燃高分子材料的制备方法，将质量浓度为8%的石墨烯水溶液与质量浓度为4%的无机盐水溶液按1：0.8的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.5%加入羧甲基纤维素，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将复配体系的阻燃剂整理液涂覆在纯棉织物或聚丙烯腈纤维表面，15min后取出，在室温下干燥，即可得到难燃纯棉织物或难燃聚丙烯腈纤维。
其中：质量浓度为8%的石墨烯水溶液是指在1L去离子水中加入80g石墨烯，搅拌均匀即得。石墨烯是指氧化石墨烯和改性石墨烯按1：1的质量比（g/g）混合均匀而得的混合物。
质量浓度为4%的无机盐水溶液是指在1L去离子水中加入40g无机盐，搅拌均匀即得。无机盐是指氯化钠与磷酸铵按1：3的质量比（g/g）混合均匀而得的混合物。
实施例3 一种难燃高分子材料的制备方法，将质量浓度为6%的石墨烯水溶液与质量浓度为2%的无机盐水溶液按1：1的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.2%加入羧甲基纤维素，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将复配体系的阻燃剂整理液沉积于聚乙烯薄膜或聚丙烯薄膜，10min后取出，在室温下干燥，即可得到难燃聚乙烯薄膜或难燃聚丙烯薄膜。
其中：质量浓度为6%的石墨烯水溶液是指在1L去离子水中加入60g石墨烯，搅拌均匀即得；石墨烯是指改性氧化石墨烯与普通石墨烯按2：1的质量比混合均匀而得的混合物。
质量浓度为2%的无机盐水溶液是指在1L去离子水中加入20g无机盐，搅拌均匀即得。无机盐是指碳酸铵与硫酸钾按1：1的质量比（g/g）混合均匀而得的混合物。
实施例4 一种难燃高分子材料的制备方法，将质量浓度为5%的改性氧化石墨烯水溶液与质量浓度为3%的无机盐水溶液按1：1.3的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.2%加入聚氨酯，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将复配体系的阻燃剂整理液打印于涤纶织物上，经室温干燥，即可得到难燃涤纶织物。
其中：质量浓度为5%的改性氧化石墨烯水溶液是指在1L去离子水中加入50g改性氧化石墨烯，搅拌均匀即得。
质量浓度为3%的无机盐水溶液是指在1L去离子水中加入30g无机盐，搅拌均匀即得. 无机盐是指碳酸铵、硫酸钠、磷酸铵按1：0.5：1.5的质量比（g/g）混合均匀而得的混合物。
实施例5 一种难燃高分子材料的制备方法，将质量浓度为5%的石墨烯水溶液与质量浓度为4%的无机盐水溶液按1：1.5的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.2%加入羟乙基纤维素，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将复配体系的阻燃剂整理液分别通过化学键合作用与纤维素织物、聚乙烯泡沫塑料、聚丙烯泡沫塑料交联，在室温下干燥，即可分别得到难燃纤维素织物、难燃聚乙烯泡沫塑料、难燃聚丙烯泡沫塑料。
其中：质量浓度为5%的石墨烯水溶液是指在1L去离子水中加入50g石墨烯，搅拌均匀即得。石墨烯是指还原氧化石墨烯与改性氧化石墨烯按1：3的质量比（g/g）混合均匀而得的混合物。
质量浓度为4%的无机盐水溶液是指在1L去离子水中加入40g无机盐，搅拌均匀即得。无机盐是指磷酸二氢钠与硝酸钠按3：1的质量比（g/g）混合均匀而得的混合物。
实施例6 一种难燃高分子材料的制备方法，将质量浓度为5%的氧化石墨烯醇溶液与质量浓度为3%的无机盐水溶液按1：2的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的1.0%加入乙基纤维素，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将复配体系的阻燃剂整理液通过交化学联作用与聚苯乙烯泡沫塑料复合，在室温下干燥，即可得到难燃聚苯乙烯泡沫塑料。
其中：质量浓度为5%的氧化石墨烯醇溶液是指在1L无水乙醇中加入50g氧化石墨烯，搅拌均匀即得。
质量浓度为3%的无机盐水溶液是指在1L去离子水中加入30g无机盐，搅拌均匀即得。无机盐是指碳酸钠与硫酸氢铵按1：2的质量比（g/g）混合均匀而得的混合物。
实施例7 一种难燃高分子材料的制备方法，将质量浓度为5%的石墨烯水溶液与质量浓度为3%的无机盐水溶液按1：2的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.2%加入羟乙基纤维素，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将复配体系的阻燃剂整理液替代三聚磷酸铝，添加于水性环氧内舱涂料中，制备得到难燃水性环氧内舱涂料。
其中：质量浓度为5%的石墨烯水溶液是指在1L去离子水中加入50g石墨烯，搅拌均匀即得。石墨烯是指氧化石墨烯与改性氧化石墨烯按1：1的质量比（g/g）混合均匀而得的混合物。
质量浓度为3%的无机盐水溶液是指在1L去离子水中加入30g无机盐，搅拌均匀即得。无机盐是指磷酸铵与碳酸铵按2：1的质量比（g/g）混合均匀而得的混合物。
实施例8 一种难燃高分子材料的制备方法，将质量浓度为6%的石墨烯水溶液与质量浓度为3%的无机盐水溶液按1：1.5的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.2~1.0%加入粘结剂，450r/min搅拌30min，得到复配体系的阻燃剂整理液；复配体系的阻燃剂整理液经冷冻干燥得到粉末阻燃剂。最后，将粉末阻燃剂作为填料添加于纯聚酯粉末涂料中，制备得到难燃纯聚酯粉末涂料。该涂料涂覆于空调、电信器材、消防器材、金属门窗、高速公路防护栏等表面达到不燃级别。
其中：质量浓度为6%的石墨烯水溶液是指在1L去离子水中加入60g石墨烯，搅拌均匀即得。石墨烯是指改性石墨烯与还原氧化石墨烯按3：1的质量比（g/g）混合均匀而得的混合物。
质量浓度为3%的无机盐水溶液是指在1L去离子水中加入30g无机盐，搅拌均匀即得。无机盐是指磷酸铵与碳酸铵按2：1的质量比（g/g）混合均匀而得的混合物。
实施例9 一种难燃高分子材料的制备方法，将质量浓度为5%的石墨烯水溶液与质量浓度为4%的无机盐水溶液按1：1.5的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.5%加入乙基纤维素，450r/min搅拌30min，得到复配体系的阻燃剂整理液；复配体系的阻燃剂整理液经冷冻干燥得到粉末阻燃剂。最后，将粉末阻燃剂作为填料添加于单组分油性聚氨酯涂料中，制备得到难燃单组分油性聚氨酯涂料。该涂料涂覆于屋顶、外墙、窗户、厨卫等表面达到不燃级别。
其中：质量浓度为5%的石墨烯水溶液是指在1L去离子水中加入50g石墨烯，搅拌均匀即得。石墨烯是指改性石墨烯与氧化石墨烯按1：1的质量比（g/g）混合均匀而得的混合物。
质量浓度为4%的无机盐水溶液是指在1L去离子水中加入40g无机盐，搅拌均匀即得。无机盐是指磷酸铵与磷酸钠按3：2的质量比（g/g）混合均匀而得的混合物。
实施例10 一种难燃高分子材料的制备方法，将质量浓度为8%的石墨烯水溶液与质量浓度为4%的无机盐水溶液按1：2的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.5%加入羧甲基纤维素，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将复配体系的阻燃剂整理液印刷于聚酯薄膜、纤维素薄膜、聚乙烯醇薄膜上，在室温下干燥，即可分别得到难燃聚酯薄膜、难燃纤维素薄膜和难燃聚乙烯醇薄膜。
其中：质量浓度为8%的石墨烯水溶液是指在1L去离子水中加入80g石墨烯，搅拌均匀即得。石墨烯是指氧化石墨烯与改性氧化石墨烯按1：4的质量比（g/g）混合均匀而得的混合物。
质量浓度为4%的无机盐水溶液是指在1L去离子水中加入40g无机盐，搅拌均匀即得。无机盐是指氯化铵、硝酸钾、碳酸氢铵按1:1:2的质量比（g/g）混合均匀而得的混合物。
实施例11 一种难燃高分子材料的制备方法，将质量浓度为5%的石墨烯水溶液与质量浓度为3%的无机盐水溶液按1：2的体积比（L/L）混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按复配体系的阻燃剂质量（单位：g）的0.5%加入醋酸树脂，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将复配体系的阻燃剂整理液分别与尼龙纤维、环氧树脂薄膜、聚酰胺薄膜交联，在室温下干燥，即可分别得到难燃尼龙纤维、难燃环氧树脂薄膜或难燃聚酰胺薄膜。
其中：质量浓度为5%的石墨烯水溶液是指在1L去离子水中加入50g石墨烯，搅拌均匀即得。石墨烯是指改性石墨烯与氧化石墨烯按1：1的质量比（g/g）混合均匀而得的混合物。
质量浓度为3%的无机盐水溶液是指在1L去离子水中加入30g无机盐，搅拌均匀即得。无机盐是指氯化钾、硝酸钾、磷酸钾按1:1:2的质量比（g/g）混合均匀而得的混合物。
上述实施例1~11中，石墨烯可以是普通石墨烯、氧化石墨烯、还原氧化石墨烯、改性石墨烯、改性氧化石墨烯中的一种或几种复配。
无机盐可以是氯化钠、氯化钾、氯化铵、硝酸钠、硝酸钾、磷酸钠、磷酸二氢钠、磷酸钾、磷酸铵、磷酸二氢铵、硫酸钠、硫酸钾、硫酸铵、硫酸氢铵、碳酸铵、碳酸钠、碳酸钾、碳酸氢铵中的一种或几种。
高分子材料可以是一维纤维材料、二维材料、三维材料、织物、涂料中的一种。一维纤维材料是指聚乙烯醇纤维、聚丙烯腈纤维、粘胶纤维、聚酯纤维、尼龙纤维、棉纤维、醋酯纤维、纤维素纤维中的一种或几种。二维材料是指聚乙烯薄膜、聚丙烯薄膜、聚酯薄膜、环氧树脂薄膜、聚酰亚胺薄膜、纤维素薄膜、聚酰胺薄膜、聚乙烯醇薄膜、聚对苯二甲酸乙二酯薄膜中的一种或几种。三维材料是指聚氨酯泡沫塑料、聚乙烯泡沫塑料、聚丙烯泡沫塑料及聚苯乙烯泡沫塑料中的一种或几种。织物是指纯棉、丙纶、涤纶、锦纶及腈纶中的一种或几种混纺。涂料是指水性、油性或粉末涂料中的一种。
对比实例1 取商用阻燃剂FRC-2，配制成5wt%的水溶液，300r/min搅拌10min，再加入0.2wt%的聚氨酯，450r/min搅拌30min，制备得FRC-2阻燃整理液。将聚氨酯泡沫塑料浸渍于上述的FRC-2阻燃整理液中，5min后取出，在室温下干燥，即得到聚氨酯阻燃泡沫塑料。
对比实例2 取商用ECO阻燃剂，配制成5wt%的水溶液，300r/min搅拌10min，再加入0.5wt%的羧甲基纤维素，450r/min搅拌30min，制备得到ECO阻燃整理液。将上述复配体系的阻燃整理液打印于纯棉织物或聚丙烯腈纤维表面，经室温干燥，即可得到阻燃织物或者阻燃聚丙烯腈纤维。
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例应用于其它领域，但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。
Claims (10)
1.一种难燃高分子材料的制备方法，其特征在于：将质量浓度为5~8%的石墨烯水溶液或石墨烯醇溶液与质量浓度为2~4%的无机盐水溶液按1：0.5~1：2的体积比混合，300r/min搅拌10min，通过分子组装形成复配体系的阻燃剂；再按所述复配体系的阻燃剂质量的0.2~1.0%加入粘结剂，450r/min搅拌30min，得到复配体系的阻燃剂整理液；最后，将所述复配体系的阻燃剂整理液与高分子材料缔合在一起，即得难燃高分子材料。
2.如权利要求1所述的一种难燃高分子材料的制备方法，其特征在于：所述质量浓度为5~8%的石墨烯水溶液或石墨烯醇溶液是指在1L去离子水或无水乙醇中加入50~80g石墨烯，搅拌均匀即得；所述石墨烯是指普通石墨烯、氧化石墨烯、还原氧化石墨烯、改性石墨烯、改性氧化石墨烯中的一种或几种复配。
3.如权利要求1所述的一种难燃高分子材料的制备方法，其特征在于：所述质量浓度为2~4%的无机盐水溶液是指在1L去离子水中加入20~40g无机盐，搅拌均匀即得；所述无机盐是指氯化钠、氯化钾、氯化铵、硝酸钠、硝酸钾、磷酸钠、磷酸二氢钠、磷酸钾、磷酸铵、磷酸二氢铵、硫酸钠、硫酸钾、硫酸铵、硫酸氢铵、碳酸铵、碳酸钠、碳酸钾、碳酸氢铵中的一种或几种。
4.如权利要求1所述的一种难燃高分子材料的制备方法，其特征在于：所述高分子材料是指一维纤维材料、二维材料、三维材料、织物、涂料中的一种。
5.如权利要求4所述的一种难燃高分子材料的制备方法，其特征在于：所述一维纤维材料是指聚乙烯醇纤维、聚丙烯腈纤维、粘胶纤维、聚酯纤维、尼龙纤维、棉纤维、醋酯纤维、纤维素纤维中的一种或几种。
6.如权利要求4所述的一种难燃高分子材料的制备方法，其特征在于：所述二维材料是指聚乙烯薄膜、聚丙烯薄膜、聚酯薄膜、环氧树脂薄膜、聚酰亚胺薄膜、纤维素薄膜、聚酰胺薄膜、聚乙烯醇薄膜、聚对苯二甲酸乙二酯薄膜中的一种或几种。
7.如权利要求4所述的一种难燃高分子材料的制备方法，其特征在于：所述三维材料是指聚氨酯泡沫塑料、聚乙烯泡沫塑料、聚丙烯泡沫塑料及聚苯乙烯泡沫塑料中的一种或几种。
8.如权利要求4所述的一种难燃高分子材料的制备方法，其特征在于：所述织物是指纯棉、丙纶、涤纶、锦纶及腈纶中的一种或几种混纺。
9.如权利要求4所述的一种难燃高分子材料的制备方法，其特征在于：所述涂料是指水性、油性或粉末涂料中的一种。
10.如权利要求1所述的一种难燃高分子材料的制备方法，其特征在于：所述缔合方式是指涂覆、浸渍、沉积、添加、复合、键合、交联、印刷中的任意一种。
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