CN116752347B - 一种复合生物基阻燃无纺布及其制备方法 - Google Patents
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Abstract
本发明公开了一种复合生物基阻燃无纺布及其制备方法,该制备方法包括如下步骤:S1、将聚酰胺纤维和海藻酸盐纤维共混后压缩,得到聚酰胺/藻酸盐混纺无纺布;S2、将聚酰胺/藻酸盐混纺无纺布浸入磷酸酯阻燃剂溶液中,进行接枝反应;S3、对反应后的无纺布进行固化干燥、洗涤、干燥即得。本发明采用海藻酸盐纤维与磷酸酯类阻燃剂对聚酰胺纤维无纺布进行双重阻燃,另外,由于阻燃剂在高温下分解产生磷酸物质,从而加速了纤维素纤维向碳的转化,进而减少了纤维的燃烧分解和易燃挥发性气体的产生,抑制可燃气体的释放,以防止海藻酸盐纤维的燃烧,二者产生协同阻燃效果。处理后的无纺布具有出色的阻燃性和热稳定性,且燃烧后残炭的形貌保存完好。
Description
技术领域
本发明涉及阻燃无纺布复合材料,具体地,涉及一种复合生物基阻燃无纺布及其制备方法。
背景技术
聚酰胺纤维俗称尼龙、锦纶,是分子主链上含有重复酰胺基团-[NHCO]-的热塑性纤维总称。尼龙纤维具有耐磨性好、回弹性高、染色性好、力学性能优良等特点,可应用与服装、建筑、化工等领域。但是目前常用的锦纶6和锦纶66的热性能不好、易燃烧,锦纶6的熔点225°C,锦纶66熔点264°C,而其热分解温度及燃烧温度在400°C以上,因而在燃烧中容易产生的熔融滴落物、造成火势蔓延。
发明内容
针对PA高度易燃,并且燃烧时伴有严重的熔体滴落的问题,本发明提供了一种复合生物基阻燃无纺布及其制备方法,该方法制得的复合生物基无纺布具有出色的阻燃性和热稳定性,燃烧后残炭的形貌保存完好。阻燃剂处理对无纺布的断裂强度和弯曲刚度影响不大,促进不可燃气体的释放,抑制可燃气体的释放。在制备工业用阻燃无纺布,具有装饰和填充材料方面显示出巨大的应用前景。
为了实现上述目的,本发明一方面提供一种复合生物基阻燃无纺布的制备方法,其特征在于,包括如下步骤:
S1、将聚酰胺纤维和海藻酸盐纤维共混后压缩,得到聚酰胺/藻酸盐混纺无纺布;
S2、将聚酰胺/藻酸盐混纺无纺布浸入磷酸酯阻燃剂溶液中,进行接枝反应;
S3、对反应后的无纺布进行固化干燥、洗涤、干燥即得。
海藻酸盐是一种主要从丰富的褐藻中提取的多糖,其中一些,包括海藻酸钙,已获得美国食品和药物管理局(FDA)的批准。到目前为止,藻酸盐已应用于许多领域,包括纺织、食品和生物医学行业,因为它们具有生物相容性、低毒性和相对较低的成本。作为一种阴离子聚合物,藻酸盐可以与大多数二价金属离子交联通过超分子相互作用位点形成“蛋盒”连接。结果,藻酸盐通过占主导地位的凝聚相活性获得固有的阻燃性;更具体地说,一些金属离子可以催化热解中间体的石墨化,从而产生稳定的焦炭层并显着减少可燃气体。
本发明将海藻酸盐纤维与聚酰胺纤维共混压缩为无纺布,在共混体系中,熔融的PA以薄膜和囊状物的形式被限制在碳化的海藻酸纤维的区域内,可快速实现自熄,而不会滴落,更具体地,PA熔体与藻酸盐纤维的残余物不相容,因此它不能被烧焦的骨架吸收作为用于燃烧的额外燃料,这应归因于海藻酸盐的特殊形态和碳/钙杂化成分。在受热过程中,由于熔化的聚酰胺纤维中存在成炭的海藻酸盐,混合材料过早点燃,但热量、烟雾和有毒气体释放明显减少,表明该材料的防火安全性优异。藻酸盐由于不易燃气体的稀释作用而显示出气相阻燃活性,具体表现为:由于藻酸盐产生的不易燃气体的燃料稀释,阻止了氧气供应并去除大部分分解热量,从而大大降低处理过的无纺布的表面温度。
磷酸酯类阻燃剂是一类无卤、低烟、低毒的环保型阻燃剂,它与高聚物的相容性好,应用较为广泛。
本发明采用海藻酸盐纤维与磷酸酯类阻燃剂对聚酰胺纤维无纺布进行双重阻燃,另外,由于阻燃剂在高温下分解产生磷酸物质,从而加速了纤维素纤维向碳的转化,从而减少了纤维的燃烧分解和易燃挥发性气体的产生,抑制可燃气体的释放,以防止海藻酸盐纤维的燃烧,二者产生协同阻燃效果。处理后的无纺布具有出色的阻燃性和热稳定性。燃烧后残炭的形貌保存完好。
优选地,步骤S1中,所述聚酰胺纤维和所述海藻酸盐纤维的质量比为1:(1~1.2)。
优选地,步骤S1中,所述压缩为将共混物在室温下压缩至15 MPa以下。
优选地,步骤S2中,所述磷酸酯阻燃剂由泛醇与磷酸进行酯化反应而得,所述醇为D-泛醇、DL-泛醇、L-泛醇或泛酸钙;酯化反应条件为:在100 ~120°C下进行2.5h以上。
上述技术方案中,在无溶剂和无甲醛条件下成功合成磷酸酯阻燃剂,是一种环保可再生P-N协同阻燃剂。经过上述磷酸酯阻燃剂处理的无纺布表现出优异的阻燃性,LOI超过5.35%,耐洗性超过8.50%。经处理的无纺布焦化得到极大改善,在空气和氮气气氛条件下的残留量分别低于54.8 wt%和65.12 wt%。
进一步地,酯化反应后向反应体系中加入脲,在160~180°C下反应2h以上,所述脲与磷酸的摩尔比为1:(2~3)。
上述技术方案中,脲在高温下产生氨气与二氧化碳,氨气再与中间体上的羟基反应生成类氨膦酸盐。
优选地,步骤S2中,以双氰胺催化剂催化接枝反应,所述磷酸酯阻燃剂的质量为所述双氰胺的2~3倍。加快接枝反应的进行。
在上述基础上,所述接枝反应条件为:温度为60~80°C,时间为2~4h。
优选地,步骤S2中,所述无纺布与所述磷酸酯阻燃剂的质量比为1:(18~25)。
优选地,步骤S3中,在固化干燥温度为160 ~200°C,时间≥5分钟;干燥温度为100~120°C,时间为≥12h。
本发明另一方面提供一种上述的制备方法制得的复合生物基阻燃无纺布。
通过上述技术方案,本发明实现了以下有益效果:
1、本发明将海藻酸盐纤维与聚酰胺纤维共混压缩为无纺布,在共混体系中,熔融的PA以薄膜和囊状物的形式被限制在碳化的海藻酸纤维的区域内,可快速实现自熄,而不会滴落,更具体地,PA熔体与藻酸盐纤维的残余物不相容,因此它不能被烧焦的骨架吸收作为用于燃烧的额外燃料,这应归因于海藻酸盐的特殊形态和碳/钙杂化成分。在受热过程中,由于熔化的聚酰胺纤维中存在成炭的海藻酸盐,混合材料过早点燃,但热量、烟雾和有毒气体释放明显减少,表明该材料的防火安全性优异。藻酸盐由于不易燃气体的稀释作用而显示出气相阻燃活性,具体表现为:由于藻酸盐产生的不易燃气体的燃料稀释,阻止了氧气供应并去除大部分分解热量,从而大大降低处理过的无纺布的表面温度。
2、本发明在无溶剂和无甲醛条件下成功合成磷酸酯阻燃剂,是一种环保可再生P-N协同阻燃剂。经过上述磷酸酯阻燃剂处理的无纺布表现出优异的阻燃性,LOI超过5.35%,耐洗性超过8.50%。经处理的无纺布焦化得到极大改善,在空气和氮气气氛条件下的残留量分别低于54.8 wt%和65.12 wt%。
附图说明
图1是本发明实施例1制备的复合生物基阻燃无纺布实物图;
图2是本发明实施例1制备的复合生物基阻燃无纺布的微观结构图;
图3是本发明实施例中磷酸酯阻燃剂的制备原理图;
图4是本发明实施例中磷酸酯阻燃剂的S1 1H核磁共振波谱图;
图5是本发明实施例中磷酸酯阻燃剂的13C核磁共振波谱图;
图6是本发明实施例中磷酸酯阻燃剂的31P核磁共振波谱图;
图7是本发明实施例中接枝反应的原理图。
具体实施方式
以下结合实施例对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
以下实施例中,聚酰胺纤维(PA6)由金天马纱线有限公司(中国盐城)提供。海藻酸钙纤维(8-12wt%氧化钙)购自青岛海赛尔新材料科技有限公司(中国青岛)。
实施例1
复合生物基阻燃无纺布的制备方法包括如下步骤:
(1)分别称取10g聚酰胺纤维和10g海藻酸钙纤维在HFX-A0开纤机(中国Sansi)上松动混合两次形成共混物;
(2)将步骤(1)制得的共混物在室温下压缩至15 MPa,最终获得PA/海藻酸钙混纺无纺布,清洗并干燥;
按图3所示原理制备磷酸酯阻燃剂:
(3)将0.05mol(10.26g)D-泛醇(图中①)和0.15mol(14.70g)磷酸(图中②)在配备有机械搅拌和温度计的250 mL烧杯中混合,在110°C下进行酯化反应2.5h,得到粘稠的白色液体中间体(即图中③);
(4)将0.30mol(18.00g)脲(图中④)加入步骤(3)制得的溶液中,同时在170°C下恒定搅拌2 h,以获得白色流体;
(5)当步骤(4)获得白色流体冷却至室温时,流体产物变成固体;产物用乙醇洗涤以进行纯化,然后在烘箱中在80°C下干燥,即得产物磷酸酯阻燃剂(图中⑤);如图4-图6所示,利用 1H NMR、13C NMR 和 31P NMR 光谱分析确定了阻燃剂的分子结构。具体归因如下:1H NMR (D2O, 600MHz) δ(ppm): 4.71(D2O), 3.69 (s, H1), 0.79 (s, H3), 3.86 (s,H4), 2.94 (t, H6), 1.90 (m, H7), 1.60 (m, H8), 3.60 (t, H9);13C NMR (D2O,600MHz) δ (ppm):62.62 (t, C1), 163.75 (s,C2), 16.32 (q, C3), 68.42 (d, C4),163.75 (s, C5), 36.95 (t,C7), 27.16 (t, C8), 59.91 (t, C9);31P NMR (D2O,600MHz) δ(ppm): 0.98, 0.70 and 0.20。
按图7所示原理进行接枝反应:
(6)将(5)制备的磷酸酯阻燃剂以20wt%磷酸酯溶液的浓度溶解在蒸馏水中。接着,将10wt%双氰胺(图中⑥)作为催化剂加入到上述溶液中;
(7)使用1:20的浴比将步骤(2)得到的无纺布浸入步骤(6)制得的溶液中,在恒温振荡器中,在70°C下,将反应混合物在室温下搅拌2h;随后,将经处理的无纺布在连续固化干燥器中在180°C下加热5分钟,然后用蒸馏水冲洗材料,最后在烘箱中在110°C下干燥至恒重,得到复合生物基阻燃无纺布。
复合生物基阻燃无纺布实物如图1所示,电镜图如图2所示(扫描电镜为产于日本的S-4800Ⅱ场发射扫描电镜FESEM)。从图2可以看出,对于PA/海藻酸钙共混物,两种纤维相互交叉,表明具有不同表面形貌和化学性质的两种纤维最终通过共混均匀混合。在这种情况下,两种纤维的良好接触有助于提高混合物的阻燃性。
实施例2
复合生物基阻燃无纺布的制备方法包括如下步骤:
(1)分别称取10g聚酰胺纤维和12g海藻酸钠纤维在HFX-A0开纤机(中国Sansi)上松动混合两次形成共混物;
(2)将步骤(1)制得的共混物在室温下压缩至13 Mpa,最终获得PA/海藻酸钠混纺无纺布,清洗并干燥;
(3)将0.05mol(10.26g)DL-泛醇和0.15mol(14.70g)磷酸在配备有机械搅拌和温度计的250 mL烧杯中混合,在100°C下进行酯化反应3h,得到粘稠的白色液体中间体;
(4)将0.45mol(27.00g)脲加入步骤(3)制得的溶液中,同时在160°C下恒定搅拌3h,以获得白色流体;
(5)当步骤(4)获得白色流体冷却至室温时,流体产物变成固体;产物用乙醇洗涤以进行纯化,然后在烘箱中在80°C下干燥,即得产物磷酸酯阻燃剂;
(6)将(5)制备的磷酸酯阻燃剂以30wt%磷酸酯溶液的浓度溶解在蒸馏水中。接着,将10wt%双氰胺作为催化剂加入到上述溶液中;
(7)使用1:18的浴比将步骤(2)得到的无纺布浸入步骤(6)制得的溶液中,在恒温振荡器中,在60°C下,将反应混合物在室温下搅拌4h;随后,将经处理的无纺布在连续固化干燥器中在160°C下加热10分钟,然后用蒸馏水冲洗材料,最后在烘箱中在100°C下干燥至恒重,得到复合生物基阻燃无纺布。
实施例3
复合生物基阻燃无纺布的制备方法包括如下步骤:
(1)分别称取10g聚酰胺纤维和11g海藻酸钙纤维在HFX-A0开纤机(中国Sansi)上松动混合两次形成共混物;
(2)将步骤(1)制得的共混物在室温下压缩至15 MPa,最终获得PA/海藻酸钙混纺无纺布,清洗并干燥;
(3)将0.05mol(10.26g)L-泛醇和0.15mol(14.70g)磷酸在配备有机械搅拌和温度计的250 mL烧杯中混合,在120°C下进行酯化反应2.5h,得到粘稠的白色液体中间体;
(4)将0.30mol(18.00g)脲加入步骤(3)制得的溶液中,同时在180°C下恒定搅拌2h,以获得白色流体;
(5)当步骤(4)获得白色流体冷却至室温时,流体产物变成固体;产物用乙醇洗涤以进行纯化,然后在烘箱中在80°C下干燥,即得产物磷酸酯阻燃剂;
(6)将(5)制备的磷酸酯阻燃剂以20wt%磷酸酯溶液的浓度溶解在蒸馏水中。接着,将10wt%双氰胺作为催化剂加入到上述溶液中;
(7)使用1:25的浴比将步骤(2)得到的无纺布浸入步骤(6)制得的溶液中,在恒温振荡器中,在80°C下,将反应混合物在室温下搅拌3h;随后,将经处理的无纺布在连续固化干燥器中在200°C下加热5分钟,然后用蒸馏水冲洗材料,最后在烘箱中在120°C下干燥至恒重,得到复合生物基阻燃无纺布。
对比例1
其他条件同实施例1,区别在于省略步骤(3)~(7)。
对比例2
其他条件同实施例1,区别在于,将步骤(1)~(2)修改为:称取10g聚酰胺纤维在HFX-A0开纤机(中国Sansi)上松动,然后在室温下压缩至15 MPa,最终获得PA无纺布,清洗并干燥。
对比例3
其他条件同实施例1,区别在于,将步骤(3)-(5)制备的磷酸酯阻燃剂替换为市购产品磷酸三异丁酯阻燃剂(TiBP,AR,98%),购自J&K Chemical(中国北京)。
性能测试
将实施例制备的复合生物基阻燃无纺布和对比例制备的无纺布进行热释放速率、总放热量和CO2/CO的测试,测试方法参考国际标准ASTME1354在35 kW/m2的辐射热通量下进行。具体测试结果如表1所示:
表1 性能测试结果
从表中可以看出,未接枝阻燃剂的PA/藻酸盐混纺无纺布(对比例1)和接枝阻燃剂的PA无纺布的总热释放(THR)、峰值放热速率(PHRR)、放热速率峰值时间(TPHRR)以及CO2/CO的比率,均远高于实施例制得的复合生物基阻燃无纺布,最终的残留百分比(Residue)均远小于实施例制得的复合生物基阻燃无纺布,可见本发明制备的复合生物基阻燃无纺布性能得到了大大提升。
以上结合实施例详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (8)
1.一种复合生物基阻燃无纺布的制备方法,其特征在于,包括如下步骤:
S1、将聚酰胺纤维和海藻酸盐纤维共混后压缩,得到聚酰胺/海藻酸盐混纺无纺布;
S2、将聚酰胺/海藻酸盐混纺无纺布浸入磷酸酯阻燃剂溶液中,以双氰胺催化剂在温度为60~80°C下催化接枝反应2~4h,其中,所述磷酸酯阻燃剂的制备方法为:先由泛醇与磷酸在100~120°C下进行酯化反应2.5h以上,酯化反应后向反应体系中加入脲,在160~180°C下反应2h以上,所述泛醇为D-泛醇、DL-泛醇、L-泛醇或泛酸钙;
S3、对反应后的无纺布进行固化干燥、洗涤、干燥即得。
2.根据权利要求1所述的复合生物基阻燃无纺布的制备方法,其特征在于,步骤S1中,所述聚酰胺纤维和所述海藻酸盐纤维的质量比为1:(1~1.2)。
3.根据权利要求1所述的复合生物基阻燃无纺布的制备方法,其特征在于,步骤S1中,所述压缩为将共混物在室温下压缩至15 MPa以下。
4.根据权利要求1所述的复合生物基阻燃无纺布的制备方法,其特征在于,所述脲与磷酸的摩尔比为1:(2~3)。
5.根据权利要求1所述的复合生物基阻燃无纺布的制备方法,其特征在于,步骤S2中,所述磷酸酯阻燃剂的质量为所述双氰胺的2~3倍。
6.根据权利要求1所述的复合生物基阻燃无纺布的制备方法,其特征在于,步骤S2中,所述无纺布与所述磷酸酯阻燃剂的质量比为1:(18~25)。
7.根据权利要求1至6中任一项所述的复合生物基阻燃无纺布的制备方法,其特征在于,步骤S3中,在固化干燥温度为160 ~200°C,时间≥5分钟;干燥温度为100~120°C,时间为≥12h。
8.权利要求1至7中任一项所述的制备方法制得的复合生物基阻燃无纺布。
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