CN106432321B - 一种基于分散染料改性的抗紫外处理剂及其制备方法 - Google Patents
一种基于分散染料改性的抗紫外处理剂及其制备方法 Download PDFInfo
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- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/54—Amino-hydroxy-anthraquinones; Ethers and esters thereof etherified
- C09B1/547—Anthraquinones with aromatic ether groups
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
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Abstract
本发明公开的一种基于分散染料改性的抗紫外处理剂的结构通式如下：其红外吸收光谱于588cm‑1，1109cm‑1和782cm‑1处出现了分别代表Si–O–Si和Si–C伸缩振动峰，于3068，2962cm‑1和1460cm‑1处出现了分别代表‑CH2–CH2‑、‑CH2–CH2–CH2‑或‑CH2–CH2–CH2–CH2‑伸缩和弯曲振动峰；其29Si NMR谱图中于‑109.63ppm处出现了代表POSS结构中硅原子的振动峰；在其溶液的紫外‑可见光吸收光谱中波长300nm以下出现了吸收峰。本发明还公开了其制备方法。本发明所得抗紫外处理剂不仅可通过高温高压处理法将抗紫外处理剂借助染料分子牢固镶嵌在纤维浅表层，达到固着于纤维上的目的，以发挥持久的抗紫外功能，且还能同时实现对合成纤维的染色。
Description
技术领域
本发明属于抗紫外剂处理剂及其制备技术领域，具体涉及一种基于分散染料改性的抗紫外处理剂及其制备方法。
背景技术
全芳香族聚酰胺(芳纶)和聚对亚苯基1,3,4-噁二唑(p-POD)等芳香族高性能纤维都具有优异的物理机械、热稳定性、电绝缘性、耐溶剂性、特殊的导电性以及电致发光等性能，常被作为耐高温滤布、渗透膜和绝缘防护材料使用(Zhang Z,Ye G,Li W,Li T,XuJ.Influence of sulfuric acid bath on morphological structure and mechanicalproperties of poly(p-phenylene-1,3,4-oxadiazole)fibers[J].Journal of AppliedPolymer Science,2009,114(3):1485-1493；Schulz B,Bruma M,Brehmer L.AromaticPoly(1,3,4-Oxadiazoe)s as Advanced materials[J].Advanced Materials,1997,9(8):601-613；赵会芳.芳纶纤维和芳纶浆粕的结构与芳纶纸特性的相关性研究[D].西安：陕西科技大学,2012；Kakida H,Chatani Y,Tadokoro H.Crystal structure of poly(m-phenylene isophthalamide)[J].Journal of Polymer Science:Polymer PhysicsEdition,1976,14(3):427-435)。但是，这类纤维的光稳定性较差，经紫外光照射后其强力损失较大(Johnson L D,Tincher W C,Bach H C.Photodegradative wavelengthdependence of thermally resistant organic polymers[J].Journal of AppliedPolymer Science,1969,13(9):1825-1832；Imai Y.Direct fiber formation and fiberproperties of aromatic polyoxadiazoles[J].Journal of Applied Polymer Science,1970,14(1):225-239)。为了提高这类纤维的耐光性，本领域的科技工作者经研究，主要提出四种解决方法：(1)采用TiO2凝胶、炭黑、聚乙烯醇和羧甲基纤维素钠等对纤维进行涂层处理。这种处理方式虽然使纤维强力的保留率有所提高，但是经三次水洗后其抗紫外性能与未涂层纤维相当(董丽楠.芳香族聚噁二唑纤维的光老化及稳定化研究[D].成都:四川大学,2010；杨潇.聚1,3,4-噁二唑(POD)老化及防护研究[D].成都：四川大学，2011)；(2)在p-POD聚合时引入对光具有选择性吸收的偶氮结构物质，以保护大分子链中的杂环结构，但是这些偶氮结构物质在纺丝过程中不仅容易造成喷丝孔堵塞，且纤维的初始强力有所下降(Zhou W,Yang X,Jia E,Wang X,Xu J,Ye G.Ultraviolet resistance of azo-containing poly(1,3,4-oxadiazole)fibres[J].Polymer Degradation and Stability,2013,98(3):691-696)；(3)选择含有偶氮结构的分散染料对纤维进行染色。但是，由于染料中的偶氮基作用有限，纤维的抗紫外性能仅能提高约30％，远不能满足使用要求(姬常青,张再兴,李文涛,邢铁玲,陈国强.分散染料对改性聚芳噁二唑纤维光稳定性的影响[J].印染,2014,40(9):1-4)；(4)采用直接整理的方法，即以具有抗紫外功能的水溶性八(γ-氨丙基)倍半硅氧烷为整理剂对纤维进行表面处理。该方法虽然操作简单，对设备要求较低，但是，由于该方法采用的是带氨基的水溶性POSS，其通过浸轧、焙烘等方法处理纤维后，POSS分子只能以吸附的形式，依靠范德华力固着在纤维表面缺陷的部位和原纤的缝隙处。因此，当对纤维或织物洗涤时，八(γ-氨丙基)倍半硅氧烷很容易会回到水相中，水洗牢度比较差，故一般三次水洗后其抗紫外性能就与未处理纤维相当了(Mao Y,Zhou W,XuJ.Ultraviolet resistance modification of poly(p-phenylene-1,3,4-oxadiazole)and poly(p-phenylene terephthalamide)fibers with polyhedral oligomericsilsesquioxane[J].Journal of Applied Polymer Science,2015,132(41))。
发明内容
本发明的目的在于克服现有技术存在的缺陷，首先提供一种基于分散染料改性的抗紫外处理剂的制备方法。
本发明的另一目的是提供一种由上述方法制备的基于分散染料改性的抗紫外处理剂。
本发明提供的基于分散染料改性的抗紫外处理剂的制备方法，其特征在于该方法的工艺步骤和条件如下：
(1)将八聚倍半硅氧烷(POSS)和分散染料分别研磨成粒径为0.5～1μm的粉末，按重量份将0.6～3份八聚倍半硅氧烷与0.3～3.2份分散染料混合均匀，在氮气氛围下，连同0.15～0.45份催化剂一起加入60～500份有机溶剂Ⅰ中搅拌直至充分溶解，然后升温回流反应18～30小时；
(2)将混合液冷却至5℃以下，然后加入0.3～1.9份有机溶剂Ⅱ中搅拌均匀，减压过滤，滤液减压蒸馏去除溶剂得到抗紫外处理剂粗产物；
(3)将抗紫外处理剂粗产物加入130～790份萃取剂中，回流萃取18～30小时，再进行减压过滤，最后对滤液进行减压蒸馏即可得到精制的抗紫外处理剂，
以上所用物料的份数均为重量份。
以上方法中所用的八聚倍半硅氧烷(POSS)具体为八乙烯基倍半硅氧烷、八丙烯基倍半硅氧烷和八丁烯基倍半硅氧烷中的至少一种，其结构式如下：
式中R为-CH＝CH2、-CH2CH＝CH2和-CH2CH2CH＝CH2中的至少一种。
以上方法中所用的分散染料为分散红60或分散黄42。
以上方法中所用的有机溶剂Ⅰ为四氯化碳、二硫化碳和苯中的至少一种。
以上方法中所用的催化剂为无水氯化铁、无水氯化镁和无水氯化铝中的至少一种。
以上方法中所用的有机溶剂Ⅱ为三乙胺、二乙胺和二氯甲烷中的至少一种。
以上方法中所用的萃取剂为三氯甲烷、二氯甲烷和甲苯中的至少一种。
本发明提供的由上述方法制备的基于分散染料改性的抗紫外处理剂，该处理剂的结构通式如下：
式中：R为-CH＝CH2、-CH2CH＝CH2和-CH2CH2CH＝CH2中的至少一种，数量为7至0个或R’为-CH2-CH2-、-CH2CH2-CH2-和-CH2CH2CH2-CH2-中的至少一种，数量为1至8个，当该处理剂中八聚倍半硅氧烷基上R数量为7时，R’数量就为1，R数量为6时，R’数量就为2，……R数量为0时，R’数量就为8；其红外吸收光谱于588cm-1，1109cm-1和782cm-1处出现了分别代表Si–O–Si和Si–C伸缩振动峰，于3068，2962cm-1和1460cm-1处出现了分别代表-CH2–CH2-、-CH2–CH2–CH2-或-CH2–CH2–CH2–CH2-伸缩和弯曲振动峰；其29Si NMR谱图中于-109.63ppm处出现了代表POSS结构中硅原子的振动峰；在其溶液的紫外-可见光吸收光谱中波长300nm以下出现了吸收峰。
与现有技术相比，本发明具有以下优点：
1.由于本发明提供的方法摒弃了现有技术采用的水溶性八(γ-氨丙基)倍半硅氧烷，选用了难溶于水的带有烯键的笼型八聚倍半硅氧烷作为基本原料，通过与分散染料接枝来制备抗紫外处理剂，因而所得抗紫外处理剂不仅可用于合成纤维的高温高压染色处理，且可通过高温高压处理法将抗紫外剂借助染料分子牢固镶嵌在纤维浅表层，达到固着于纤维上的目的，发挥持久的抗紫外功能。
2.由于本发明提供的方法是通过Friedel-Crafts烷基化反应，利用笼型的八聚倍半硅氧烷结构中所含的烯键巧妙的与分散染料分子中的独立苯环上的氢原子进行接枝反应，使染料分子接枝在了具有抗紫外性能的笼型八聚倍半硅氧烷上，因而不仅为抗紫外处理剂领域提供了一种新的品种，且也为八聚倍半硅氧烷的接枝改性提供了一条新思路。
3.由于本发明提供的抗紫外处理剂中接枝在笼型的八聚倍半硅氧烷结构上的分散染料与合成纤维具有较高的亲和力，可通过常规的高温高压处理工艺牢固地镶嵌在纤维浅表层，因而不仅解决了带烯键的笼型八聚倍半硅氧烷因无水溶性不能直接用于纤维抗紫外处理的问题，且还能在纤维表面形成一层八聚倍半硅氧烷的防护层，能更有效地提高紫外光照射后纤维的强力保留率。
4.由于本发明提供的方法所选用的不管是含有烯基的笼型八聚倍半硅氧烷、分散染料，还是所用的溶剂和催化剂均为市售的常规试剂，因而不仅原料易得，无毒环保，且合成工艺简单，易于控制，对合成设备也无其他特殊要求，更适宜于工业化生产。
附图说明
图1为分散红60和用其改性含有烯基的笼型八聚倍半硅氧烷后所得的抗紫外处理剂的红外吸收光谱曲线。从图中两条谱线首先可见，分散红60在改性含有烯基的笼型八聚倍半硅氧烷前后整体形状变化不大，说明改性含有烯基的笼型八聚倍半硅氧烷后没有引起该染料的母体结构和主要发色基团显著改变，因而可以推测染料的主色调没有发生变化。其次可见，于588cm-1，1109cm-1和782cm-1处新增了三个较强吸收峰，分别对应Si–O–Si和Si–C伸缩振动峰；于3068，2962cm-1和1460cm-1处出现三个中等强度吸收峰，分别代表-CH2–CH2-、-CH2–CH2–CH2-或-CH2–CH2–CH2–CH2-伸缩和弯曲振动峰，这说明分散红60分子已经接在了含有烯基的笼型八聚倍半硅氧烷的主要官能团上了。
图2为本发明用分散红60改性POSS后所得的抗紫外处理剂的核磁氢谱1H NMR图。图中显示，2.08和1.25ppm处的吸收峰对应为染料与POSS连接的烷基氢原子；14.07和5.30ppm处单峰分别对应为染料母体上的羟基和氨基上的氢原子；6.41～8.38ppm的多重吸收峰则由芳环上的氢原子产生的。
图3为本发明用分散红60改性POSS后所得的抗紫外处理剂的核磁13C NMR图。从图中可见，于15.68和29.06ppm处有由连接染料和POSS烷基碳原子产生的吸收峰；139.14ppm处有与POSS相连的苯环上碳原子的吸收峰；图中其他的吸收峰都归属于蒽醌环上各个碳原子，具体归属情况见图。
图4为本发明用分散红60改性POSS后所得的抗紫外处理剂的核磁29Si NMR谱图。从图中可见，于-109.63ppm处出现了属于POSS结构中硅原子(SiO4)的振动峰。
此外，图1～3中未注明的1H NMR：δ5.88～6.13ppm和13C NMR：δ76.70～77.33ppm分别表示POSS分子中未参与反应的烯基剩基的氢原子(3H CH＝CH2)和碳原子(2C CH＝CH2)。
图5为分散红60溶液和用其改性POSS后所得的抗紫外处理剂溶液(浓度均为0.02g/L)的紫外-可将光吸收光谱。从图中可见，相对于原分散红60染料，改性后的抗紫外处理剂中染料部分仍在可见光波长范围内，吸收峰的位置也没有发生变化，但在紫外光部分，抗紫外处理剂的吸收峰均向小波长方向移动了。这一现象表明，抗紫外剂对紫外光的选择性吸收增强，可以使处理后纤维获得显著的抗紫外性能。
具体实施方式
下面给出实施例以对本发明进行具体描述，有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术熟练人员根据上述本发明的内容对本发明作出的一些非本质的改进和调整仍属于本发明的保护范围。
值得说明的是，用以下实施例制备的抗紫外处理剂处理后的p-POD、PPTA和PMIA纤维的强力和水洗测试是分别按照(GB/T 3923.1—1997)和(GB/T 3921－2008)(10次)进行的；纤维的K/S值是这样测量的，即先将测试样品均匀缠绕在不透明的塑料薄片上(2×2×0.1cm)，为了防止透光，缠绕纤维分别沿两个垂直方向各缠绕一层，缠绕后的试样放在电脑测色配色仪(Spectra Flash SF 600,Datacolor,USA)上，采用D65光源10°标准视角进行测量的。
实施例1
将分别研磨成粒径为0.5～1μm粉末的八乙烯基倍半硅氧烷0.3份、八丙烯基倍半硅氧烷0.3份和分散红60染料0.8份混合均匀，在氮气氛围下，连同0.15份无水氯化铝一起加入60份二硫化碳和60份四氯化碳中搅拌直至充分溶解，然后升温至混合溶剂沸点，保温回流反应24小时；停止加热后，用冰水将混合液冷却至0℃，然后加入0.4份三乙胺和0.3份二乙胺混合液中搅拌均匀，减压过滤，除去不溶的催化剂，滤液减压蒸馏去除溶剂得到抗紫外处理剂粗产物；将粗产物加入250份二氯甲烷中，在索氏提取器中回流萃取18小时，再进行减压过滤，除去未溶解的原染料，最后对滤液进行减压蒸馏即可得到精制的抗紫外处理剂。所得精制产品收率为73.9％。
采用所得抗紫外处理剂处理后的p-POD纤维K/S值分别为8.63，直接经72小时紫外光照射强力保留率(以原纤维强力为标准)为89.3％，水洗10次后经72小时紫外光照射强力保留率为88.1％。
实施例2
将分别研磨成粒径为0.5～1μm粉末的八丙烯基倍半硅氧烷0.6份和分散红60染料1.2份混合均匀，在氮气氛围下，连同0.15份无水氯化铁一起加入60份苯中搅拌直至充分溶解，然后升温至混合溶剂沸点，保温回流反应30小时；停止加热后，用冰水将混合液冷却至2℃，然后加入1.9份二乙胺中搅拌均匀，减压过滤，除去不溶的催化剂，滤液减压蒸馏去除溶剂得到抗紫外处理剂粗产物；将粗产物加入65份二氯甲烷和65份甲苯中，在索氏提取器中回流萃取30小时，再进行减压过滤，除去未溶解的原染料，最后对滤液进行减压蒸馏即可得到精制的抗紫外处理剂。所得精制产品收率为75.4％。
采用所得抗紫外处理剂处理后的p-POD纤维K/S值为9.56，直接经72小时紫外光照射强力保留率(以原纤维强力为标准)分别为91.2％，水洗10次后经72小时紫外光照射强力保留率为89.5％。
实施例3
将分别研磨成粒径为0.5～1μm粉末的八丁烯基倍半硅氧烷0.6份和分散黄42染料3.2份混合均匀，在氮气氛围下，连同0.22份无水氯化铁和0.23份无水氯化镁一起加入300份二硫化碳和200份苯中搅拌直至充分溶解，然后升温至混合溶剂沸点，保温回流反应18小时；停止加热后，用冰水将混合液冷却至4℃，然后加入1.5份二乙胺和1.5份二氯甲烷混合液中搅拌均匀，减压过滤，除去不溶的催化剂，滤液减压蒸馏去除溶剂得到抗紫外处理剂粗产物；将粗产物加入450份二氯甲烷和340份三氯甲烷中，在索氏提取器中回流萃取24小时，再进行减压过滤，除去未溶解的原染料，最后对滤液进行减压蒸馏即可得到精制的抗紫外处理剂。所得精制产品收率为69.9％。
采用所得抗紫外处理剂处理后的p-POD纤维K/S值为10.61，直接经72小时紫外光照射强力保留率(以原纤维强力为标准)为88.6％，水洗10次后经72小时紫外光照射强力保留率为86.2％。
实施例4
将分别研磨成粒径为0.5～1μm粉末的八乙烯基倍半硅氧烷1.5份、八丁烯基倍半硅氧烷1.5份和分散黄42染料0.3份混合均匀，在氮气氛围下，连同0.12份无水氯化镁和0.03份无水氯化铝一起加入25份苯和95份四氯化碳中搅拌直至充分溶解，然后升温至混合溶剂沸点，保温回流反应20小时；停止加热后，用冰水将混合液冷却至1℃，然后加入0.35份三乙胺和0.35份二氯甲烷混合液中搅拌均匀，减压过滤，除去不溶的催化剂，滤液减压蒸馏去除溶剂得到抗紫外处理剂粗产物；将粗产物加入300份三氯甲烷中，在索氏提取器中回流萃取20小时，再进行减压过滤，除去未溶解的原染料，最后对滤液进行减压蒸馏即可得到精制的抗紫外处理剂。所得精制产品收率为77.1％。
采用所得抗紫外处理剂处理后的p-POD纤维K/S值为10.67，直接经72小时紫外光照射强力保留率(以原纤维强力为标准)为85.4％，水洗10次后经72小时紫外光照射强力保留率为85.1％。
实施例5
将分别研磨成粒径为0.5～1μm粉末的八乙烯基倍半硅氧烷1.2份和分散红60染料2份混合均匀，在氮气氛围下，连同0.3份无水氯化铁一起加入300份四氯化碳中搅拌直至充分溶解，然后升温至混合溶剂沸点，保温回流反应28小时；停止加热后，用冰水将混合液冷却至3℃，然后加入1.2份三乙胺中搅拌均匀，减压过滤，除去不溶的催化剂，滤液减压蒸馏去除溶剂得到抗紫外处理剂粗产物；将粗产物加入500份甲苯中，在索氏提取器中回流萃取28小时，再进行减压过滤，除去未溶解的原染料，最后对滤液进行减压蒸馏即可得到精制的抗紫外处理剂。所得精制产品收率为79.2％。
采用所得抗紫外处理剂处理后的p-POD纤维K/S值为10.81，直接经72小时紫外光照射强力保留率(以原纤维强力为标准)为86.2％，水洗10次后经72小时紫外光照射强力保留率为87.3％。
比较例
将未经本发明抗紫外处理剂处理的p-POD纤维经72小时紫外光照射后强力保留率为30.8％；采用正常处理工艺对p-POD纤维分别进行处理，用分散红60试样的K/S值为9.32，直接经72小时紫外光照射强力保留率为31.6％，水洗10次后经72小时紫外光照射强力保留率为31.5％；用分散黄42试样的K/S值为11.26，直接经72小时紫外光照射强力保留率为31.6％，水洗10次后经72小时紫外光照射强力保留率为31.5％。
Claims (4)
1.一种基于分散染料改性的抗紫外处理剂的制备方法，其特征在于该方法的工艺步骤和条件如下：
(1)将八聚倍半硅氧烷和分散染料分别研磨成粒径为0.5～1μm的粉末，将0.6～3份八聚倍半硅氧烷与0.3～3.2份分散染料混合均匀，在氮气氛围下，连同0.15～0.45份催化剂一起加入60～500份有机溶剂Ⅰ中搅拌直至充分溶解，然后升温回流反应18～30小时；
(2)将混合液冷却至5℃以下，然后加入0.3～1.9份有机溶剂Ⅱ中搅拌均匀，减压过滤，滤液减压蒸馏去除溶剂得到抗紫外处理剂粗产物；
(3)将抗紫外处理剂粗产物加入130～790份萃取剂中，回流萃取18～30小时，再进行减压过滤，最后对滤液进行减压蒸馏即可得到精制的抗紫外处理剂，
以上所用物料的份数均为重量份；所用的八聚倍半硅氧烷具体为八乙烯基倍半硅氧烷、八丙烯基倍半硅氧烷和八丁烯基倍半硅氧烷中的至少一种，其结构式如下：
式中R为-CH＝CH2、-CH2CH＝CH2和-CH2CH2CH＝CH2中的至少一种；所用的分散染料为分散红60或分散黄42。
2.根据权利要求1所述的基于分散染料改性的抗紫外处理剂的制备方法，其特征在于该方法中所用的有机溶剂Ⅰ为四氯化碳、二硫化碳和苯中的至少一种；所用的有机溶剂Ⅱ为三乙胺、二乙胺和二氯甲烷中的至少一种。
3.根据权利要求1或2所述的基于分散染料改性的抗紫外处理剂的制备方法，其特征在于该方法中所用的催化剂为无水氯化铁、无水氯化镁和无水氯化铝中的至少一种；所用的萃取剂为三氯甲烷、二氯甲烷和甲苯中的至少一种。
4.一种由权利要求1所述方法制备的基于分散染料改性的抗紫外处理剂，该处理剂的结构通式如下：
式中：R为-CH＝CH2、-CH2CH＝CH2和-CH2CH2CH＝CH2中的至少一种，数量为7至0个或R’为-CH2-CH2-、-CH2CH2-CH2-或-CH2CH2CH2-CH2-中的至少一种，数量为1至8个；其红外吸收光谱于588cm-1，1109cm-1和782cm-1处出现了分别代表Si–O–Si和Si–C伸缩振动峰，于3068，2962cm-1和1460cm-1处出现了分别代表-CH2–CH2-、-CH2–CH2–CH2-或-CH2–CH2–CH2–CH2-伸缩和弯曲振动峰；其29Si NMR谱图中于-109.63ppm处出现了代表POSS结构中硅原子的振动峰；在其溶液的紫外-可见光吸收光谱中波长300nm以下出现了吸收峰。
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