【作者】 高传花；

【导师】 郑强； 林薇薇；

【作者基本信息】 浙江大学 ， 材料加工工程， 2009， 博士

【摘要】 通常将经过物理或化学改性并赋予其特殊功能的织物称为技术织物或功能织物。这类织物技术含量高，与通用纺织品相比较，价格敏感性低，可获得更高利润。拒水织物和阻燃织物是技术织物中需求量最大、应用面最广的两类织物。随着环境保护的日益加强，绿色环保的无溶剂型水分散织物整理剂的开发已迫在眉睫。有机硅具有耐高低温性能好，表面能低、生理惰性等特性，经有机硅处理的织物拒水性好、滑爽、柔软。然而，有机硅织物整理剂存在着与织物粘着力低、机械强度较低、不耐水洗与价格较高的不足之处。聚氨酯具有良好的粘接强度、韧性与耐磨性，已广泛用作皮革与织物的防水透湿涂层剂。基于这两种材料的特性，本论文采用有机硅与聚氨酯共聚，将两者有机结合起来，实现上述两种材料优势互补，性能可调。考虑环保因素，研制水分散有机硅-聚氨酯嵌段共聚物作为织物拒水整理剂。利用其在整理织物过程中表面能低的有机硅链段可向织物表面迁移富集，而聚氨酯链段靠近织物，通过氢键和化学键与织物紧密粘接，兼顾实现拒水和与织物粘接性均较好的目的。采用端羟基聚二甲基硅氧烷（PDMS）与氨丙基甲基二甲氧基硅烷（DB-912）反应，制备一系列不同分子量的端氨烃基聚二甲基硅氧烷齐聚物（NS）作为扩链剂，从而制备了水分散有机硅-聚氨酯嵌段共聚物（WPSUR）。研究了亲水剂类型、羧基含量、二羟基聚醚类型、蓖麻油用量、扩链剂类型、NS分子量、有机硅含量、水分散液固含量等与WPSUR分散液粒径、稳定性与流变特性的相互关系，考察了其对WPSUR成膜物吸水性、与水的表面接触角、机械性能、耐热稳定性、与织物的粘接性及整理后织物的拒水性、耐静水压与耐水洗等特性的影响。本文选用的亲水剂有两种：一种是由丙三醇与马来酸酐反应制备的甘油半酯（GSE），另一种是二羟甲基丙酸（DMPA）。甘油半酯作亲水剂制得的水分散液价格较低，成膜物柔软，但羧基含量需达到2．5wt％以上才可获得稳定的水分散液；而采用DMPA为亲水剂，羧基含量高于1．6wt％时，即可制得稳定的水分散液。采用含有三羟基和长脂肪烃链甘油酯的蓖麻油为原料，在体系中引入内交联以提高拒水性和机械性能等特性。采用NS作扩连剂制得的WPSUR与用脂肪二胺、低分子氨烃基硅烷偶联剂的WPU相比，其薄膜耐水性大大提高，与水的表面接触角可达100°以上，耐热性和机械强度也均有提高。采用PDMS与DB-912反应，制备的侧链含有长链有机硅链段的端氨烃基聚二甲基硅氧烷齐聚物（S₃N₂）作为扩链剂，可进一步提高体系中聚硅氧烷链段的含量，提高了薄膜的拒水性且改善了整理剂的手感。研究结果表明，当NS与S₃N₂的比例为75：25、有机硅含量为30wt％、蓖麻油含量为15wt％、羧基含量为1．8wt％、固含量为30wt％时，制备的WPSUR综合性能最佳。经该拒水型WPSUR整理的涤棉织物，静水压可达41KPa，沾水等级和水洗后拒水等级均为3级，与织物的粘接强度高达7．0N／cm，薄膜的拉伸强度达5．2 MPa，脆化温度低至-30℃。表明该拒水型织物整理剂稳定性良好、性能优异、具有良好的应用前景。本工作的创新点是：选用了端氨烃基聚硅氧烷齐聚物替代常规脂肪二胺和低分子氨烃基硅烷偶联剂作扩链剂，使合成的WPSUR分子链中有机硅氧烷链段含量大大增加，提高了薄膜的拒水性与耐热稳定性等性能。选用了蓖麻油作为原料，在WPSUR分子中引入内交联和疏水的长脂肪链，进一步提高了耐水性。利用有机蒙脱土（MMT）的隔热、增强增韧和阻燃作用，制备了剥离型WPSUR／MMT纳米复合材料。MMT的引入，显著改善了WPSUR薄膜的表面疏水性、机械性能和耐热稳定性。当MMT含量为1wt％时，WPSUR／MMT复合材料的拉伸强度和断裂伸长率较之WPSUR分别提高了22．8％与9．6％，达到了既增强又增韧的效果；其耐热性也有所改善，较之PU，其热失重第二分解峰值温度提高了20℃。本文采用分子链中含有磷元素的多元醇为原料，蓖麻油为内交联剂，NS为扩连剂，合成了磷、氮、硅协同阻燃的阻燃型水分散有机硅-聚氨酯嵌段共聚物（P-WPSUR）。该P-WPSUR是一种集酸源、碳源和发泡源于一身的“三位一体”水分散膨胀型阻燃剂。考察了磷、硅含量对水分散液稳定性、流变特性、成膜性、与织物的粘接性，整理织物后的极限氧指数（LOI）、垂直燃烧撕毁长度、阴燃与续燃、耐水洗性、耐热稳定性，成炭率及燃烧后碳残渣的微观形态变化等的影响。结果表明，磷含量的提高比硅含量的提高能更有效地阻燃棉织物。热重分析（TGA）结果表明，无论在空气还是氮气氛围中，P-WPSUR均具有良好的热稳定性及优异的成炭能力。P-WPSUR整理后的棉织物可显著降低质量损失速率，并使材料的LOI大幅提升。经磷含量为7．1 wt％、有机硅含量为20wt％的P-WPSUR整理后的棉织物的综合性能最佳。经该P-WPSUR整理后的棉织物，垂直燃烧撕毁长度＜100 mm，无阴燃、无续燃，无熔融、滴落；经8次家庭洗涤．烘干循环之后的垂直燃烧撕毁长度＜130mm。复合阻燃剂整理后的棉织物，水洗前的氧指数为34，洗涤10次后的氧指数为30。该乳液制备的薄膜拉伸强度达4．2 MPa，脆化温度低至-30℃；与织物的粘接强度（T型剥离试验）高达11．1N／cm，与织物具有良好的粘接性，耐水洗性良好。且薄膜与水的表面接触角＞100°，表明该整理剂处理后的织物不但具有良好的阻燃性，还可具有一定的防水性、良好的滑爽性等性能，有良好的应用前景。更多还原

【Abstract】 Technical textile is physically and chemically modified textile with specialfunctions. Compared with the general textiles, technical textile is profitable. Textileswith high water resistance and fire retardancy are under great demand and applied inmany fields. Industrial pollution is getting more serious and it is imminent to prepareenvironment-friendly finishing agent with non-organic solvent and non-halogen.Siloxane is an important novel material with peculiar properties, such as excellentheat resistance, cold resistance, weather resistance, aging resistance, water-proof,fire resistance and physiologically inert. Textiles finished with siloxane-basedfinishing agent show excellent water resistance and soft handle. However, theapplication of siloxane-based finishing agent is limited because of the poormechanical properties, low surface adhesive strength and high cost. Polyurethanes（PUs） have been widely used as waterproof and breathable textile coatings due totheir properties of high mechanical strength and toughness, good resistance tochemical attacks and mechanical wear, excellent adhesion and extensibility.However, general PUs exhibit poor thermal stability and surface properties, limitingtheir applications in some fields. Recently, PU modification through siloxane attractsworldwide concern. It is expected to improve thermal stability, water resistance andsurface property of PU without substantially losing PU’s excellent mechanicalproperties. The great difference in solubility parameters leads to poor compatibilitybetween PU and siloxane. Besides, the bonding force is weak because of the narrowinterfacial minor region of hard segments. The previous studies mainly focused onthe modification of thermoplastic, thermoset or moisture-curing PU using siloxane.There have been few studies about the synthesis of waterborne polysiloxaneurethanecopolymer as the textile finishing agent.In this dissertation, a novel waterborne polysiloxaneurethane copolymer （WPSUR）endued with the advantages of PU and siloxane was synthesized, which was main used as water resistance finishing agent for truerancotton textile. Series of stableWPSUR were prepared using amino-terminated polydimethylsiloxane （NS）,dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluenediisocyanate （TDI）. Meanwhile, NS with different molecular weights weresynthesized by hydroxyl-terminated polydimethylsiloxane （PDMS） reacting withaminopropylmethyldimethoxyl silane （DB-912） with a ratio of 1:2. Effect ofcarboxyl diols type, carboxyl contents, dihydroxy polyether type, castor oil contents,chain extender type, NS molecular weight, siloxane contents and the polymercontents on the particle size, storage stability and rheological properties of WPSURdispersion, meanwhile, effect of these factors on the water resistance, water contactangle, mechanical properties, heat degradation and stability of WPSUR films andadhesion between WPSUR and textile, were studied. Moreover, the water resistance,hydrostatic pressure resistance and water resistance durance of the truerancottontextile treated by water resistant WPSUR were also examined.Two types of carboxyl diols were used. One is glycol semi-ester （GSE）synthesized by glycerol and maleic anhydride, and the other is dimethylolpropionicacid （DMPA）. Experiment results reveal that carboxyl contents of WPSUR exceed2.5 wt% and 1.6 wt% when using GSE and DMPA, respectively, and the resultedWPSUR possesses excellent storage stability.It is noted that castor oil with unsaturation and hydroxyl function groups has beenwidely used in polyurethane preparation. The multi-functional nature of castor oilmay contribute to the toughness of PU structure, and the long fatty acid chainprovides the properties of high flexibility and water resistance. WPSUR filmsexhibite more excellent water resistance and mechanical properties as compared withPU films. Their water contact angles reach 100°. Moreover, WPSUR films using NSas soft co-segment show high thermal degradation temperature about 413℃,approximately 30℃higher than that of typical PUs using hexamethylene diamine（HDA） and 3-（2-aminoethylamino） propyl dimethoxymethyl silane （APDMS） as thechain extenders. In order to further increase polysiloxane segment contents, longsiloxane side-chain amino-terminated polysiloxane S₃N₂ was synthesized using PDMS and DB-912 （PDMS:DB-912 = 3:2）. Because of the higher molecular weightof S₃N₂, the WPSUR dispersions show poor storage stability when S₃N₂ was onlyused as the soft co-segment. WPSUR shows good general performance with thecondition of organic siloxane content being 30 wt%, castor oil content being 15 wt%,carboxyl content being 1.8 wt%, solid content being 30 wt% and the ratio of NS toS₃N₂ being 75:25. Tests of truerancotton textile treated with this kind of WPSUR areas follows: the hydrostatic pressure is 41 KPa, the degree of water resistance is classthree, the bonding strength is 7.0 N/cm, tensile strength is 5.2 MPa, and brittletransition temperature is -30℃. This textile finishing agent presents good stabilityand performance with promising application.The main innovation of this dissertation is using NS and S₃N₂ as the softco-segment instead of conventional low molecular weight fatty diamine andammonium alkyl silane coupling agent. The siloxane contents of WPSUR increasesignificantly, resulting in excellent water resistance and mechanical properties forWPSUR. Castor oil is used to get some crosslinking and long fatty hydrophobicchain, improving the water resistance.Waterborne polysiloxaneurethane/montmorillonite （WPSUR/MMT） was synthesizedusing castor oil, polypropylene glycol, TDI, DMPA and MMT. Morphology andphysical properties of WPSUR/MMT were tested and analysised by using WXRDand TEM. Results reveal that the clay platelets are fully dispersed and exfoliated.WPSUR/MMT films possess high water resistance and mechanical properties, due tothe ionic interactions between the clay and hard segments of WPSUR. Besides, thetensile strength and elongation at break of WPSUR/MMT composites containing 1wt % MMT are about 23% and 9.6% respectively, higher than those of the pristineWPSUR sample. Moreover, both organic clay and NS soft co-segment can improvethe thermal stability of WPSUR/MMT films.Flame retardant WPSUR （P-WPSUR）, a novel phosphorous-nitrogen-siloxanecontaining intumescent flame retardant, was synthesized using polyols containingphosphorus, castor oil, polypropylene glycol, TDI, DMPA and NS. The phosphorus,nitrogen and siloxane present synergistic flame-retardant effect. Both phosphorus and siloxane can be used as flame retardant of cotton textile, but the increase ofphosphorus contents is more effective than increase of siloxane contents. P-WPSURpossesses good performance with 7.1 wt% phosphorus content and 20 wt% siloxanecontent. The char length of cotton textile treated with P-WPSUR is less than 100 nmwithout further smolding and continued burning, and the treated cotton textiles showgood flame retardancy property after eight home laundering wash/dry processes. TheLOI is 34 before home laundering wash, and 30 after 10 home laundering wash/dryprocesses. The tensile strength and brittle transition temperature of cotton textiletreated with P-WPSUR are 4.2 MPa and -30℃, respectively. The bonding strengthbetween P-WPSUR and cotton textile is 11.1 N/cm. The flame retardant WPSURalso presents good water resistance.更多还原