甲苯二异氰酸酯与水基聚乙烯醇胶粘剂交联反应的研究

本文研究甲苯二异氰酸酯 (TDI)与聚乙烯醇 (PVA)胶水的交联反应。采用正交实验法 ,探讨PVA的浓度、TDI的加入量及交联反应的温度等因素对该胶粘剂 180°剥离强度的影响。并结合该交联反应进行程度 ,即交联度的结果一起讨论该交联反应。结果发现少量TDI的加入 ,可较大程度地提高PVA胶水的粘合性能和耐水性能     

成排钢纤维用环保胶粘剂的研制与应用

以次氯酸钠(NaClO)为氧化剂,在碱性条件下将氧化淀粉与聚乙烯醇(PVA)进行接枝反应,制备出成排钢纤维用胶粘剂。探讨了胶粘剂配方中淀粉/PVA质量比、反应温度和反应时间等对PVA/淀粉胶粘剂的胶接强度和水溶性等影响。研究结果表明:当m(淀粉)∶m(PVA)=6∶1、反应时间为50 min和反应温度为60℃时,胶粘剂的应用性能相对最好。     

聚乙烯醇缩乙醛酸树脂的研制

聚乙烯醇缩醛型胶粘剂可通过聚乙烯醇(PVA)与醛类缩合而得,其性质取决于原料PVA的结构、水解程度、醛类的化学结构和缩醛化程度等。将PVA与乙醛酸(无毒、无味和不挥发)进行缩醛化反应,可制备出一种安全环保型聚乙烯醇缩乙醛酸树脂(PVGa)胶粘剂。以n(乙醛酸)∶n(PVA中-OH基)比例、反应时间、反应温度和PVA水溶液浓度为试验因素,缩醛度为衡量指标,采用正交试验法优选出制备PVGa的最适宜工艺条件。结果表明:当反应温度为80℃、PVA水溶液浓度为15%、n(乙醛酸)∶n(PVA中-OH基)=1∶5和反应时间为40min时,PVGa的缩醛度为39.85%;PVGa的吸湿性能比PVA高4～6倍,PVGa的力学性能优于PVA,两者的热失重情况基本相似。     

TDI交联改性聚乙烯醇水性胶粘剂的合成工艺研究

TDI(甲苯二异氰酸酯)交联改性PVA(聚乙烯醇)能明显提高PVA胶粘剂的耐水性和粘接性能。以PVA掺量、羧甲基纤维素(CMC)掺量、交联剂TDI掺量、催化剂-X掺量、交联温度和交联时间为试验因素,压缩剪切强度为考核指标,采用正交试验法优选出合成该改性PVA胶粘剂的最佳工艺条件。研究结果表明:当PVA为12 g/100 m L、CMC为3.2 g/100 m L、φ(TDI)=3%、φ(催化剂-X)=0.4%(均相对于胶粘剂体积而言)、交联温度为30℃和交联时间为45 min时,所合成的单组分TDI改性PVA胶粘剂具有良好的环保性、粘接性,可广泛应用于林产工业、纸品工业以及建筑行业等领域。     

I_2/KI溶液改性PVA纤维的制备及其性能研究

采用摩尔浓度比为1∶2的I2/KI溶液对聚乙烯醇(PVA)初生凝胶丝条进行超声浸泡处理,制备了改性PVA(I-PVA)纤维;探讨了I2/KI溶液浓度对纤维拉伸性能的影响,并对I-PVA纤维的结构与性能进行了研究。结果表明:I2在PVA纤维中主要以I-5的形态存在,I2的加入会阻碍PVA分子链之间的氢键形成,纤维的拉伸倍数得到提高,强度和模量也有提高;I-PVA纤维的最佳热拉伸温度为150℃,比未改性PVA纤维最佳热拉伸温度降低了50℃;PVA初生纤维在空气中拉伸3倍,采用0.1 mol/L的I2/KI溶液于40℃超声浸泡1 h后,于150℃拉伸10倍,得到的I-PVA纤维的断裂强度可达14.7 c N/dtex,比未改性PVA纤维提高9.7%,最大拉伸倍数提高到36。     

聚乙烯醇改性大豆蛋白胶粘剂的制备与性能研究

以12%PVA(聚乙烯醇)溶液为共混改性剂,制备了胶合板用改性大豆蛋白胶粘剂。着重探讨了PVA溶液用量、热压温度和热压时间对胶合板粘接性能的影响,并对该胶粘剂的结构进行了表征。研究结果表明:随着PVA溶液用量的增加,胶粘剂的黏度增大,但胶合板的粘接强度呈先降后升态势;当w(PVA)=80%(相对于大豆蛋白胶粘剂质量而言)、热压温度为130℃和热压时间为15 min时,胶合板的粘接性能相对最好;PVA和纯大豆蛋白之间存在较强的氢键作用,这是提升改性大豆蛋白胶粘剂粘接强度的主要原因。     

聚乙烯醇缩丁醛胶粘剂的制备

以聚乙烯醇(PVA)与正丁醛的质量比、反应体系的pH值、反应温度以及保温时间等作为制备聚乙烯醇缩丁醛(PVB)及其胶粘剂的主要因素,通过测定PVB的缩丁醛基含量、PVB胶粘剂的某些性能(如持粘力、黏度和固含量等)优选出制备PVB胶粘剂的最佳工艺条件。结果表明:当m(PVA)∶m(正丁醛)=100∶70、反应体系的pH值为2.0、反应温度为85℃、保温时间为3 h以及正丁醛的滴加速率为20~30滴/min时,PVB的缩醛度较高且形态较好,PVB胶粘剂的持粘力、黏度和固含量等指标均相对较高。     

正交试验法优化聚乙烯醇缩甲醛胶粘剂的合成条件

以聚乙烯醇(PVA)和甲醛为主要原料,采用缩聚法合成了PVF(聚乙烯醇缩甲醛)胶粘剂;然后以反应温度、反应时间、体系pH和甲醛含量等为试验因素,黏度为考核指标,采用正交试验法优选出合成PVF胶粘剂的最优方案。结果表明:当m(水)∶m(PVA)∶m(甲醛)=10∶1∶0.7、反应温度为90℃、反应时间为105 min、体系pH为2.0和V(甲醛)=4.5 mL时,PVF胶粘剂的综合性能相对较好。     

木材用玉米淀粉胶粘剂的改性研究

以玉米淀粉为原料、次氯酸钠为淀粉的氧化剂和过硫酸铵(APS)为聚乙烯醇(PVA)的氧化剂,在碱性条件下将氧化玉米淀粉与氧化PVA进行接枝改性,制备出-种木材用胶粘剂。考察了PVA浓度、纳米蒙脱土(MMT)含量和固含量等对淀粉胶粘剂干、湿态胶接强度的影响。结果表明:当固含量为28.57%、u(PVA)=5%和w(纳米MMT)=2%时,相应淀粉胶粘剂的综合性能相对最好。     

环保型脲醛树脂胶粘剂的合成

以聚乙烯醇(PVA)、三聚氰胺为改性剂,采用单因素试验法优选出制备低n(甲醛):n(尿素)比例的环保型脲醛树脂(UF)胶粘剂的最佳工艺条件。结果表明:当n(甲醛):n(尿素)=1.14:1、w(三聚氰胺)=19%、w(PVA)=1.7%(相对于尿素质量而言)、反应温度为88～90℃和反应时间为3 h左右时,制成的UF胶粘剂具有良好的综合性能;由该胶粘剂生产的人造板,其甲醛释放量达到E1级标准要求。     

甲苯二异氰酸酯和硼砂交联改性聚乙烯醇胶水的研究

探讨了硼砂和甲苯二异氰酸酯 ( TDI)对聚乙稀醇 ( PVA)胶水进行交联改性。采用正交实验法研究硼砂和 TDI的加入量对 PVA粘合剂的耐水性能和剥离强度的影响。利用硼砂、TDI与 PVA反应产物的水不溶性判断该交联反应的进程。研究结果表明 ,少量硼砂和 TDI能较大程度地提高 PVA胶水的耐水性能和粘结性能     

聚乙烯醇商标胶耐水性研究

以甲苯二异氰酸酯(TDI)为化学交联剂、羧酸类有机物(氯乙酸、乙酸酐或醋酸)为酯化改性剂,制备改性聚乙烯醇(PVA)商标胶。以耐冰水性能为考核指标,以TDI和羧酸类有机物含量为试验因素,采用单因素试验法优选出制备改性PVA商标胶的最佳工艺条件。结果表明:当PVA为60 g、TDI为1.1 mL和乙酸酐为1.5 mL时,相应的改性PVA商标胶的耐冰水性能(耐冰水时间为49 h)相对最好。     

Characterization and performance of PVA/Psf composite hollow fiber UF membrane prepared with interfacial polymerization

A new composite hollow fiber ultrafiltration (UF) membrane was prepared with the interfacial polymerization method. A dense layer of polyvinyl alcohol (PVA) was coated on the surface and embedded into the pores of the support polysulfone (PSf) membrane through a dead‐end filtration process and cross‐linked reaction with diisocyanate (TDI) at room temperature. The surface morphology and functional groups of the composite membrane were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and Fourier transformation infrared spectrometer (FTIR). Anti‐fouling experiments were conducted to study the hydrophilicity and anti‐fouling properties of the support and composite membranes. The performances of the composite membrane were significantly influenced by preparation conditions. The composite membrane that performed most efficiently was prepared at an optimal condition: 30 min of dead‐end filtration, 0.25 wt% of PVA, 0.50 vol% of TDI, and 60 sec of interfacial reaction. Laboratory scale tests demonstrated that the new composite PVA/PSf membrane has a higher anti‐fouling capability and higher flux for oily wastewater treatment. The hydrophilic groups (? OH) enriched in the PVA molecules on the composite surface could play an important role for the improvement of the anti‐fouling property and the enhancement of flux recovery rate of the composite membrane. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

NDI型聚氨酯弹性体的合成与其耐热性能研究

以1,5-萘二异氰酸酯(NDI)和甲苯二异氰酸酯(TDI)分别与聚己二酸乙二醇丙二醇酯二醇(PEPA)合成了聚氨酯弹性体,通过热失重分析和差示扫描量热分析发现,NDI型聚氨酯弹性体的热分解温度比TDI型聚氨酯弹性体高,说明NDI型聚氨酯弹性体具有更好的耐热性能;通过不同温度下弹性体的力学性能高温保持率对比分析,也说明了NDI型聚氨酯弹性体的耐热性能优于TDI型聚氨酯弹性体。     

Thin layer concentrated emulsion copolymerization of PUASi/Styrene/Methyl methacrylate

Stable concentrated emulsions of polymerizable polysiloxane‐containing polyurethane (PUASi)/Styrene (St)/Methyl methacrylate (MMA) were prepared using sodium dodecyl sulphate (SDS)/nonyl polyoxyethylene ether (OS15)/polyvinyl alcohol (PVA) as composite surfactant and azobisisobutyronitrile (AIBN) as initiator. A novel polymerization method, thin layer polymerization was used to carry out the concentrated emulsion copolymerization at 55°C. The effects of TDI/PPG molar ratio, surfactant concentration, different kinds of surfactants, and temperature on polymerization stability were studied. The effects of the thickness of the thin layer, the outside temperature of the reactor, as well as polymerization environment on the volatilization rate of water, and monomer in the system were investigated. The conversion‐time relationships of the thin layer polymerization and the tube polymerization, as well as the effect of polymerization environment on the polymerization rate were also investigated. The morphology of latex particles was determined with transmission electron microscope (TEM). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

采用薄膜蒸发器从聚氨酯预聚物中分离TDI(英文)

从聚氨酯预聚体分离游离的二异氰酸酯的方法有许多种,最好的方法是使用薄膜蒸发器进行分离。采用内冷凝式薄膜蒸发器和二次蒸馏技术研究了从甲苯二异氰酸酯(TDI)/三羟甲基丙烷(TMP)型聚氨酯预聚体分离游离TDI的方法及影响TDI分离的主要因素。研究工作通过使用MD-S80内冷式薄膜蒸发器,并调整蒸馏温度和真空度使产物中游离TDI低于0 5%。相应的蒸馏参数是:原料流速1 0kg/h,原料Ⅰ温度100℃,原料Ⅱ温度110℃,一次蒸馏温度150℃,二次蒸馏温度200℃,第一次蒸馏余压5000Pa,二次蒸馏余压35Pa;刮板转动速度150r/min。二次蒸馏后用醋酸丁酯稀释成质量分数为75%的溶液。预聚体中TDI质量分数为0 4%。异氰酸基含量高于12 7%,达到了分离的目标。结果表明内冷式薄膜蒸发器进行二次蒸馏有效地从TDI TMP预聚体分离了游离的TDI。     

微量离子液体对聚乙烯醇热稳定性的影响研究

聚乙烯醇由于其分解温度与熔融温度接近,长期以来一直存在热塑性加工难的问题。希望采用少量离子液体作为聚乙烯醇(PVA)的热稳定剂,提高PVA热分解温度,从而获得PVA的热塑性加工窗口。实验结果表明:离子液体可使PVA的热分解温度及最快分解温度得到极大的提高。与纯的PVA相比,甲基丙烯酰氧乙基三甲基氯化铵(DMC,0. 6%)和1-乙烯基-3-乙基咪唑四氟硼酸盐(BF4IL,3%)的加入分别为PVA提供了一个约90℃和100℃的加工窗口,并且它们的加入几乎不会影响PVA本身优异的透光性能。这将为PVA膜的热塑性加工提供出一个新的思路。     

Effect of iodine absorption on the characteristics of syndiotacticity‐rich high molecular weight poly(vinyl alcohol) microfibril

Iodination of syndiotacticity‐rich high molecular weight poly(vinyl alcohol) (PVA) microfibril, which was obtained from the saponification of poly(vinyl pivalate) without a spinning procedure, was conducted before and after zone drawing at various conditions. The resulting PVA microfibrils were characterized by differential scanning calorimetry and scanning electron microscopy. Surface morphologies of these PVA microfibrils showed some differences between PVA microfibrils iodinated after and before drawing. Crude shapes of PVA microfibrils iodinated after drawing indicated that iodine decreased the structural regularity severely. On the other hand, PVA microfibrils iodinated before drawing showed relatively ordered surfaces. This was ascribed to the enhanced molecular ordering of PVA microfibrils due to zone drawing. Iodinated PVA microfibrils showed a decrease in the crystal melting temperature of about 100°C compared to the untreated sample. PVA microfibrils drawn after iodination showed a relatively higher crystal melting temperature than those of microfibrils iodinated after drawing. These results were considered as proof of the changes in the crystalline lattice of the PVA microfibrils by iodine absorption. Effects of the drawing temperature on the sublimation of iodine were also evaluated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1519–1524, 2003     

A recycling model of excess toluene diisocyanate isomers in the preparation of polyurethane prepolymer

Reaction kinetics of dropwise addition of trimethylolpropane (TMP) to toluene diisocyanate (TDI‐80) at various temperatures and initial stoichiometry was studied. The progress of the polymerization reaction was monitored by measuring the concentration of isocyanate groups and TDI isomers by means of backtitration and high performance liquid chromatography (HPLC), respectively. The kinetics of dropwise addition method, compared with the conventional one‐shot method, was well described by a second order equation. This procedure was optimized by comparing the deviations between experimental data and theoretically calculated data. The effects of temperature, initial stoichiometry and TDI isomers on the amount of excess 2,4‐TDI and 2,6‐TDI were investigated. Three commercially available TDI mixtures, 65 : 35, 80 : 20, and 100 : 0 ratio of 2,4‐TDI/2,6‐TDI, respectively, were used. A recycling model of unreacted TDI isomers and solvent was established to reach a stable process and yield polyurethane prepolymer with good reproducibility. This model has been applied in the chemical plant to prepare polyurethane prepolymer with precisely defined chemical compositions in a continuous process. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013