腰果壳油生物基多元醇的合成及硬泡领域的应用

采用腰果壳油、甲醛及二乙醇胺发生曼尼希反应(Mannich)合成了腰果壳油生物基多元醇,并以此多元醇制备了低吸水率硬质聚氨酯泡沫。合成实验结果表明:腰果壳油/甲醛/二乙醇胺的最佳投料摩尔比1∶1.2∶1,最佳反应温度为80℃,反应时间为1.5 h。发泡结果表明:腰果壳油生物基多元醇制备的硬质聚氨酯泡沫具有良好的低吸水率性能,且在使用份数为40~45份时吸水率最低达到1.3%。腰果壳油生物基多元醇在低吸水率硬质聚氨酯泡沫领域具有一定的应用前景。     

曼尼希反应合成碱木质素胺基多元醇的研究

以碱法制浆造纸废弃物碱木质素为原料,碱木质素提纯后,利用曼尼希反应对其进行改性,合成碱木质素胺基多元醇。通过单因素实验,研究了二乙醇胺、甲醛与碱木质素的物料比及反应温度、滴加甲醛时间以及总反应时间等因素对碱木质素胺基多元醇羟基值的影响。实验结果表明:物料比m(碱木质素)∶m(二乙醇胺)∶m(甲醛)=1∶2∶1.2,反应温度80℃,甲醛滴加时间1 h,总反应时间3 h,得到的产物羟基值最高,达到159.94 mg/g。通过傅里叶红外光谱对产物进行了表征。     

玉米基多元醇副产物树脂制备改性聚氨酯泡沫塑料及性能的研究

提出了由玉米基多元醇副产物树脂制备改性聚氨酯泡沫塑料的工艺,分别探讨了玉米基多元醇副产物树脂加入量对聚氨酯泡沫塑料外观、密度及力学性能的影响.当玉米副产物树脂加入量在5份左右时,制备的聚氨酯泡沫塑料可以满足保温材料的相关要求.利用此工艺使聚氨酯泡沫塑料的生产成本大幅度降低,同时也使玉米副产物树脂得到了综合利用.     

葵花籽油基多元醇的合成与表征

以葵花籽油为原料,在冰醋酸和过氧化氢的共同作用下进行环氧化,制备葵花籽油基环氧化产物(SOEP);再以氢氧化锂为催化剂与二乙醇胺发生环氧开环反应,制备得到葵花籽油基多元醇(SOPOL)。探讨了反应温度和时间、冰醋酸/过氧化氢摩尔比对SOEP和SOPOL性能的影响,并采用核磁共振表征了SOEP和产物SOPOL的结构。结果表明,制备SOEP较为理想的反应温度为65℃,反应时间为10 h,葵花籽油(以双键计)、冰醋酸与过氧化氢的摩尔比为1∶2∶4;在135℃进行环氧基开环反应制备的SOPOL羟值可达到176 mgKOH/g,平均官能度为4.2。该SOPOL可替代传统石油基多元醇合成生物基聚氨酯树脂。     

桐油基聚氨酯的制备及性能研究

以桐油基酸酐和丁二醇为原料通过酯化及酯交换反应合成了桐油基多元醇,并进一步以制备的桐油基多元醇和/或聚丙二醇为羟基组分,与异佛尔酮二异氰酸酯反应制备了桐油基聚氨酯.考察了桐油基聚氨酯的耐水性、耐醇性和漆膜硬度,并讨论了桐油基多元醇和聚丙二醇比例对聚氨酯性能的影响.结果表明桐油基多元醇可提高漆膜硬度、耐水性及耐醇性.     

磨具磨料用酚醛树脂的合成

采用苯酚和甲醛合成了磨具磨料用液态热固性酚醛树脂,考察了催化剂种类、原料配比,反应温度、反应时间等对产品性能的影响。结果表明,苯酚和甲醛最佳物质的量比为0.81～0.82∶1,100℃下采用二乙醇胺为催化剂预反应30min,而后在85℃下采用碳酸钠催化反应2h,反应缓和易控制,合成树脂的固含量,游离酚和水的质量分数分别为82.51%,11.32%,7.86%,产率为128%(相对于苯酚),满足磨具磨料用酚醛树脂指标要求。     

N-甲基二乙醇胺的合成研究

以二乙醇胺、甲醛、甲酸为原料,采用埃谢伟勒-克拉克反应制取N-甲基二乙醇胺,考察了物料配比、反应温度和时间等参数对反应及产品性能的影响,找出了最佳合成条件.     

稻壳液化产物用于聚氨酯胶黏剂的制备与性能

将稻壳在多元醇中液化制备具有反应活性的稻壳基多元醇,然后以所制备的稻壳基多元醇、低聚物多元醇、二苯基甲烷二异氰酸酯(MDI)和小分子交联剂等为主要原料合成聚氨酯(PU)乳液。分别从预聚反应温度、稻壳基多元醇的添加量、低聚物多元醇种类、R值(-NCO与-OH的摩尔比)以及小分子交联剂种类5个方面进行研究。通过对所制备的聚氨酯乳液进行红外光谱、黏度、稳定性和力学性能等分析测试,结果表明:在预聚反应温度为70℃、聚己二酸丁二醇酯1000(PBA1000)为原料、稻壳基多元醇添加量为10%、R值为1.2、三羟甲基丙烷(TMP)为交联剂的条件下,合成的PU胶黏剂效果最佳。     

国内外专利速报

20060401含氨基甲酸酯基多元醇的涂料组成及其在食品罐壁表面的应用世界知识产权组织专利W O2004101690,2004-11-25.题述涂料是一种水分散型涂料,具有较好的挠曲性和耐热老化性。该涂料包含:(A)每分子中至少含有一个氨基甲酸酯基多元醇官能团,这个氨基甲酸酯基多元醇官能团是由至少一个脂肪族或芳香族多元醇、至少一个环氧烷烃基和至少一个烷基氨基甲酸酯基反应制得的;(B)至少一种交联剂,交联剂中含有可以与氨基甲酸酯基多元醇官能团反应的基团,例如氨基树脂;(C)含有至少一种丙烯酸单体的成膜树脂(可选)。该专利还介绍了在食品罐外壁表面…     

一种利用大豆油合成的硬质聚氨酯泡沫塑料

以大豆油与环氧化剂反应,生成环氧大豆油;在催化剂的存在下与含活泼氢的亲核试剂发生环氧键开环反应,生成混合羟基脂肪酸甘油酯;加入醇并升温进行醇解反应,生成混合羟基脂肪酸单酯,即大豆油基多元醇。将大豆油基多元醇与异氰酸酯(MDI)等反应即可制得硬质聚氨酯泡沫塑料,具体配方为100份大豆油基多元醇,80~150份MDI、0.3~4份三乙醇胺、0.5~4份匀泡剂、0.5~3份蒸馏水。     

Urethane foams from animal fats: IX. Polyols based upon tallow and trimethylolpropane; preparation under acidic and basic catalysis

A series of polyols was prepared from epoxidized tallow, by reaction with trimethylolpropane in refluxing toluene, sequentially under basic and acidic catalysis. In preliminary experiments, under catalysis by sodium methoxide alone, the trimethylolpropane reacted rapidly with glyceride linkages and very slowly with oxirane groups. Under catalysis by p-toluenesulfonic acid alone, oxirane was rapidly consumed. Polyols were prepared by the following sequences: (A) reaction under acidic followed by basic catalysis; (B) reaction under basic followed by acidic catalysis; (C) reaction under basic catalysis followed by further treatment with HBr gas to introduce fire retardance; (D) treatment of whole tallow first with trimethylolpropane under basic conditions and secondly with bromine; (E) reaction of epoxidized tallow with diethanolamine under basic catalysis; and (F) treatment of epoxidized tallow first with trimethylolpropane under acidic conditions and then with diethanolamine under basic catalysis. The polyols described were adjusted to equivalent weights of 100 and 120 with added triisopropanolamine and treated with a polymeric isocyanate to give rigid foams. Densities ranged from 1.5–1.8 lb/ft³. Open cell content, for foams made at the equivalent wt of 100, ranged from 14–21%; at the equivalent wt of 120, from 17–27%. Compressive strengths ranged from 14–23 psi, being lower than those of the best previous epoxidized tallow-trimethylolpropane products. Presented at the AOCS Meeting, Mexico City, Mexico, May 1974. ARS, USDA.     

Rigid polyurethane foams from diethanolamides of carboxylated oils and fatty acids

New polyols of high hydroxyl content and reactivity were made from linseed and soybean oils and acids by catalytic carboxylation followed by reaction with diethanolamine. Urethane foams made with these diethanolamides were stronger than those made with castor oil at equivalent polyol wt. Because of their higher hydroxyl content, a larger amount of diethanolamides could be incorporated in foam formulations than is possible with castor oil. The rigid urethane foams prepared with the new polyols meet the requirements of commercial products with respect to density, compressive strength, and dimensional stability. National Flaxseed Processors Association Fellow, 1969–1973. Present address: Avery Products, Technical Center, 325 North Altadena Dr., Pasadena, CA 91107.     

植物油基聚酯酰胺多元醇的合成及其在水性聚氨酯中的应用

以菜籽油和二乙醇胺为原料制备了脂肪醇酰胺混合多元醇RDEA,进一步和己二酸等原料反应合成了系列的聚酯酰胺多元醇,并对两类多元醇进行了表征。以聚酯酰胺多元醇、二羟甲基丙酸、异佛尔酮二异氰酸酯、苯乙烯和丙烯酸丁酯等原料合成了水性聚氨酯脲（PUU）分散液及聚氨酯脲-乙烯基聚合物（PUA）复合水分散液,并对其流变性能及稳定性进行了研究。     

甲基二乙醇胺双脂肪酸酯的合成与表征

研究了不同碳链长度的脂肪酸与N-甲基二乙醇胺的酯化反应。以月桂酸为原料,通过正交实验考察了反应温度、物料摩尔比、回流液温度、催化剂用量等因素对该酯化反应的影响,确定了较优的工艺条件为:反应温度200℃,n(月桂酸)∶n(N-甲基二乙醇胺)=1.8∶1.0,回流液温度70℃,催化剂用量(相对于反应原料的质量)0.3%。在该工艺条件下,酯化产物中甲基二乙醇胺双月桂酸酯(双酯胺)的质量分数可达98%以上。并对正辛酸、正癸酸、棕榈酸和硬脂酸与N-甲基二乙醇胺的酯化反应条件进行了优化,得到的产物中双酯胺的质量分数达98%以上。采用IR和1HNMR对双酯胺的结构进行了表征。     

溴碳聚氨酯硬质泡沫塑料的研制

采用二乙醇胺、自制四溴双酚A环氧树脂(E-21)为原料合成了阻燃聚醚多元醇组分;采用2,4-甲苯二异氰酸酯(TDI)、聚乙二醇(PEG)、三羟甲基丙烷(TMP)为原料,在二月桂酸二丁基锡的作用下,通过逐步聚合反应得到异氰酸酯组分;将两组分按一定比例进行发泡得到阻燃聚氨酯硬质泡沫塑料。利用热重分析仪、水平燃烧测定仪等手段进行了表征,研究了异氰酸酯指数、发泡剂以及阻燃剂对聚氨酯硬质泡沫塑料性能的影响。结果表明,与不添加阻燃剂的聚氨酯硬质泡沫塑料相比,阻燃聚氨酯硬质泡沫塑料的吸热峰温度从294.8℃提高到303.8℃。     

二乙醇胺开环环氧大豆油制备大豆多元醇及其性能表征

以大豆油、冰乙酸和过氧化氢为原料,硫酸为催化剂,合成了不同环氧值的环氧大豆油。再由合成的环氧大豆油与二乙醇胺在四氟硼酸作催化剂的条件下．通过开环加成反应制备了羟基值分别为261mgKOH／g、285mgKOH／g、312mgKOH／g、340mgKOH／g的4种大豆多元醇。用滴定法测定多元醇羟值,用傅立叶变换红外光谱、差示扫描量热法、热重分析法对多元醇进行了分析和表征。结果表明4种多元醇的熔点和热稳定性都随多元醇羟值增大而增大。     

Cu/ZrO2催化剂用于二乙醇胺脱氢合成亚氨基二乙酸的研究

用共沉淀法制备的Cu/ZrO₂催化剂进行二乙醇胺催化脱氢合成亚氨基二乙酸,分别考察了催化剂用量、原料配比、反应温度、反应压力和反应时间等因素对反应的影响。结果表明,最佳反应条件为:二乙醇胺68.5 g、去离子水140 g、催化剂的加入量为二乙醇胺质量的20%、n(氢氧化钠)∶n(二乙醇胺)=2.3∶1、反应温度170 ℃、反应压力0.8 MPa和反应时间5 h。在此条件下,亚氨基二乙酸收率可达92.3%。催化剂经重复使用8次后,亚氨基二乙酸收率仍然保持在90%以上。     

愈创木酚胺基多元醇的合成及表征

以木质素模型化合物愈创木酚、二乙醇胺及多聚甲醛为原料,通过Mannich反应合成了愈创木酚胺基多元醇,研究了物料滴加顺序、物料配比、反应温度及时间等因素对Mannich反应的影响。实验结果表明:反应物料按物质的量比n(愈创木酚):n(甲醛):n(二乙醇胺)1:1:1,甲醛与二乙醇胺60℃反应2 h生成1,3-氧氮杂环戊烷,再将其滴入愈创木酚中,80~90℃反应3~4 h,二乙醇胺的转化率最高可达到90.71%。并采用HPLC、LC-MS及FT-IR表征了愈创木酚胺基多元醇的化学结构。     

Synthesis,characterization, and properties of polyols from hydrogenated terpinene–maleic ester type epoxy resin

Three kinds of polyfunctional polyols with hydroxyl values of 180–320 mg/g were prepared by the reaction of hydrogenated terpinene–maleic ester type epoxy resin with secondary amines (diethylamine, N‐methylethanolamine, and diethanolamine), and the chemical structures were characterized by Fourier transform infrared spectroscopy and NMR spectroscopy. These polyols were used in place of commonly used polyols to prepare two‐component polyurethanes when reacted with polyisocyanates. The crosslinking reactions of the polyols with polyisocyanate could be catalyzed by the tertiary amine groups included in the polyols, and the reaction rate was affected by hydrochloric acid and the polarity of the solvents. The mechanical, water‐resistance, and chemical‐resistance properties of the crosslinked products of the polyols were evaluated by standard tests, and the thermal properties were examined by differential scanning calorimetry and thermogravimetric analysis. The results show that these epoxy–urethane polymers, with glass‐transition temperatures (T_g's) in the range ?5 to 37°C, had good thermally resistant properties, and the temperatures at 5% weight loss were in the range 235–280°C. All of the polymers formed transparent, strong, flexible films, with good chemical‐resistance properties and excellent impact strengths of greater than 50 cm, a flexibility of 0.5 mm, adhesions of 1–2, and pencil hardnesses of HB–2H. The larger OH functionality and OH value of the polyol resulted in higher T_g and pencil hardness values and better alcohol resistance and thermal stability in the crosslinked product of the polyol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009