蓖麻油基聚酯多元醇的制备及表征

以可再生资源蓖麻油、苯酐和小分子醇为原料,钛酸正丁酯为催化剂,经酯化、缩聚合成蓖麻油基聚酯多元醇,考察了反应时间对聚酯多元醇酸值的影响以及不同官能度的小分子醇对醇解蓖麻油结构和羟值的影响。采用红外光谱仪（FT—IR）、凝胶色谱（GPC）、热失重仪（TGA）对醇解蓖麻油、蓖麻油基聚酯多元醇的相对分子质量、热稳定性进行了表征。结果表明,随着小分子醇官能度的增加,醇解体系中单酯和二酯含量明显减少,转化率也相应减小;甘油醇解蓖麻油和蓖麻油基聚酯多元醇较普通聚醚多元醇635具有更高的热稳定性。     

无溶剂蓖麻油聚酯多元醇的合成及应用研究

以蓖麻油、甘油、己二酸和乙二醇为原料,酯化缩聚合成低黏度的蓖麻油聚酯多元醇,并将该蓖麻油聚酯多元醇与HDI聚异氰酸酯制备无溶剂涂料。研究了醇酸比[n(—OH)：n(—COOH)]对蓖麻油聚酯多元醇及其涂层性能的影响。结果表明：在醇酸比为1.32时,蓖麻油聚酯多元醇所制涂层的耐水性、耐冲击性、耐擦伤性、柔韧性等综合性能良好。     

蓖麻油基聚醚多元醇的制备及其表征

以双金属氰化物(DMC)为催化剂、蓖麻油为起始剂制备了新型蓖麻油基聚醚多元醇.采用傅立叶变换红外(FTIR)、核磁共振(1H-NMR)、凝胶色谱(GPc)及热失重(TG)等分析手段对合成产物的结构和热稳定性进行表征.结果表明,蓖麻油基聚醚多元醇结构中既含有蓖麻油的酯基和双键,又含有聚醚的烷基醚基团;本实验的蓖麻油基聚醚多元醇相对分子质量分布随相对分子质量的增大而变窄;与普通聚醚多元醇相比具有更高的热稳定性.     

草酸二乙二醇的合成及其在聚酯多元醇制备中的应用

提出了一种草酸聚酯多元醇的制备方法。首先采用草酸和乙二醇反应制备草酸二乙二醇单体,然后与甘油、苯酐进行共缩聚制备目标产物。研究表明:采用草酸和乙二醇为反应物、环己烷为反应介质,二氯化亚锡为催化剂,在50~60℃下,持续回流分水3 h,制得一种草酸二乙二醇单体,产率达97%。将草酸二乙二醇、甘油、苯酐在200℃下进行熔融共缩聚制备出一种数均和重均分子量分别为4357和9150、酸值为1.0、无色透明黏性的草酸聚酯多元醇。它的热稳定性及各项参数相近于相同条件下制备的己二酸聚酯多元醇。     

聚酯多元醇合成中催化剂的应用研究

以苯酐、己二酸和甲基丙二醇为原料合成了聚酯多元醇,在基本相同的反应条件下,分别采用乙二醇锑Sb2(EG)3、三氧化二锑(Sb2O3)、醋酸锌Zn(Ac)2、钛酸四丁酯(TBT)和钛酸四异丙酯(TPT)等催化剂进行聚酯多元醇的合成反应。研究结果表明,在本反应体系中TPT是最佳催化剂;随着聚酯多元醇理论相对分子质量的增大,反应越难以进行,因此催化剂用量应相应增加,但其质量分数以不超过0.04%为宜。     

蓖麻油聚醚多元醇在聚氨酯软泡中的应用

利用双金属催化剂(DMC)制备了相对分子质量在2000～5600之间的聚氨酯(PU)软泡用蓖麻油聚醚多元醇,并通过发泡实验与常用软泡聚醚多元醇H-330进行了性能比较。结果表明,相对分子质量2000的蓖麻油聚醚多元醇制备的泡沫拉伸强度、伸长率和压陷硬度等均优于H-330聚醚,表明蓖麻油聚醚多元醇完全可以取代普通聚醚多元醇用于普通软泡生产。     

环保无溶剂型双组分聚氨酯结构胶的研制

在传统PU(聚氨酯)胶粘剂组成体系中,以蓖麻油作为PAPI(多亚甲基多苯基异氰酸酯)固化剂的改性剂,并引入芳烃基聚酯多元醇和催化剂等,制备出一种适合工业化生产的环保无溶剂型双组分PU结构胶。研究了固化剂的改性、芳烃基聚酯多元醇类型及含量、无机填料和催化剂含量等对PU结构胶黏度和粘接性能的影响。结果表明:固化剂的适当改性有助于提高PU结构胶的粘接强度;当w[芳烃基聚酯多元醇(样8#)]=18%(相对于B组分质量而言)时,PU结构胶的综合性能相对最好,其剪切强度为10.9 MPa、90°剥离强度为50.2 N/cm;无机物填料的引入虽能降低PU结构胶的生产成本,但也会降低其粘接强度;催化剂的引入能有效提高PU结构胶的固化速率,其含量可根据不同地区、不同季节和不同用途进行调节。     

二元醇对合成木质素基聚酯多元醇性能的影响

利用玉米秸秆木质素替代部分丙三醇用于合成木质素基聚酯多元醇,采用癸二酸、丙三醇、木质素与不同配比的乙二醇和新戊二醇混合物,以甲基磺酸作催化剂,通过对所合成聚酯多元醇的酸值、羟值、相对分子质量、黏度、基团结构表征以及热失重分析研究了二元醇对合成木质素基聚酯多元醇性能的影响。实验结果表明,二元醇中新戊二醇的引入对所合成木质素基聚酯多元醇的酸值、羟值、相对分子质量等性能以及分子结构影响较大。采用新戊二醇作为二元醇参与合成木质素基聚酯多元醇,所得产物的羟基特征峰及木质素基特征峰较乙二醇产品更为突出,且热稳定性也有所提高,同时可以得到使用更为方便的液体产品。     

己二酸系聚酯多元醇的合成

以己二酸和不同多元醇为原料,经酯化、缩聚合成已二酸系聚酯多元醇。考察了醇酸摩尔比、催化剂种类和用量等因素对酯化反应的影响。研究表明,当采用四异丙基钛酸酯为催化剂,质量分数为总投料量的0．03％,醇酸摩尔比为1．2～1．3,反应温度为220℃,真空度为85～90kPa时,合成的己二酸系多元醇酯化率可达99％。     

磺酸阴离子型离子液体催化合成己二酸聚酯

以己二酸(AA)、乙二醇(EG)为原料,经过酯化及缩聚过程合成数均分子量2000~3000聚己二酸乙二醇酯(PEA),在基本相同的条件下,分别采用1-甲基-2-吡咯烷酮对甲苯磺酸盐([Hnmp]PTSA)、N-甲基咪唑对甲苯磺酸盐([Hmim]TsO)、1-(3-磺酸)丙基-3-甲基咪唑对甲苯磺酸盐([HSO_3-pmim]pTSA)、对甲苯磺酸(PTSA)进行聚酯多元醇的反应。通过化学滴定的方法,计算出聚合物的酸值、羟值及数均分子量。探究结果表明:酸醇摩尔比=1:1.3、([Hnmp]PTSA)为催化剂、催化剂用量为AA质量的0.1%、反应温度190℃为宜。     

The kinetics of polyesterifications. IV. Polyol from BHET and adipic acid and its urethanes

New polyol containing aromatic rings was prepared from BHET, or BHET/ethylene glycol mixtures and adipic acid. In this new system, the kinetics of polyesterification were investigated and were shown to follow the kinetic equations proposed by Lin and his co-workers which were obtained by modifying Flory's theory. Polyurethane elastomers were prepared by reacting these polyols and toluene diisocyanate (TDI) in DMF solution with NaCN as a crosslinking catalyst at room temperature. Their physical properties such as density, gel fraction, swelling ratio, mechanical properties, etc., were measured. High values of elastic modulus are due to the rigid segment of BHET. By varying the molar ratio of diisocyanate and polyester, polyurethanes with different crosslinking densities can be obtained. The relationship between physical properties and crosslinking density was shown to follow the general theory of rubber elasticity.     

Polyester polyols for polyurethanes from pet waste: Kinetics of polycondensation

The kinetics of polyesterification of the glycolyzed PET waste with adipic acid is reported. Glycolysis of PET waste was carried out with ethylene glycol at three different ratios of PET waste to glycol. The glycolyzed products could be readily polyesterified by reacting with adipic acid, to give polyester polyols with low acid number. Kinetics of polyesterification of the glycolyzed product made from 62.5% ethylene glycol (EG) and 37.5% waste were investigated further at different hydroxyl to carboxyl ratios. Reaction conditions were nonisothermal, comparable to the industrial process scheme consisting of two isothermal regions at 170° and 200°C. The kinetic results of the polyesterification of glycolyzed PET waste are compared to the polyesterification of pure diols, namely ethylene glycol and bis(hydroxyethyl) terephthalate (BHET) with adipic acid. The reactions follow second-order kinetics at 170°C and the rate of polyesterification of the mixed diol system from PET waste lies intermediate between those of the pure diols, namely, EG and BHET. Ethylene glycol exhibited the highest reactivity. At 200°C the kinetic plots of the mixed diols from PET waste were nonlinear, and thus the reaction may not follow second-order kinetics. The nonlinearity is explained in terms of the different reactivities of the different diol species in the reaction mixture. The polyester polyols, when cured with polymeric 4,4′ diphenyl methane diisocyanates, gave polyurethane rigid foams and elastomers.     

减少DMC催化合成聚醚多元醇中高相对分子质量拖尾部分的研究

以双金属氰化物络合物(DMC)为催化剂,采用间歇法合成了聚醚多元醇,讨论了催化剂用量、反应温度、反应压力等因素对聚醚多元醇相对分子质量分布的影响。结果表明,硫酸质量分数为总量的0.004%、环氧丙烷预投量为起始聚醚质量分数的16%、DMC催化剂质量分数为总量的0.006%、反应温度在120～130℃和反应压力为0.1 MPa时,所制备的聚醚多元醇中高相对分子质量拖尾部分减少,相对分子质量分布窄,且其它物理性能也较好。     

基于二聚酸/己二酸聚酯多元醇的合成及表征

以二聚酸、己二酸和新戊二醇为原料,在高温氮气保护下,合成一种相对分子质量为2000的二聚酸类聚酯多元醇。考察醇酸比、最高反应温度、反应时间、保温脱水时间、催化剂种类及用量对反应结果的影响。通过红外光谱分析表征了产物中的基团。结果表明:合成基于二聚酸聚酯多元醇的最优条件是醇酸比为1.24∶1,总反应时间为8 h,最高反应温度为220℃,二月桂酸二丁基锡为催化剂且质量分数为0.12%。     

聚醚-酯嵌段共聚物提高聚氨酯弹性体水解稳定性的研究

采用双金属络合催化剂(DMC),以脂肪族己二酸系聚酯多元醇为起始剂,与环氧丙烷、环氧乙烷进行烷氧基化反应,制得聚醚酯多元醇用于聚氨酯弹性体(PUE)的合成,可得到综合性能优良的PUE材料.在相同硬段含量下,聚醚酯型PUE的力学性能接近纯聚酯型PUE,优于纯聚醚型PUE,并且其耐水解性能得到较大的提高,接近纯聚醚型PUE...     

Comparison of Adipic Versus Renewable Azelaic Acid Polyester Polyols as Building Blocks in Soft Thermoplastic Polyurethanes

In this study, novel polyester diols of 2000 molecular weight (MW) were synthesized by reacting azelaic acid (AZ) with 1,3‐propanediol (1,3‐PDO) and diethylene glycol (DEG) in the esterification reaction catalyzed with a small amount of butyltintris(2‐ethylhexanoate). As a reference, polyester polyols of 2000 MW were synthesized from adipic acid (AA) with 1,3‐PDO and DEG. The properties of polyester polyols were evaluated. The polyester polyol based on AZ and 1,3‐PDO is 100 % renewable polyol; 1,3‐PDO used in the syntheses is renewable product produced by fermentation process of sugar. Both 1,3‐PDO‐polyester polyols exhibited crystalline transition above room temperature, while DEG‐polyester polyols were liquid at room temperature. The polyester polyols were chain‐extended with 4,4′‐diphenylmethane diisocyanate (Mondur M) and 1,4‐butanediol (BDO) to form thermoplastic polyurethanes (TPU). TPU were evaluated for mechanical and water resistance properties, and their morphology were studied via differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), and atomic force microscope (AFM). TPU based on azelate and adipate polyols were relatively soft elastomeric materials with high melting temperatures. AFM analyses of TPU indicated better phase separation in 1,3‐PDO polyester polyols with the highest phase separation observed in TPU based on 1,3‐PDO/azelaic acid polyols. Water resistance of TPU based on azelate polyols was improved as compared to TPU based on adipate polyols.     

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。