本期导读

<正>近几年,在全行业的共同努力下,涂料环保取得了极大的进展。陈昆等通过自制的二元醇、自制的六臂型阻燃单体引入到UV固化水性聚氨酯体系中,制备了一种含氟UV固化水性星型阻燃聚氨酯,对水性聚氨酯进行改性,以提高其性能。孙旗龄等在全氟聚醚段上引入碳氢链段,在一定程度上改善UV固化涂层的机械性能。王姚等提出以地沟油为原料,制备地沟油基水性醇酸树脂防腐涂料,利废环保,质优价廉。冯春苗等通过引入叔碳缩水甘油酯单体,并采取分步骤合法工艺合成高固体分聚酯树     

基于黄色二元醇的黄色水性聚氨酯的合成与性能研究

通过自制一种黄色二元醇[(N,N-二(2-羟乙基)-4-硝基苯胺,简称HENA)]作为扩链剂,并改变HENA与1,4-丁二醇(BDO)比例,引入聚氨酯主链合成了一系列黄色水性聚氨酯,实现了有色小分子和聚氨酯在分子水平的结合.通过FTIR、NMR等证实该二元醇成功制备及被成功引入聚氨酯主链中.进一步通过紫外-可见光谱、热...     

新型含氟UV固化水性聚氨酯的合成及其性能研究

文章以三羟甲基丙烷、马来酸酐为原料合成出一种新型的亲水二元醇(T.M),将其与聚丙二醇(PPG-1000)、甲苯-2,4-二异氰酸酯(TDI),和全氟辛醇等合成出含氟UV固化水性聚氨酯(TPTMF),并通过傅立叶红外光谱(FTIR)对其进行了表征,并通过热重分析等仪器对乳液和涂膜性能进行测试。结果表明:所合成的树脂具有具有光固化性能;将含氟辛醇引入主链中,所得到的固化膜具有良好的疏水性、耐热性、自清洁性等[1-2]。     

硅氧烷改性水性聚氨酯的交联机理及成膜性能研究

通过一种温和的反应合成了一种侧链含有硅氧烷基团的二元醇,利用FTIR对其结构进行了表征。将该二元醇作为扩链剂引入水性聚氨酯主链中,将含硅基团引入聚氨酯分子中,由于硅氧烷基团的水解作用形成分子链间交联结构。实验结果发现,改性后的水性聚氨酯材料表现出良好的表面性能,同时材料的耐水性、耐溶剂性、耐化学品性以及机械性能得到明显提高。     

侧基含铵盐的新型阳离子UV固化阴极电泳涂料

将叔胺位于主链的N-甲基二乙醇胺(MDEA)和叔胺位于侧基的7,12-二氧-3,16-二氮-3,16-二乙基-5,14-十八二醇(DDDOD)分别作为亲水单体,与聚己内酯二元醇(PCL)、异佛尔酮二异氰酸酯(IPDI)等反应,制备聚氨酯分散体。通过聚氨酯的分散性、分散体平均粒径,比较了亲水基位于聚氨酯主链和侧基的两种单体的亲水性。结果表明,亲水基团位于侧基时,亲水效果比位于主链的好。将叔氨基位于侧基的单体DDDOD作为亲水单体,与PCL、IPDI反应,制备了聚氨酯,加入UV固化单体,分散得到UV固化的阴极电泳涂料。研究了涂料的乳液性能和UV固化后双键转化率和膜性能。     

UV固化环氧丙烯酸酯的增韧研究

对UV固化涂料中常用的环氧丙烯酸酯(EA)进行增韧改性,改善了其脆性大,柔韧性不足的缺点。首先合成一种含聚醚二元醇/聚己内酯二元醇链段的双酯扩链剂,并将其用于EA树脂的增韧改性,最后进行紫外光固化。研究结果如下:随着双酯扩链剂中聚二元醇的分子量的提高,改性EA的黏度、玻璃化温度、拉伸强度、拉伸模量均降低,弯曲性能获得提高;当分子量相近时,采用聚己内酯二元醇合成的扩链剂的增韧效果优于聚醚二元醇合成的样品。     

紫外光固化松香基聚氨酯丙烯酸酯的合成

采用松香基聚酯二元醇(RP)改性可紫外光固化的聚氨酯丙烯酸酯(PUA),进一步降低UV固化树脂的成本。考察了反应温度、物质的量的比、反应时间和催化剂用量对合成产物的影响。通过实验得到了合成松香基聚氨酯丙烯酸酯的最佳工艺条件。应用FT-IR对产品的结构进行表征,测试了最终固化涂膜的附着力、铅笔硬度、耐冲击性和耐候性等各项性能。     

高性能多烯型紫外光固化水性聚氨酯的研制及应用

UV固化水性聚氨酯结合了UV固化的优点和水性聚氨酯的优点,未来有很好的发展前景。用季戊四醇与丙烯酸直接酯化制备季戊四醇二丙烯酸酯单体,研究了二者不同物质的量比对物质结构的影响,得到了最佳配比;通过FTIR和1HNMR谱证实了产物的结构。将季戊四醇二丙烯酸酯作为扩链剂,在聚氨酯分子的侧基引入双键,制得高性能UV固化水性聚氨酯树脂。讨论了不同物质的量比的季戊四醇和甲基丙烯酸羟乙酯对树脂中双键含量、树脂相对分子质量及对涂膜性能的影响。对研制的UV固化水性聚氨酯涂料进行了性能测试。     

一种阴离子-非离子型水性聚氨酯的合成与性能研究

通过在合成聚氨酯时引入一种自制的含非离子性亲水基团的二元醇参与扩链,制备出了一种阴离子-非离子混合型水性聚氨酯,提高了水性聚氨酯在p H=6~7弱酸溶液下的稀释分散性,使其能够稳定应用于弱酸性的纺织浆料中;进一步通过乙二胺扩链后提高了聚氨酯成膜物的耐磨性与硬度,其磨耗仅为0.23 g/100 r,该水性聚氨酯能够在纺织浆料中替换目前广泛使用的聚乙烯醇。     

低表面能UV固化水性柔感塑料涂料的研究

将季戊四醇三丙烯酸酯（PETA）和聚二甲基硅氧烷（PDMS）引入水性聚氨酯的主链,制得硅氧烷改性的UV固化水性聚氨酯乳液,通过FTIR红外光谱对乳液的结构进行表征。将该乳液与助剂复配,制得水性塑料涂料,并对涂层的固化动力学和表面性能进行研究。与未改性的涂料相比,硅氧烷改性的UV固化水性涂料具有良好的耐水性和耐溶剂性,同时保留了优良的手感,可用作水性柔感塑料涂料。     

聚氨酯弹性体耐热性的影响因素

讨论了多异氰酸酯，聚合物多元醇，扩链剂，分子内基团，杂环，离子基团对聚氨酯弹性体耐热性能的影响。指出开发新原料，引入热稳定杂环，严格控制反应条件和原料的纯度及配比，是提高聚氨酯弹性体耐热性的有效途径。     

耐热型聚氨酯的合成研究

以自制的含硅聚醚、聚氧化丙烯二醇(N-210)和2,4-甲苯二异氰酸酯(TDI)为主要原料,以氨丙基三甲氧基硅烷(DB-550)作为封端剂,制备耐热型PU(聚氨酯)。采用红外光谱(FT-IR)法、热失重分析(TGA)法对改性PU的结构和热稳定性能进行了分析,并探讨了各种因素对PU及其预聚体性能的影响。结果表明:当R值为1.5、预聚时间为3 h、预聚温度为40℃和m(自制含硅聚醚)∶m(N-210)=1∶7时,改性PU的耐热性和综合性能较好。     

Modification of aqueous polyurethane dispersions via tetraphenylethane iniferters

Aqueous polyurethane (PU) dispersions containing tetraphenylethane iniferter groups were prepared from 4,4′‐diphenylmethane diisocyanate, poly(propylene oxide)glycols, dimethylol propionic acid, and 1,1,2,2‐tetraphenylethane‐1,2‐diol. To improve the water resistance of the dispersions, methyl methacrylate monomers were added into these dispersions and block‐copolymerized onto the main PU chain. The viscosity and particle size of the dispersions were determined. Dispersion‐cast films were characterized in terms of the contact angle, the swell in water, and the mechanical properties. Contact‐angle and water‐swell measurements showed that the hydrophilicity of the films was decreased significantly when methyl methacrylate was polymerized in the presence of tetraphenylethane containing aqueous PU dispersions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2993–3000, 1999     

聚氨酯防水透湿涂层剂的合成

以聚丙二醇(PPG)/聚乙二醇(PEG)混合多元醇作为聚醚二醇组分,与二苯基甲烷二异氰酸酯(MDI)进行预聚,然后用1,4-丁二醇扩链合成有防水透湿性的聚氨酯涂层剂,经红外光谱分析确定为目标产物。研究了不同的工艺条件对涂层剂合成的影响,讨论了R值〔n(—NCO)/n(—OH)〕对涂层剂黏度的影响。结果表明,n(MDI)∶n(聚醚二醇)=1.42∶1,反应温度82℃,预聚反应时间1h,扩链反应时间2h,R值为1.02～1.07时,制得的涂层剂耐静水压值达到20.4kPa,透湿量达到4533g/(m2·d)。经与比利时UCB公司的产品UCcoat2000和日本Toray公司的产品EntrantGⅡTX进行比较,本涂层剂耐静水压和透湿量指标更优越。     

纳米SiO_2改性PU的合成与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇(PCD、PCL)、环氧树脂(EP)和1,4-丁二醇等为主要原料,纳米SiO2为改性剂,二月桂酸二丁基锡(DBTDL)为催化剂,成功合成了纳米SiO2改性聚氨酯(PU)。结果表明:纳米SiO2的加入,提高了PU的热稳定性、致密性、耐水性、硬度及耐黄变等性能;当w(纳米SiO2)=1.5%(相对于单体总质量而言)时,改性PU的综合性能较好。     

Tuning physical properties of polyurethane hard segments through extender chain length variation and doping of pentaerythritol and their effect on in vitro protein adsorption

This study explores the synthesis and characterization of polyurethanes (PUs) derived from hexamethylene diisocyanate (HDI) and 1,n-alkane diols with varying chain lengths (n = 4, 6, and 10). Additionally, pentaerythritol (PE) is introduced as a dopant in PU6 at different weight percentages (25%, 50%, 75%, and 1:1%w/w). The research encompasses a comprehensive analysis of PU properties, including morphology, crystallinity, surface area, porosity, thermal behavior, rheological properties, and electrical conductivity. Of particular interest is the evaluation of protein adsorption capabilities employing bovine serum albumin (BSA) and fibrinogen proteins in in vitro tests. The study emphasizes the crucial role played by the chain length between isocyanate and diol groups and the nature and strength of hydrogen bonds among chains in shaping the polymer's properties, especially crystallinity and biocompatibility. Among the synthesized PUs, PU6 emerges as the top performer in terms of crystallinity and biocompatibility. Furthermore, the addition of PE is found to act as a plasticizer, reducing the glass transition temperature (T_g) from 75°C to 31°C. Electrochemical Impedance Spectroscopy shows that doping influences charge transfer processes, rendering the material semi-conducting, as evidenced by decreased conductance when adding silver nanoparticles to PU6. Notably, protein adsorption studies reveal that undoped PU6 displays superior protein resistance compared to its doped counterpart, with fibrinogen exhibiting a higher adsorption affinity than BSA. The study discusses a plausible mechanism underlying protein adsorption.     

Thermal and mechanical properties of multiple‐component aliphatic degradable polyurethanes

Macroscopic thermal and mechanical properties of complex aliphatic polycarbonate‐based polyurethane (PU) films containing degradable ester units in PU backbone were studied by a combination of several experimental techniques. Differential scanning calorimetry (DSC) revealed that the synthesized oligomeric diol (DL‐L) contributes (in addition to polycarbonate diol) to the formation of soft‐segment domains, while the hard‐segment domains are formed from 1,6‐diisocyanatohexane (HDI) and butane‐1,4‐diol (BD). Three main phase transitions were detected by DSC and by dynamic mechanical thermal analysis. Thermogravimetric analysis (TGA) of two‐component PUs showed that the PU made from DL‐L and HDI is the least thermostable product, while the PU made from polycarbonate diol and HDI is the most stable one. The differences in the thermal stability of different four‐component PUs are not important. Tensile properties very sensitively reflect the changes in composition and in microstructure of PU samples; the best tensile properties exhibits the degradable sample containing the equimolar ratio of hydroxyl groups of macrodiol, oligomeric diol DL‐L and butane‐1,4‐diol. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41872.     

聚己二酸己二醇酯型聚氨酯水乳液的合成及性能研究

以己二酸、己二醇为原料合成聚己二酸己二醇酯二醇，并制备成聚氨酯水乳液。研究了乳液成膜物的耐水解性和物理性能。结果表明：聚己二酸己二醇酯为基础的聚氨酯乳液，其成膜物拉伸强度高、硬度大、耐水解性能优良，可用作皮革涂饰剂。     

Transparent polyester polyol-based polyurethane coatings: the effect of alcohols

A series of polyester polyols were synthesized using 1,6-hexanediol (HDO), 1,4-cyclohexanedimethanol (1,4-CHDM) and trimethylol propane (TMP), alone or in combination with 1,4-cyclohexanedicarboxylic acid and adipic acid. The polyester polyols were reacted with isocyanate trimers to form polyurethane (PU) coatings. Physical properties of the polyesters such as hydroxyl value, acid value, molecular weight, viscosity, and glass transition temperature (T _g) had been determined, and the IR spectroscopic analyses of polyesters/PU were reported. The properties (impact resistance, film flexibility, hardness, optical transmittance, chemical resistance, water absorption, thermostability, and phase separation) of the PU coatings so prepared were characterized. The viscosities of polyester polyols were dependent on the structure of the alcohols. Polyester polyol containing only linear aliphatic diol (HDO) was a transparent liquid at room temperature. The viscosity was increased by raising the molar ratio of 1,4-CHDM and/or TMP. All PU coatings had excellent flexibility, impact resistance, and hardness. The coatings derived from diol CHDM had the highest hardness, and the PU derived from diol HDO had the lowest hardness. The chemical resistance and water absorption improved with greater molar ratios of 1,4-CHDM or TMP. Results of differential scanning calorimetry and wide-angle X-ray diffraction indicated that there was no obvious crystallinity in the PU networks. Dynamic mechanical analysis (DMA) results revealed that both CHDM and TMP can increase the T _g of PU, and the crosslinking density improved with increased molar ratio of TMP. Atomic force microscope (AFM) and DMA analysis revealed that the PU coatings had no obvious microphase separation, which enabled them to have excellent properties, and the different composition in polyols did not have significant influence on transmittance in the visible region. Results of thermogravimetric measurements indicated that all the PU coatings had good thermal stability.     

聚碳酸酯基水性聚氨酯的合成与性能研究

以聚碳酸酯二醇(PCDL)为主要原料合成水性聚氨酯(WPU)树脂,并与聚四氢呋喃(PTMEG)、聚醚(PO)、聚酯(PS)材料进行对比研究,同时探讨交联剂对成膜性能的影响。研究结果表明,适度交联可提高胶膜的拉伸强度及耐水性,交联使膜的断裂伸长率降低。液态材料PCDLT-981合成的WPU树脂的成膜光泽及断裂伸长率较好,固态材料PCDLT-5652合成的WPU树脂的拉伸强度及耐介质性能更佳。4种多元醇合成的WPU树脂,PCDL水性PU性能最优,有望取代溶剂型合成革树脂。