水性聚氨酯防水透湿涂层剂的合成与应用

选择聚酯和聚醚混合二元醇,异佛尔酮二异氰酸酯(IPDI),二羟甲基丙酸(DMPA),三乙胺(TEA)为主要原料,合成水性聚氨酯防水透湿涂层剂乳液。讨论了R值,DMPA用量,聚酯聚醚比例对薄膜吸水率和织物防水透湿性的影响。优化的防水透湿涂层剂的合成工艺为:聚酯多元醇和聚醚多元醇摩尔比=2/1,DMPA3.0%,R=1.9。经聚氨酯乳液涂层的织物的透湿量可到达4500g/(m2×24h),接触角可达137°。     

水性聚氨酯防水透湿涂层剂的合成与性能

选择聚酯和聚醚混合二元醇,异佛尔酮二异氰酸酯(IPDI),二羟甲基丙酸(DMPA)为主要原料,三乙胺(TEA)为中和剂,合成水性聚氨酯防水透湿涂层剂乳液。讨论了R值,DMPA用量,聚酯聚醚比例对乳液稳定性,乳液粘度和粒径,薄膜的力学性能以及对织物防水透湿性的影响。优化的防水透湿涂层剂的合成工艺为:聚酯多元醇和聚醚多元醇摩尔涂层的织物的透湿量可到达4500g/(m2×24h),静水压可达到5.6kpa。     

聚酯-聚醚混合型水性聚氨酯的合成工艺研究

以聚己二酸丁二醇酯二醇（PBAG）和聚乙二醇（PEG）为软链段,以异佛尔酮二异氰酸酯（IPDI）和二羟甲基丙酸（DMPA）为硬链段,采用预聚体法制备了水性聚氨酯（WPU）,研究了R值（NCO／OH摩尔比）、DMPA用量、聚酯与聚醚摩尔比等对乳液的粘度、粒径、稳定性和聚氨酯胶膜力学性能的影响。结果表明,选用尺值为2．0、DMPA质量分数为3．5％、聚酯与聚醚摩尔比为2．5,制备的聚酯-聚醚混合型WPU的粒径可以达到310nm,粘度达到65mPa·s,其离心稳定性和wPU膜力学性能良好。经WPU涂层整理织物的耐静水压达到6．08kPa,透湿量达4550g／（m2×24h）,符合服用性能的要求。     

影响聚氨酯薄膜透湿性能的因素

以二苯基甲烷二异氰酸酯,1,4-丁二醇和聚醚二元醇为原料合成聚氨酯,采用干法涂膜制备了亲水性无孔薄膜。讨论了铸膜液浓度,薄膜的放置时间,聚醚的相对分子质量,软段的质量分数以及湿度和透湿温度等几个因素对透湿量的影响,并对亲水透湿机理进行了分析。     

有机硅烷偶联剂改性紫外光固化超支化聚醚基水性聚氨酯的性能

采用超支化聚酯Boltorn H 20与丁二酸酐反应,制备了亲水性超支化聚酯,然后与甲基丙烯酸酯基改性的聚醚基聚氨酯预聚体和3-异氰酸酯基丙基三乙氧基硅烷(IPTS)反应,合成了有机硅烷偶联剂改性紫外光固化聚醚基超支化水性聚氨酯(WHPU)。考察了有机硅烷偶联剂用量对WHPU的耐酸性、固化时间、凝胶质量分数、附着力、水接触角、水吸附率、乳液粒径分布及热稳定性的影响。结果表明,当IPTS与Boltorn H 20中羟基的摩尔比为6/16时,固化后的WHPU膜的凝胶质量分数为92%,在玻璃表面的附着力达到0级;与不含有机硅烷偶联剂的WHPU相比,该涂膜的水接触角和热稳定性分别提高了34°和22℃,其吸水率从13.8%降低到4.3%。     

两步法合成防水透湿型水性聚氨酯的研究

预聚体制备中采用异氰酸酯两步投料法(两步法),通过在分子链的软段中引入亲水性的聚乙二醇合成了防水透湿型阴离子水性聚氨酯(WPU).研究了聚乙二醇的相对分子质量、第一阶段预聚合中nNCO/nOH比值、异氰酸酯的复配对WPU乳胶的粒径、胶膜的力学性能和涂层织物的防水透湿性的影响.结果表明,在总/nNCO/nOH=1.3,第一阶段预聚合nNCO/nOH=1.1,聚己内酯二元醇/聚乙二醇(PEG)为70/30(其中PEG包括PEG1000和PEG2000,质量分数分别为24%和6%),DMPA质量分数为6%,异氰酸酯IPDI/MDI质量比为50/50时,合成出的WPU涂层织物在38℃时的透湿量超过4000g/(m2·d),且耐静水压力达到4.3 kPa,具有良好的防水透湿性.     

PET-PEG共聚物及其纤维的制备及性能研究

通过共聚反应合成了含不同相对分子质量聚乙二醇(PEG)及其添加量的聚对苯二甲酸乙二醇酯(PET)-PEG嵌段共聚物,经熔融纺丝制备PET-PEG共聚酯纤维。利用核磁共振氢谱、差示扫描量热分析、X射线衍射(XRD)等手段对共聚酯的结构及其热性能进行了表征。结果表明:核磁共振氢谱证实了共聚酯为PET-PEG目标产物;随着PEG相对分子质量从800增加到6 000,PET-PEG共聚酯的熔融温度从243.97℃增加到253.55℃,冷却结晶温度从176.32℃增加到189.25℃,表面接触角从74.2°下降到62.3°,共聚酯纤维在标准环境下的回潮率从0.51%增加到0.68%;在PEG相对分子质量为2 000时,添加PEG相对对苯二甲酸(PTA)质量分数为0~20%时,共聚酯的熔融温度与冷却结晶温度随着PEG添加量的增加呈下降趋势,共聚酯纤维的回潮率呈指数增加;PEG添加量相对PTA质量分数为20%时,共聚酯可纺性较差;XRD表明PEG在结晶过程中并不进入PET晶格中,为了保证共聚酯的良好吸湿性能和力学性能,PET-PEG的共聚合反应时,PEG适宜的相对分子质量为2 000,添加量相对PTA的质量分数为10%。     

聚氨酯弹性体的动态力学性能的影响因素

综述了聚氨酯弹性体动态力学性能的多种影响因素,讨论了软段类型(聚酯和聚醚)、软段相对分子质量、硬段类型(二异氰酸酯和扩链剂)、硬软段质量分数对PU弹性体动态力学性能的影响。在PU弹性体中,聚酯软段比聚醚软段的Tg高,弹性模量依PPG、PEG、PTMG软段顺序增加。     

超滤深度提纯银杏黄酮

利用截留相对分子质量(MWCO)为10000的磺化聚醚砜(SPES)平板超滤膜对银杏黄酮提取物(GBE)粗原料产品进一步纯化分离,从w(银杏黄酮)=21 3%的粗原料中得到w(银杏黄酮)=39 2%的高纯GBE产品。实验测定了不同温度和压力下的超滤效果,结果表明:温度从30℃上升到40℃,透过通量从7 5L/(m2·h)上升到11 2L/(m2·h);压力从0 15MPa上升到0 25MPa,透过通量从6 1L/(m2·h)上升到10 0L/(m2·h),但是温度、压力的变化对选择性影响不大。     

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。     

PEG对生物可降解聚氨酯性能影响的研究

以不同相对分子质量的聚乙二醇(PEG)为引发剂,通过开环聚合引发丙交酯和己内酯单体合成聚己内酯–丙交酯–聚乙二醇(PCLA–PEG)的共聚物;用六亚甲基二异氰酸酯(HDI)对合成的共聚物进行封端,并进行扩链反应制备一系列PEG含量不同的生物可降解聚氨酯。通过红外以及DSC研究了PEG含量对聚氨酯材料结构的影响,发现采用相对分子质量较高的PEG制备的材料,其软硬段相分离程度较高;另外对样品的力学性能、亲水性及降解性进行了测试,发现PEG含量增加,样品的力学性能下降,亲水性能提高,降解速度加快。     

Structural characterization and mass transfer properties of segmented polyurethane: influence of block length of hydrophilic segments

An attempt has been made to investigate the effect of the block length of hydrophilic segments on the structure and mass transfer properties of segmented polyurethane (HSPU). Three different block lengths of hydrophilic poly(ethylene glycol) (PEG) segments were used, namely PEG‐200, PEG‐2000 and PEG‐3400, where the numbers indicate the molecular weight of the PEG in g mol^?1. The HSPU were characterized using Fourier‐transform infrared (FTIR) spectroscopy, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and tensile testing. Mass transfer properties were measured by sorption and water vapour flux (WVF) measurements. The control sample polyurethanes without PEG and a sample with PEG‐200 showed amorphous structure and an unclear phase separation as detected by WAXD, DSC and DMTA. There is evidence that the introduction of PEG blocks into the polyurethane matrix aids soft‐segment crystallization. The percentage crystallinity of soft segments was the highest with PEG‐2000 and an increase of PEG block length to 3400 g mol^?1 resulted in a decrease in crystallinity. Mechanically, polyurethane without PEG is tough while percentage strain at maximum load increased with increasing block length of PEG. In addition, sorption and WVF increased linearly with increasing PEG block length and with temperature. The permeability of such HSPUs is a function of temperature and showed a good fit to an Arrhenius form. Copyright © 2005 Society of Chemical Industry     

Structural characterization and mass transfer properties of polyurethane block copolymer: influence of mixed soft segment block and crystal melting temperature

An attempt has been made to investigate the influence of mixed soft segment on structure and mass transfer properties of segmented polyurethane (SPU). For this purpose polyurethane block copolymer containing soft segment such as polycaprolactone glycol (number‐average molecular weight 3000, PCL 3000), PCL 3000–polypropylene glycol (number‐average molecular weight 3000, PPG 3000), PCL 3000–polytetramethylene glycol (number‐average molecular weight 2900, PTMG 2900), PPG 3000–PTMG 2900, were synthesized using a two‐step or three‐step synthesis process. All the SPUs were modified with the hydrophilic segment, i.e. diol‐terminated poly(ethylene oxide) (number‐average molecular weight 3400, PEG 3400). Fourier‐transform infrared, wide‐angle X‐ray diffraction, differential scanning calorimetry, and dynamic mechanical thermal analysis were used to characterize the polyurethanes. The mass transfer properties were measured by equilibrium sorption and water vapor permeability measurements. Mixed blocks loosen the inter‐chain interaction due to phase mixing which decreases the crystallization of the soft segment in the resulting SPU. The crystallinity of mixed polyol block SPU increases when both polyols are crystallizable in the pure state. Highest loss tan δ value was observed for the sample containing PTMG 2900–PPG 3000 mixed soft segment due to their flexible and phase mixed structure which increases the chain mobility; this sample performed best among all four SPUs in equilibrium water sorption as well as water vapor permeability owing to their loose and nearly amorphous structure. Soft segment crystal melting further enhances the water vapor permeability significantly, which would make the membrane suitable for breathable textiles, packaging and medical applications. Copyright © 2006 Society of Chemical Industry     

Structure–property relationships of poly(urethane‐urea)s with ultralow monol content poly(propylene glycol) soft segments. III. influence of mixed soft segments of ultralow monol poly(propylene glycol), poly(tetramethylene ether glycol), and tri(propylene glycol)

Recent advances in the catalyst technology associated with the production of poly(propylene glycol) (PPG) have allowed for the fabrication of ultralow monol content PPG macrodiols (Acclaim? polyols), which are highly bifunctional and can be produced in substantially higher molecular weights and with narrower molecular weight distributions than previously possible. These factors have enabled the preparation of higher value elastomers and may allow for the first manufacture of economically attractive PPG‐based poly(urethane‐urea) (PUU) fibers. In the past, many performance polyurethane and PUU elastomers used poly(tetramethylene ether glycol) (PTMEG) for the soft segments either alone or in combination with other macrodiols. The work presented here details the investigation of the morphological features of PUU systems with mixed soft segments of PPG, PTMEG, and a low molecular analog of PPG, tri(propylene glycol) (TPG) in an effort to ascertain the influence of structural features on the mechanical and thermal properties of the elastomers. Also of interest was whether the incorporation of PPG and TPG would either prohibit or greatly hinder the formation of strain‐induced PTMEG crystallites. It was found that, even when only 60 wt % of the soft segments consisted of PTMEG, those soft segments were still able to undergo recognizable strain‐induced crystallization as detected by wide‐angle X‐ray scattering. It was also seen that, as the ratio of PPG to PTMEG was varied, there were systematic changes in the soft segment glass transition and cold crystallization characteristics. Inclusion of PPG and TPG resulted in PTMEG's diminished ability to undergo cold and strain‐induced crystallization, as seen with differential scanning calorimetry and wide‐angle X‐ray scattering. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3520–3529, 2003     

聚乙烯醇/聚乙二醇复合材料的热塑加工性能

通过热塑加工方法制备了增塑改性聚乙烯醇(mPVA)/聚乙二醇(PEG)复合材料,研究了PEG相对分子质量和含量对mPVA/PEG复合材料热性能、热塑加工性能,转矩流变性能和力学性能的影响.结果表明:加入适量PEG可降低mPVA的熔点,表明PEG对mPVA有一定的增塑作用;随着PEG用量的增加,mPVA的熔体流动速率增大...     

Synthesis and hydrophilicity of poly(butylene 2,6‐naphthalate)/poly(ethylene glycol) copolymers

Poly(butylene 2,6‐naphthalate) (PBN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two‐step melt copolymerization process of dimethyl‐2,6‐naphthalenedicarboxylate (2,6‐NDC) with 1,4‐butanediol (BD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structures, thermal properties, and hydrophilicities of these copolymers were studied by ¹H NMR, DSC, TGA, and by contact angle and moisture content measurements. In particular, the intrinsic viscosities of PBN/PEG copolymers increased with increasing PEG molecular weights, but the melting temperatures (T_m)_, the cold crystallization temperatures (T_cc)_, and the heat of fusion (ΔH_f) values of PBN/PEG copolymers decreased on increasing PEG contents or molecular weights. The thermal stabilities of the copolymers were unaffected by PEG content or molecular weight. Hydrophilicities as determined by contact angle and moisture content measurements were found to be significantly increased on increasing PEG contents and molecular weights. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2677–2683, 2006     

PEG/PCL基复合软段降解型PUF力学与动态力学特性研究

采用一步法制备了聚乙二醇/聚己内酯（PEG/PCL）复合软段聚氨酯泡沫塑料（PUF）,研究了PEG/PCL复合软段配比、软段相对分子质量等对PUF力学性能和动态力学性能的影响。结果表明,无论是采用相对分子质量为400还是相对分子质量为1000的PEG与PCL-210N复合,随软段中PCL含量的增大,材料的拉伸强度、断裂伸长率、定应变应力均提高;随着PEG相对分子质量的增大,材料的断裂伸长率提高,拉伸强度、定应变应力降低;玻璃化转变温度（Tg）顺序为Tg（PEG400）> Tg（PCL210N）> Tg（PEG1000）。     

Acrylonitrile-based copolymer membranes containing reactive groups: effects of surface-immobilized poly(ethylene glycol)s on anti-fouling properties and blood compatibility

The anti-fouling properties and blood compatibility of poly(acrylonitrile-co-maleic acid) (PANCMA) membranes were improved by the immobilization of poly(ethylene glycol)s (PEG) on membrane surface. It was found that the reactive carboxyl groups on PANCMA membrane surface could be conveniently conversed into anhydride groups and then esterified with PEG. Chemical and morphological changes as well as biocompatibility on membrane surface were analyzed by Fourier transform infrared spectroscopy, elemental analysis, scanning electron microscopy, water contact angle, protein adsorption, and platelet adhesion. Results revealed that, with the immobilization of PEG, the hydrophilicity and blood compatibility of the acrylonitrile-based copolymer membranes were improved obviously. The molecular weight of PEG had an obvious influence on the properties of the PEG-immobilized membranes. Permeation behaviors for the studied membranes were investigated by water and bovine serum albumin (BSA) filtration experiments. Compared with the original PANCMA membrane, the membrane immobilized with PEG 400 (M_w=400 g/mol) showed a three-fold increase in a BSA solution flux, a 40.4% reduction in total fouling, and a 57.9% decrease in BSA adsorption.     

PCL及PCL-PEG-PCL共聚物的合成与表征

以辛酸亚锡[Sn(Oct)2]作为引发剂,采用ε-己内酯(ε-CL)开环均聚合制备聚ε-己内酯(PCL),考察了n(ε-CL)/n[Sn(Oct)2]、反应温度和反应时间等因素对聚合产物特性黏数的影响。以Sn(Oct)2为催化剂,聚乙二醇(PEG)为引发剂,合成了不同相对分子质量的PCL-PEG-PCL三嵌段共聚物,研究了ε-CL均聚物及共聚物的结构、热性能和结晶形态。PCL最佳合成工艺为:n(ε-CL)/n[Sn(Oct)2]为400,温度130℃,反应时间4 h。随着PEG相对分子质量从2×103增加到8×103,三嵌段共聚物的熔融温度、熔融焓和结晶温度逐渐升高;结晶温度及PEG相对分子质量对PCL-PEG-PCL三嵌段共聚物球晶的形态和尺寸影响很大。     

氯化聚丙烯接枝聚乙二醇的合成与性能

以用等规聚丙烯改性氯化制得的氯化聚丙烯（MCPP）与聚乙二醇（PEG）为原料,在金属钠作用下,合成了以MCPP为主链、PEG为支链的梳形结构的两亲性高聚物。用傅里叶变换红外光谱、核磁共振氢谱和核磁共振碳谱表征了高聚物的结构,并测试了MCPP接枝前后的吸水性和水在其表面的接触角。结果表明,两亲性高聚物的吸水性能随着PEG含量的增加而增强,水在其表面的接触解随着PEG含量的增加而减少。