PTMG/PPG基CPU的相分离及力学性能研究

分别以聚四氢呋喃二醇(PTMG)、聚氧化丙烯二醇(PPG)及两者共混物(PTMG/PPG)作为软段,以2,4-甲苯二异氰酸酯(TDI)和扩链剂3,3'-二氯-4,4'-二氨基二苯甲烷(MOCA)作为硬段,采用预聚体法,制备了5种不同PTMG/PPG配比的浇注型聚氨酯弹性体(CPU)。研究了PTMG/PPG不同的配比对CPU的力学性能和微观相分离的影响。结果表明,纯PTMG型聚氨酯力学性能优于纯PPG型聚氨酯性能,随着PPG在混合聚醚多元醇的比例增加,所形成的CPU的力学性能出现一定程度的下降。纯PTMG型聚氨酯的玻璃化转变温度(Tg)低于纯PPG型聚氨酯的Tg,随着PPG在混合聚醚中的配比增加,所合成相应的聚氨酯弹性体的Tg移向高温区,微观相分离程度减小。     

低模量聚醚型PU弹性体力学性能的研究

研究了由聚醚二醇(PPG、PTMG)、80/20-TDI和扩链剂制备的PU弹性体,并讨论了聚醚软段,聚醚分子量,弹性体交联点分子量和硬段浓度对弹性体力学性能的影响.     

PTMG中冠醚分析方法的研究

将聚四氢呋喃二醇(PTMG)进行萃取处理,通过超高效液相色谱串联高分辨质谱仪对其中冠醚类物质分离定性;进一步利用液相-蒸发光散射检测器对其进行定量;最后系统研究冠醚类物质对于氨纶应用的影响。研究表明:PTMG中冠醚类物质为四氢呋喃的3-9聚体,含量为246.2 mg/kg;该物质不参与氨纶聚合反应,对预聚体的-NCO基团含量无影响,但会导致纺丝原液黏度上升。PTMG中冠醚类物质的分析及应用研究,为氨纶工业稳定生产提供了理论依据和数据支持。     

基于四氢呋喃聚醚聚氨酯弹性体力学性能的研究

以四氢呋喃聚醚（PTMG）、二异氰酸酯（TDI、或MDI）和扩链剂（MOCA、或BDO）为原料,制备了浇注型和热塑型聚氨酯弹性体。研究了预聚体的NCO基质量份、PTMG的分子量和硬段质量份数对PU弹性体力学性能的影响。结果表明：PU弹性体的硬度和模量随NCO含量和硬段质量份数增加而增加。逐渐提高PTMG的分子量,PU弹性 的拉伸强度降低,而拉断伸长率增加。2000分子量的PTMG－PU弹性体的冲击弹性比1000分子量的PTMG－PU好。     

聚醚型水性聚氨酯的制备与性能

分别用生物基聚1,3-丙二醇(PO3G)、聚四氢呋喃二醇(PTMG)和聚氧化丙烯二醇(PPG)制备了3种不同的水性聚氨酯(WPU)分散液。采用红外分析、差热分析和原子力显微镜等研究了聚醚结构对WPU分散液的形态与性能的影响。结果表明,用PO3G制备的WPU的黏度最低;PO3G制备的WPU膜的玻璃化转变温度(Tg)、拉伸强度和吸水率介于PTMG和PPG制备的WPU膜之间。     

PPG/PTHF对MC尼龙结晶行为的影响

采用DSC、SEM、解偏振光法研究了共聚醚对MC尼龙结晶行为的影响,发现PPG/PTHF-PA共聚物是一个半相容体系,不同分子量的共聚醚与MC尼龙的相容性不同,随着共聚醚分子量、含量的增加,相容性、结晶度呈现先上升而后下降峰形变化,球晶变小,结晶也不完善.共聚醚在MC尼龙结晶过程中起异相成核作用.研究发现,PPG/PTHF部分向尼龙部分渗透,在尼龙保持完整球晶同时,PPG/PTHF能均匀分散在PA基体中,此时共聚物具有优良的力学性能.     

中国氨纶行业的现状与对策

介绍了中国氨纶的发展,指出目前中国氨纶产能已超过全球的1/3,处于供大于求的局面。就目前氨纶行业所面临的价格、原料、利润、技术、人才等问题作了阐述。认为中国氨纶生产企业应发展规模化,走可持续发展道路,不断提高工艺技术及管理水平,积极开展后道应用研究,同时应加强行业自律、规范市场,并积极开拓国内外市场,这样才能在激烈的市场竞争中立于不败之地。     

2005年4月PU原料市场分析

进入4月份，起初国内行情随着3月份的惯性继续上扬，但是到了下半个月之后行情上升就受到了阻力。氨纶行业持续低迷，由化纤协会牵头行业内自发要求“限产保价”，PTMEG需求也随之下降。加之，零散交易市场也不理想，在月底的时候行情有小幅的下跌。月底，2000分子量进口产品的人民价格在29800—30100元／吨之间，1000分子量产品在31500—33500元／吨。氨纶厂家采购进口产品价格平均在2950—3080美元／吨之间，总体变化不大，但是部分厂家采购价格有所降低。     

聚醚软段对HMDI基透明聚氨酯弹性体性能的影响

以环己基甲烷二异氰酸酯(HMDI)、聚氧化乙烯二醇(PEG)、聚氧化丙烯二醇(PPG)和聚四氢呋喃醚二醇(PTMG)为主要原料,采用预聚法合成了一系列透明聚氨酯(PU)弹性体。通过红外光谱、热重分析、动态机械性能、拉伸性能和光学性能测试等方法讨论了不同聚醚多元醇组分对所合成的透明PU弹性体的热性能、结晶性能和机械性能的影响。结果表明,相同条件下,PTMG基PU薄膜的热稳定性、软硬段相容性以及力学强度要明显优于PPG基和PEG基PU薄膜;由于软段结晶能力的不同,PPG、PTMG基PU薄膜的透光度和雾度均明显好于PEG基薄膜。     

卡基材料用水性聚氨酯覆膜胶的合成及应用

以异佛尔酮二异氰酸酯(IPDI)、聚己二酸丁二醇酯(PBA)、聚氧化丙烯二醇(PPG)、聚四氢呋喃二醇(PTMG)、二羟甲基丁酸(DMBA)和甲基丙烯酸-β-羟乙酯(HEMA)等为主要原料,合成了卡基材料用阴离子型WPU(水性聚氨酯)覆膜胶。研究结果表明:采用单因素试验法优选出制备WPU覆膜胶的最优配方是初始R=n(-NCO)/n(-OH)=4、m(PPG):m(PTMG):m(PBA)=10:20:70、w(DMBA)=5.5%和w(HEMA)=4.5%(相对于预聚体用原料总质量而言),此时活泼的-NCO基已被封闭,羟基丙烯酸酯已成功引入到WPU大分子链中;与普通WPU覆膜胶相比,由最优配方制成的WPU覆膜胶的固含量(41%)较高、剥离强度较大且稳定性较佳,将其应用于卡基材料中,可得到高剥离强度和高耐湿热老化性能的覆膜色卡。     

小形变下聚氨酯/聚氨基甲酸酯纤维复合材料的增强和阻尼性

利用聚氨基甲酸酯纤维织物、3,3′-二氯-4,4′-二氨基二苯基甲烷(MOCA)分别与聚丙二醇(PPG)型预聚体和聚四氢呋喃醚二醇(PTMG)型预聚体经浇注一体成型制备聚氨酯/聚氨基甲酸酯纤维复合材料,研究了聚氨基甲酸酯纤维织物对聚氨酯基体小形变下的抗张应力和阻尼性能的影响。结果表明,聚氨基甲酸酯纤维织物对聚氨酯基体小形变下的抗张应力和阻尼性能均具有明显的增强作用;与各自基体相比,PPG型和PTMG型复合材料的弹性模量分别提高了16.33 %和11.39 %,其 100 %定伸应力分别提高了55.81 %和46.51 %;而且二者的一次拉伸回复滞后率分别高达55.10 %和62.83 %,较各自基体分别提高了26.12 %和14.03 %。     

软段分子量对氨纶的微相分离程度与拉伸性能的影响

分别采用分子量为1 400,1 800,2 200,2 600,3 000的不同聚四亚甲基醚二醇和4,4'–二苯基甲烷–二异氰酸酯反应,得到预聚体,用N,N–二甲基乙酰胺作为溶剂配制34.5%的预聚体溶液,后用乙二胺/丙二胺混合物扩链,制成纺丝原液。然后采用溶液干法纺丝得到5种氨纶样品,利用傅立叶变换红外光谱分析仪测试分析了上述样品的氢键化程度,再采用小角X射线系统和动态力学分析仪研究了软段分子量对氨纶的微相分离程度的影响,最后选择万能材料试验机测试其拉伸性能。结果表明:随着软段分子量增加,硬段含量减少,氨纶的氢键化程度、微相分离程度和断裂强力均为先增大后减小,在分子量为2 200时达到最大值;同时,断裂伸长率先减小后增大,在分子量为2 200时为最小值。     

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     

Comparison of properties of thermoplastic polyurethane elastomers with two different soft segments

Two series of thermoplastic polyurethane elastomers [poly(propylene glycol) (PPG) based PP samples and poly(oxytetramethylene)glycol (PTMG) based PT samples] were synthesized from isophorone diisocyanate (IPDI)/1,4-butanediol (BD)/PPG and IPDI/BD/PTMG. The IPDI/BD based hard segments contents of polyurethane prepared in this study were 40–73 wt %. These polyurethane elastomers had a constant soft segment molecular weight (average M_n, 2000) but a variable hard segment block length (n, 3.5–17.5; average M_n, 1318–5544). Studies were made on the effects of the hard segment content on the dynamic mechanical thermal properties and elastic behaviors of polyurethane elastomers. These properties of PPG based PP and PTMG based PT samples were compared. As the hard segment contents of PP and PT samples increased, dynamic tensile modulus and α-type glass transition temperature (T_g) increased; however, the β-type T_g decreased. The permanent set (%) increased with increasing hard segment content and successive maximum elongation. The permanent set of the PT sample was lower than that of the PP sample at the same hard segment content. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1349–1355, 1998     

聚合工艺对低不饱和度高相对分子质量聚醚性能的影响

采用双金属氰化络合物催化剂（DMC）合成了低不饱和度高相对分子质量聚醚（DL-4000D）,讨论了聚合温度、聚合压力、低聚物脱水时间等聚合工艺条件对DL-4000D及其制品性能的影响。结果表明,聚合温度在115~125℃、低聚物脱水时间在2 h左右,聚合压力小于100 kPa等工艺条件下,制备的聚醚不饱和度低,相对分子质量分布窄,由其制得的聚氨酯制品的综合性能好。     

聚醚对环氧-聚氨酯互穿网络制备的影响

研究了聚丙二醇醚（PPG）、聚四氢呋喃醚及二者的共聚醚分别形成的聚氨酯预聚体与低分子羟基化合物和环氧树脂的反应性,应用聚氨酯对环氧进行了IPN改性,测试了其红外光谱和冲击强度.结果说明：聚四氢呋喃醚型聚氨酯的反应活性太大,不适宜用于环氧树脂的IPN改性 聚丙二醇醚及其与聚四氢呋喃的共聚醚型的聚氨酯反应活性适中,适合作为环氧IPN改性的聚氨酯组分.采用PPG型聚氨酯对环氧进行了IPN改性,改性后的环氧体系冲击强度大大提高.     

Preparation and properties of UV-curable polyurethane acrylate ionomers

Ultraviolet (UV)-curable polyurethane acrylate ionomer (PUAI) prepolymers were synthesized from isophorone diisocyanate (IPDI), poly(methylene ether) glycol (PTMG), 2,2-bis(hydroxymethyl) propionic acid (DMPA), triethylamine (TEA), 2-hydroxy ethyl acrylate (HEA), and dibutyl tin dilaurate (DBT) as a catalyst. UV-curable polyurethane acrylate ionomer aqueous dispersion was formulated from the prepolymers, water (30 wt %), and 1-hydroxycyclohexylhenyl ketone (Irgacure 184) as a photoinitiator. The films of UV-cured polyurethane acrylate ionomer were formed by curing the dispersion using a medium-pressure mercury lamp (80 W/cm; λ max = 365 nm). Gel content decreased with increasing water content in the aqueous dispersion. Effects of DMPA content and molecular weight of PTMG and the degree of neutralization on the physical properties were investigated. It was found that the storage modulus increased with increasing DMPA content. Tensile modulus and strength decreased with increasing the molecular weight of PTMG from 650 to 2000. The glass transition temperature shifted to a higher temperature as the content of DMPA increased. As the degree of neutralization increased, the tensile strength and modulus decreased. However, the elongation at break increased. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2153–2162, 1998     

喷涂聚脲弹性体耐水性能的研究

以不同种类多元醇与二苯基甲烷二异氰酸酯（MDI）和液化MDI合成预聚物作为A组分,端胺基聚醚、胺类扩链剂为R组份,制成喷涂聚脲弹性体。讨论了多元醇种类及其相对分子质量、A组分的NCO含量、扩链剂等对喷涂聚脲弹性体耐水性能的影响。结果表明,由二聚体聚酯二醇制得的喷涂聚脲弹性体耐水性能最好,其次是聚四氢呋喃多元醇,聚氧化丙烯醚二醇的耐水性最差;随着多元醇相对分子质量的增加,聚氧化丙烯醚二醇和聚四氢呋喃醚二醇的耐水性提高,而二聚体聚酯二醇的耐水性能变化不大;A组分的NCO含量增加,耐水性提高;不同扩链剂的耐水性有很大差异,依次为3,3’．二氯4,4’-二苯基甲烷二胺〉二乙基甲苯二胺〉3,5-二甲硫基甲苯二胺〉4,4’-双仲丁胺基二苯基甲烷。     

HTBN/PTMG双软段聚氨酯弹性体的制备及力学性能研究

以甲苯二异氰酸酯(TDI)、端羟基聚丁二烯-丙烯腈共聚物(HTBN)、聚四氢呋喃醚二醇(PTMG)为主要原料,3,5-二甲硫基甲苯二胺(DMTDA)为扩连剂,采用浇铸法制备了聚氨酯弹性体。研究了聚氨酯预聚体中NCO含量、HTBN/PTMG质量比、PTMG相对分子质量和改变扩链剂用量以及热处理时间对聚氨酯弹性体力学性能的影响。结果表明,低相对分子质量PTMG和高热处理温度有利于提高聚氨酯弹性体的力学性能,当聚氨酯预聚体中HTBN/PTMG的质量比为50∶50、NCO质量分数为5.98%、NCO/NH2摩尔比为1.20、115℃下热处理2 h时,聚氨酯弹性体的力学性能最佳。     

E-300扩链聚氨酯弹性体的力学性能研究

以多元醇(PEA，PPG，PTMG)，PDI，E-300为原料，制备了PU弹性体。研究了多元醇类型，NCO基含量，扩链剂用量和硫化时间等因素对PU弹性体力学性能的影响。结果表明：拉伸强度、拉断伸长率和冲击弹性最高的分别是PEA-PU，PPG-PU和PTMG-PU；PU的硬度、强度和模量随预聚体NCO基含量增加而增加；扩链剂的用量为90％时，PU的力学性能最佳。