聚酯型聚氨酯乳液的合成及性能

以异佛尔酮二异氰酸酯（ IPDI）、六亚甲基二异氰酸酯（HDI）和聚己二酸 1,4-丁二醇酯二醇（ PBA）为主要原料制备系列水性聚氨酯乳液（ WPU）。采用红外光谱仪、差式扫描量热仪、 X-射线衍射仪、电子拉力机等对 WPU进行结构表征;为了从聚集状态上对聚氨酯结晶性有更深层次的探究,对 WPU进行了定伸情况下的测试。结果显示：随着硬段含量的增加,硬段 -软段间的氢键相互作用减小,微相分离程度增加,结晶性能降低;随着伸长率的增加,氢键相互作用和结晶性能都表现出先减小后增大的趋势。当硬段含量为 14. 73%时,聚氨酯胶膜拉伸强度达到 40. 11 MPa,剥离强度为 93. 7 N/（25 mm）。     

水性聚氨酯的结晶动力学参数及其在鞋用胶黏剂的应用

以聚己二酸1,4-丁二醇酯（PBA）、六亚甲基二异氰酸酯（HDI）和异佛尔酮二异氰酸酯（IPDI）为主要原料,制备了不同软段分子量和不同硬段含量的水性聚氨酯（WPU）乳液。采用DSC技术表征了WPU胶膜在非等温和等温条件下的结晶行为,并以莫志深方程和Avrami方程为模型,对WPU胶膜的结晶行为进行了研究。WPU胶膜的非等温结晶动力学分析结果表明,随着WPU相对结晶度的增加,非等温结晶动力学参数F（T）增大,说明适当提高活化温度可提高WPU胶黏剂的结晶速率和初黏强度;WPU胶膜的等温动力学分析结果表明,不同软段分子量和不同硬段含量的WPU胶膜的等温结晶动力学参数t_1/2与相应WPU胶黏剂的开放时间存在对应关系,即t_1/2较大者,相应WPU胶黏剂的开放时间较长。     

硬段对PCDL型水性聚氨酯的结构与性能的影响

以聚碳酸酯二元醇(PCDL)为软段,分别以异氟尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚基二异氰酸酯(HDI)为硬段,采用丙酮法制备了四种不同硬段组成的PCDL型水性聚氨酯(WPU).综合对比,研究了硬段类型对PCDL型WPU结构与性能的影响.结果表明,芳香族WPU的力学...     

Structure‐property relationship of L‐tyrosine‐based polyurethanes for biomaterial applications

The structure‐property relationship of L ‐tyrosine‐based polyurethanes was demonstrated by using different polyols and diisocyanates. L ‐tyrosine‐based chain extender, desaminotyrosyl tyrosine hexyl ester (DTH), was used to synthesize a series of polyurethanes. Polyethylene glycol (PEG) or poly caprolactone diol (PCL) was used as the soft segment and hexamethylene diisocyanate (HDI) or dicyclohexylmethane 4,4′‐diisocyanate (HMDI) was used with DTH as the hard segment. The polyurethanes were characterized to investigate the effect of structure on different polyurethane properties. From FTIR and DSC, these polyurethanes exhibit a wide range of morphology from phase‐mixed to phase‐separated structure. The decreasing molecular weight of the PEG soft segment leads to relatively more phase mixed morphology whereas for PCL‐based polyurethanes the extent of phase mixing is less with decreasing PCL molecular weight. Results show that PCL‐based polyurethanes are mechanically stronger than PEG‐based polyurethanes but PCL‐based polyurethanes degrade slower and absorb less water compared with PEG‐based polyurethanes. The HMDI‐based polyurethanes are less crystalline and comparatively more hydrophobic than HDI‐based polyurethanes. The characterization results show that the polyurethane properties are directly related to the structure and can be varied easily for a different set of properties that are pertinent for biomaterial applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

环氧大豆油和硅氧烷改性水性聚氨酯胶黏剂

以环氧大豆油(ESO)与3-氨基丙基三乙氧基硅烷(KH550)双重交联改性水性聚氨酯(WPU).通过FTIR、TG、DSC、DMA、AFM、粒径分析仪、拉力试验机等仪器对改性的水性聚氨酯进行了表征.研究了ESO和KH550的含量对水性聚氨酯乳液、胶膜以及胶黏剂性能的影响.分析了KH550对水性聚氨酯结晶性能和微相分离的影响.研究发现,随着ESO与KH550的加入,水性聚氨酯乳液的性能得到改善,胶膜的吸水率先减小后增大,拉伸强度逐渐增大,断裂伸张率逐渐减小.水性聚氨酯胶黏剂对PVC的T-剥离强度先增大后减小.随着KH550含量的增加,热稳定性逐步改善,结晶性降低,软段与硬段相混合程度提高.当ESO为4%、KH550为2%(均为质量分数)时,水性聚氨酯胶黏剂的综合性能最好.     

磺酸盐型水性聚氨酯胶粘剂的研究

以聚己二酸-1,4-丁二醇酯(PBA)和聚丙二醇醚(PPG)为软段、N-(2-氨乙基)-2-氨基乙磺酸钠(AAS-Na)为亲水基团、六亚甲基二异氰酸酯(HDI)和异佛尔酮二异氰酸酯(IPDI)为硬段,采用丙酮法合成了磺酸盐型水性聚氨酯(WPU)分散体(PUDs),并以此作为WPU胶粘剂的基体树脂。结果表明:不同配方的PUDs乳液均具有较低的黏度(1 000 mPa.s)、较小的粒径(200 nm)、较高的固含量(≥50%)和较好的储存稳定性(180 d无沉淀),不同配方的PUDs胶膜均具有良好的耐热性(250℃以下无降解)和耐水性(吸水率4%);当w(PPG)=4%、n(HDI)∶n(IPDI)=9∶1时,PUDs胶粘剂的成品剥离强度达到最大值(13.52 N/mm),此时初期剥离强度也相对较高(2.11 N/mm)。     

Structure-property behavior of segmented polyurethaneurea copolymers based on an ethylene-butylene soft segment

Novel segmented polyurethaneurea copolymers were synthesized using a poly(ethylene-butylene) glycol based soft segment and either hydrogenated diphenyl methane diisocyanate (HMDI) or hexamethylene diisocyanate (HDI) in addition to either ethylene diamine (EDA) or 2-methyl-1,5-diaminopentane (DY) as the chain extender. Dynamic mechanical analysis (DMA), small angle X-ray scattering (SAXS) and in some cases atomic force microscopy (AFM) established the presence of a microphase-separated structure in which hard microdomains are dispersed throughout a soft segment matrix. Wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) imply that the materials are amorphous. Samples that are made with HMDI/DY and have hard segment contents in the range of 16-23 wt% surprisingly exhibit near-linear mechanical deformation behavior in excess of 600% elongation. They also show very high levels of recoverability even though their hysteresis is also considerable. The materials have all proven to be melt processable in addition to solution processable.     

HDI/IPDI对水性聚氨酯及胶膜性能的影响

采用预聚体分散法制备了一系列固含量为50%的水性聚氨酯(WPU),并通过傅里叶红外光谱(FT-IR)、粒径分析仪、X射线衍射(XRD)、差示扫描量热分析(DSC)、拉力试验机等仪器进行表征,研究了HDI/IPDI摩尔比对WPU的乳液性能和胶膜结晶性能、力学性能、耐水性能,以及基材EVA/PVC粘接性能的影响,分析了不同摩尔比的HDI/IPDI和粘接时间与WPU胶黏剂对EVA/PVC粘接性能的关系。研究发现,随着HDI/IPDI摩尔比增加,水性聚氨酯的乳液性能、软硬段的结晶性都得到提高,而胶膜拉伸强度呈先增大后减小的趋势,断裂伸长率则先减小后增大。所有WPU胶膜都有很好耐水性,胶膜吸水率都在5.0%（质量）以下。粘接实验结果表明,WPU胶黏剂对EVA/PVC具有优异的粘接性能,24 h后可对基材产生界面破坏,随着HDI/IPDI摩尔比增加,胶黏剂的粘接强度增大。当HDI/IPDI=7∶1时,水性聚氨酯的综合性能最好。     

AAS/DMPA对水性聚氨酯胶膜结晶性能的影响

以聚己二酸1,4-丁二醇酯(PBA)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)为主要原料,以混合的乙二胺基乙磺酸钠(AAS)和二羟甲基丙酸(DMPA)为亲水性扩链剂,通过丙酮法合成了固含量为50%的磺酸/羧酸盐型水性聚氨酯(WPU)乳液。采用DSC、XRD、透光率等测试技术表征了AAS/DMPA摩尔比对WPU胶膜结晶性的影响,并从吸水率和热失重两个方面分析了结晶性对胶膜耐水性和耐热性的影响。研究结果表明,随着AAS/DMPA摩尔比的增大,WPU胶膜的结晶性提高,胶膜的耐水性和耐热性在一定程度上得到了改善。     

软硬段比对磺酸盐型水性聚氨酯性能的影响

以聚己二酸乙二醇酯二醇(PBA)、异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)为主要原料,以乙二胺基乙磺酸钠为亲水性扩链剂,合成了固含量为50%的磺酸盐型水性聚氨酯(WPU)乳液。考察了软硬段比对乳液黏度、粒径及其分布、聚合物重均相对分子质量(Mw)、胶膜结晶性以及力学性能等影响。结果表明:当软硬段比值为2.96时,可以制得固含量为50%的磺酸盐型WPU乳液,其平均粒径为146.0 nm、黏度为143 mPa.s,聚合物Mw为128 488,结晶熔融温度为50℃,结晶性相对最好;此时WPU胶膜的拉伸强度(31.6 MPa)和断裂伸长率(1 702%)相对较大;WPU胶粘剂的初始剥离强度(118.6 N/cm)和最终剥离强度(156.3 N/cm)相对最高。     

高固含量聚醚型水性聚氨酯的合成与影响因素

以异佛尔酮二异氰酸酯(IPDI)和六次甲基二异氰酸酯(HDI)为硬段、聚醚(N-220)为软段,二羟甲基丙酸(DMPA)为亲水性物质、乙二胺为后扩链剂和三羟甲基丙烷(TMP)为交联剂等,合成了高固含量的聚醚型水性聚氨酯(WPU)乳液。采用衰减全反射红外光谱(ATR)对其结构进行了表征,并探讨了溶剂(丙酮)和DMPA含量、反应过程中预聚体的黏稠度、扩链剂的加料顺序和扩链时间等因素对WPU乳液固含量的影响。实验结果表明,在保持其他条件不变的情况下,即n(-NCO)∶n(-OH)=1.2∶1、m(HDI)∶m(IPDI)=2∶1和n(TMP中-OH)∶n(聚醚中-OH)=1∶4、w(DMPA)=1.5%(相对于树脂而言)且w(丙酮)=50.4%～75.5%(相对于树脂而言)时,在预聚反应过程中,若体系较稀(即黏度较低),在乳化时先加入乙二胺,待反应4～7min后再加入水,如此易制得稳定的高固含量(40%～46%)聚醚型WPU乳液。     

Influence of preparation method on adhesion and drying performances of polyurethane dispersion

Waterborne polyurethane (WPU) dispersions with a high solid content were prepared by one-step and two-step methods with polyester and polyether type macromolecular diols as the main raw materials. The effects of two synthesis methods on the properties of WPU of polyester and polyether were studied. Fourier transform infrared spectroscopy, particle size and distribution, and Thermogravimetric analysis (TGA) measurements were utilized to characterize the structure. The dryness test results showed that the WPU synthesized with polyester diol as the soft segment by the two-step method had the best drying. In addition, the microstructure of WPU was characterized by transmission electron microscopy, which confirmed that WPU was mainly spherical structure. TGA and scanning electron microscopy results showed that the microphase separation between the soft and hard segments of WPU prepared by the two-step method was weaker, the hydrogen bonding was stronger, the adhesion, and thermal stability of WPU was improved.     

Synthesis of a silicone containing allylic monomer and its uses in the waterborne polyurethane/vinyl acetate–acrylic hybrid emulsion copolymers

A new silicone containing allylic monomer, allyl 3-(triethoxysilyl) propyl carbamate (ATESPC), based on (3-isocyanatopropyl) triethoxysilane (ICPTES) and allyl alcohol (AAL) has been synthesized for formulation of waterborne polyurethane (WPU). Then a series of new siliconized WPU, vinyl acetate (VAc)/2-ethylhexylacrylate (2-EHA) and ATESPC hybrid latexes P(VAc-2-EHA)/PU/Si have been successfully synthesized by the emulsion copolymerization in the presence of a WPU dispersion by using potassium persulfate (KPS) as an initiator. The WPU dispersion has been synthesized by a polyaddition reaction of hexamethylene diisocyanate (HMDI), on polypropylene glycol (PPG-1000) and dimethylol propionic acid (DMPA) as chain extender. The NCO chain ends being reacted with water (which act as a further chain extender producing some urea bonds). Films were obtained for different hybrid latexes of various compositions. The resulted monomer characterized by Fourier transformer infrared spectroscopy (FTIR), proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes, respectively. The copolymers also were characterized by using Fourier transform infrared spectroscopy (FT-IR). Thermal properties of the copolymers were studied by using thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). The morphology of copolymers was investigated by scanning electron microscopy (SEM) and then the effects of silicone concentrations on the water absorption ratio, was examined.     

硬段含量对水性聚氨酯软段结晶性能的影响

以异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、聚己二酸丁二醇酯为主要原料合成了水性聚氨酯(WPU),通过FT-IR、DSC、XRD、SEM表征手段,研究了硬段含量对软段结晶性及WPU粘结性能的影响。研究表明,随着硬段含量的增加,WPU分子链上氨基甲酸酯键之间的氢键化程度提高,软硬两相相混严重,WPU软段结晶熔融焓变小,熔融温度变低;结晶衍射峰变弱,软段结晶性变差;粘结性能测试表明,在硬段含量较低时,聚氨酯体现出良好的结晶性能,初粘性较好。     

Characterization of thermoplastic polyurethane adhesives with different hard/soft segment ratios containing rosin as an internal tackifier

Three thermoplastic polyurethanes (TPUs) containing different hard/soft (h/s) segment ratios (1.05-1.4) were prepared using the prepolymer method. MDI (diphenylmethane-4,4′diisocyanate) and polyadipate of 1,4-butanediol (M _w = 2440) were allowed to react to produce the prepolymer. To provide the polyurethanes with high immediate adhesion to different substrates, a rosin + 1,4-butanediol mixture (1 : 1 equivalent%) was used as chain extender (TPU-Rs). These TPU-Rs had two types of hard segments: (i) Urethane hard segments, produced by reaction of the isocyanate and the 1,4-butanediol, and (ii) Urethan-amide hard segments, produced by reaction of the isocyanate and the carboxylic acid functionality of the rosin. The TPUs and TPU-Rs were characterized using FTIR spectroscopy, gel permeation chromatography, differential scanning calorimetry, stress-controlled plate-plate rheology, stress-strain measurements, and Brookfield viscosity. The TPUs and TPU-Rs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC joints. The addition of rosin as an internal tackifier increased the average molecular weight, more markedly in the TPU-Rs containing higher hard/soft segment ratios, but the elastic and viscous moduli decreased. An increase in the hard/soft segment ratio of the TPU-Rs retarded the kinetics of crystallization (which was determined by the soft segment content in the polyurethane), and increased the immediate T-peel strength in PVC/polyurethane adhesive/PVC joints (which was determined by the urethan-amide hard segments). Furthermore, addition of rosin to the polyurethanes decreased the final adhesion, although always reasonably high peel strength values were obtained.     

高固含量双组分混合聚酯型水性聚氨酯的合成

以异佛尔酮二异氰酸酯(IPDI)为硬段、混合双组分聚酯二元醇和1,4-丁二醇(BDO)为软段、二羟甲基丙酸(DMPA)为亲水扩链剂、三乙胺(TEA)为中和剂和乙二胺(EDA)为后扩链剂等,采用预聚体分散法合成了系列高固含量的水性聚氨酯(WPU)乳液。以固含量、黏度和吸水率等为衡量指标,比较了不同聚酯二元醇的混合效果。结果表明:当混合聚酯中n(PBA或PCDL)∶n(PEBA或PCDL)=1∶1、w(DMPA)≈3.4%(相对于预聚体而言)、n(-NCO)∶n(-OH)=1.03∶1和中和度为96%时,由PBA2000/PCDL2000混合聚酯二元醇制取的WPU乳液,其固含量较高(48.70%)、黏度最低(542 mPa.s)且综合性能相对较好。     

Microphase-separated structure and mechanical properties of norbornane diisocyanate-based polyurethanes

Norbornane diisocyanate (NBDI: 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane) is a new commercialized diisocyanate. NBDI-based polyurethane elastomers (PUEs) were prepared from poly(oxytetramethylene) glycol (PTMG), NBDI and 1,4-butanediol (BD) by a prepolymer method. Microphase-separated structure and mechanical properties of the NBDI-based PUEs were compared with general aliphatic and cycloaliphatic diisocyanate-based PUEs. The diisocyanates used were isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI). Regular polyurethanes were also prepared as hard segment models from each isocyanate and BD to understand the feature of each hard segment chain. The HDI-based PUE showed the largest Young's modulus and tensile strength in the four PUEs due to the ability of crystallization of the hard segment component and the strongest microphase separation. HMDI has both properties of aliphatic and cycloaliphatic diisocyanates because of its high symmetrical chemical structure compared with NBDI and IPDI. On the other hand, the NBDI- and IPDI-based PUEs have an inclination to phase mixing, leading to decreased Young's modulus and tensile strength. The NBDI-based PUE exhibited better thermal properties at high temperatures due to stiff structure of NBDI.     

Study of the physical structure of PVC by infrared techniques: A short review

Infrared spectroscopy is an important analytical technique for investigating polymeric materials. The physical properties of poly(vinyl chloride) (PVC) depend on its chemical and physical structure. Fourier transform infrared spectroscopy (FTIR) and other infrared techniques are commonly used for studying crystallinity, configurational and conformational changes, and chain orientation in plasticized and non-plasticized PVC. The C-Cl stretching region is particularly sensitive to the macromolecular structure and important changes may be detected depending on fundamental parameters.     

Microdomain composition and properties differences of biodegradable polyurethanes based on MDI and HDI

The study of the effect of the diisocyanate structure on the microstructure and macroscopic properties of polyurethanes was the main aim of this work. Biodegradable segmented thermoplastic elastomeric polyurethanes based on a poly(hexamethylene carbonate‐co‐caprolactone)diol (PHM‐co‐PCL) as soft segment were synthesized using 1,4‐butanediol (BD) as chain extender and both 4,4′‐diphenylmethane diisocyanate (MDI) and 1,6‐hexamethylene diisocyanate (HDI) as components of the hard segment by the two shoot synthesis procedure. Microphase structure and properties were analyzed using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) as complementary techniques, used to characterize thermal transitions of the polyurethanes and to assign them to determinate functional groups interactions. Gaussian deconvolution technique was used to decompose carbonyl region in four peaks and to study the hydrogen bonding within the different polyurethanes. Both DSC and FTIR showed that MDI‐based biodegradable polyurethanes were less phase segregated than to those based on HDI, and thus that diisocyanate structure has an important role on microdomain composition and polyurethanes properties. Macroscopic properties as hardness and water‐polymer contact angles are related to polyurethanes microphase compositions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Polyurethane elastomers based on molecular weight advanced poly(ethylene ether carbonate) polyols. III. Effects of diisocyanate modified diols

A series of diisocyanate-modified, molecular weight advanced poly(ethylene ether carbonate) diols has been prepared, characterized, and formulated into polyurethane elastomers using a prepolymer process. Properties were compared to a polyurethane elastomer control in which the only variable was the diisocyanate modification. The diisocyanate modification produces polymers with increased modulus (445–730% at 25°C), improved tensile strength and hardness properties and reduced (improved) coefficients of linear thermal expansion, while still passing the notched Izod impact test. The tensile strength at break increases with increasing number of urethane moieties in the soft segment and the elongation at break also increases. The plaques studied appear to have a three-phase morphology—a soft segment continuous phase containing amorphous hard segment, an amorphous hard segment phase plasticized by about 11% of the soft segment material, and a crystalline hard segment. The polymers based on the diisocyanate modified polyols are significantly more phase mixed than the control due to the increased amount of hard segment-soft segment interactions taking place. The improved properties of the polymers made with the modified polyols are due to their higher hydrogen bonding protential which gives more physically crosslinked polymers.