扩链法制备高分子量聚对二氧环己酮的研究

以辛酸亚锡为催化剂对对二氧环己酮单体(PDO)开环聚合合成聚对二氧环己酮(PPDO),在聚合的后期,用1,6-六亚甲基二异氰酸酯(HDI)为扩链剂进行扩链反应.研究了扩链剂用量对扩链反应的影响,加入相对于PPDO用量的0.78 wt%的HDI就能得到粘均分子量为2.35×105的PPDO.在分子量相近的情况下,扩链后产物的热稳定性和玻璃化转变温度均比未扩链的高,扩链前后的晶型没有发生变化,但结晶度大幅度降低,拉伸性能变化不大.     

脂肪族水性聚氨酯的力学性能研究

考察了软段的种类、分子量大小、混合软段的组成对产物力学性能的影响作用。同时还研究了二羟甲基丙酸(DMPA)用量以及中和剂的影响作用．实验结果表明。软段结构对脂肪族水性聚氨酯成膜的力学性能影响很大，聚酯型产物具有较高的模量和拉伸强度。聚醚型产物则具有较高的伸长率．混合软段对产物力学性能的影响较为复杂，随着软段中聚醚含量的升高，产物的硬度和模量均大幅度下降，但拉伸强度和伸长率的变化并不是一个线性关系．产物的模量随软段分子量的提高而降低，但伸长率和拉伸强度却有所提高．当DMPA用量较高时。产物的模量和拉伸强度均较高：当DMPA用量较低时，产物则具有较高的伸长率．中和剂的种类对产物力学性能的影响明显，当以NaOH为中和剂时，产物具有较高的硬度、模量、拉伸强度：以三乙胺为中和剂时，产物具有较高的伸长率．     

Polyurethane Ionomers from Cycloaliphatic Diisocyanate and Polytetramethylene Glycol

Abstract

Segmented polyurethane (PU) ionomers were prepared from cycloaliphatic diisocyanate [methylene bis(4-cyclohexyl isocyanate) (H₁₂MDI) and isophoron diisocyanate (IPDI)] and polytetramethylene glycol (PTMG) by using an anionic-type chain extender, viz., dimethylol propionic acid (DMPA). The effect of ionic content and butanediol (BD) on the state of dispersion and physical properties of emulsion-cast film was determined using Autosizer, transmission electron microscopy (TEM), Instron, and Rheovibron. With increased incorporations of DMPA in PU, particle size of emulsion decreased asymptotically, tensile modulus and strength increased, and the glass transition temperature (T _g) moved toward the higher temperature. On the other hand, with increased incorporation of BD in PU, particle size of emulsion, tensile modulus, and strength of the emulsion cast film increased, and the major transition of soft segment moved toward higher temperature. With regard to the structural effect of the isocyanate, H₁₂MDI gave finer dispersion and better mechanical properties over IPDI.     

侧链为光敏感基团的可生物降解聚氨酯的合成及表征

设计合成2-甲基-2-肉桂酰氧甲基-1,3-丙二醇(MCO)作为扩链剂,并以聚乳酸二醇(PLA diol)为软段,异佛尔酮二异氰酸酯(IPDI)和MCO为硬段制备了一系列侧链含有肉桂基团的可生物降解聚氨酯.结果表明MCO具有较高的反应活性,可满足制备高分子量聚氨酯的要求.聚氨酯结构中的肉桂双键可在紫外光和光引发剂的共同作用下,发生快速的交联反应,短时间内形成交联结构.软段结构相同时,凝胶含量随MCO含量的增加而增加.硬段结构相同时,凝胶含量随软段分子量的增加而减少.适度的交联可提高拉伸强度和形变回复率.     

Preparation and characterization of biodegradable poly(lactic acid)‐ block‐poly(ε‐caprolactone) multiblock copolymer

Biodegradable copolymers of poly(lactic acid)‐block‐poly(ε‐caprolactone) (PLA‐b‐PCL) were successfully prepared by two steps. In the first step, lactic acid monomer is oligomerized to low molecular weight prepolymer and copolymerized with the (ε‐caprolactone) diol to prepolymer, and then the molecular weight is raised by joining prepolymer chains together using 1,6‐hexamethylene diisocyanate (HDI) as the chain extender. The polymer was carefully characterized by using ¹H‐NMR analysis, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). The results of ¹H‐NMR and TGA indicate PLA‐b‐PCL prepolymer with number average molecular weights (M_n) of 4000–6000 were obtained. When PCL‐diols are 10 wt%, copolymer is better for chain extension reaction to obtain the polymer with high molecular weight. After chain extension, the weight average molecular weight can reach 250,000 g/mol, as determined by GPC, when the molar ratio of –NCO to –OH was 3:1. DSC curve showed that the degree of crystallization of PLA–PCL copolymer was low, even became amorphous after chain extended reaction. The product exhibits superior mechanical properties with elongation at break above 297% that is much higher than that of PLA chain extended products. Copyright © 2009 John Wiley & Sons, Ltd.     

UV-curable poly(ethylene glycol)–based polyurethane acrylate hydrogel

Poly(ethylene glycol) (PEG) with molecular weight (M_n) of 1000, 2000, 3000, and 4000 g/mol, four types of diisocyanate [hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI), isophorone diisocyanate (IPDI), and toluene diisocyanate (TDI)], two types of comonomers [acrylamide (AAm) and acrylic acid (AAc)] that comprised up to 60% of the total solid were used to prepare UV-curable PEG–based polyurethane (PU) acrylate hydrogel. The gels were evaluated in terms of mechanical properties, water content as a function of immersion time and pH, and X-ray diffraction profiles of dry and swollen films. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2703–2709, 1999     

Functionalization of graphene oxide with different diisocyanates and their use as a reinforcement in waterborne polyurethane composites

Abstract

To examine the reinforcing effects of isocyanated graphene oxide (NCO-GO) on a waterborne polyurethane matrix, the surface of GO was respectively modified by isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and toluene diisocyanates (TDI) and then confirmed by FT-IR, Raman, TGA, XRD, TEM, AFM and SEM-EDS. The dispersity behavior between different NCO-GO and polymer was evaluated by FESEM and XRD. The nanocomposites’ chemical structure, emulsion morphology, hydrophobicity, thermal and mechanical properties were investigated by FT-IR, TEM, TGA, tensile testing machine and water contact angle test, respectively. It was shown that these properties of nanocomposites including tensile strength, initial thermal degradation and hydrophobicity were increased by the incorporation of NCO-GO, in which, particularly, the tensile stress and initial degradation temperature were respectively increased from 13.32 to 18.80?Mpa and 249 to 288?°C after the addition of TDI-GO. These superior reinforcing effects were attributed to the two-dimensional structure of NCO-GO as well as the good interfacial adhesion between the NCO-GO and WPU matrix.     

Synthesis and characterization of poly(p-dioxanone)-based degradable copolymers with enhanced thermal and hydrolytic stabilities

Herein, we presented a novel biodegradable copolymer via the chain extending reaction of poly(p-dioxanone)-co-poly(2-(2-hydroxyethoxy) benzoate) (PPDO-co-PDHB) prepolymer with hexamethylene diisocyanate (HDI) as a chain extender. The structures and molecular weight of PPDO-co-PDHB prepolymer and PPDO-co-PDHB-PU chain-extended copolymer are characterized via hydrogen nuclear magnetic resonance spectroscopy (¹H NMR) and viscosity test. The relationship between the molecular structures and properties of the chain-extended copolymers is established. The PPDO-co-PDHB-PU copolymers possess a better thermal stability comparing with the PPDO homopolymer. The study of mechanical properties shows that the elongation-at-break of PPDO-co-PDHB-PU is much higher than that of PPDO. The investigation of hydrolytic degradation behaviors indicates the degradation rate of PPDO can be controlled by adjusting the PDHB compositions, and proves that chain-extended copolymers exhibit an excellent hydrolytic stability being better than that of PPDO.     

Toughening polylactide by dynamic vulcanization with castor oil and different types of diisocyanates

Dynamic vulcanization of polylactide (PLA) with castor oil (CO) and three different diisocyanates, namely 4,4′-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI), was performed to study the effect of diisocyanate type on the vulcanization process and on the morphology as well as mechanical properties of the PLA/CO-based polyurethane blends. The reactivity of the three diisocyanate followed the order of MDI > HDI > IPDI when reacting with castor oil. Interfacial compatibilization between PLA and the CO-based polyurethane occurred when the less reactive HDI and IPDI was used. Among all the blends, PLA/CO-IPDI showed the finest morphology and the best toughening efficiency. Incorporation of 20 wt% CO-IPDI increased the elongation at break and notched impact strength of PLA by 47.3 and 6.6 times, respectively. Cavitation induced matrix plastic deformation was observed as the toughening mechanism for the PLA blends with CO-based polyurethane. The effect of CO-IPDI content on the morphology and mechanical properties of PLA was studied in detail. The particle size of dispersed CO-IPDI and the elongation at break increased gradually, the tensile strength and Young's modulus decreased gradually, while the impact strength first increased and then decreased with increasing CO-IPDI content from 5 to 30 wt%. The maximum impact strength appeared for the blends with 20 wt% CO-IPDI.     

阻燃型聚乳酸基聚氨酯的合成与表征

以聚乳酸二醇、六次甲基二异氰酸酯和二溴新戊二醇设计合成出一系列阻燃型聚乳酸基聚氨酯。 通过核磁、凝胶色谱和红外等表征了材料的结构性能。 结果表明,二溴新戊二醇作为扩链剂可满足制备高相对分子质量聚氨酯的要求,材料的热学性能随聚乳酸二醇相对分子质量和硬段质量分数的增加而增加。 同时该类聚氨酯具有较好的力学性能,拉伸强度在50 MPa附近,接近工业级别的聚乳酸。 材料的阻燃性能随着溴质量分数的增加而增强。 当溴质量分数为8.6%,聚氨酯的极限氧指数(LOI)为28,属于难燃级别材料。     

Study on siloxane‐modified polyurethane dispersions from various polydimethylsiloxanes

In this work, various polydimethylsiloxanes (PDMS) are incorporated with isophorone diisocyanate (IPDI), 2,2‐bis(hydroxymethyl)propionic acid (DMPA), and poly(tetramethylene oxide) (PTMO) by the prepolymer process to synthesize a series of siloxane‐modified polyurethane dispersions (PUDs) with 35 wt % solid content, viscosities of 20–100 cps, and particle sizes of 40–130 nm. Hydrophobic PDMS was introduced into the PU chain either based on random distribution or through the block segment arrangement. We also establish the composition‐property relationship of PDMS‐PUD, which includes PDMS's type and molecular weight and PDMS‐PUD film's contact angle and mechanical property. The tensile strength of PDMS‐PUD film is decreased with increasing amount of PDMS. Scanning electron microscopy for chemical element analysis indicated that PDMS migrated to the surface much more easily in the block arrangement than in the random distribution. Also, some PDMS‐PUD films show a peau‐like surface, so their PUDs are considered promising to be used in processes for textiles. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3482–3490, 2005     

Polyurethane cationomers. I. Structure-property relationships

Polyether polyurethane cationomers are prepared using poly (tetramethylene oxide) of molecular weight 2000 as soft segments, N-methyl-diethanolamine as chain extender, glycolic acid as quaternization agent, methyl ethyl ketone as solvent, and three different diisocyanates. The three diisocyanates are 4,4′-diphenylenemethylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), and toluene diisocyanate (TDI). Properties of the films cast from solutions of the three series of ionomers are studied by infrared spectroscopy, dynamic mechanical analysis, thermogravimetric analysis, differential scanning calorimetry, wide angle x-ray diffraction, and tensile elongation testing. In the un-ionized and ionized systems, the hard segments exhibit disordered and ordered arrangements, respectively. Ionization disrupts the order and produces increased cohesion in the hard domains, which have opposing effects on the tensile elongation properties. In the MDI and TDI systems, cohesion is predominant, leading to an increased tensile strength and modulus and decreased elongation at break. But in the HDI system, the disruption of the order is predominant, leading to decreased tensile strength and only insignificant reduction in the elongation at break. In the TDI system, the tensile strength is rather low, which is attributed to the poor order in the hard domains resulting from the high content of the asymmetric 2,4-isomer of the urethane.     

Synthesis and Characterization of Comb-like Methoxy Polyethylene Glycol-grafted Polyurethanes via ‘Click’ Chemistry

In this study, a series of comb-like methoxy polyethylene glycol (MPEG) functionalized polyurethanes (PUs) (PU–g–MPEG) were successfully prepared via ‘click’ chemistry and polyaddition reaction. The copper catalyzed Huisgen 1,3-dipolar cycloaddition was firstly carried out between 3,5-bis(hydroxymethyl)-1-propargyloxybenzene (PBM) and methoxy polyethylene glycol azide (MPEG–N₃) to obtain MPEGylated diol PBM (MPEG–PBM). Then, the comb-like PUs having MPEG located on the backbones (PU–g–MPEG) were synthesized through the polyaddition of MPEGylated diol PBM and hexamethylene diisocyanate (HDI). Fourier transform infrared (FTIR), ¹H NMR spectroscopy, size exclusion chromatography (SEC), and thermo gravimetric analyses (TGA) were used to characterize these synthesized MPEG-functionalized comb-like PUs (PU–g–MPEG). Compared with PU without MPEG grafts, PU–g–MPEG show a better wettability.     

Robust self-healing waterborne polyurethane coatings via dynamic covalent Diels-Alder bonds for corrosion protection

For waterborne polyurethanes (PUs), balancing robust mechanical performances and excellent self-healing ability is a great challenge. Here, we show that this goal can be achieved by a rational tuning of the PU chemistry. In particular, we synthesized an anionic self-healing waterborne PU using acetone process, in which 2,2-bis(hydroxymethyl)propionic acid (DMPA) serves as inner emulsifier, thermally dynamic Diels-Alder bonds act as healing motifs and hexamethylene diisocyanate trimer is the crosslinker. The mechanical performance can be tuned by increasing DMPA concentration due to the gradually increased hard segment contents and ionic interactions. The tensile stress and elongation at break of films containing 5.6 wt% of DMPA are 24.9 MPa and 911.9%, respectively. Moreover, dynamic reversible Diels-Alder bonds located in main chains and cross-linking points ensure excellent self-repairing capability. Upon mechanical damage, the tensile stress can be restored to 95% of its initial value. Electrochemical impedance spectroscopy also points out an outstanding barrier ability and excellent corrosion protection performance of the coatings, which can be recovered even after serious damages.     

The influence of hard‐segments on two‐phase structure and shape memory properties of PCL‐based segmented polyurethanes

Poly(ε‐caprolactone)‐based segmented polyurethanes (PCLUs) were prepared from poly(ε‐caprolactone) diol, diisocyanates (DI), and 1,4‐butanediol. The DIs used were 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluenediisocyanate (TDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, small‐angle X‐ray scattering, and dynamic mechanical analysis were employed to characterize the two‐phase structures of all PCLUs. It was found that HDI‐ and MDI‐based PCLUs had higher degree of microphase separation than did IPDI‐ and TDI‐based PCLUs, which was primarily due to the crystallization of HDI‐ and MDI‐based hard‐segments. As a result, the HDI‐based PCLU exhibited the highest recovery force up to 6 MPa and slowest stress relaxation with increasing temperature. Besides, it was found that the partial damage in hard‐segment domains during the sample deformation was responsible for the incomplete shape‐recovery of PCLUs after the first deformation, but the damage did not develop during the subsequent deformation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 557–570, 2007     

Synthesis of a Novel UV Curable Aqueous Dispersion Polyurethane PDHA-PEDA-PU and the Properties of Cured Film

Because of the merits in environmental protection and lower energy consumption, ultraviolet (UV) curable coatings have been gained more and more attention and speedy development in the past decades. UV curable waterborne polyurethane has been employed pop…     

2-Ethy-4-methylimidazole terminated polyurethane prepolymer as functional latent curing agents for epoxy resin crosslinking

Three kinds of 2-ethyl-4-methylimidazole (EMI)-terminated polyurethane prepolymer were prepared through the reaction between diethylene glycol (DEG), polyethylene glycol 400 (PEG-400) and different isocyanates (toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylenediisocyanate (HDI)). The storage stability, curing temperature and curing time of diglycidyl ether of bisphenol A (DGEBA) with EMI derivatives have been investigated by viscometer, DSC, and FTIR, respectively. It was proved that DGEBA/EMI derivatives exhibited superior storage stability than that of DGEBA/EMI. And the DGEBA can be effectively cured by the EMI derivatives at 120–140?°C without the generation of harmful species. Moreover, the higher impact strength and lower glass transition temperature (Tg) suggested an improvement of stiffness. The results of tensile test and TGA indicated that the excellent bonding strength with steel and unconspicuous compromise in thermal stability were simultaneously achieved.     

Fluoropolyether coatings: Relationships of electrochemical impedance spectroscopy measurements,barrier properties,and polymer structure

Ten model coatings, selected and obtained from a family of fluorinated resins synthesized by the reaction of perfluoroether oligomeric diols of different molecular weights with polyisocyanurates of hexamethylenediisocyanate (HDI) and isophoronediisocyanate (IPDI), were characterized with differential scanning calorimetry, mechanical testing, and electrochemical impedance spectroscopy measurements. The electrochemical and chemico‐physical measurements show that the glass‐transition temperature of the starting isocyanate trimers greatly influences the properties of the final urethane coatings; the IPDI trimer gives harder coatings with lower water permeabilities than the corresponding HDI‐based materials. Moreover, for each class of materials (from IPDI or HDI), the fluorine content plays a relevant role: the higher the fluorine percentage, the lower the water absorption into the coatings. Furthermore, the chain length of the polyols used for the synthesis of the prepolymers is a variable that exhibits great influence on the coating properties: coatings containing shorter perfluoropolyether segments show better barrier properties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 52–64, 2002     

Synthesis and degradation profile of cast films of PPG-DMPA-IPDI aqueous polyurethane dispersions based on selective catalysts

Waterborne polyurethane (WBU) dispersions synthesized from poly(propylene glycol) (PPG), dimethylolpropionic acid (DMPA), and isophorone diisocyanate (IPDI) with catalysts of different selectivity were prepared via by the conventional prepolymer isocyanate process. Two types of chain extenders were used, ethylene glycol (EG) and propylene glycol (PG), producing polyurethanes. The dispersions were neutralized by the addition of triethylamine. The thermal stability of the materials, obtained as cast films prepared from aqueous dispersions was evaluated by thermogravimetry (TG). It was observed that initial degradation temperatures were above 140 °C, with two-step degradation profiles. The use of a more selective catalyst in the formulations led to materials with higher thermal stability. DTG curves exhibited stages not perceptible in the curves of weight loss, which were mainly influenced by the differences in the formulations. Thermal decomposition of the obtained polyurethanes was followed by TG coupled with FTIR spectroscopy.     

Preparation, characterization and hydrolytic degradation of poly[p-dioxanone-(butylene succinate)] multiblockcopolymer

A series of poly[p-dioxanone-(butylene succinate)] (PPDOBS) copolymers were prepared from p-dioxanone (PDO), 1,4-butanediol and succinate acids through a two-step process including the initial prepolymer preparation of poly(p-dioxanone)diol (PPDO-OH) and poly(butylene succinate)diol (PBS-OH) and the following copolymerization of the two kinds of prepolymers by coupling with hexamethylene diisocyanate (HDI). The molecular structures of the prepared PPDO-OH, PBS-OH and PPDOBS were characterized by hydrogen nuclear magnetic resonance spectroscopy (¹H NMR). The crystallization of the copolymers was investigated by using differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide angle X-ray diffraction (WAXD). It has been shown that the crystallization rate and the degree of crystallization increases with the increase of the weight fraction of poly(butylene succinate) (PBS) blocks in the copolymers. In phosphate buffer solution with pH 7.4 at 37 °C for 18 weeks, the hydrolytic degradation behaviors of the copolymers were studied. The changes of retention weight, water absorption, pH value, and surface morphologies with the degradation time showed that the hydrolytic degradation rate of PPDOBS could be controlled by adjusting the weight fraction of poly(p-dioxanone) (PPDO) and PBS blocks in the copolymers. The changes of the thermal properties of PPDOBS during the degradation were also investigated by DSC.