Properties of waterborne polyurethane‐fluorinated marine coatings: The effect of different types of diisocyanates and tetrafluorobutanediol chain extender content

Three series of waterborne polyurethane‐ (WBPU) fluorinated coatings were prepared with single aliphatic (4,4′‐dicyclohexylmethane diisocyanate, H₁₂MDI), aromatic (4,4′‐diphenylmethane, MDI) and a mixture of aliphatic and aromatic diisocyanates (1 : 1). Different contents of 2,2,3,3‐tetrafluoro1,4‐butanediol (TFBD) as a chain extender were used in the WBPU coatings. The fluoro‐enriched surface of the WBPU coatings was obtained with a combination of a high TFBD content (8.77 mol %) as well as the aliphatic or mixed diisocyanates. The tensile strength, Young's modulus, elongation at break (%) and adhesive strength were characterized with respect to the TFBD contents. The mechanical strength and adhesive strength increased with increasing TFBD content in the three series. In artificial salt water, the maximum adhesive strength of WBPU was observed for this coating, which was achieved by TFBD bonded H₁₂MDI of mixed diisocyanates with a higher TFBD content (8.77 mol %). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39905.     

Properties of Waterborne Polyurethane Adhesives: Effect of Chain Extender and Polyol Content

A series of waterborne polyurethane (WBPU) adhesives were prepared with various ratios of polyol, poly(tetramethylene oxide glycol) (PTMG), and chain extender, ethylene diamine (EDA), at a fixed content of diisocyanate, 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI) and hydrophilic agent, 2,2-dimethylol propionic acid (DMPA). WBPU adhesives were characterized by IR and ¹H-NMR spectroscopies, X-ray diffraction (XRD) and gel permeation chromatography (GPC). It was found that the extent of hydrogen bonds between hard–hard segment (i.e., hydrogen bonds between the NH and carbonyl groups) increased with increasing chain extender content (decreasing polyol content). Moreover, the disordered hydrogen bond of carbonyl group (hydrogen bond of urethane groups in the interfacial region) increased with increasing chain extender content (decreasing polyol content). The cyclic urea and allophanate group, which are attributed to the side reaction and cross-linking reaction, respectively, were found above a molar ratio 0.17 of chain extender to diisocyanate. The adhesive strength was maximum with 0.95 wt% and 63.10 wt% chain extender and soft segment (PTMG), respectively (H2 sample) at room temperature for the WBPU adhesive. However, with increasing application temperature the adhesive strength decreased for all samples.     

Influence of the length of the chain extender on the properties of thermoplastic polyurethanes

Three polyurethane elastomers (PUs) were prepared using MDI (diphenylmethane-4,4'-diisocyanate), polyadipate of 1,4-butanediol, and three linear chain extenders with different lengths (ethylene glycol, 1,4-butanediol, and 1,6-hexanediol). The prepolymer procedure was used to prepare the PUs. The PUs were characterized using gel permeation chromatography, differential scanning calorimetry, wide angle X-ray diffraction, dynamic mechanical thermal analysis, and stress-controlled rheometry. The surface properties were evaluated from contact angle measurements. The PUs were used as raw materials for solvent-based adhesives, the adhesion properties of which were assessed from T-peel tests of solvent-wiped poly(vinyl chloride) (PVC)/polyurethane adhesive joints. The use of a short-chain extender produced phase separation, high crystallinity, and adequate rheological properties in the PUs. The length of the chain extender used in this study did not affect the surface properties of the PUs nor the T-peel strength of PVC/polyurethane adhesive joints but a change in the locus of failure was obtained: the decrease in the length of the chain extender, i.e. the improved crystallinity and the high degree of phase separation in the PUs, favoured the interfacial failure.     

消防水带用聚氨酯胶黏剂的研制

采用具有较高结晶性的聚酯多元醇,以及合适的扩链剂和异氰酸酯为原料制备高初粘强度的消防水带用聚氨酯胶黏剂,并且分析了聚酯多元醇种类及数均相对分子质量(n)、扩链剂种类及用量、异氰酸酯指数(R)、纳米白炭黑及水解稳定剂对聚氨酯胶黏剂性能的影响。实验结果表明,采用n为3000左右的聚己二酸1,4-丁二醇酯,扩链剂采用1,4-丁二醇,R取1.02～1.03,并且加入经过表面改性的纳米白炭黑TS-720,加入0.5%～0.7%(与聚酯的质量比)的水解稳定剂,反应后得到的聚氨酯胶黏剂具有较高的初粘强度、较好的耐水解性能和耐老化性能。     

Properties of Waterborne Polyurethane Adhesives with Aliphatic and Aromatic Diisocyanates

A series of waterborne polyurethane (WBPU) adhesives were prepared with various ratios of aliphatic/aromatic diisocyanates, namely 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI) as an aliphatic diisocyanate and 4,4′-diphenylmethane diisocyanate (MDI) as an aromatic diisocyanate with poly(tetramethyleneoxideglycol) (PTMG), ethylene diamine (EDA) and dimethylol propionic acid (DMPA). ¹H-NMR spectroscopy was utilized to investigate the side reaction at the dispersion step during synthesis of WBPU dispersions with respect to aliphatic, aromatic and mixed diisocyanates. The tensile strength, Young's modulus, elongation at break (%), storage modulus, glass transition temperature and adhesive strength were measured with respect to aliphatic/aromatic diisocyanate contents. The adhesive strength was maximum using mixed diisocyanates containing 25 mol% MDI in WBPU adhesives.     

Synthesis,properties, and dyeing application of nonionic waterborne polyurethanes with different chain length of ethyldiamines as the chain extender

This study deals with the synthesis of some nonionic waterborne polyurethanes (PUs), using ethyldiamines of different chain length, such as ethylenediamine (EDA) and diethyltriamine (DETA), as the chain extender in the reaction, and examines the thermal properties, mechanical properties, and dyeing properties of the PU products and their blends. As far as each PU by itself is concerned, we found that the T_g of the one made with DETA is the highest, followed by that with EDA, and the one with 1,4‐butanediol (1,4‐BD) is the lowest. The PU made with 1,4‐BD as the chain extender has no T_m, while the two others, using diamines as chain extenders, have a clear T_m, the one with DETA being higher than that with EDA. However, the enthalpy data are just the opposite. The tensile strengths of the two PUs, made with diamines as the chain extender, are larger than that made with 1,4‐BD, but their respective elongation properties are just the opposite. A comparison within PUs made with diamines showed that the one made with EDA is greater in both strength and elongation categories than that made with DETA. However, the one made with DETA is far superior to both of those made with 1,4‐BD and EDA in their dye‐exhaustion ratio, color yield (K/S), fixation rate, and color fastness. In respect to the various PU mixtures that we examined, we found that both PUs synthesized with EDA or DETA as the chain extender would have their T_g's greatly increased by blending in some PU made using 1,4‐BD as the chain extender. Among them, in particular, a blend of PU, made separately with DETA and 1, 4‐BD as the chain extender, showed great improvements in both tensile strength and elongation and also demonstrated better dyeability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2824–2833, 2003     

Preparation and properties of emulsifier-/solvent-free slightly crosslinked waterborne polyurethane-acrylic hybrid emulsions for footwear adhesives (III)–effect of trimethylol propane (TMP)/ethylene diamine (EDA) content

Stable emulsions of emulsifier-/solvent-free slightly crosslinked waterborne polyurethane-acrylic hybrids (WPU/AC-Ts) with a fixed acrylic monomer content (20 wt.%) and different trimethylol propane (TMP)/ethylene diamine (EDA) (0/0.20, 0.02/0.17, 0.04/0.14, 0.06/0.11, 0.08/0.08, the number indicated the mole% of TMP/EDA) for footwear adhesive materials were successfully prepared in this study. The as-polymerized hybrid emulsion containing 0.10/0.05 mole% of TMP/EDA content was found to be unstable, indicating that near 0.10/0.05 mole% of TMP/EDA content was beyond the limit value of crosslinkable TMP component for self-emulsifing. This study examined the effect of mole% of TMP/EDA on the stability and viscosity of hybrid emulsions, the tensile properties and dynamic mechanical thermal properties of hybrid film samples, and the adhesive strengths of formulated adhesives for footwear at both dry and wet states. As TMP content increased, the tensile strength/modulus/storage modulus/hardness of WPU/AC-Ts film samples increased, however, their elongation at break and water swelling% decreased significantly. The adhesive strength (peel strength) of formulated adhesives was found to be dependent upon the degree of drying, but almost not upon the TMP content in WPU/AC-Ts. The adhesive strength of footwear (EVA/leather) dried at room temperature for 24 h was higher than that of footwear dried for 30 min. However, the adhesive strength at wet state increased significantly with increasing TMP content. The optimum TMP/EDA contents were found to be 0.06/0.11 and 0.08/0.08 mole% to achieve the desired high performance adhesive properties such as high strength in wet state.     

Preparation and properties of polydimethylsiloxane (PDMS)/polytetramethyleneadipate glycol (PTAd)-based waterborne polyurethane adhesives: Effect of PDMS molecular weight and content

Waterborne polyurethane (WBPU) dispersions were prepared by pre-polymer process using siloxane polyol, namely polydimethylsiloxane (PDMS), and polyester polyol, namely poly(tetramethyleneadipate glycol) (PTAd), as a soft segment. Three different molecular weights (M_n = 550, 6000, 110,000) of PDMS and one fixed molecular weight of PTAd (M_n = 2000) was used during preparation of WBPU dispersions. This research aims to explore the potential use of PDMS in complementing WBPU by boosting flexibility, water resistance, and adhesive strength. The water swelling (%), tensile strength, and adhesive strength of WBPUs were investigated with respect to PDMS molecular weight and PDMS content (PDMS mol %). The water swelling (%) and tensile strength decreased with increasing PDMS molecular weight at a fixed PDMS content (mol %) in mixed polyol of WBPU films. By contrast, the peel adhesive strength peaked at 6.64 mol % and 4.43 mol % with molecular weight of PDMS at 550 and 6000, respectively, while it only decreased when the molecular weight of PDMS stood at 110,000. The adhesive strength was almost unaffected with optimum content (6.64 mol %) of lower PDMS molecular weight (M_n = 550) in mixed polyol-based WBPU after immersing the adhesive bonded nylon fabrics in water for 48 h among all of the samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of waterborne polyurethane adhesives containing different amount of ionic groups (I)

A series of waterborne polyurethanes (WBPU) containing different amount of 2,2‐bis(hydroxymethyl) propionic acid (DMPA) were synthesized using prepolymer mixing process. Relationships between the DMPA content and physical, mechanical, and thermal properties as well as adhesive behavior at different condition were investigated. Stable aqueous dispersions of WBPU were obtained when the DMPA content was more than 10 mol %. At higher DMPA content, the particle size of the WBPU dispersion was lower but the viscosity of the dispersion was higher. Water swelling and tensile strength of the films increased with increasing of DMPA content. The optimum adhesive strength of WBPU adhesives was found to be depended on the DMPA content, pressing temperature, and pressure on adhesion process. The adhesive strength of WBPU adhesives increased with increasing DMPA content. The optimum pressing temperature decreased with increasing DMPA content. The adhesive strength of WBPU adhesives increased with increasing pressure up to 15 kg f/cm² and then leveled off. The optimum pressing temperature of WBPU adhesives samples containing 24.02, 22.05, and 17.05 mol % DMPA was about 100, 120, and 140°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5684–5691, 2006     

阴离子型水性聚氨酯的合成及其性能研究

以甲苯二异氰酸酯(TDI)、聚丙二元醇(N210)为主要原料,二羟甲基丙酸(DMPA)为亲水性扩链剂,1,4-丁二醇(BDO)和乙二胺(EDA)为小分子扩链剂,采用预聚体法合成了系列阴离子型水性聚氨酯乳液。讨论了硬段含量、DMPA用量、-NCO／-OH物质的量比值及扩链剂用量对水性聚氨酯乳液及胶膜性能的影响,得出了制备阴离子型水性聚氨酯的最佳配方。     

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。     

Studying the effects of chain extenders chemical structures on the adhesion and mechanical properties of a polyurethane adhesive

Chain extenders including diethanol amine (DEA) and 2-cyano-N,N-bis-hydroxyethyl acetamide (CNBA) were utilized to enhance the adhesion and mechanical properties of a polyurethane (PU) adhesive. The adhesion and mechanical properties of the adhesives were studied by peel test, tensile test and dynamic thermal analysis (DMTA) respectively. Results revealed that both chain extenders (DEA and CNBA) increased peel test modulus. The cross-linking density and toughness of the adhesive were significantly increased using chain extenders. Results showed that chain extender without side chain (DEA) could improve the adhesion and mechanical properties of the adhesive greater than chain extender with aliphatic side group (CNBA).     

扩链剂对基于聚酯/MDI聚氨酯弹性体力学性能的影响

用聚酯多元醇(PBA、PEA、PEPA、PCL)、4,4'-二苯基甲烷二异氰酸酯(MDI)和混合扩链剂等原料合成了浇注型聚氨酯弹性体(PUE)。考察了聚酯多元醇种类、预聚体-NCO质量分数、扩链剂和扩链系数(R)等对PUE力学性能的影响,并比较了MDI/混醇体系与2,4-甲苯二异氰酸酯(TDI)/MOCA体系的性能。结果表明,PUE的硬度、模量和撕裂强度随预聚体-NCO含量增加而增加,随交联密度提高,撕裂强度和扯断伸长率下降,R>1.05时,PUE的力学性能急剧变化,MDI/混醇体系比TDI/MOCA体系的冲击弹性好。     

Properties of Waterborne Polyurethane/Clay Nanocomposite Adhesives with Various Countercations of Carboxyl Acid Salt Group

Four series of waterborne polyurethane (WBPU)/clay nanocomposite adhesives were prepared using three different countercations, namely triethylamine (TEA), lithium hydroxide (LiOH) and copper hydroxide (Cu(OH)₂ ) as well as one mixed countercation of TEA and Cu(OH)₂ (1:0.5). The interaction of carboxyl acid salt group using different countercations with clay platelet was characterized by SEM and TEM, and the interaction effects on properties such as water swelling (%), thermal stability, tensile strength, glass transition temperature ( T _g ), and adhesive strength were investigated. The tensile strength, water resistance and adhesive strength increased with increasing clay content up to an optimal value at which point the maximum tensile strength, water resistance and adhesive strength were recorded for each series. However, the optimal clay contents were 1.00 and 0.50 wt% for TEA/LiOH mixed countercation series and (Cu(OH)₂ ) series, respectively. Among all of the samples the maximum tensile strength, water resistance and adhesive strength were found using mixed countercation (TEA and Cu(OH)₂ = 1:0.5) with 1 wt% clay content.     

Preparation and properties of waterborne polyurethane adhesives modified by polystyrene

Waterborne polyurethane (WPU) adhesives modified by polystyrene (PS) were prepared through a prepolymer mixing process from diisocyanates, an anionic polyester, internal emulsifiers, a neutralizer, a chain extender, and PS dispersions. The latter was preformed via the in situ polymerization of styrene in poly(1,4‐butanediol adipate) diol. Transmission electron microscopy, Fourier transform infrared spectroscopy, and ¹H‐NMR techniques were used to characterize the PS dispersions and polyurethane (PU)–PS prepolymer. Experimental results with respect to the performance of the PU–PS adhesives indicate that suitable PS/polyester diol weight ratios improved the mechanical properties, thermal stability, water resistance, and initial adhesive strength of the pristine WPU adhesives. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

蓖麻油和丙烯酸酯双重改性水性聚氨酯复合乳液的研制

以1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)和乙二胺(EDA)为扩链剂,蓖麻油(C.O.)为内交联剂,以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)改性聚氨酯(PU)制得水性聚氨酯-丙烯酸酯复合乳液(PUA).研究了C.O.、DMPA和BA对乳液及涂膜性能的影响.     

复合薄膜用水性聚氨酯胶粘剂的研究

以聚已二酸1,4-丁二醇酯(PBA)、甲苯二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)等为主要原料合成了水性聚氨酯复膜胶,讨论了亲水性扩链剂DMPA用量对水性聚氨酯复膜胶的稳定性、耐水性、粘接强度等的影响;使用差示扫描量热仪(DSC)和原子力显微镜(AFM)观察了分子结构中的软、硬段微相结构分布。结果表明,当DMPA质量分数占预聚体总质量的2.67%～5.34%时能够制得稳定乳液;水性复膜胶乳液的粘度以及胶膜的吸水率随着亲水性扩链剂DMPA用量的增加而增加,而乳液的粒径随着亲水性扩链剂DMPA用量的增加而减小;硬段含量的增加会降低软段结晶,增加水性聚氨酯复膜胶高分子链的极性和粘接强度,当硬段质量分数为22.79%时,胶膜具有较好的T型剥离强度;提高复合压力能够显著提高T型剥离强度;该复膜胶对聚对苯二甲酸乙二醇酯(PET)膜有着比聚丙烯(OPP)膜更好的粘接效果。     

环氧改性水性聚氨酯的合成工艺及性能研究

采用甲苯二异氰酸酯(TDI)、聚醚二元醇(GE-210)、1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)、环氧树脂(E-128)和丙烯酸羟丙酯(HPA)为主要原料,制备环氧改性水性聚氨酯乳液。研究预聚体中的—NCO和—OH物质的量之比(R)及小分子扩链剂、亲水扩链剂、环氧树脂的加入量,对粒径、黏度、贮存稳定性和涂膜耐水性的影响。实验结果表明:预聚体中R值为6～7;小分子扩链剂BDO用量为7%～8%;亲水扩链剂DMPA的用量为6%～7%;环氧树脂添加量为6%～7%时,乳液外观及稳定性最好,涂膜的耐水性能优异,可以作为一种性能优异的涂料用水性聚氨酯树脂。     

Effect of chain extender structure on the properties and morphology of polyurethanes based on H12MDI and mixed macrodiols (PDMS–PHMO)

The effect of chain extender structure on properties and morphology of α,ω‐bis(6‐hydroxyethoxypropyl) polydimethylsiloxane (PDMS) and poly(hexamethylene oxide) (PHMO) mixed macrodiol‐based aliphatic polyurethane elastomers was investigated using tensile testing, differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA). All polyurethanes were based on 50 wt % of hard segment derived from 4,4′‐methylenecyclohexyl diisocyanate (H₁₂MDI) and a chain extender mixture. 1,4‐Butanediol was the primary chain extender, while one of 1,3‐bis(4‐hydroxybutyl)tetramethyldisiloxane (BHTD), 1,3‐bis(3‐hydroxypropyl)tetramethyldisiloxane (BPTD), hydroquinonebis(2‐hydroxyethyl)ether (HQHE), 1,3‐bis(3‐hydroxypropyl)tetramethyldisilylethylene (HTDE), or 2,2,3,3,4,4‐hexafluoro‐1,5‐pentanediol (HFPD) each was used as a secondary chain extender. Two series of polyurethanes containing 80 : 20 (Series A) and 60 : 40 (Series B) molar ratios of primary and secondary chain extenders were prepared using one‐step bulk polymerization. All polyurethanes were clear and transparent and had number‐average molecular weights between 56,000 and 122,100. Incorporation of the secondary chain extender resulted in polyurethanes with low flexural modulus and high elongation. Good ultimate tensile strength was achieved in most cases. DSC and DMTA analyses showed that the incorporation of a secondary chain extender disrupted the hard segment order in all cases. The highest disruption was observed with HFPD, while the silicon‐based chain extenders gave less disruption, particularly in Series A. Further, the silicon chain extenders improved the compatibility of the PDMS soft segment phase with the hard segment, whereas with HFPD and HQHE, this was not observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2979–2989, 1999