Addition of different amounts of a urethane-based thickener to waterborne polyurethane adhesive

To adjust the rheology of waterborne polyurethane adhesives, different amounts of a hydrophobically modified ethoxylated polyurethane thickener (HEUR) were added. The thickened adhesive solutions were characterized by flow rheology, pH measurements, particle size, solids content and confocal microscopy. The thickened solid adhesive films were characterized by IR spectroscopy, plate-plate rheology, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis. The adhesion was measured from T-peel test of plasticized PVC/polyurethane adhesive/plasticized PVC and leather/polyurethane adhesive/SBR rubber joints. The addition of the HEUR thickener increased the viscosity of the polyurethane dispersion, and a shear-thinning behaviour was observed due to polyurethane–thickener interactions. The addition of thickener improved the rheological properties of the polyurethane, more noticeable as the content of the thickener increased. The crosslinking of the thickened polyurethane was studied by confocal microscopy. Although the addition of the thickener did not greatly affect the thermal properties of the polyurethane, an improvement in the adhesive strength of leather/adhesive/SBR rubber joints was obtained.     

Characterization of waterborne polyurethane adhesives containing different amounts of ionic groups

Waterborne polyurethane adhesives are an interesting alternative to the current solvent-based polyurethane adhesives used in footwear industry. In this study, different aqueous polyurethane dispersions were prepared by using the prepolymer mixing process. The ionic groups content in the polyurethane ionomer structure was varied by changing the amount (5 and 8 wt% (with respect to the prepolymer weight) of the internal emulsifier—dimethylolpropionic acid (DMPA). The decrease in the DMPA content slightly increased the particle size in number due to the decrease in both the hydrophilicity of the polyurethane ionomer, and the electrolytic stability of the aqueous polyurethane dispersion. Furthermore, the lower the DMPA amount, the lower the hard segment content in the ionomer and the higher the crystallinity of the polyurethane; however, the resistance to flow under temperature (i.e. thermoplasticity) was reduced. The resistance to thermal degradation of the polyurethane ionomer increased by decreasing the DMPA content due to the lower hard segment content. Finally, high initial adhesive strength was obtained and the adhesion to PVC increased as the DMPA content in the polyurethane ionomer decreased.     

Influence of the solids content on the properties of waterborne polyurethane dispersions obtained with polycarbonate of hexanediol

Waterborne polyurethane adhesives are an interesting alternative to the current solvent-borne polyurethane adhesives used in the industry. Different aliphatic waterborne polyurethane dispersions (PUDs) with different solids content were synthesised by reacting isophorone diisocyanate (IPDI) with a polycarbonate derived from hexanediol via the acetone method. The PUDs were characterised by Brookfield viscosity, pH, particle size, transmission electron microscopy (TEM) and solids content measurement. The dry polyurethane films were characterised by ATR-IR spectroscopy, plate–plate rheology, differential scanning calorimetry (DSC) and thermal gravimetry (TGA). Their adhesion was evaluated from T-peel tests of flexible PVC/waterborne polyurethane dispersion/flexible PVC joints and single lap-shear tests of aluminium/waterborne polyurethane dispersion/aluminium joints.The PUDs showed bimodal particle size distribution. The mean particle size of the PUDs decreased by increasing their solids content but the particle size distribution of the PUDs increased by decreasing their solids content. As the solids content increased the Brookfield viscosity of the PUDs increased due to lower mean particle size where particle crowding was favoured, the PUD having 44 wt% solids content was an exception (higher particle size but lower polydispersity). On the other hand, the increase in the solids content increased the hard segments content and the degree of phase separation of the polyurethanes. The greater the solids content of the polyurethanes, the lower their glass transition temperatures values and the lower the elastic moduli. Adhesive strength under peel stresses were not affected by the solids content in the polyurethanes but the single lap-shear strength values decreased by increasing the solid contents in the polyurethanes due to lower hard segments content.     

The influence of type and concentration of inorganic pigments on the polyurethane adhesive properties and adhesion of laminates

The introduction of white pigments into an adhesive layer is the new and economically favourable method of obtaining white laminates. In this work studies of the influence of the type and concentration of white pigments in polyurethane adhesive layer of laminates on their whiteness (opacity) and tensile strength are presented. The pigments used were titanium dioxide, zinc white and lithopone. They were added to a polyurethane adhesive in concentrations of 10–20 wt%. In order to determine the applicability of the described solution on an industrial scale, studies of viscosity, rheology and DSC thermograms of adhesives were performed as well as Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) of whitened laminates and leak testing of packaging formed from these laminates. Moreover the morphology of used pigments was analysed by measuring average particle size distribution on a laser diffraction Mastersizer 2000 and on scanning electron microscopy.     

原料及配方对单组分聚氨酯胶粘剂性能的影响

以不同性质的聚醚多元醇（210，220，330，3050）、TD1－80等为主要原料，分别采用一步法和预聚物法合成单组分聚氨酯胶粘剂，并用该胶粘结橡胶粉压制成铺垫材料。研究了不同多元醇、各多元醇的不同配比、合成工艺及不同异氰酸酯指数等因素对橡胶粉粘接料（以下简称粘接料）的影响。结果表明：以220和3050的1：1混合物，TDI为主要原料，用预聚物法合成的游离NCO含量为5％的单组分聚氨酯，其拉伸强度、扯断伸长率、耐水性、耐热性等均能满足橡胶粉粘结料的性能要求。     

含液晶基元聚氨酯对普通聚氨酯性能的影响

合成了一类既含有刚性液晶基元又含有柔性链段的主链型含液晶基元聚氨酯(LCPU)，以端羟基四氢呋喃-环氧乙烷共聚醚为基体材料，多异氰酸酯N-100为固化剂，探讨这类含液晶基元聚氨酯对聚氨酯弹性体力学性能的影响。结果表明，5种含液晶基元聚氨酯随着柔性链段长度的变化和在聚氨酯弹性体中加入比例的变化。表现出对聚氨酯弹性体力学性能的影响有较大的差异。与未改性聚氨酯弹性体相比，改性后聚氨酯弹性体共混物垃伸强座量大提高71％倍．断裂伸长率最大提高8．7倍．     

Effect of 3-Aminopropyltriethoxysilane on polycarbonate based waterborne polyurethane transparent coatings

A series of waterborne polyurethane (WPU) dispersions modified with different contents of 3-aminopropyltriethoxysilane (APTES) were synthesized based on poly(1,6-hexyl 1,2-ethylcarbonate) diol (PHEC) and isophorone diisocyanate (IPDI), and the films were obtained by casting the dispersions on Teflon molds. Effects of APTES content on the particle size and viscosity of the dispersions were studied. The structure and properties of the resulting films were investigated by Fourier transform infrared spectroscopy, wide angle X-ray diffraction measurement, dynamic mechanical analysis, thermogravimetric analysis and mechanical testing. The experimental results showed that the incorporation of APTES played an important role in the enhancement of the water and toluene resistance and mechanical properties of the SPU films. Young's moduli and ultimate tensile strengths were improved from 8.0 to 451 MPa and 6.5–19 MPa respectively as the APTES content increased from 1 wt.% to 20 wt.%. The ability of scratch resistance was enhanced, when the content of APTES increased to 20 wt.%, the 3H pencil could not mar the surface. Moreover, the transmittance spectra indicated that the coatings showed high transparence.     

Preparation and properties of starch thermoplastics modified with waterborne polyurethane from renewable resources

A waterborne polyurethane (PU) aqueous dispersion was synthesized from castor oil, and blended with thermoplastic starch (TPS) to obtain a novel biodegradable plastic with improved physical properties. The effect of PU content on the morphology, miscibility and physical properties of the resulting blends was well investigated by scanning electron microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis and measurements of mechanical properties and water sensitivity. The research results show that the blends exhibit a higher miscibility when PU content is lower than 15 wt% due to the hydrogen bonding interaction between urethane groups and hydroxyl groups on starch, whereas obviously phase separation occurs in the blends with more than 15 wt% PU. Incorporating PU of 4-20 wt% in TPS results in the blends with improved Young's modulus (40-75 MPa), tensile strength (3.4-5.1 MPa), elongation at break (116-176%). Further, PU also plays an important role in improving the surface- and bulk-hydrophobicity and water resistance of the resulting blends.     

UV-curing behavior and physical properties of waterborne UV-curable polycarbonate-based polyurethane dispersion

Waterborne UV-curable polyurethane dispersions were synthesized from C5/C6 copolymers of polycarbonate diol(PCDL)s and different end-capping groups. The effects of the polyol molecular weight on the UV-curing behavior and physical properties were examined according to the molecular weight (800, 1000, 2000 g/mol) of PCDL. The UV-curing behavior was analyzed by Fourier transform infrared spectroscopy and photo-differential scanning calorimetry. The influence of the functionality of the end-capping group on the UV-curing behavior and physical properties were also investigated in a similar manner. 2-Hydroxyethylmethacrylate, 2-hydroxyethylacrylate and pentaerythritol tri-acrylate were used to impart mono-methacrylate, mono-acrylate and tri-acrylate functionality to the end-capping group, respectively. The pendulum hardness, curing rate and conversion increased with decreasing molecular weight of the PCDL. The pendulum hardness, curing rate and conversion of dispersion with tri-acrylate functionality on end-capping groups were much higher than those of the other dispersions with mono-methacrylate or mono-acrylate functionality.     

Effect of polyisocyanate hardener on adhesive force of waterborne polyurethane adhesives

A series of waterborne polyurethane (WBPU)/hardener adhesives were obtained from mixing of WBPU containing different types of polyol as a soft segment with aliphatic and aromatic polyisocyanates hardeners. By characterization of allophanate and biuret bonds formed from the reaction of hardener NCO with urethane/urea groups of WBPU using ¹HNMR spectroscopy. It was found that the optimum number ratio (molar ratio) of NCO group of hardener to urethane/urea group of WBPU that shows the highest adhesion force was depended on the type of hardener (aliphatic/aromatic polyisocyanate) and dimethylol propionic acid (DMPA) content (total content of urethane/urea groups); however independent of the type of soft segment (polyol) of WBPU. The optimum number ratio (molar ratio) of NCO group of aromatic polyisocyanate hardener to urethane/urea was higher than that of aliphatic hardener to achieve the highest adhesion force of WBPU. The adhesive force increased with increasing hardener content up to the optimum point and then decreased. Poly(tetramethylene adipate glycol) (PTAd) based WBPUs with aliphatic hardener show higher adhesive force than Poly(tetramethylene oxide glycol) (PTMG) and aliphatic hardener‐based WBPUs at the optimum number ratio (molar ratio) of NCO group of hardener to urethane/urea group of WBPU. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3663–3669, 2007     

丙烯酸酯类低聚物改性水性聚氨酯压敏胶的性能研究

以聚醚多元醇和IPDI(异佛尔酮二异氰酸酯)为主要原料,以自制的DJW-330(丙烯酸酯类低聚物)为WPU(水性聚氨酯)乳液的化学改性剂,采用自乳化法合成了性能良好的改性WPUA(水性聚氨酯丙烯酸酯)乳液。结果表明:当R=n(-NCO)/n(-OH)=0.95、w(DJW-330)=1.4%时,改性WPUA乳液的稳定性较好,其粒径分布变宽,耐热性略高于未改性WPU乳液;由于DJW-330与WPU分子间是以化学键的形式结合,故此时改性WPUA压敏胶的初粘力(14#号球)、持粘力(100 min)和180°剥离强度(5.38 N/cm)同时达到最大值。     

环氧树脂对层压复合用水性聚氨酯性能的影响

采用异佛尔酮二异氰酸酯(IPDI)、聚己二酸丁二醇酯(PBA)、二羟甲基丙酸(DMPA)、环氧树脂等原料制备了层压复合用水性聚氨酯(WPU)胶粘剂,考查了环氧树脂用量对其性能的影响。结果表明,随着环氧树脂用量的增加,WPU乳液黏度增加,粒径逐渐变大,稳定性变差;经环氧树脂改性的WPU,胶膜的耐水性优于未改性胶膜,力学性能得到提高。     

Preparation and photochromic properties of waterborne polyurethane containing spirooxazine groups

Two novel photochromic spirooxazines, SO 1 and SO 3, were successfully prepared and characterized by Fourier transform infrared spectroscopy (FTIR), ¹H-NMR, and mass spectrometry with electrospray ionization (ESI-MS). SO 1 was doped and grafted with waterborne polyurethane (WPU) to afford D₁-WPU and G₁-WPU. D₃-WPU was prepared by doping SO 3 with waterborne polyurethane. FTIR spectra indicated that SO 1 was grafted onto waterborne polyurethane successfully. Scanning electron microscopy proved that spirooxazines of D-WPU can be effectively dispersed in a waterborne polyurethane matrix, and spirooxazines of G-WPU are evenly distributed in the copolymer. The results showed that the light transmittance of modified waterborne polyurethane films decreased compared with pure waterborne polyurethane films, but the water resistance and tensile strength were better. Ultraviolet–visible spectra demonstrated that the thermal stability of spirooxazine derivatives improved significantly after being modified. The fading rate constant of the D₃-WPU film (k = 0.0079 s^-1) during the discoloration process decreased 9.77 times in contrast to SO 3 in ethanol, which showed that the thermal stability of spirooxazine in WPU film was obviously enhanced. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47067.     

聚碳酸酯二醇型水性聚氨酯胶粘剂的研究

采用预聚体分散法制备了一系列聚碳酸酯二醇(PCDL)型水性聚氨酯(WPU)胶粘剂,并借助傅里叶变换红外光谱(FT-IR)法来跟踪预聚体的合成过程,同时还考察了该WPU胶粘剂的粘度、热稳定性和初粘强度等性能。实验结果表明,PCDL的结构和相对分子质量对该WPU胶粘剂的性能影响很大;以PCDLT-6002为原料制备的WPU胶粘剂,其粘度最低(175 mPa.s)、热稳定性最好、软链段玻璃化转变温度(Tg)最低(-33.97℃)、有软段结晶熔融峰且初粘强度最高(81N/25 mm,此时活化温度为70℃)。     

Effect of polyurethane structure on mechanical properties of nylon-66/polyurethane blends

A polyamide (nylon-66, N66) was blended with a series of polyurethanes (PU) based on different polyols or chain extenders. The effects of PU structure and content on the mechanical properties of the blends were investigated. The morphology of the polyblends was examined by scanning electron microscopy. The Izod impact strength of the blends increased with increasing PU content and showed a maximum value at the composition of 15 wt % PU. The effects of moisture content on the mechanical properties of the blends were also investigated. It was found that the water-toughened N66 could be further toughened by the addition of PU. Polyester-type PU rather than polyether type PU was recommended for the toughening of N66 because the blends containing the former showed higher tensile strength and Izod impact strength except at very low moisture (0.3 wt %) content. Carboxyl groups was introduced into the molecular chains of PU by using dimethylol propionic acid as chain extender replacing part of 1,4-butanediol. The blends containing PU with carboxyl groups showed a lower Izod impact strength than those without carboxyl groups in the structure of PU.     

水性聚氨酯胶粘剂改性研究进展

简要介绍了水性聚氨酯胶粘剂的特点,综述了几种改性方法,指出了目前水性聚氨酯胶粘剂所存在的问题,并展望了其发展趋势。     

聚酯二元醇侧基与酯基含量对水性聚氨酯胶粘剂性能的影响

以甲苯二异氰酸酯(TDI),二羟甲基丙酸(DMPA),一缩二乙二醇(DEG)为主要原料,改变聚酯二元醇的结构,合成了不同酯基和侧基含量的稳定水性聚氨酯胶粘剂;傅里叶红外测试表征了聚氨酯结构,并对聚氨酯胶膜进行了拉伸测试、耐水性测试和T型剥离测试,结果表明在聚氨酯结构中酯基含量增加有利于力学强度的提升,而侧基含量增加降低了胶膜的力学性能;酯基含量相差不大的情况下,侧基含量越多,其耐水性能越好;酯基,侧基含量越高,粘接强度越大。     

The impact of new crystalline lamellae formation during annealing on the properties of polypropylene based films and membranes

Cast films, based on polypropylene (PP), were prepared via melt extrusion and, then, annealed below the melting temperature. The effect of annealing conditions on the properties of the films and the microporous membranes formed by stretching was investigated. It is shown that annealing is an effective method to improve the physical properties of semi-crystalline polymers by promoting chain rearrangement and creating secondary lamellae in the amorphous region. DSC results for annealed samples revealed the appearance of a shoulder endothermic peak and a new peak in the correlation function from the SAXS patterns was observed. The annealed films exhibited double yield points in the tensile deformation curves. A direct linear relationship was found between the strength of the second yield point and the fraction of the lamellae. From mercury porosimetry and SEM images of the membranes larger pore sizes and porosity were observed as the annealing time and temperature increased.