Waterborne Poly Urethane-urea Research Articles

Structural characterization of polyurethane ureas and waterborne polyurethane urea dispersions made with mixtures of polyester polyol and polycarbonate diol

Waterborne polyurethane urea dispersions (WPUUs) intended for coatings and adhesives were synthesized with mixtures of polyester polyol (PE) and polycarbonate diol (PCD) for combining the advantages of the polyurethane ureas made with pure polyols. WPUUs made with mixtures of polyols had higher mean particle size and lower viscosity than the ones made with one polyol only. Two types of hard segments totally separated (i.e. −(IPDI-DMPA/TEA-IPDI)- and −(IPDI-HZ-IPDI)-) and two types of soft segments (i.e. −(IPDI-PCD-IPDI)- and −(IPDI-PE-IPDI)-) were produced in polyurethane ureas made with PE + PCD mixtures. The segmented structure and phase separation of the polyurethane ureas made with PE + PCD mixtures differed depending on their PCD content, affecting the thermal, rheological and crystallinity properties. The adhesion of chlorinated vulcanized styrene-butadiene rubber/WPUU/roughened leather joints made with WPUUs prepared with PE + PCD mixtures was very similar to the ones made with PCD and PE only. After ageing in water at 70 °C for 1-2 days, the adhesive strength of joints made with WPUUs containing more than 50 wt% PCD is excellent. The properties of the polyurethane ureas made with mixtures of polyols containing 50 wt% or more PCD were determined by lower degree of phase separation and interactions between hard and soft domains via carbonate groups.

Synthesis of waterborne polyurethane-urea dispersions with chain extension step in homogeneous and heterogeneous media

HypothesisThe possibility of tailoring the final properties of environmentally friendly waterborne polyurethane and polyurethane-urea dispersions and the films they produce makes them attractive for a wide range of applications. Both the reagents content and the synthesis route contribute to the observed final properties. ExperimentsA series of polyurethane-urea and polyurethane aqueous dispersions were synthesized using 1,2-ethanediamine and/or 1,4-butanediol as chain extenders. The diamine content was varied from 0 to 4.5wt%. Its addition was carried out either by the classical heterogeneous reaction medium (after phase inversion step), or else by the alternative homogeneous medium (prior to dispersion formation). Dispersions as well as films prepared from dispersions have been later extensively characterized. Findings1,2-Ethanediamine addition in heterogeneous medium leads to dispersions with high particle sizes and broad distributions whereas in homogeneous medium, lower particle sizes and narrow distributions were observed, thus leading to higher uniformity and cohesiveness among particles during film formation. Thereby, stress transfer is favored adding the diamine in a homogeneous medium; and thus the obtained films presented quite higher stress and modulus values. Furthermore, the higher uniformity of films tends to hinder water molecules transport through the film, resulting, in general, in a lower water absorption capacity.

자동차 내장재용 열가소성 폴리프로필렌에 적용되는 선처리제용 친환경 수분산 폴리우레탄-우레아의 제조 및 성질

The significance of thermoplastic polyolefin polypropylene (PP) lies in its potential to replace polyvinyl chloride (PVC), the most widely used material for automobile interiors (door trim, dash board), which discharges harmful compounds in certain conditions. Another benefit of PP (0.855 amorphous 0.946 crystalline g/cm) is its low density compared to that of PVC (1.1-1.45 g/cm), which reduces vehicle weight. Market demand for eco-friendly water-based adhesive/coating material is rising significantly as a substitute for solvent-based adhesive/coating material which emits VOC and causes harmful working conditions. 232 * To whom correspondence should be addressed. E-mail: kimhd@pusan.ac.kr http://cleantech.or.kr/ct/ doi: 10.7464/ksct.2014.20.3.232 pISSN 1598-9721 eISSN 2288-0690 This is an Open-Access article distributed under the therms of the Ceative Commens Attribution Non-Commercial License (http://creativecommons.org/licences/ by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is property cited.. 자동차 내장재용 열가소성 폴리프로필렌에 적용되는 선처리제용 친환경 수분산 폴리우레탄-우레아의 제조 및 성질 233 Under such context, in this study, a series of eco-friendly waterborne polyurethane-urea primer (a paint product that allows finishing paint to adhere much better than if it were used alone) for hydrophobic PP were prepared from different mix of DMPA content, NCO/OH molar ratio, various wt% of silicone diol and various soft segment content, among which DMPA of 21 mole %, NCO/OH molar ratio of 1.2, modified silicone diol of 5 wt% and soft segment content of 73 wt% led to good adhesion strength. Additionally, the incorporation of optimum content of additives (0.5 wt% dispersing agent, 0.5 wt% levelling agent, 1.5 wt% antifoaming agent, 3.0 wt% matting agent) into the optimum waterborne polyurethane-urea also enabled good stability, levelling, antifoaming and non-glossy.

Preparation of dendritic waterborne polyurethane-urea/Ni–Zn ferrite composite coatings and investigation of their microwave absorption properties

This study shows the preparation of microwave absorbing composite material by using Ni–Zn ferrite filler and dendritic waterborne polyurethane-urea (WPU) polymer as a matrix. Initially, waterborne polyurethane prepolymers were synthesized by using PEG1500 (WPU1) and PPG1000 (WPU2) polyols via prepolymer mixing process. Then, chain extended with water in the presence of hexamethylenetetramine (HMTA) as crosslinker. Then, 1/1 (w/w) amount of Ni–Zn ferrite was dispersed in the WPU polymer to be converted into a microwave absorbing composite coating (CWPU1 and CWPU2). Structural, mechanical and morphological properties were investigated. The microwave absorption measurements were performed by using transmission/reflection method via waveguide method in the frequency range of 8.2–12.4GHz. Permittivity and permeability measurements were performed in the frequency range of 8.2–12.4GHz. It has been found that CWPU1 which was prepared by using WPU1 polymer indicated broader microwave absorption between 9.4 and 11.7GHz due to its dendritic structure. Besides, permittivity and permeability results indicated that CWPU1 and CWPU2 have distinctive magnetic properties.

Soybean Oil–Isosorbide‐Based Waterborne Polyurethane–Urea Dispersions

A series of soybean oil-based amide diol-isosorbide waterborne polyurethane-urea (PUU) dispersions have been successfully prepared, with amounts of isosorbide ranging from 0 to 20 wt % of the total diol content. The thermal and mechanical properties of the resulting PUU films have been characterized by dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, and mechanical testing. The results reveal that the glass transition temperature is increased with increased amounts of isosorbide, and the mechanical properties are improved significantly with the incorporation of isosorbide. For example, the Young's modulus increases from 2.3 to 63 MPa and the ultimate tensile strength increases from 0.7 to 8.2 MPa when the isosorbide amount is increased from 0 to 20 wt %. The thermal stability decreases slightly with the incorporation of isosorbide. This work provides a new way of utilizing biorenewable materials, such as isosorbide and a soybean oil-based amide diol, for the preparation of high-performance polyurethane-urea coatings.

Preparation and characterization of waterborne polyurethaneurea composed of C9-diol-based polyester polyol

A series of polyurethaneurea (PUU) aqueous dispersions were prepared with C9-diol-based polyester polyol (POA) and/or poly(neopentylene adipate) polyol (PNA). The particle size and viscosity of the PUU aqueous dispersions consisting of POA were close to those of a comparable system prepared with PNA, and the high-temperature stability and freeze–thaw stability for all the aqueous dispersions were excellent. The PUU film prepared only with the POA exhibited the lowest water-absorbing amount, the highest tensile strength (51.3 MPa), and the best hydrolytic stability across all PUU films studied. The experimental results also showed a high degree of hydrogen bonding for urea groups and a perfect, ordered structure of hard segments in this kind of PUU film, resulting in excellent water-resistance performance and mechanical properties.

Preparation and water resistance of crosslinked waterborne polyurethaneurea

Two series of cross-linked polyurethaneurea (PUU) aqueous dispersions with polyoxypropylene glycerol and pentaerythritol as internal cross-linking agents were prepared and characterised. The results revealed that in comparison with the uncross-linked one, the cross-linked PUU films exhibited excellent waterproof performance and mechanical properties. The amount of water absorption was as low as 2⋅5 wt-%, the contact angle of water on the surface of this kind of film was as high as 96°, and the tensile strength was as high as 42⋅8 MPa. The cross-linked PUU films with polyoxypropylene glycerol and pentaerythritol as cross-linked agents showed different properties at the same cross-linking agent content. The prepared triol-cross-linked or tetra-cross-linked PUUs had great potential application in meeting the highly diversified demands in modern technologies such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes, where high water resistance and durability were required.

Preparation and properties of well‐defined waterborne polyurethaneurea with fluorinated siloxane units in hard or soft segments

AbstractTwo series of well‐defined polyurethaneurea (PUU) aqueous dispersions consisting of fluorinated siloxane units in the hard and the soft segments, respectively, were prepared from polyester polyol, α,ω‐dihydroxypoly[(3,3,3‐trifluoropropyl) methylsiloxane] (PTFPMS), dimethylolpropionic acid, isophorone diisocyanate, and ethylenediamine. These anionic aqueous dispersions were stable at the ambient temperature for more than 6 months. The experimental results showed that the water‐resistance performance of the PUU films prepared with the insertion of PTFPMS units into the hard segments (HFS series) were better than those prepared with the insertion of PTFPMS units into the soft segments (SFS series). The film prepared from the PUU aqueous dispersion incorporating 5 wt % PTFPMS in the hard segments exhibited the lowest water absorption amount (2.3 wt %) with the contact angle of water on the film surface greater than 90°. In comparison with the PUU film without adding PTFPMS, the waterproof performance and the mechanical properties of both HFS and SFS series were enhanced markedly. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5005–5016, 2007

Preparation and properties of waterborne polyurethane‐urea/sodium alginate blends for high water vapor permeable coating materials

AbstractTo improve the water vapor permeability of coating materials, aqueous sodium alginate (SA) solution was blended with waterborne polyurethane‐urea (WBPU) dispersions synthesized by prepolymer mixing process. The content of SA for stable WBPU/SA dispersions was found to be below 30 wt %. As the SA content increased, the number and density of total micropores (tunnel‐like micropores/isolated micropores) formed after dissolution of SA in water increased, and the water vapor permeability of coated Nylon fabric also increased remarkably. These results clearly demonstrate that utilizing WBPU/water soluble polymer SA blends as coating materials and then dissolving SA in water surely facilitate obtaining prominent breathable fabrics. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

Polyurethaneurea aqueous dispersions prepared with diethyltoluenediamine as chain extender

A series of polyurethaneurea (PUU) aqueous dispersions either with diethyltoluenediamine (DETDA) or ethylenediamine (EDA) as chain extender were prepared with polyester polyol, isophorone diisocyanate and dimethylol propionic acid (DMPA), and characterized. It was found that the physical properties of the PUU aqueous dispersions prepared with DETDA were similar to or better than those prepared with EDA. Compared with the EDA-extended waterborne PUU films, the water resistance and the mechanical properties of the DETDA-extended waterborne PUU films were enhanced appreciably; these enhancements are attributed to the strong hydrogen bonding in urea carbonyl groups and the ordered structure of hard segments in the systems. The DETDA-extended PUU film with 40 wt.% of hard segment and 4.0 wt.% of DMPA unit showed the lowest water-absorbing amount (2.6 wt.%) over all PUU films studied. The hydrophobic surface of the DETDA-extended PUU film modified with a small amount of aminoethylaminopropyl polydimethylsiloxane (AEAPS) was observed and its hydrophobicity was enhanced by increasing the AEAPS content further.

Phase Change Materials-Embedded Coatings Prepared by In-situ Polymerisation of Water-borne Polyurethane-urea

Waterborne polyurethane-urea (WBPU) emulsions embedded with phase change materials (PCM; hexadecane, octadecane, and eicosane) as microspheres were prepared by in-situ polymerisation in an emulsion system. Polyamide fabrics were coated with coating materials formulated from PCM embedded WBPU/thickener/hardener. The maximum /optimum contents of embeddable PCM in WBPU dispersions for stable WBPU emulsions were found to be about 30 wt%. By DSC analysis,)Hfusion,)Hcrystallization, and the embedding efficiencies of PCM of film samples were found to increase with increasing PCM contents of up to 30 wt% to reach their maximum values. The maximum buffering temperature of polyamide fabrics coated with PCM (30 wt%) embedded WBPU were about ± 3 °C around the phase transition points of PCM. The PCM (30 wt%) embedded WBPUs dispersions prepared here by in-situ polymerisation show excellent potential as coating materials, with good heating and cooling functions.

Preparation and properties of waterborne polyurethane-urea/poly(vinyl alcohol) blends for high water vapor permeable coating materials

High water vapor permeable coating materials were prepared by blending aqueous poly(vinyl alcohol) (PVA) solution with waterborne polyurethane-urea (WBPU) dispersions synthesized by prepolymer mixing process. Stable WBPU/PVA dispersions were achieved at PVA content below 30 wt%. As the water soluble polymer PVA content increased, the number and density of total micro-pores (tunnel-like/isolated micro-pores) formed after the dissolution of PVA in water increased, and the water vapor permeability of coated Nylon fabric also increased significantly. Using WBPU/water soluble polymer PVA blends as a coating material and then dissolving PVA in water was confirmed to be an effective method to obtain prominent breathable fabrics.

Preparation and properties of waterborne polyurethaneurea consisting of fluorinated siloxane units

AbstractA series of polyurethaneurea (PUU) aqueous dispersions were prepared via a prepolymer process from polyester polyol, α,ω‐dihydroxypoly[(3,3,3‐trifluoropropyl) methylsiloxane] (PTFPMS), dimethylolpropionic acid, isophorone diisocyanate, and ethylenediamine. These anionic‐type aqueous dispersions were stable at the ambient temperature for more than 6 months, with particle sizes ranging from 69 to 127 nm. For these aqueous dispersions, the surface tension decreased with increasing PTFPMS content, but the particle size increased with a maximum value. The film prepared from the PUU aqueous dispersion consisting of 5 wt % PTFPMS (APU‐FS‐5) exhibited excellent waterproof performance. Furthermore, the tensile strength of the APU‐FS‐5 film increased nearly 3 times compared with that of the PUU film without PTFPMS, whereas the elongation at break only decreased a little; this indicated that the water‐resistant and mechanical properties could be enhanced markedly and simultaneously for the PUU films containing both silicon and fluorine groups. The experimental results showed a high degree of hydrogen bonding for urea groups and an increased microphase‐separation degree between the hard and soft segments in the PTFPMS‐modified system, which resulted in the excellent mechanical properties of these films. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3365–3373, 2006

Preparation and Characterization of Waterborne Polyurethaneurea Composed of Dimer Fatty Acid Polyester Polyol

A series of polyurethaneurea (PUU) aqueous dispersions, which were stable at ambient temperature for more than 1 year, were prepared with C 36‐dimer‐fatty‐acid‐based polyester polyol, isophorone diisocyanate, dimethylol propionic acid, and ethylenediamine. The particle size of all these PUU (DPU) aqueous dispersions (<100 nm) was less than that of comparable specimens, that is, poly‐(neopentyl glycol adipate) polyester‐polyol‐based PUU (APU) aqueous dispersions, and the polydispersity index was very narrow (≤1.13). The films prepared with the DPU aqueous dispersions exhibited excellent waterproof performance, such as low amount of water absorption (1.3 wt%), and good mechanical properties (hardness and tensile strength), resulting from the strong hydrogen bonding in urea carbonyl groups and the perfect ordered structure of hard segments compared with those prepared with the APU aqueous dispersions. The surface hydrophobicity of the films prepared with modified DPU aqueous dispersions, which were modified with a fluorinated polyacrylate emulsion, was excellent, as the water contact angle on the surface of such films rose up to 100. The mechanical properties of such modified DPU films were further enhanced.

Preparation and properties of waterborne polyurethane?urea anionomers?influences of the type of neutralizing agent and chain extender

Waterborne polyurethane–urea anionomers were prepared by polyaddition reaction using isophorone diisocyanate (IPDI), poly(tetramethylene ether) glycol (PTMG, Mn=1000), dimethylolbutanoic acid (DMBA), and hydrazine monohydrate (HD), ethylene diamine (EDA), 1,4-butane diamine (BDA) as a chain extender, followed by neutralization of pendant COOH groups by NH4OH/Cu(OH)2 or triethylamine (TEA) as a neutralizing agent. The effects of the types of neutralizing agent such as NH4OH/Cu(OH)2 and TEA with various chain extenders on the properties of waterborne polyurethane–urea ionomers were investigated. Two loss modulus peaks for all samples are observed owing to the glass transition temperature of soft segments (Tg s) and the glass transition temperature of hard segments (Tg h). The conductivity, Tg h, ΔTg, and tensile strength/modulus of TEA-based samples increased in the order of BDA>EDA>HD; however, those of NH4OH/Cu(OH)2-based samples increased in the order of HD>EDA>BDA. TEA-based film samples were found to have higher thermal stability, Tg h, ΔTg, tensile strength/modulus, and storage modulus than NH4OH/Cu(OH)2-based ones at the same chain extender. On the other hand NH4OH/Cu(OH)2-based samples had higher conductivity and stronger antibacterial halo than TEA-based samples.

Preparation and properties of waterborne polyurethane–urea anionomers. I. The influence of the degree of neutralization and counterion

AbstractTwo series of waterborne polyurethane–urea anionomers were prepared by a polyaddition reaction with isophorone diisocyanate, poly(tetramethylene oxide) glycol (weight‐average molecular weight = 1000), dimethylol propionic acid (DMPA), and ethylene diamine as chain extenders. Triethylamine (TEA) or 28:1 mol/mol ammonium hydroxide (NH4OH)/cupric hydroxide [Cu(OH)2] was used as a neutralization agent [NH(C2H5) or NH/Cu2+ counterion] for the pendant COOH group of DMPA. The effects of the degree of neutralization and counterion on the particle size of the dispersions, the conductivity, and the antibacterial and mechanical properties of polyurethane–urea anionomer films were investigated. The particle sizes of the two sample series dispersions decreased with an increasing degree of neutralization. Aqueous dispersions of polyurethane–urea anionomers with particle sizes of 30–120 nm were stable for about 3 months. By infrared spectroscopy, it was found that TEA‐based samples (T series) had higher fractions of hydrogen‐bonded carbonyl groups in the ordered region than NH4OH/Cu(OH)2‐based samples (S series). However, the fractions of hydrogen‐bonded carbonyl groups in the disordered region of the S‐series samples were higher than those of the T‐series samples. The conductivities of the S‐series film samples were higher than those of the T‐series samples. However, the T‐series film samples commonly had higher tensile strengths and initial moduli than the S‐series samples. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2375–2383, 2002