scholarly journals New Waterborne Polyurethane-Urea Synthesized with Ether-Carbonate Copolymer and Amino-Alcohol Chain Extenders with Tailored Pressure-Sensitive Adhesion Properties

Materials ◽  
2020 ◽  
Vol 13 (3) ◽  
pp. 627 ◽  
Author(s):  
Mónica Fuensanta ◽  
Abbas Khoshnood ◽  
Francisco Rodríguez-Llansola ◽  
José Miguel Martín-Martínez
Keyword(s):  
Amino Alcohol ◽  
Peel Test ◽  
Waterborne Polyurethane ◽  
Chain Extender ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Adhesion Properties ◽  
Oh Groups ◽  
Pressure Sensitive ◽  
Chain Extenders

New waterborne polyurethane-urea dispersions with adequate adhesion and cohesion properties have been synthesized by reacting isophorone diisocyanate, copolymer of ether and carbonate diol polyol and three amino-alcohols with different number of OH groups chain extenders using the prepolymer method. The waterborne polyurethane-urea dispersions were characterized by pH, particle-size distribution, and viscosity, and the polyurethane-urea films were characterized by attenuated total reflectance infrared (ATR-IR) spectroscopy, differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and plate-plate rheology (temperature and frequency sweeps). Polyurethane-urea pressure-sensitive adhesives (PUU PSAs) were prepared by placing the waterborne polyurethane dispersions on polyethylene terephthalate (PET) films and they were characterized at 25 °C by creep test, tack and 180° peel test. The waterborne polyurethane-urea dispersions showed mean particle sizes between 51 and 78 nm and viscosities in the range of 58–133 mPa·s. The polyurethane-urea films showed glass transition temperatures (Tgs) lower than −64 °C, and they showed a cross of the storage and loss moduli between −8 and 68 °C depending on the number of OH groups in the amino-alcohol chain extender. Different types of PUU PSAs (removable, high shear) were obtained by changing the number of OH groups in the amino-alcohol chain extender. The tack at 25 °C of the PUU PSAs varied between 488 and 1807 kPa and the 180° peel strength values ranged between 0.4 and 6.4 N/cm, and their holding times were between 2 min and 5 days. The new PUU PSAs made with amino-alcohol chain extender seemed very promising for designing environmentally friendly waterborne PSAs with high tack and improved cohesion and adhesion property.

scholarly journals Structural and Viscoelastic Properties of Thermoplastic Polyurethanes Containing Mixed Soft Segments with Potential Application as Pressure Sensitive Adhesives

Polymers ◽  
2021 ◽  
Vol 13 (18) ◽  
pp. 3097
Author(s):  
Mónica Fuensanta ◽  
José Miguel Martín-Martínez
Keyword(s):  
Phase Separation ◽  
Potential Application ◽  
Viscoelastic Properties ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Adhesion Properties ◽  
Pressure Sensitive Adhesives ◽  
Thermoplastic Polyurethanes ◽  
Pressure Sensitive ◽  
Soft Segments

Thermoplastic polyurethanes (TPUs) were synthetized with blends of poly(propylene glycol) (PPG) and poly(1,4-butylene adipate) (PAd) polyols, diphenylmethane-4,4′-diisocyanate (MDI) and 1,4-butanediol (BD) chain extender; different NCO/OH ratios were used. The structure and viscoelastic properties of the TPUs were assessed by infrared spectroscopy, differential scanning calorimetry, X-ray diffraction, thermal gravimetric analysis and plate-plate rheology, and their pressure sensitive adhesion properties were assessed by probe tack and 180° peel tests. The incompatibility of the PPG and PAd soft segments and the segregation of the hard and soft segments determined the phase separation and the viscoelastic properties of the TPUs. On the other hand, the increase of the NCO/OH ratio improved the miscibility of the PPG and PAd soft segments and decreased the extent of phase separation. The temperatures of the cool crystallization and melting were lower and their enthalpies were higher in the TPU made with NCO/OH ratio of 1.20. The moduli of the TPUs increased by increasing the NCO/OH ratio, and the tack was higher by decreasing the NCO/OH ratio. In general, a good agreement between the predicted and experimental tack and 180° peel strength values was obtained, and the TPUs synthesized with PPG+PAd soft segments had potential application as pressure sensitive adhesives (PSAs).

scholarly journals Structure–Properties Relationship in Waterborne Poly(Urethane-Urea)s Synthesized with Dimethylolpropionic Acid (DMPA) Internal Emulsifier Added before, during and after Prepolymer Formation

Polymers ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 2478
Author(s):  
Mónica Fuensanta ◽  
Abbas Khoshnood ◽  
José Miguel Martín-Martínez
Keyword(s):  
Particle Size ◽  
Phase Separation ◽  
Ph Value ◽  
Peel Test ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Adhesion Properties ◽  
Structural Differences ◽  
Higher Temperature ◽  
Structure Properties

Dimethylolpropionic acid (DMPA) internal emulsifier has been added before, during and after prepolymer formation in the synthesis of waterborne poly(urethane-urea)s (PUDs) and their structure–properties relationships have been assessed. PUDs were characterized by pH, viscosity and particle size measurements, and the structure of the poly(urethane-urea) (PU) films was assessed by infra-red spectroscopy, differential scanning calorimetry, X-ray diffraction, thermal gravimetric analysis, plate–plate rheology and dynamic mechanical thermal analysis. The adhesion properties of the PUDs were measured by cross-hatch adhesion and T-peel test. The lowest pH value and the highest mean particle size were found in the PUD made by adding DMPA after prepolymer formation, all PUDs showed relatively ample mono-modal particle size distributions. The highest viscosity and noticeable shear thinning were obtained in the PUD made by adding DMPA during prepolymer formation. Depending on the stage of addition of DMPA, the length of the prepolymer varied and the PU films showed different degree of micro-phase separation. Because the shortest prepolymer was formed in the PU made with DMPA added before prepolymer, this PU film showed the lowest storage moduli and early melting indicating higher degree of micro-phase separation. The highest storage modulus, later melting, higher temperature and lower modulus at the cross between the storage and loss moduli corresponded to the PU made by adding DMPA after prepolymer formation, because the longer prepolymer produced during synthesis. The lowest thermal stability corresponded to the PU made by adding DMPA during prepolymer formation and the structures of all PU films were dominated by the soft domains, the main structural differences derived from the hard domains. Whereas DMPA-isophorone diisocyanate (IPDI) urethane and urea hard domains were created in the PU film made by adding DMPA during prepolymer formation, the other PU films showed DMPA-IPDI, polyester-IPDI and two different DMPA-IPDI-polyester hard domains. Finally, the adhesion properties of the PUDs and PU coatings were excellent and they were not influenced by the structural differences caused by adding DMPA in different stages of the synthesis.

New Polyurethane Sealants Containing Rosin for Non-Invasive Disc Regeneration Surgery

2013 ◽  
Vol 583 ◽  
pp. 67-79 ◽  
Author(s):  
Pilar Carbonell-Blasco ◽  
Iulian Antoniac ◽  
Jose Miguel Martin-Martinez
Keyword(s):  
Peel Test ◽  
Peel Strength ◽  
Chain Extender ◽  
Polymer Chains ◽  
Scanning Calorimetry ◽  
Disc Regeneration ◽  
Non Invasive ◽  
Lap Shear ◽  
Chain Extenders ◽  
Butane Diol

Different polyurethane sealants were prepared by reacting methylene dyísocyanate and polyadipate of 1,4 butane diol (Mw : 2500 daltons) by using the prepolymer method and different mixtures of rosin and 1,4 butane diol were used as chain extenders. The polyurethanes were characterized by plate-plate rheology, molecular weight distribution, Differential Scanning Calorimetry (DSC), and Laser Confocal Microscopy. The tack of the polyurethanes sealants was obtained by using a modified probe tack method, and their adhesion was obtained by T-peel test of leather/polyurethane sealant/leather joints and by single lap-shear tests of aluminium/polyurethane sealant/aluminium joints. Depending on the rosin content in the chain extender the structure of the polyurethanes was different, i.e. more urethane and urethane-amide hard segments were created up to 50 eq% rosin in the chain extender, and separation of domains was prevailing in the polyurethanes with higher rosin content. Furthermore, the addition of rosin caused an increase in the length of the polymer chains and in the storage modulus (particularly in the polyurethane containing 50 eq% rosin), and decrease in the melting enthalpy. Moreover, the crystallinity of the polyurethanes containing up to 50 eq% rosin showed lower number and smaller spherulites, Finally, the tack at 37 °C and the peel strength increased in the joints made with the polyurethane sealants containing rosin whereas the adhesive shear strength decreased when the polyurethane sealant contained 50 eq% rosin or less.

scholarly journals Balanced Viscoelastic Properties of Pressure Sensitive Adhesives Made with Thermoplastic Polyurethanes Blends

Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1608 ◽  
Author(s):  
Fuensanta ◽  
Vallino-Moyano ◽  
Martín-Martínez
Keyword(s):  
Phase Separation ◽  
Viscoelastic Properties ◽  
Simple Procedure ◽  
Peel Strength ◽  
Similar Degree ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Pressure Sensitive Adhesives ◽  
Thermoplastic Polyurethanes ◽  
Pressure Sensitive

Pressure sensitive adhesives made with blends of thermoplastic polyurethanes (TPUs PSAs) with satisfactory tack, cohesion, and adhesion have been developed. A simple procedure consisting of the physical blending of methyl ethyl ketone (MEK) solutions of two thermoplastic polyurethanes (TPUs) with very different properties—TPU1 and TPU2—was used, and two different blending procedures have been employed. The TPUs were characterized by infra-red spectroscopy in attenuated total reflectance mode (ATR-IR spectroscopy), differential scanning calorimetry, thermal gravimetric analysis, and plate-plate rheology (temperature and frequency sweeps). The TPUs PSAs were characterized by tack measurement, creep test, and the 180° peel test at 25 °C. The procedure for preparing the blends of the TPUs determined differently their viscoelastic properties, and the properties of the TPUs PSAs as well, the blending of separate MEK solutions of the two TPUs imparted higher tack and 180° peel strength than the blending of the two TPUs in MEK. TPU1 + TPU2 blends showed somewhat similar contributions of the free and hydrogen-bonded urethane groups and they had an almost similar degree of phase separation, irrespective of the composition of the blend. Two main thermal decompositions at 308–317 °C due to the urethane hard domains and another at 363–373 °C due to the soft domains could be distinguished in the TPU1 + TPU2 blends, the weight loss of the hard domains increased and the one of the soft domains decreased by increasing the amount of TPU2 in the blends. The storage moduli of the TPU1 + TPU2 blends were similar for temperatures lower than 20 °C and the moduli at the cross over of the moduli were lower than in the parent TPUs. The improved properties of the TPU1 + TPU2 blends derived from the creation of a higher number of hydrogen bonds upon removal of the MEK solvent, which lead to a lower degree of phase separation between the soft and the hard domains than in the parent TPUs. As a consequence, the properties of the TPU1 + TPU2 PSAs were improved because good tack, high 180° peel strength, and sufficient cohesion were obtained, particularly in 70 wt% TPU1 + 30 wt% TPU2 PSA.

scholarly journals Thermal stability of segmented polyurethane elastomers reinforced by clay particles

2009 ◽  
Vol 63 (6) ◽  
pp. 621-628 ◽  
Author(s):  
Jelena Pavlicevic ◽  
Jaroslava Budinski-Simendic ◽  
Mészáros Szécsényi ◽  
Nada Lazic ◽  
Milena Spirkova ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Thermal Properties ◽  
Chain Extender ◽  
Hexamethylene Diisocyanate ◽  
Scanning Calorimetry ◽  
Modulated Differential Scanning Calorimetry ◽  
Polyurethane Elastomers ◽  
Oh Groups ◽  
Clay Nanoparticles ◽  
Thermal Stability Of

The aim of this work was to determine the influence of clay nanoparticles on thermal properties of segmented polyurethanes based on hexamethylene- diisocyanate, aliphatic polycarbonate diol and 1,4-butanediol as chain extender. The organically modified particles of montmorillonite and bentonite were used as reinforcing fillers. The structure of elastomeric materials was varied either by diol type or chain extender content. The ratio of OH groups from diol and chain extender (R) was either 1 or 10. Thermal properties of prepared materials were determined using modulated differential scanning calorimetry (MDSC). Thermal stability of obtained elastomers has been studied by simultaneously thermogravimetry coupled with DSC. The glass transition temperature, Tg, of soft segments for all investigated samples was about -33?C. On the basis of DTG results, it was concluded that obtained materials were very stable up to 300?C.

Study on thermal properties of polyurethane-urea elastomers prepared with different dianiline chain extenders

2013 ◽  
Vol 33 (1) ◽  
pp. 87-94 ◽  
Author(s):  
Majid Barikani ◽  
Naghmeh Fazeli ◽  
Mehdi Barikani
Keyword(s):  
Thermal Properties ◽  
Chain Extender ◽  
Polymerization Reaction ◽  
Dsc Analysis ◽  
Scanning Calorimetry ◽  
Polymer Characterization ◽  
Cast Films ◽  
Mechanical Measurements ◽  
Chain Extenders ◽  
Thermal Stability Of

Abstract A number of polyurethane prepolymers based on polycaprolactone diol (PCL) and 4,4′-diphenyl methane diisocyanate (MDI) were synthesized and extended with different dianilines such as: 4,4′-methylenebis(2,6-diisopropylaniline) (M-DIPA), 4,4′-methylenebis(2,6diethylaniline) (M-DEA), 4,4′-methylenebis(ortho chloroaniline) (MOCA), 4,4′-methylenebis(2-isopropyl-6-methylaniline) (M-MIPA) and 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (M-CDEA). Infrared (IR) spectroscopy was used to check the end of the polymerization reaction in addition to the polymer characterization. The effect of the dianiline structure on the thermal properties of the cast films were studied through dynamic mechanical measurements (DMTA), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis. It was found that the thermal properties and thermal stability of polyurethane are strongly affected by the molecular structure of the dianiline chain extender.

scholarly journals Addition of Graphene Oxide in Different Stages of the Synthesis of Waterborne Polyurethane-Urea Adhesives and Its Influence on Their Structure, Thermal, Viscoelastic and Adhesion Properties

Materials ◽  
2020 ◽  
Vol 13 (13) ◽  
pp. 2899 ◽  
Author(s):  
Abir Tounici ◽  
José Miguel Martín-Martínez
Keyword(s):  
Graphene Oxide ◽  
Waterborne Polyurethane ◽  
Peel Strength ◽  
Lower Percentage ◽  
Gravimetric Analysis ◽  
Water Addition ◽  
Covalent Bonds ◽  
Adhesion Properties ◽  
Lap Shear ◽  
Before And After

In this study, 0.04 wt % graphene oxide (GO) was added in different stages (before and after prepolymer formation, and during water addition) of the synthesis of waterborne polyurethane-urea dispersions (PUDs) prepared by using the acetone method. The structural, thermal, mechanical, viscoelastic, surface and adhesion properties of the polyurethane-ureas (PUUs) containing 0.04 wt % GO were studied. The addition of GO before and after prepolymer formation produced covalent bonds between the GO sheets and the NCO groups of the isocyanate, whereas the GO sheets were trapped between the polyurethane chains when added during water addition step. As a consequence, depending on the stage of the PUD synthesis in which GO was added, the degree of micro-phase separation between the hard and soft segments changed differently. The addition of GO before prepolymer formation changed more efficiently the polyurethane-urea structure, i.e., the covalently bonded GO sheets disturbed the interactions between the hard segments causing lower percentage of free urethane groups, higher crystallinity, lower storage modulus, higher yield stress and T-peel strength. The interactions between the GO sheets and the polymeric chains have been evidenced by plate-plate rheology, thermal gravimetric analysis and spectroscopy. On the other hand, physical interactions between GO and the polyurethane-urea chains were produced when GO was added in water during the synthesis, i.e., GO was acting as a nanofiller, which justified the improved mechanical properties and high lap-shear strength, but poor T-peel strength.

scholarly journals Influences of liquefied lignin content on the properties of waterborne polyurethane prepared with different chain extenders

Holzforschung ◽  
2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Wen-Jau Lee ◽  
Ming-Shan Hu ◽  
Chao-Yun Yu ◽  
Yi-Chun Chen
Keyword(s):  
Tensile Deformation ◽  
Lignin Content ◽  
Soft Segment ◽  
Waterborne Polyurethane ◽  
Chain Extender ◽  
Average Particle ◽  
Thermal Activity ◽  
Thermogravimetric Analyzer ◽  
Particle Dimension ◽  
Chain Extenders

Abstract Waterborne polyurethane resins (WPUs) were prepared from polytetramethylene ether glycol (PTMG) and PTMG/polyhydric alcohol liquefied lignin (LL) with isophorone diisocyanate (IPDI), and ethylenediamine (EDA) and 1,4-butanediol (1,4-BD) were used as chain extenders. The effects of LL and the kind of chain extender on the properties of the WPU suspensions and dried films were studied. WPU suspensions prepared with PTMG/LL as the polyol had higher viscosity and larger average particle dimension than those with PTMG alone. WPU films prepared with EDA as the chain extender had higher tensile strength with less tensile deformation. LL can enhance the stiffness of WPU films, but the breaking deformation decreases. Dynamic mechanical analyzer (DMA) results showed that the main effect of LL was reduced thermal activity of the soft segment. Thermogravimetric analyzer (TGA) results showed WPU films prepared with EDA as the chain extender had better heat-resistance than those with 1,4-BD.

MODIFICATION OF SKIM RUBBER BLENDED WITH POLY (VINYL ALCOHOL) TO BE APPLIED AS A BIODEGRADABLE PRESSURE-SENSITIVE ADHESIVE: EFFECT OF 2,6-DI-T-BUTYL-4-METHYLPHENOL AND HYDROCARBON RESIN

2012 ◽  
Vol 85 (4) ◽  
pp. 547-558 ◽  
Author(s):  
Sa-Ad Riyajan ◽  
Nataphon Pheweaw
Keyword(s):  
Vinyl Alcohol ◽  
Chain Scission ◽  
Contact Angle Measurement ◽  
Angle Measurement ◽  
Poly Vinyl Alcohol ◽  
Pressure Sensitive Adhesive ◽  
Scanning Calorimetry ◽  
Adhesion Properties ◽  
Pressure Sensitive ◽  
Adhesive Effect

ABSTRACT Pressure-sensitive adhesives (PSAs), or self-adhesives, are used in many applications, including safety labels for power equipment, automotive interior trim assembly, and sound/vibration–damping films. The objective of this study was to develop a biodegradable skim rubber–based bioadhesive blended with poly (vinyl alcohol) (PVA), which has the advantage of being biodegradable and biocompatible to humans. PSAs were produced from saponified low-protein skim rubber (S-LPSR) alone using a hydrocarbon resin as a tackifier and blends of S-LPSR/PVA containing tackifier, via solution and emulsion, respectively. The influence of 2,6-di-t-butyl-4-methylphenol (BHT) and the hydrocarbon resin content in the adhesive formulation was studied. Various methods were used to evaluate the properties of the adhesives produced including scanning electron microscopy, differential scanning calorimetry, contact angle measurement, dynamic mechanical thermal analysis, and Fourier transform infrared spectroscopy. The optimal concentration of PVA for a good PSA was found to be 20 phr because of its emulsion form. The adhesion properties of a PSA containing 50–60 phr of hydrocarbon resin and 1% BHT displayed excellent tack and peel compared with other samples because there was no chain scission of the skim rubber and good compatibility and interaction between the S-LPSR/PVA blend and the hydrocarbon resin, which maximized the adhesion properties of the adhesive.

scholarly journals Synthesis and Properties of Novel Polyurethanes Containing Long-Segment Fluorinated Chain Extenders

Polymers ◽  
2018 ◽  
Vol 10 (11) ◽  
pp. 1292 ◽  
Author(s):  
Jia-Wun Li ◽  
Hsun-Tsing Lee ◽  
Hui-An Tsai ◽  
Maw-Cherng Suen ◽  
Chih-Wei Chiu
Keyword(s):  
Hard Segment ◽  
Soft Segment ◽  
Mechanical Analysis ◽  
Chain Extender ◽  
Scanning Calorimetry ◽  
Force Microscopy ◽  
Atomic Force ◽  
Chain Extenders ◽  
Relationship Of ◽  
The Relationship

In this study, novel biodegradable long-segment fluorine-containing polyurethane (PU) was synthesized using 4,4′-diphenylmethane diisocyanate (MDI) and 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD) as hard segment, and polycaprolactone diol (PCL) as a biodegradable soft segment. Nuclear magnetic resonance (NMR) was used to perform 1H NMR, 19F NMR, 19F–19F COSY, 1H–19F COSY, and HMBC analyses on the PFD/PU structures. The results, together with those from Fourier transform infrared spectroscopy (FTIR), verified that the PFD/PUs had been successfully synthesized. Additionally, the soft segment and PFD were changed, after which FTIR and XPS peak-differentiation-imitating analyses were employed to examine the relationship of the hydrogen bonding reaction between the PFD chain extender and PU. Subsequently, atomic force microscopy was used to investigate the changes in the microphase structure between the PFD chain extender and PU, after which the effects of the thermal properties between them were investigated through thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Finally, the effects of the PFD chain extender on the mechanical properties of the PU were investigated through a tensile strength test.

Sign in / Sign up

Export Citation Format

Share Document