Rheology of Thermoplastic Polyurethanes

2007 ◽  
Author(s):  
Chang Dae Han
Keyword(s):  
Rheological Behavior ◽  
Thermoplastic Polyurethane ◽  
Complete Characterization ◽  
Chain Extender ◽  
Reaction Sequence ◽  
Molecular Weights ◽  
Soft Segments ◽  
Hard Segments ◽  
A Chain ◽  
Long Chain

Thermoplastic polyurethane (TPU) has received considerable attention from both the scientific and industrial communities (Hepburn 1982; Oertel 1985; Saunders and Frish 1962). Applications for TPUs include automotive exterior body panels, medical implants such as the artificial heart, membranes, ski boots, and flexible tubing. Figure 10.1 gives a schematic that shows the architecture of TPU, consisting of hard and soft segments. Hard segments, which form a crystalline phase at service temperature, are composed of diisocyanate and short-chain diols as a chain extender, while soft segments, which control low-temperature properties, are composed of difunctional long-chain polydiols with molecular weights ranging from 500 to 5000. The soft segments form a flexible matrix between the hard domains. TPUs are synthesized by reacting difunctional long-chain diol with diisocyanate to form a prepolymer, which is then extended by a chain extender via one of two routes: (1) by a dihydric glycol chain extender or (2) by a diamine chain extender. The most commonly used diisocyanate is 4,4’-diphenylmethane diisocyanate (MDI), which reacts with a difunctional polyol forming soft segments, such as poly(tetramethylene adipate) (PTMA) or poly(oxytetramethylene) (POTM), to produce TPU, in which 1,4-butanediol (BDO) is used as a chain extender. There are two methods widely used to produce TPU: (1) one-shot reaction sequence and (2) two-stage reaction sequence. The reaction sequences for both methods are well documented in the literature (Hepburn 1982). It should be mentioned that MDI/BDO/PTMA produces ester-based TPU. One can also produce ether-based TPU when MDI reacts with POTM using BDO as a chain extender. TPUs are often referred to as “multiblock copolymers.” In order to have a better understanding of the rheological behavior of TPUs, one must first understand the relationships between the chemical structure and the morphology; thus, a complete characterization of the materials must be conducted. The rheological behavior of TPU depends, among many factors, on (1) the composition of the soft and hard segments, (2) the lengths of the soft and hard segments and the sequence length distribution, (3) anomalous linkages (branching, cross-linking), and (4) molecular weight.

scholarly journals Green TPUs from Prepolymer Mixtures Designed by Controlling the Chemical Structure of Flexible Segments

2021 ◽  
Vol 22 (14) ◽  
pp. 7438
Author(s):  
Paulina Kasprzyk ◽  
Ewa Głowińska ◽  
Paulina Parcheta-Szwindowska ◽  
Kamila Rohde ◽  
Janusz Datta
Keyword(s):  
Chemical Structure ◽  
Melt Flow Index ◽  
Molar Ratio ◽  
Flow Index ◽  
Step Method ◽  
Elongation At Break ◽  
Molecular Weights ◽  
Trimethylene Glycol ◽  
Hard Segments ◽  
A Chain

This study concerns green thermoplastic polyurethanes (TPU) obtained by controlling the chemical structure of flexible segments. Two types of bio-based polyether polyols—poly(trimethylene glycol)s—with average molecular weights ca. 1000 and 2700 Da were used (PO3G1000 and PO3G2700, respectively). TPUs were prepared via a two-step method. Hard segments consisted of 4,4′-diphenylmethane diisocyanates and the bio-based 1,4-butanodiol (used as a chain extender and used to control the [NCO]/[OH] molar ratio). The impacts of the structure of flexible segments, the amount of each type of prepolymer, and the [NCO]/[OH] molar ratio on the chemical structure and selected properties of the TPUs were verified. By regulating the number of flexible segments of a given type, different selected properties of TPU materials were obtained. Thermal analysis confirmed the high thermal stability of the prepared materials and revealed that TPUs based on a higher amount of prepolymer synthesized from PO3G2700 have a tendency for cold crystallization. An increase in the amount of PO3G1000 at the flexible segments caused an increase in the tensile strength and decrease in the elongation at break. Melt flow index results demonstrated that the increase in the amount of prepolymer based on PO3G1000 resulted in TPUs favorable in terms of machining.

scholarly journals The Green Approach to the Synthesis of Bio-Based Thermoplastic Polyurethane Elastomers with Partially Bio-Based Hard Blocks

Materials ◽  
2021 ◽  
Vol 14 (9) ◽  
pp. 2334
Author(s):  
Ewa Głowińska ◽  
Paulina Kasprzyk ◽  
Janusz Datta
Keyword(s):  
Mechanical Properties ◽  
Thermoplastic Polyurethane ◽  
Viscoelastic Behavior ◽  
Polymeric Materials ◽  
Building Blocks ◽  
Chain Extender ◽  
Sustainable Chemistry ◽  
Polyurethane Elastomers ◽  
Thermoplastic Polyurethane Elastomers ◽  
Hard Segments

Bio-based polymeric materials and green routes for their preparation are current issues of many research works. In this work, we used the diisocyanate mixture based on partially bio-based diisocyanate origin and typical petrochemical diisocyanate for the preparation of novel bio-based thermoplastic polyurethane elastomers (bio-TPUs). We studied the influence of the diisocyanate mixture composition on the chemical structure, thermal, thermomechanical, and mechanical properties of obtained bio-TPUs. Diisocyanate mixture and bio-based 1,4-butanediol (as a low molecular chain extender) created bio-based hard blocks (HS). The diisocyanate mixture contained up to 75 wt % of partially bio-based diisocyanate. It is worth mentioning that the structure and amount of HS impact the phase separation, processing, thermal or mechanical properties of polyurethanes. The soft blocks (SS) in the bio-TPU’s materials were built from α,ω-oligo(ethylene-butylene adipate) diol. Hereby, bio-TPUs differed in hard segments content (c.a. 30; 34; 40, and 53%). We found that already increase of bio-based diisocyanate content of the bio-TPU impact the changes in their thermal stability which was measured by TGA. Based on DMTA results we observed changes in the viscoelastic behavior of bio-TPUs. The DSC analysis revealed decreasing in glass transition temperature and melting temperature of hard segments. In general, obtained materials were characterized by good mechanical properties. The results confirmed the validity of undertaken research problem related to obtaining bio-TPUs consist of bio-based hard building blocks. The application of partially bio-based diisocyanate mixtures and bio-based chain extender for bio-TPU synthesis leads to sustainable chemistry. Therefore the total level of “green carbons” increases with the increase of bio-based diisocyanate content in the bio-TPU structure. Obtained results constitute promising data for further works related to the preparation of fully bio-based thermoplastic polyurethane elastomers and development in the field of bio-based polymeric materials.

Preparation of microporous thermoplastic polyurethane by low-temperature supercritical CO2 foaming

2016 ◽  
Vol 53 (2) ◽  
pp. 135-150 ◽  
Author(s):  
Chien-Chia Chu ◽  
Shu-Kai Yeh ◽  
Sheng-Ping Peng ◽  
Ting-Wei Kang ◽  
Wen-Jeng Guo ◽  
...  
Keyword(s):  
Polyurethane Foam ◽  
Supercritical Co2 ◽  
Thermoplastic Polyurethane ◽  
Saturation Temperature ◽  
Phenyl Isocyanate ◽  
Blowing Agent ◽  
Soft Segments ◽  
Hard Segments ◽  
Poly Propylene ◽  
Foam Production

Thermoplastic polyurethane possesses many special characteristics. Its flexibility, rigidity, and elasticity can be adjusted by controlling the ratio of soft segments to hard segments. Due to its versatile physical properties, thermoplastic polyurethane is commonly used in transportation, construction, and biomaterials. However, methods for thermoplastic polyurethane foam production using CO2 are still under investigation. We have previously prepared nanoporous thermoplastic polyurethane foam using commercially available thermoplastic polyurethane; however, in this study, thermoplastic polyurethane was synthesized using 4,4′-methylenebis(phenyl isocyanate), poly(propylene glycol) and 1,4-butanediol, without solvents, using a pre-polymer method. The properties of the synthesized thermoplastic polyurethane were characterized by Fourier transform infrared spectroscopy, thermal analysis, and their mechanical properties were measured. The synthesized thermoplastic polyurethane was foamed by batch foaming using supercritical CO2 as the blowing agent. The effect of saturation temperature and saturation time on the cell morphology of the thermoplastic polyurethane foam was examined.

Synthesis and blood compatibilities of novel segmented polyurethanes containing phosphatidylcholine analogous moieties in the main chains and long-chain alkyl groups in the side chains

1999 ◽  
Vol 14 (9) ◽  
pp. 3789-3798 ◽  
Author(s):  
Arata Korematsu ◽  
Yu-Jun Li ◽  
Takayuki Murakami ◽  
Tadao Nakaya
Keyword(s):  
Platelet Adhesion ◽  
Platelet Rich Plasma ◽  
Side Chains ◽  
Alkyl Groups ◽  
Low Degree ◽  
Soft Segments ◽  
Hard Segments ◽  
Segmented Polyurethanes ◽  
Methylenediphenyl Diisocyanate ◽  
Long Chain

New segmented polyurethanes containing phospholipid moieties in the main chains and long-chain alkyl groups in the side chains were synthesized. The soft segments used in this study were poly(butadiene), poly(isoprene), hydrogenated poly(isoprene), and poly(1,6-hexyl-1,2-ethylcarbonate) diol. The hard segments of these polyurethanes were 4,4′-methylenediphenyl diisocyanate, bis[2-(2-hydroxyethyldimethylammonio)ethyl]2-cetyl- 1,3-propanediphosphate, and 1,4-butanediol. The blood compatibilities of the new polymers were evaluated by platelet-rich plasma contact studies and viewed by scanning electron microscopy using medical grade BioSpan® and nonphospholipid polyurethane as references. These new materials have good surfaces in terms of platelet adhesion, and the morphology of adhered platelets undergoes a relatively low degree of variation.

scholarly journals Mechano-responsive hydrogen-bonding array of thermoplastic polyurethane elastomer captures both strength and self-healing

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Youngho Eom ◽  
Seon-Mi Kim ◽  
Minkyung Lee ◽  
Hyeonyeol Jeon ◽  
Jaeduk Park ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Thermoplastic Polyurethane ◽  
Healing Process ◽  
Polyurethane Elastomer ◽  
Self Healing ◽  
Static Mode ◽  
Soft Segments ◽  
Hard Segments ◽  
Thermoplastic Polyurethane Elastomer ◽  
Dynamic Exchange

AbstractSelf-repairable materials strive to emulate curable and resilient biological tissue; however, their performance is currently insufficient for commercialization purposes because mending and toughening are mutually exclusive. Herein, we report a carbonate-type thermoplastic polyurethane elastomer that self-heals at 35 °C and exhibits a tensile strength of 43 MPa; this elastomer is as strong as the soles used in footwear. Distinctively, it has abundant carbonyl groups in soft-segments and is fully amorphous with negligible phase separation due to poor hard-segment stacking. It operates in dual mechano-responsive mode through a reversible disorder-to-order transition of its hydrogen-bonding array; it heals when static and toughens when dynamic. In static mode, non-crystalline hard segments promote the dynamic exchange of disordered carbonyl hydrogen-bonds for self-healing. The amorphous phase forms stiff crystals when stretched through a transition that orders inter-chain hydrogen bonding. The phase and strain fully return to the pre-stressed state after release to repeat the healing process.

Gelation of thermoplastic polyurethane/2-butanone solutions

e-Polymers ◽  
2005 ◽  
Vol 5 (1) ◽  
Author(s):  
Sonia Florez ◽  
María Eugenia Muñoz ◽  
Anton Santamaría
Keyword(s):  
Hard Segment ◽  
Critical Concentration ◽  
Thermoplastic Polyurethane ◽  
Crystallization Rate ◽  
Solution Viscosity ◽  
Scanning Calorimetry ◽  
Soft Segments ◽  
Gelation Concentration ◽  
Hard Segments ◽  
Chain Entanglements

AbstractNew features of thermoplastic polyurethane (PUR)/2-butanone gels are investigated, using dynamic viscoelastic measurements and differential scanning calorimetry. The work is focused on the effect of the hard-segments content on the gelation process. In the case of PUR with the highest hard-segment fraction (30%), soft segments are not able to crystallize on cooling from solution; consequently, gels are not formed. The copolymer with the lowest hard-segment content (12%) gives the shortest gel times. This is attributed to the low solution viscosity of this copolymer, which enhances the crystallization rate. All gels melt at 7°C, giving rise to a viscoelastic solution in a thermoreversible process. The critical gelation concentration is below the critical concentration for polymer chain entanglements.

Poly[( N-Acylimino)ethylene] Derivatives for Advanced Materials

2009 ◽  
Vol 21 (5) ◽  
pp. 596-607 ◽  
Author(s):  
Geta David ◽  
Bogdan C. Simionescu
Keyword(s):  
Phenyl Isocyanate ◽  
Chain Extender ◽  
Advanced Materials ◽  
Inorganic Component ◽  
Poly Ethylene Oxide ◽  
Hard Segments ◽  
Segmented Polyurethanes ◽  
Poly Ethylene ◽  
A Chain ◽  
Tetramethylene Oxide

New segmented polyurethanes containing soft and hard segments of different polarity and hydrophilicity, based on 4,4′-methylenebis-(cyclohexyl isocyanate, 4,4′-methylenebis-(phenyl isocyanate) and poly(tetramethylene oxide) or poly(ethylene oxide) were prepared including poly[( N-acylimino) ethylene] sequences as a chain extender. They were comparatively characterized by spectral, thermal and mechanical techniques. Some preliminary investigations on their nanocomposites with montmorillonite as an inorganic component are presented.

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