热塑性聚氨酯与聚氯乙烯共混研究进展

综述了热塑性聚氨酯与聚氯乙烯共混改性研究进展，重点介绍了热塑性聚氨酯与聚氯乙烯共混物的相容性、共混方式、热塑性聚氨酯的类型和组分、助剂和第三组分聚合物等对共混物性能的影响及其应用。     

Reactive blending of thermoplastic polyurethane in situ with poly(vinyl chloride)

In this study, a novel reactive blending process was developed for producing poly(vinyl chloride)/thermoplastic polyurethane (PVC/TPU) blends. An alternative to melt or solution blending, the advantages to such a blending technique are fewer processing steps and less cost, no solvent removal, reduced PVC degradation, and the potential for producing otherwise unobtainable blend morphologies and properties. Using an internal mixer, PVC was compounded and plasticized with the polyol and chain extender of a polyester‐based TPU. Then, upon addition of the stoichiometric amount of TPU diisocyanate, a high molecular weight TPU was polymerized in situ with PVC. Because of reaction‐induced phase separation, the resulting partially miscible PVC/TPU blends were characterized by heterogeneous, multiphase morphologies. In addition, they exhibited excellent tensile properties intermediate between that of neat PVC and TPU. POLYM. ENG. SCI., 45:876–887, 2005. © 2005 Society of Plastics Engineers     

热塑性聚氨酯与聚氯乙烯共混改性研究

采用机械共混法制备了热塑性聚氨酯(TPU)与聚氯乙烯(PVC)共混物。探讨了共混比对TPU／PVC共混物性能的影响，优化出TPU／PVC共混比30／70(质量比)，在此基础上研究了增塑剂、热稳定剂、填料对TPU／PVC共混物力学性能、流变性能和耐油、耐溶剂性能的影响。研究结果表明，TPU／PVC共混物的力学性能在共混时有协同作用，耐油、耐溶剂性均较好，从成本和实用两方面出发，选择TPU／PVC=30／70共混比更有实用性。随增塑剂DOP的增加，共混物的力学性能呈下降趋势。在所选热稳定剂中，以硬脂酸钙制得共混物的力学性能最好；在所选填料中，白炭黑的补强效果最好。扫描电镜观察共混物的微观结构显示，TPU／PVC共混比为30／70有较好的相容性，这与力学性能结果相一致。TGA分析显示，TPU的加入提高了共混物的热稳定性。红外光谱分析表明，TPU和PVC共混只是一个简单的物理共混过程。     

Reaction kinetics of thermoplastic polyurethane polymerization in situ with poly(vinyl chloride)

In this study, the reaction kinetics of thermoplastic polyurethane (TPU) polymerization in situ with poly(vinyl chloride) (PVC) was characterized with differential scanning calorimetry. The presence of PVC appeared to enhance the thermodynamic drive for TPU hard segment phase separation and domain ordering from the PVC/TPU reactant mixture. Prior to hard segment phase separation, and thus some critical conversion, TPU polymerization in situ with PVC obeyed the same nth order, phenomenological kinetic rate law followed by neat TPU polymerization. In addition, the overall rate constant employed in the rate law increased in the presence of PVC. After hard segment phase separation, and the resulting physical cross-linking of the PVC/TPU reactant mixture, the reaction kinetics of TPU polymerization in situ with PVC became diffusion controlled.     

弹性体改性软质聚氯乙烯性能的研究

讨论了不同品种的弹性体对软质氯乙烯的改性结果，包括不同品种和不同含量的弹性体对ＰＶＣ力学性能等性能的影响，实验了得到了性能较好的改性ＰＶＣ软质材料。     

Tailoring morphology to improve the gas‐barrier properties of thermoplastic polyurethane/ethylene‐vinyl alcohol blends

The morphology and helium‐barrier properties of thermoplastic polyurethane (TPU)/ethylene‐vinyl alcohol (EVOH) blends with and without dicumyl peroxide (DCP) were investigated by melting blending. A lamellar dispersion of EVOH with good helium‐barrier properties was observed in the TPU matrix with DCP. The evolution of the morphology of the blends is mainly related to the variation of the viscosity ratio between the dispersed phase and the matrix phase. Compared with pure TPU, lamellar morphology increased the helium‐barrier properties of the TPU/EVOH (60/40) blend by as much as 10‐fold. We also explored the effects of composition, DCP content, and blending sequence on the morphology and helium‐barrier properties of the TPU/EVOH blends. The morphology of the blends ranged from a droplet‐matrix to a lamellar structure. We determined the optimum amount of DCP to improve the helium barrier of the blends. The helium‐barrier properties of the blends prepared by direct blending were superior to those of the blends prepared by two‐segment blending, and the blends prepared by direct blending exhibited a well‐developed lamellar morphology. We compared the permeability of the samples with the theoretical results to explain the relationship between morphology and helium‐barrier properties. POLYM. ENG. SCI., 56:922–931, 2016. © 2016 Society of Plastics Engineers     

Dynamic mechanical properties of poly(vinyl chloride) and polyurethane carboxylate blends

The miscibility of thermoplastic polyurethane elastomers (TPUs) with poly(vinyl chloride) (PVC) was studied. PVC blends with TPUs, prepared from 4,4-diphenylmethane diisocyanate as diisocyanate, hydroxy-terminated poly(butylene adipate) (PBA) as the soft segment, and dimethylolpropionic acid as the chain extender carrying a latent anionic site for neutralization by triethylamine, showed a single glass transition temperature (T_g), irrespective of neutralization of latent anionic sites of TPU. But in neutralized TPU/PVC blends, limited intimate segmental mixing was perceived from the mechanical properties observed. When hydroxy-terminated poly(propylene glycol) was used as the soft segment instead of hydroxy-terminated PBA, PVC/TPU blends showed two separate T_g's of PVC and TPU, irrespective of neutralization. © 1994 John Wiley & Sons, Inc.     

Preparation of novel syndiotactic poly(vinyl alcohol) microspheres through the low‐temperature suspension copolymerization of vinyl pivalate and vinyl acetate and heterogeneous saponification

Syndiotactic poly(vinyl alcohol) (PVA)/poly(vinyl pivalate/vinyl acetate) [P(VPi/VAc)] microspheres, with a skin–core structure, were prepared through the heterogeneous saponification of copolymers of vinyl pivalate (VPi) and vinyl acetate (VAc). For the preparation of P(VPi/VAc) microspheres with various particle sizes and a uniform particle size distribution (which are promising precursors of syndiotactic PVA embolic materials to be introduced through catheters for the management of gastrointestinal bleeders, arteriovenous malformations, hemangiomas, and traumatic rupture of blood vessels), VPi and VAc were suspension‐copolymerized at 30°C with a room‐temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile). The effects of the polymerization conditions were investigated in terms of the size and size distribution of the suspension particles. P(VPi/VAc) microspheres, with various syndiotactic dyad (s‐dyad) contents, were produced through the control of the monomer feed ratio. In addition, monodisperse P(VPi/VAc) particles of various particle diameters were obtained by the separation and sieving of the polymerization product. Monodisperse P(VPi/VAc) microspheres of various particle sizes were partially saponified in the heterogeneous system, and the effects of the particle size and particle size distribution on the saponification rate were investigated in terms of the tacticity and the saponification time and temperature. Novel skin–core PVA/P(VPi/VAc) microspheres of various s‐dyad contents and degrees of saponification were successfully produced through the control of the various polymerization and saponification parameters. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1539–1548, 2005     

Synthesis and flocculation properties of poly(diallyldimethyl ammonium chloride–vinyl trimethoxysilane) and poly(diallyldimethyl ammonium chloride–acrylamide–vinyl trimethoxysilane)

Poly(diallyldimethyl ammonium chloride–vinyl trimethoxysilane) [P(DADMAC–VTMS)] and poly(diallyldimethyl ammonium chloride–acrylamide–vinyl trimethoxysilane) [P(DADMAC–AM–VTMS)], the latter a new cationically charged and hydrophobically modified flocculant, were obtained by radical polymerization initiated by potassium persulfate. The effects of the vinyl trimethoxysilane (VTMS) feed ratio on the intrinsic viscosity and solubility of the polymers were examined. The effects of the flocculants on turbidity removal, decolorization, and oil removal in water treatment were also studied. The introduction of VTMS increased the intrinsic viscosities of P(DADMAC–VTMS) and P(DADMAC–AM–VTMS) in comparison with the viscosities of poly(diallyldimethyl ammonium chloride) and poly(diallyldimethyl ammonium chloride–acrylamide), respectively, but reduced their solubilities. The introduction of VTMS also enhanced the flocculation properties of P(DADMAC–VTMS) and P(DADMAC–AM–VTMS), including turbidity removal, decolorization, and oil removal. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 335–342, 2002; DOI 10.1002/app.10339     

Dynamic mechanical and morphological studies on the compatibility of plasticized PVC/thermoplastic polyurethane blends

In this work, the compatibility of blends of plasticized poly(vinyl chloride) (p‐PVC) and thermoplastic polyurethane (TPU) was investigated using a dynamic mechanical analyzer and scanning electron microscopy. Two kinds of TPU with different ratios of hard to soft segments, i.e., TPU90 and TPU70 were compared. p‐PVC/TPU90 and p‐PVC/TPU70 blends with variable weight ratios (100/0, 90/10, 80/20, 70/30, 60/40, 50/50, 0/100) were prepared by melt blending. PVC was plasticized with 40 phr of dioctyl phthalate. It was found that TPU with a lower hard segment (i.e., TPU70) is more compatible with plasticized PVC than TPU with a higher hard segment (i.e., TPU90) in over the composition ranges examined. It was concluded that the compatibility of plasticized PVC and TPU are dependent on the ratio of hard to soft segments in TPU. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 415–422, 1999     

Constructing the core–shell structured island domain in polymer blends to achieve high dielectric constant and low loss

Carbon nanotubes (CNTs) and barium titanate (BaTiO₃) (BT) were simultaneously introduced into the immiscible blend poly(ethylene‐co‐vinyl acetate)/thermoplastic urethane (EVA/TPU), and the EVA/TPU/CNT/BT quaternary polymer composite blends with core–shell structured island TPU domain were successfully prepared, in which CNTs in the TPU domain act as the core and the BT spheres at the interface of the TPU and EVA act as the shell. A core–shell structured island can lead to the formation of micro‐capacitors and further accumulate electron storage owing to the incorporation of CNTs and BT; on the other hand, a BT shell can be assembled along the TPU spheres, reducing the possibility of formation of a conductive CNT network, resulting in suppressed dielectric loss. Therefore, CNTs and BT were tailor‐made into blend composites with a core–shell structured domain, which can achieve an increased dielectric constant by 176% and decreased low dielectric loss by 80% compared with the blend composites with only CNTs in the TPU domain. © 2019 Society of Chemical Industry     

Effect of the fiber content and plasticizer type on the rheological and mechanical properties of poly(vinyl chloride)/green coconut fiber composites

A series of poly(vinyl chloride) (PVC)/green coconut fiber (GCF) composites, with dioctyl phthalate (DOP) or thermoplastic polyurethane (TPU) as a plasticizer, were prepared by melt mixing. Their properties were studied in the molten state with an advanced nonlinear harmonic testing technique; in the solid state, the hardness and impact resistance were evaluated, and scanning electron microscopy was used for fractured surfaces. The effect of the fiber loading was investigated, as well as the role of the plasticizer. PVC–GCF composites are heterogeneous materials that, in the molten state, exhibit essentially a nonlinear viscoelastic character, in contrast to pure PVC, which has a linear viscoelastic region up to 50–60% strain. The complex modulus increases with the GCF content but in such a manner that the observed reinforcement is at best of hydrodynamic origin, without any specific chemical (i.e., permanent) interaction occurring between the polymer matrix and the fibers. As expected, PVC offers good wetting of GCFs, as reflected by the easy mixing and the rheological and mechanical properties. Fibers can be incorporated into PVC up to a 30% concentration without any problem, with the PVC/plasticizer ratio kept constant. Higher GCF levels could therefore be considered. Replacing DOP in part with TPU gives some benefit in terms of impact resistance, likely because of the viscoelastic nature of the latter and the associated energy absorption effects. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Compatibilization and properties of ethylene vinyl acetate copolymer (EVA) and thermoplastic polyurethane (TPU) blend based foam

Ethylene vinyl acetate copolymer/thermoplastic polyurethane (EVA/TPU) blending foams are rarely reported so far because of their poor compatibility, and addition of a compatibilizer to the blend system was our major interest, which can improve interfacial adhesion between the two phases. In this paper, TPU-grafted EVA (EVA-g-TPU), as a compatibilizer, was simply prepared using maleic anhydride-grafted EVA (EVA-g-MAH) and 4,4′ diamino diphenyl methane in the mixing process of TPU and EVA matrix. Fourier transform infrared spectroscopy and differential scanning calorimetry were used to investigate the structures of EVA-g-TPU and the interfacial reaction in the mixing process, and the effect of EVA-g-TPU on compatibilization between the two phases of EVA/TPU blends was investigated using scanning electron microscopy. Finally, EVA/EVA-g-TPU/TPU foams based on the good compatibility of the resin blends were prepared, and the physical properties directly related to the compatibility were investigated as a function of the theoretical quantity (molar mass) of EVA-g-TPU (n _EVA-g-TPU) in the foams. Moreover, the tensile strength, elongation at break, tear strength and compression set were improved by 19.0, 9.3, 43.6 and 7.5 %, respectively. Overall, EVA/EVA-g-TPU/TPU foams with excellent mechanical properties were obtained without sacrificing other important physical properties (lower density etc.) through popular and friendly means in this research.     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Polyblends based on vinyl chloride/propylene copolymer

Blends of vinyl chloride/propylene copolymer (VCM–P) with aromatic polycarbonate (PC) and with ABS terpolymer were studied. Particular emphasis was on characteristics of deflection temperature under load (DTUL), simply referred to as heat deflection temperature (HDT). In a binary system which contained PC and VCM–P, the HDT–composition plot exhibited an S-shaped curve, suggesting incompatibility. In contrast, a straight-line correlation, indicating compatibility, was found for VCM–P/ABS blends. These observations are consistent with dynamic measurements by viscoelastometer (Vibron Model DDV-II). Compatibility of the VCM–P/PC system was improved through incorporation of ABS copolymer, as indicated by the broadening of tan δ peak. Electron photomicrographs revealed that, in a 50% VCM–P binary blend, polycarbonate existed in a string-like morphology which differed from the compatible ABS system where the ABS copolymer was dispersed in a form of discrete particles.     

Exploring the Influence of Methylene Diphenyl Diisocyanate as a Modifier for Ethylene Vinyl Acetate/Thermoplastic Polyurethane Blends

Ethylene vinyl acetate (EVA)/thermoplastic polyurethane (TPU) blend at various blend ratios has been modified via reactive processing with 4,4′-methylene diphenyl diisocyanate (MDI). Modification of the blends with even small amount of MDI shows significant improvement in physico-mechanical properties for EVA/TPU 50/50 and 30/70 blends, and it is also supported by the superior melt rheological behavior and dramatic improvement in oil resistance property. After the treatment of electron beam (dose range: 50–150?kGy), radiation crosslinked EVA/TPU (30:70) blend reveals further improvement in various properties. This particular material can find potential application as cable sheathing component.     

Physicochemical characterization of hydrogels based on polyvinyl alcohol–vinyl acetate blends

Hydrogels made of polyvinyl alcohol–vinyl acetate and its blends with water soluble polymer were studied in terms of swelling behavior, microstructure, and dynamic mechanical properties. Hydrogels prepared by blending polyvinyl alcohol–vinyl acetate with either polyacrylic acid or poly(4‐vinyl pyridine) exhibited a strong pH dependency. When poly(vinyl pyrrolidone) was used for blending, an unusual pH dependency was observed. An increase in the equilibrium water content in all systems resulted in an increase in the freezable water as determined by DSC. Critical point drying led to a striated surface on polyacrylic acid–polyvinyl alcohol–vinyl acetate hydrogels, whereas a porous structure was observed on the freeze‐dried poly(vinyl pyrrolidone)–polyvinyl alcohol–vinyl acetate gels. Hydrogels with elevated storage modulus were obtained when either polyvinyl alcohol–vinyl acetate alone or polyacrylic acid–polyvinyl alcohol–vinyl acetate blends were thermally treated at high temperatures (i.e., 150°C). Low storage modulus was observed for both poly(vinyl pyrrolidone) and poly(4‐vinyl pyridine)‐containing hydrogels. Temperature dependency of storage modulus from 20 to 60°C was observed only for poly(4‐vinyl pyridine)–polyvinyl alcohol–vinyl acetate hydrogels. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3578–3590, 2001     

Preparation and characterization of colloidal dispersions of vinyl alcohol–vinyl acetate copolymers: application as stabilizers for vinyl chloride suspension polymerization

Well‐defined colloidal dispersions of vinyl alcohol–vinyl acetate copolymers (PVAs) with different degrees of hydrolysis (DH) were prepared by a coacervation technique. Colloidal particles in the size range 150–250 nm, with an acetate‐rich core and a hydrophilic PVA corona, were obtained using a combination of a hydrophobic PVA (PVA II) having an average DH ( ) value of 43 mol% with a ‘blocky’ hydrophilic PVA (PVA I) with a value of 72 mol%. The core–shell structure of these particles was demonstrated using ¹H NMR and using fluorescence‐labelled PVA I. The stabilization efficiency of PVA I and PVA II and their combination was examined for 1‐chlorobutane–water emulsions, as a ‘model solvent’ for vinyl chloride–water emulsions. Preliminary tests of vinyl chloride suspension polymerization confirmed the beneficial effect of PVA I and PVA II combinations as stabilizers on the granulometry and the porosity specifications of the poly(vinyl chloride) grains. Copyright © 2006 Society of Chemical Industry     

Modification and characterization of the poly(vinyl chloride)/thermoplastic polyurethane foam composite material

The polyvinyl chloride (PVC)/thermoplastic polyurethane (TPU) foam composite was modified by glycidyl methacrylate (GMA) innovative and prepared by sheet molding method with foaming agent azodicarbon amide (AC) and crosslinking agent bis‐tert‐butylperoxy diisopropylbenzene (BIPB). The properties of PVC/TPU foam composites effected by GMA content were investigated by the density, impact, tensile, and flexible test. The experiment indicated that with the addition of GMA, the impact strength tensile strength and flexible modulus were firstly rose to maximum at a fast rate and then decreased slightly. The properties significantly increased at a low content of modifier GMA. The results observed by differential scanning calorimetry indicated that new crosslinking network between PVC and TUP formed after the addition of GMA. The foam quality and cell morphology were studied by SEM and then statistics. With the addition of 0.6 phr BIPB and 0.5 phr GMA, the cell size of PVC/TPU composite is 80–130 μm and cell wall is 10–15 μm. Furthermore, the cells have more uniform distribution and fewer collapse when compared with the material without GMA. POLYM. COMPOS., 35:1716–1722, 2014. © 2013 Society of Plastics Engineers     

Fabrication of superhydrophobic unplasticized poly(vinyl chloride)/nanosilica sheets using Taguchi design methodology

This study introduces a relatively simple technique for the manufacture of superhydrophobic coatings on polymeric surfaces. Plastics such as unplasticized poly(vinyl chloride) (UPVC ) do not have a strong hydrophobic nature that is characterized by their low contact angles. Techniques of both increasing surface roughness and lowering surface energy are required to change their hydrophilicity to superhydrophobicity. In the present study, a coating of a low‐surface‐energy thermoplastic polyurethane (TPU ) was spin‐coated with chemically treated nanosilica to reduce the surface energy of UPVC . Nanosilica particles were embedded on the surface using a hot‐press. Taguchi design was used to optimize multiple processing parameters. Samples spin‐coated with 10 g L^?1 nanosilica suspension in ethanol at a rate of 400 rpm for 5 s and then hot‐pressed at 155 °C under 2 atm (203 kPa ) for 4 min had a contact angle of ca 157° and sliding angle of ca 6°, which are characteristic of superhydrophobic surfaces. Atomic force microscopy (AFM) and scanning electron microscopy (SEM ) imaging showed that these superhydrophobic surfaces were highly rough with nanoscale features. Peel test and SEM analysis showed that silica nanoparticles embedded in the TPU coating were more stable than particles immobilized on UPVC sheet without TPU coating, proving that a layer of more flexible coating can improve the longevity of superhydrophobic surfaces manufactured using this facile method. © 2016 Society of Chemical Industry