Synthesis and application of hyperbranched poly(urethane‐urea) finishing agent with amino groups

The isocyanate‐terminated linear polyurethane prepolymer (LPPU) was successfully synthesized via step‐by‐step polymerization, with isophorone disocyanate (IPDI) and polytetramethylene ether glycol (PTMG, M_n = 2000 g/mol) used as raw materials, dibutyltin dilaurate (DBTDL) as the catalyst, 1,4‐butanediol (BDO) as the chain extender and anhydrous ethanol (EtOH) as the blocking agent. Then the hyperbranched poly (urethane‐urea) (HBPU) containing amino groups was synthesized by grafting LPPU on amino‐terminated hyperbranched polymers (NH₂‐HBP). The molecular structure of LPPU and HBPU were characterized by means of FT‐IR and ¹H‐NMR. It was founded that LPPU and HBPU were successfully synthesized as anticipated. The thermal stability and crystalline morphology of LPPU and HBPU were characterized and analyzed by TG and XRD. Additionally, it was also found that, after addition of 10% HBPU, the water absorption rate, water vapor transmission rate, and water vapor permeability increased markedly by 162.02%, 400.00%, 260.00%, respectively. The tensile strength of membrane decreased by 24.57% and the elongation at break increased by 26.92%. Compared with the leather finished by commercial PU finishing agent, the leather finished by HBPU presented better properties. The water vapor permeability of the leather finished by increased by 13.0%, and the dry‐ and wet‐rub resistances and the physical and mechanical performances were excellent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44139.     

Synthesis and thermal properties of poly(urethane‐imide)

The synthesis and thermal properties of thermoplastic poly(urethane‐imide) (PUI) resins were studied. Model reaction studies on the reactions of 4,4′‐diphenylcarbamatodiphenylmethane and 4,4′‐diisocyanatodiphenylmethane with phthalic anhydride were performed. We found that the reaction of anhydrides with urethane groups could take place under certain reaction conditions. According to the model reaction studies, N‐2‐methyl‐pyrrolidone was employed as a solvent, and no catalyst was used in the polymerization. To restrain the side reaction of anhydrides with urethane groups, we adopted a two‐step chain‐extending procedure in a chain‐extending reaction. The inherent viscosity of PUI was 0.83–0.99 dL/g. The prepared polymers not only exhibited improved solubility in organic solvents but also formed flexible films. Thermogravimetric analysis showed that PUI exhibited a two‐step thermal weight‐loss pattern. The first step of the thermal degradation of PUI was attributed to the thermooxidizing cleavage of weak and labile linkage, such as urethane groups, isopropylidene, and methylene, except for imide rings. The polymer inherent viscosity decreased sharply during the first step of thermal degradation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 773–781, 2001     

Synthesis and characterization of calcium‐containing poly(urethane‐urea)s

A calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)2] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Four different bisureas like hexamethylene bis(ω,N‐hydroxyethylurea), tolylene 2,4‐bis(ω,N‐hydroxyethylurea), hexamethylene bis(ω,N‐hydroxypropylurea), and tolylene 2,4‐bis(ω,N‐hydroxypropylurea) were prepared by reacting ethanolamine or propanolamine with hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI). Calcium‐containing poly(urethane‐urea)s (PUUs) were synthesized by reacting HMDI or TDI with 1:1 mixtures of Ca(HEEP)2 and each of the bisureas using di‐n‐butyltin dilaurate as a catalyst. The PUUs were well characterized by Fourier transform infrared, 1H‐ and 13C‐NMR (nuclear magnetic resonance), solid‐state 13C cross‐polarization–magic angle spinning NMR, viscosity, solubility, elemental, and X‐ray diffraction studies. Thermal properties of the polymers were also studied by using thermogravimetric analysis and differential scanning calorimetry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3488–3496, 2003     

Synthesis and characterization of poly(acrylate amic acid) and its application as negative‐tone photosensitive polyimides

The dianhydride monomer 3,3′,4,4′‐benzophenone tetracarboxylic acid dianhydride and two diamine monomers, 4,4′‐diamino‐3,3′‐biphenyldiol (HAB) and 2,4‐diaminophenol dihydrochloride (DAP), were used to synthesize a series of poly(hydroxyl amic acid). Further functionalization by grafting acrylate groups yields the corresponding poly(acrylate amic acid) that underwent a crosslinking reaction on exposure to UV‐light and was used as a negative‐tone photosensitive polyimide (PSPI). The analysis of chemical composition and molecular weight of these poly(amic acid)s determined by nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy, and gel permeation chromatography revealed that the molecular weight of the poly(hydroxyl amic acid) increased with the molar content of HAB in the feedstock, because HAB exhibited higher polymerization reactivity than DAP. Moreover, the degree of grafting acrylate groups onto poly(hydroxyl amic acid) was determined by ¹H‐NMR spectroscopy. The photoresist was formulated by adding 2‐benzyl‐2‐N,N‐dimethylamino‐1‐(4‐morpholinophenyl) butanone (IRG369) and isopropylthioxanthone as a photoinitiator, tetra(ethylene glycol) diacrylate as a crosslinker, and tribromomethyl phenyl sulfone as a photosensitizer. The PSPI precursor exhibited a photosensitivity of 200 mJ/cm² and a contrast of 1.78. A pattern with a resolution of 10 μm was observed in an optical micrograph after thermal imidization at 300°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The photosensitive properties of polysiloxane acrylate resin containing tertiary amine groups

The photosensitive properties of a novel oligomer, di (N,N‐diacrylolyl)‐α, ω‐diaminopolysiloxane (ANS) with tertiary amine groups and acryloyl groups in its molecular structure were investigated using FTIR and gel yield method. It was noted that the ANS system showed a notable photosensitive property and its photosensitivity in air could be up to16.3 mJ/cm². The UV‐curing behavior of the ANS was studied by electron spin resonance (ESR). The results showed that amino‐alkyl radicals can be formed by excited BP abstracting hydrogen at a‐carbon bonded with nitrogen in the ANS molecule under UV irradiation, which can mitigate the oxygen inhibition in radical polymerization. It is proven that tertiary amine groups introduced into ANS could boost photosensitivity of the photopolymerization system. The oligomer ANS may find application in photopolymerization to improve the properties of UV‐curing coating materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Some physicochemical properties of poly (ethyl acrylate) emulsions containing carboxyl groups

Conductometric and potentiometric titration behavior of emulsions of ethyl acrylate copolymers with acrylic acid and methacrylic acid was investigated. On the conductometric titration curves of the emulsions of the copolymers with more than 5 mole-% of the acids, two equivalence points, based on the copolymerized acids, were observed, but only one equivalence point was observed on potentiometric titration. Almost all of the copolymerized acids could be detected by both titration methods. The change in optical density of the dilute emulsions with their pH was measured. The particles of these emulsions were studied under an electron microscope. These results showed that, when the pH of the emulsions was raised, the surface layers of the particles began to dissolve and their cores started to swell near the pH of their first equivalence points. When the pH was again lowered the dissolved polymers coagulated, tiny particles were formed, and the swollen cores were dehydrated. The surface layers thickened with increasing amount of the copolymerized acid. These behaviors were very similar in the emulsions of the copolymers with acrylic acid and methacrylic acid. The quantity of water-soluble polymers formed in the course of the emulsion copolymerization was approximately 3–4% or slightly more. This quantity depended only slightly upon the amount and type of the copolymerized acid. The acid contents of the water-soluble polymers were higher in cases of the copolymers with acrylic acid than in those with methacrylic acid. No relationship with the amount of copolymerized acid was established.     

Preparation and properties of flame retardant poly(urethane‐imide)s containing phosphine oxide moiety

The preparation of new poly(urethane‐imide)s (PUIs) having acceptable thermal stability and higher flame resistance was aimed. Two new aromatic diisocyanate‐containing methyldiphenylphosphine oxide and triphenylphosphine oxide moieties were synthesized via Curtius rearrangement in situ and polymerized by various prepared diols. Four aliphatic hydroxy terminated aromatic based diols were synthesized by the reaction between ethylene carbonate and various diphenolic substances. Chemical structures of monomers and polymers were characterized by FTIR, ¹H NMR, ¹³C NMR, and ³¹P NMR spectroscopy. Thermal stabilities and decomposition behaviors of the PUIs were tested by DSC and TGA. Thermal measurements indicate that the polymers have high thermal stability and produce high char. Polymers exhibit quite high fire resistance, evaluated by fire test UL‐94. The films of the polymers were prepared by casting the solution. Inherent viscosities, solubilities, and water absorbtion behaviors of the polymers were reported in. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of excellent transparency poly(urethane‐methacrylate)

A series of novel crosslinked poly(urethane–methacrylate) (PUA) was synthesized. PUA was polymerized in a three‐step process: The low number average molecular weight unsaturated polyester (UPE) containing hydroxyl groups was synthesized by 1,2‐propanediol (PG), 2‐butyl‐2‐ethyl‐1,3‐propanediol (BEPD) and maleic anhydride (MA). A series of prepolymers, which had double bonds at the end of the chain, was prepared from isophorone diisocyanate (IPDI), UPE, and β‐hydroxyethyl methacrylate (HEMA) in the presence of dibutytin dilaurate (DBTL) as catalyst. The novel functional prepolymer was initiated by 2,2‐azobis‐isobutyronitrile(AIBN) to form thermosetting materials. The structure of the thermosetting materials was characterized by Fourier Transform Infrared (FTIR). Mechanical, thermal, and optical properties were tested. The results showed that the advanced PUA had good thermal and mechanical properties and high transparence. The throughput of PUA was above 90%, thus the PUA was possible to be used as excellent optical material. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization, and pervaporation properties of segmented poly(urethane‐urea)s

Poly(urethane‐urea)s (PUUs) from 2,4‐tolylene diisocyanate (2,4‐TDI), poly(oxytetramethylene)diols (PTMO) or poly(butylene adipate)diol (PBA), and various diamines were synthesized and characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, differential scanning calorimetry, and density measurements. Transport properties of the dense PUU‐based membranes were investigated in the pervaporation of benzene–cyclohexane mixtures. It was shown that the pervaporation characteristics of the prepared membranes depend on the structure and length of the PUU segments. The PBA‐based PUUs exhibit good pervaporation performance along with a very good durability in separation of the azeotropic benzene–cyclohexane mixture. They are characterized by the flux value of 25.5 (kg μm m⁻² h⁻¹) and the separation factor of 5.8 at 25°C, which is a reasonable compromise between the both transport parameters. The PTMO‐based PUUs display high permeation flux and low selectivity in separation of the benzene‐rich mixtures. At the feed composition of 5% benzene in cyclohexane, their selectivity and flux are in the range of 3.2 to 11.7 and 0.4 to 40.3, respectively, depending on the length of the hard and soft segments. The chemical constitution of the hard segments resulting from the chain extender used does not affect the selectivity of the PUU membranes. It enables, however, the permeability of the membranes to be tailored. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1615–1625, 1999     

Transport modeling and thermophysical properties of cellular poly(urethane‐isocyanurate)

Transport behavior, thermophysical properties and kinetics of cellular poly(urethane‐isocynurate) were investigated. The heat and momentum transport of the flowing and reacting polymers systems was modeled using a computational fluid dynamics (CFD) approach. Two models were developed and compared with the experimental results in order to provide insight into the optimum processing. The models allowed prediction of the temperature profiles under a variety of operating conditions. The model prediction of momentum and heat transport agreed with the experimental results well. the thermophysical properties of the polymer system were obtained from experimental data and were used in the transport model. These properties included heat capacity and thermal conductivity. Reaction kinetics were investigated using differential scanning calorimetry (DSC). The rate constant, activation energy and heat of reaction and the rate constant were obtained from the experimental data.     

Synthesis and properties of poly(urethane‐imide) diacid/epoxy composites cured with an aziridine system

A poly(urethane‐imide) diacid (PUI), a diimide‐diacid with a soft structure unit, was directly synthesized from the reaction of trimellitic anhydride and isocyanate terminated polyurethane prepolymer. FT‐IR and NMR were used to characterize its chemical structure. Then PUI was blended with two types of epoxy resins with different chemical structures, diglycidyl ether of bisphenol A (DGEBA) and novolac epoxy (EPN). After curing the blends with polyfunctional aziridine CX‐100, novel polyurethane/epoxy composites were obtained as transparent yellowish films. Thermal, chemical, and morphological properties of the cured composites were investigated using thermal analysis, SEM, TEM, chemical resistance, respectively. All experimental data indicated that epoxy modified PUI composites possessed higher thermal stability than that unmodified PUI, and that modified PUI had much better chemical resistance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of novel poly(meth)‐acrylates containing tricyanocyclopropyl groups for piezoelectric applications

o‐(2,2,3‐Tricyano‐3‐carbomethoxycyclopropyl)phenoxyethyl acrylate ( 5a ) and o‐(2,2,3‐tricyano‐3‐carbomethoxycyclopropyl)phenoxyethyl methacrylate ( 5b ) were prepared by reactions of bromomalononitrile with methyl o‐(2‐acryloyloxyethoxy)benzylidenecyanoacetate and methyl o‐(2‐methacryloyloxyethoxy)benzylidenecyanoacetate respectively. The dipole moments of 5a and 5b , calculated by atom superposition and electron delocalization molecular orbital method, were 2.75–3.47 D. Monomers 5a and 5b were polymerized with free‐radical initiators to obtain the polymers with tricyanocyclopropane ring as a piezoelectric chromophore in the pendant group. The resulting polymers 6a and 6b were soluble in common organic solvents such as acetone and DMF. Polymers 6a and b showed thermal stability up to 280 °C in TGA thermograms. T_g values obtained from DSC thermograms were in the range 125–140 °C. Piezoelectric coefficients (d₃₁) of the poled films were 1.2–1.4 pC N^?1. These polymers showed good temporal and long‐term thermal stabilities which are acceptable for piezoelectric device applications. Copyright © 2003 Society of Chemical Industry     

Siloxane‐based segmented poly(urethane‐urea) elastomer: Synthesis and characterization

A series of segmented poly(urethane‐urea) block copolymers were synthesized with varying proportions of polydimethylsiloxane diols in combination with polytetramethylene ether glycol (PTMG) using 4,4'‐methylenediphenyl diisocyanate followed by chain extension with a (50:50 mol %) mixture of 4,4'‐methylene‐bis(3‐chloro‐2,6‐diethylaniline) (M‐CDEA) and 1,4‐butanediol (BD). The molecular structures of polydimethylsiloxane urethane‐ureas were characterized by ATR‐FTIR and ¹H‐NMR spectroscopic techniques. Distribution of siloxane domain and its influence on surface roughness were investigated by scanning electron microscopy (SEM) and atomic forced microscopy (AFM), respectively. The mechanical and thermal properties of the elastomers were studied by thermogravimetric analysis, dynamical mechanical thermal analysis, and tensile measurement. The results showed that by incorporation of polydimethylsiloxane diol and M‐CDEA chain extender in polyurethane formulation, some improvements in thermal stability, fire resistance and surface hydrophilicity were achieved. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1743–1751, 2013     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Synthesis and properties of metal poly(butyl acrylate)

Butyl acrylate colloids were obtained by codeposition at 77 K of the monomer with several metals such as Pd, Au, Ag, Cu, Zn, Cd, Ga, In, Ge, Sn, Sb, and Bi. The colloids were polymerized with different amounts of an initiator (AIBN) at 65°C for 0.5 h and a wide range of viscosity‐average molecular weights (M _v, 10⁴–10⁵ g/mol) were obtained depending upon the metal used. The metal colloid concentration and stability are reported. The thermal stability and metal composition are also described. The polymers are stable even at 400°C, with Ga–poly(butyl acrylate) being the most stable at 407°C. The metal content ranged between 0.10 and 1.32% w/w for the highest MW fraction and between 0.11 and 1.09% w/w for the lowest MW fraction. Polymers with several colors were obtained depending on the metal used. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 547–550, 1999     

Synthesis and study of new poly(ester‐imide)s containing triptycene groups

A new triptycene‐containing dicarboxylic acid monomer was successfully synthesized by refluxing the diamine, bis(4‐aminophenoxy)phenyl triptycene with trimellitic anhydride in glacial acetic anhydride. A series of novel thermally stable poly(ester‐imide)s were prepared from dicarboxylic acid, bis(4‐trimellitimido phenoxy)phenyl triptycene with various diols by the direct polycondensation. The polymers were obtained in quantitative yields with inherent viscosities of 0.27–0.74 dL g^?1. The resulting polymers dissolved in N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethyl sulfoxide, and pyridine. These polymers were fairly stable up to a temperature >450°C and lost 10% weight in the range of 477°C and 575°C in nitrogen. The UV–V is absorption spectra revealed that most of the polymers had absorption maxima around 310 and 341 nm. POLYM. ENG. SCI., 54:2252–2257, 2014. © 2013 Society of Plastics Engineers     

Synthesis,characterization and thermal properties of functionalized poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing ethylenic,aldehydic, hydroxyl and acrylate pendant groups

New functionalized poly(2,6‐dimethyl‐1,4‐phenylene oxide)s (PPOs) containing ethylenic, aldehydic, hydroxyl and acrylate pendant groups were synthesized and their structure, properties and curing kinetics were investigated. The incorporation of polar functional groups resulted in an improvement in the glass transition temperature in the order aldehydic PPO > acrylate PPO > hydroxyl PPO > vinyl PPO > brominated PPO > pristine PPO. Upon thermal curing, the electron‐donating substituent in the vinyl PPO resulted in an increase in the activation energy in the order –Pr, –Bu > –Ph > –H, whereas the electron‐withdrawing substituent in the acrylate PPO caused a slight decrease in the activation energy. Copyright © 2011 Society of Chemical Industry     

UV固化含磷环氧丙烯酸酯的合成与性能研究

以三氯氧磷(POC l3)和丙烯酸羟乙脂(HEA)为原料合成了二丙烯酰氧乙基磷酸酯,并将其继续与环氧树脂E-51反应,合成了一种四官能度的UV固化含磷环氧丙烯酸酯。确定了上述2步反应的最佳反应条件。对含磷环氧丙烯酸酯低聚物配制的胶液进行了物理力学性能测试。结果表明:POC l3、HEA的物质的量比为2∶1,以三乙胺做缚酸剂,反应温度60~65℃,合成的二丙烯酰氧乙基磷酸酯颜色浅,收率90%,纯度93.2%。二丙烯酰氧乙基磷酸酯和环氧树脂E-51的物质的量比为2∶1,反应温度70~75℃,含磷环氧丙烯酸酯纯度88%以上。将含磷环氧丙烯酸酯低聚物配成胶液后,和环氧丙烯酸酯相比,黏度降低了95%倍,剪切强度和附着力提高了2倍,固化时间和体积收缩率大大降低。     

Fluorinated poly(meth)acrylate: Synthesis and properties

Due to good reactivity of fluorinated (meth)acrylates with other monomers or polymer segments, fluorinated poly(meth)acrylates possess more economical and convenient synthesis routes than other fluoropolymers. This feature article initially summarizes different types of fluorinated (meth)acrylates, which can be divided into fluorinated alkyl (meth)acrylates and fluorinated aryl (meth)acrylates. Subsequently, various approaches for synthesizing fluorinated poly(meth)acrylates including random, block, graft or star copolymers are described. Conventional free radical polymerization can be used in synthesizing random copolymers, while controlled/“living” radical polymerization can provide well-defined copolymers with accurate control over molecular weight and special structures as expected. In particular, introduction of fluorinated components into as-prepared copolymers offers an alternative route to synthesize fluorinated poly(meth)acrylates which are difficult to be obtained directly via polymerization. The incorporation of fluorine can confer unique and highly desirable properties to poly(meth)acrylates such as low surface energy, thermal stability, chemical and weather resistance, low refractive index, and self-organization characteristics. Such properties are described in great details based on many recent articles.     

Synthesis,characterization, and UV‐curing properties of silicon‐containing (Meth)acrylate monomers

Eight different silicon‐containing (meth)acrylate monomers are synthesized by the substitution reaction of chlorosiloxanes with 2‐hydroxyethyl methacrylate or 2‐hydroxyethyl acrylate. Their molecular structures are confirmed by IR, ¹H‐NMR, and ¹³C‐NMR spectroscopic analyses. The effects of silicon content on the UV‐curing behavior, physical, surface, and thermal properties are investigated. The UV‐curing behavior is analyzed by photo differential scanning calorimetry. The surface free energy of the UV‐cured film is calculated from contact angles measured using the Lewis acid‐base three liquids method. The silicon‐containing (meth)acrylate monomers perform much better than traditional (meth)acrylate monomers on UV‐curing. The silicon‐containing monomers have higher final conversions and fast UV‐curing rates in photopolymerization. The surface free energy decreases with increasing silicon content, because silicon in the soft segment is transferred to the surface, producing a UV‐cured film; this is confirmed by X‐ray photoelectron spectroscopy measurements. All these advantageous properties enable these synthetic silicon‐containing monomers to perform better in applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013