四羟甲基硫酸鳞的合成及测定研究

以黄磷、锌粉、硫酸和甲醛为原料，成功合成了四羟甲基硫酸鳞（THIS），详细探讨了不同合成条件对THIS产率的影响，并通过正交实验确定最佳合成工艺为：黄磷：锌粉：硫酸：甲醛=1：2．5：7．5：5（摩尔比），反应温度为85℃，反应时间为6h。建立了测定其活性物含量的离子交换法，测得THIS的含量为79．20％。用36％乙酸对产品进行重结晶，成功得到了THIS针状晶体。     

四羟甲基硫酸鏻的合成及测定研究

以黄磷、锌粉、硫酸和甲醛为原料,成功合成了四羟甲基硫酸鏻(THPS),详细探讨了不同合成条件对THPS产率的影响,并通过正交实验确定最佳合成工艺为:黄磷∶锌粉∶硫酸∶甲醛=1∶2.5∶7.5∶5(摩尔比),反应温度为85℃,反应时间为6 h。建立了测定其活性物含量的离子交换法,测得THPS的含量为79.20%。用36%乙酸对产品进行重结晶,成功得到了THPS针状晶体。     

Durable flame resistance via reaction of cotton cellulose bearing aromatic amino groups with tetrakis(hydroxymethyl)phosphonium chloride

Chemically modified cotton fabric samples having different amounts of aromatic amino groups were prepared. These modified samples were reacted with tetrakis(hydroxymethyl)phosphonium chloride (THPC) under a variety of conditions using the pad-dry–thermofixation technique. The extent of the reaction (expressed as %P) was dependent of the degree of chemical modification of cotton, temperature and time of heating, and pH of the treating bath as well as incorporation of Lyofix CHN (N-methylol finishing agent), MgCl₂·6H₂O (catalyst), and urea at various concentrations. THPC did react with the modified cotton having a nitrogen content over a range of 0.4%–1.3% even in the absence of catalyst at a temperature as low as 30°C for 10 min to impart durable flame resistance to cotton. Increasing the temperature up to 80°C enhanced considerably the extent of reaction; he latter remained practically constant upon further increase in temperature. The reaction was favored in acidic media (pH 4–6), whereas alkaline media (pH 9–11) inhibited it. Incorporation of Lyofix CHN (9%), MgCl₂6H₂O (1%), and urea (5%) along with THPC (25%) in the treating bath required a curing temperature of 120°C and a curing time of 5 min to achieve a fabric containing as much as 2.7% phosphorus with excellent durable flame resistance. A tentative mechanism of the reaction between THPC and the modified cotton was also elicited.     

Degradable polyurethane foams based on disaccharides

New functional elastic polyurethane foams (PUF) degradable under environmental abiotic and biotic factors, retaining all the inherent properties of the conventional foams were synthesized using isocyanate precursors based on disaccharides (DS): lactose, maltose and saccharose. It was shown by the model reactions of monosaccharide glucose, and DS lactose and saccharose, with phenylisocyanate that both the primary and secondary hydroxyls of the carbohydrates reacted to form urethanes. The main properties of DS‐based foams (PUF/DS) were found to be similar to PUF foam (matrix) prepared with conventional polyols. However, the new PUF/DS were found to undergo enhanced acid/alkaline hydrolysis and degradation compared with PUF matrix when incubated in soil. Mass losses of incubated PUF/DSs significantly exceeded the actual carbohydrate content 28.6%, and in 12 months reached 39.58 (PUF‐4), 53.31(PUF‐8), and 47.25 (PUF‐12). In contrast, under the same conditions PUF matrix lost only 2–2.5%, confirming that incorporation of natural compounds into the polymer chain impacted the degradation processes. PUF/DS were characterized by FTIR, ¹H NMR, ebullioscopy, and exclusion chromatography (molecular masses and molecular mass distribution of the oligomeric model), physical and mechanical tests (density, tensile strength, relative elongation, moisture absorption, vapor permeability), morphology, and degradation in the soil. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42131.     

Synthesis and characterization of starch-based polyurethane foams

Starch-based polyurethane foams were synthesized by reacting a mixture of starch and polycaprolactone triol with an aliphatic diisocyanate, in the presence of water as blowing agent. Some foams were also prepared by adding a certain amount of polyethyleneglycol. The reaction kinetics is affected by the presence of starch due to the higher viscosity related to the presence of the high molecular weight polysaccharide. Starch-based polyurethanes show higher glass transition temperatures and lower thermal stability. Cellular materials with different mechanical properties can be obtained by varying the amount of starch and by controlling the relative amount of polycaprolactone triol and polyethyleneglycol in the composition. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:739–745, 1998     

一种含磷自修复水性聚氨酯的合成及性能

采用异佛尔酮二异氰酸酯（IPDI）和聚丙二醇（PPG）为原料,通过前扩链的方式将二羟乙基二硫化物（HEDS）引入到水性聚氨酯（WPU）分子链中,并用含磷阻燃剂OP550进行阻燃改性,成功制备了兼具阻燃和自修复两种特殊功能的水性聚氨酯（OHWPU）,研究了阻燃剂OP550对本征型自修复水性聚氨酯的性能影响。结果表明,OP550含量为20%时制备的OHWPU（OHWPU-20%）极限氧指数达到29.0%,相比HWPU提高了7.4%;在80 ℃,修复时间为3 h的条件下,OHWPU-20%的拉伸强度为4.71 MPa,损伤后的自修复效率达到107.9%。     

一种含磷自修复水性聚氨酯的合成及性能

采用异佛尔酮二异氰酸酯、聚丙二醇和2,2-二羟甲基丙酸为主要原料,以无卤含磷阻燃剂Exolit OP550(记为OP550,下同)为软段扩链剂,通过前扩链方式将二羟乙基二硫化物引入到水性聚氨酯(WPU)分子链中,成功制备了兼具阻燃和自修复两种特殊功能的水性聚氨酯(记为OHWPU)乳液.采用FTIR和激光粒度仪对OHWP...     

Sustainable rigid polyurethane foams based on recycled polyols from chemical recycling of waste polyurethane foams

The preparation and characteristics of rigid polyurethane foams (RPUFs) based on recycled polyol obtained by glycolysis of waste RPUF scraps from end-of-life refrigerators were investigated. To deactivate the amine adducts derived from isocyanates, the recycled product obtained after depolymerization was chemically modified via addition polymerization of propylene oxide. Two kinds of recycled polyols with different hydroxyl values and viscosity were blended with conventional virgin polyether polyol to prepare the RPUFs. The effects of the recycled polyols on the physical properties of RPUFs such as cell structures, compressive strength, thermal conductivity, and limiting oxygen index were discussed. It was found that the RPUFs from recycled polyols showed superior compressive strength, thermal insulation property, and self-extinguishing property compared with conventional control foam. The results of this study reveal that the recycled polyols could be used as feedstock for RPUFs with superior performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47916.     

Rigid polyurethane foams based on soybean oil

Both HCFC‐ and pentane‐blown rigid polyurethane foams have been prepared from polyols derived from soybean oil. The effect of formulation variables on foam properties was studied by altering the types and amounts of catalyst, surfactant, water, crosslinker, blowing agent, and isocyanate, respectively. While compressive strength of the soy foams is optimal at 2 pph of surfactant B‐8404, it increases with increasing the amount of water, glycerin, and isocyanate. It also increases linearly with foam density. These foams were found to have comparable mechanical and thermoinsulating properties to foams of petrochemical origin. A comparison in the thermal and thermo‐oxidative behaviors of soy‐ and PPO‐based foams revealed that the former is more stable toward both thermal degradation and thermal oxidation. The lack of ether linkages in the soy‐based rather than in PPO‐based polyols is thought to be the origin of improved thermal and thermo‐oxidative stabilities of soy‐based foams. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 467–473, 2000     

Porous polyurethane foams based on recycled poly(ethylene terephthalate) for oil sorption

In using recycled poly(ethylene terephthalate) (PET) as a petroleum sorbent we tried to achieve two important objectives simultaneously. PET waste was glycolized using trimethylolpropane (TMp) or pentaerytheritol (PEr) to produce suitable polyol oligomers for polyurethane (PU) foams. The glycolysis was carried out in the presence of manganese acetate as a catalyst under normal pressure in m‐cresol at 220 °C. Producing polyols, PEr degraded PET into lower molecular weights than TMp. So prepared oligomers were reacted with 2,4‐toluene diisocyanate providing several types of PU foam. The effect of various variables (polyol reactivity, water content, type of catalyst, isocyanate amount and surfactant) on the foam structure and properties were analyzed. Porosity of the PU foams was examined using environmental scanning electron microscopy. Foams based on glycolized TMp contain small uniform cells whereas other foams form less uniform cells with varying sizes including closed cells. Dynamic mechanical analysis gives much lower storage moduli for TMp‐based PUs that for those based on PEr, an effect of dangling ethylene chains in the former case. The glass transition temperatures T_g are higher when PEr rather than TMp is used. Our PU foams show good sorption properties and sufficient reusability. Copyright © 2012 Society of Chemical Industry     

Synthesis and flame-retardant properties of phosphorus-containing polymers based on poly(4-hydroxystyrene)

Phosphorus-containing polystyrene was obtained through incorporating phosphate groups onto poly(4-hydroxystyrene). This was achieved by esterification with diethylchlorophosphate. The phosphorylation was confirmed by IR, ¹H-NMR, and ³¹P-NMR analysis. By varying the feeding ratios of the reactants, the phosphorus content in the polymers could be successfully tailored and gave values of 12.8 to 4.9% by weight. This was further corroborated by elemental analysis. Thermal characteristics and temporal stability of the phosphorylated polymers were evaluated by DSC and TGA. High char yields (64% by weight) and LOI values of 41 were found for these polymers. Such properties make these polymers useful in flame retardants. © 1996 John Wiley & Sons, Inc.     

Rigid polyurethane foams based on activated soybean meal

Soybean meal (SM), an abundant biomass resource, was used as the surrogate to partially replace polyols in rigid polyurethane foam synthesis. Compared with polyurethanes based on other soybean‐based resources, such as soybean protein isolate (SPI), polyurethane foams based on activated SM showed better thermal and mechanical properties. The amount of SM in the final polyurethane foams can be as high as 30 wt % (base on the total weight of foam), which dramatically decreases the cost of the foams. The results also showed that SM played a vital role in improving the foam properties, which could be attributed to the participation of the functional groups in SM in the polyurethane foam synthesis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of waterborne and phosphorus-containing flame retardant polyurethane coatings

Phosphorus-containing flame retardant water-dispersed polyurethane coatings were produced by incorporating different amounts of a phosphorus compound onto the polyurethane main chain. The novel phosphorus containing compound (phosphorus phenyl dihydroxy) was synthesized in three steps using benzaldehyde, pentaerythritol, phenyl phosphonic dichloride, and acetic acid. The addition of phosphorus phenyl dihydroxy to the main chain of polyurethane, in which NCO/OH ratio was kept constant at 1.5 and the amount of dimethylolpropionic acid (DMPA) at 3.5 wt%, increased the hardness and abrasion resistance, but only slightly decreased the gloss values of the polyurethane paints. All the samples showed superior impact resistance and flexibility. Moreover, increasing the phosphorus content increased the char yield, and the maximum fire retardancy was reached at 1.5% P content with a limiting oxygen index (LOI) value of 29. Kimya B?lümü, 06531 Ankara, Turkey.     

Thermal degradation studies on rigid polyurethane foams blown with pentane

The effect of sodium dihydrogenphosphate, trisodium pyrophosphate, and sodium aluminocarbonate on the thermal decomposition of rigid polyurethane (PUR) foams, based on diphenylmethane‐4,4‐diisocyanate, diphenyl‐2,2‐propane‐4,4‐dioxyoligo(ethylene oxide), and oxyalkylenated toluene‐2,6‐diamine, blown with pentane, was studied. Thermogravimetric (TG) data have shown that there is a stabilization effect of additives in the initial stage of degradation, both in nitrogen and air atmosphere, and the decomposition proceeded in two steps up to 600°C. Results of the kinetic analysis by the isoconversional methods of Ozawa–Flynn–Wall and Friedman yielded values of (apparent) activation energy (E_a) and preexponential factor (A). For phosphate‐stabilized PUR samples, E_a remained stable over a broad area of the degree of conversion, while for carbonate‐containing sample two regions of E_a were observed. Further advanced kinetic analysis by a nonlinear regression method revealed the form of kinetic function that was the best approximation for experimental data—for a two‐stage consecutive reaction the first step was the Avrami–Erofeev nucleation‐dependent model, and the second step was a chemical reaction (1st or nth order) model. The integrated thermogravimetric (TG)/Fourier transform infrared (FTIR) technique probed the thermal degradation of modified PURs by analyzing the evolved gases. The solid residue remaining at different temperatures was identified by diffuse reflection FTIR (Kubelka–Munk format). The complex thermal behavior was discussed on the basis of the obtained results—it can be shown that the global stabilization effect is a multistage process whose initial conditions are of critical importance in governing the nature of the entire process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2319–2330, 2003     

Synthesis and characterization of polyurethane/poly(vinylidene chloride) interpenetrating polymer networks

A series of polyurethane (PU)/poly(vinylidene chloride) (PVDC) interpenetrating polymer networks (IPNs) were synthesized through variations in the amounts of the prepolyurethane and vinylidene chloride monomer via sequential polymerization (80/20, 60/40, 50/50, 40/60, 30/70, and 20/80 PU/PVDC). The physicomechanical and optical properties of the IPNs were investigated. Thermogravimetric analysis (TGA) studies of the IPNs were performed to establish their thermal stability. TGA thermograms showed that the thermal degradation of the IPNs proceeded in three steps. Microcrystalline parameters, such as the crystal size and lattice disorder, of the PU/PVDC IPNs were estimated with wide‐angle X‐ray scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1375–1381, 2007     

Synthesis and performance of different polyurethane foams as oil sorbents

Oil sorption (g g^?1) through different polyurethane foams has been investigated in this study. Polyurethane foams were synthesized with different additives: glycerol, propylene glycol, polyethylene glycol 400, and 1‐dodecanol. All foams were applied as sorbents of diesel, motor oil, gasoline, kerosene, and crude oil. The foams were characterized using Fourier transform infrared spectroscopy, thermogravimetry and differential scanning calorimetry, compressive resistance at 10% deformation and the elastic modulus, scanning electron microscopy, and apparent density. The best performance of oil sorption was achieved with PUF‐3, which has the greatest amount of the chain extender polyethylene glycol 400 and lowest density of all the evaluated foams. The sorption capacities (g g^?1) of PUF‐3 were 16.8 (diesel), 15.7 (gasoline), 20.7 (oil motor), 25.4 (kerosene), and 29.8 (crude oil) and 100% removal of diesel from water was achieved, approximately. The foams with chain extenders and lower density values performed better as oil sorbents. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45409.     

Synthesis and EPR studies of a near infrared absorbing tetrakis(2-naphthoxy)vanadylphthalocyanine

Vanadylphthalocyanine with four naphthoxy pendant groups on the periphery was prepared by cyclotetramerization of 4-(2-naphthoxy)phthalonitrile. The new compound was characterized by elemental analyses, Mass, IR and UV–Vis spectral data. The electronic spectra exhibit an intense absorption peak at 703 nm indicating the C_4v symmetry of VOPc. VO²⁺ ion in this structure was studied using electron paramagnetic resonance (EPR) technique at room temperature. The covalent bonding parameter for VO²⁺ ion and Fermi contact term were calculated using the principal axis values of the g and hyperfine splitting obtained from powder EPR spectrum.     

Characterization of flexible polyurethane foams based on soybean‐based polyols

Two series of flexible polyurethane foams were fabricated by substituting conventional petroleum‐based polyols with increasing amounts of soy‐based polyols (SBP) having different hydroxyl numbers. The mechanical properties of the foams were characterized by stress–strain analysis in the compression mode and DMA in tension mode, the cellular morphology was analyzed by SEM and the microphase‐separation of the foams was noted by SAXS. Our results showed that the cellular morphology and mechanical properties of the flexible foams were affected significantly by the foam fabrication method and SBP hydroxyl numbers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

含异氰脲酸酯基团浇注型聚氨酯弹性体的合成及其耐热性能的研究

在催化剂作用下,合成了TDI-100型异氰脲酸酯,并与己二酸乙二醇丙二醇酯（PEPA）合成了浇注型聚氨酯弹性体,通过不同温度下的热失重分析（TGA）和弹性体的力学性能高温保持率对比分析表明,在TDI型聚氨酯弹性体中引入异氰脲酸酯基团,可明显提高弹性体的耐热性能。     

H_(12)MDI型端硅烷基聚氨酯预聚物的合成

以H12MDI(4,4′-二环己基甲烷二异氰酸酯)和不同Mr(相对分子质量)的PPG(聚丙二醇醚)为原料、DBTDL(二月桂酸二丁基锡)为催化剂和A1170[双-(γ-三甲氧基硅丙基)胺]为封端剂,合成了SPU(端硅烷基聚氨酯)预聚物。研究结果表明:SPU预聚物的合成包括PU预聚物的合成和封端反应两个阶段;PU(聚氨酯)预聚物的合成反应速率随催化剂用量增加而加快,当催化剂用量约为50 mg/kg、反应温度为80℃和反应时间为4 h时,PU预聚物的合成反应可基本完成;封端反应的最佳温度为70℃,反应3 h后体系—NCO含量可降至0;通过调节R值[即n(—NCO)/n(—OH)]和PPG的Mr,可使SPU预聚物的黏度控制在56.70~229.92 Pa·s范围内。