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1.

The direct conversion of natural products to useful engineering materials is desirable from both economic and environmental considerations. We describe the synthesis and properties of 100?% oil-based epoxy resins generated from three epoxidized oils. The catalyst, tris(pentafluorophenyl)borane (B(C6F5)3) in toluene, allowed for controlled cationic polymerization at a very low concentration. Epoxidized oils (derived from triolein, soybean, and linseed oil) had varying epoxy content, rendering resins of different cross-link density. The polymerization was carried out at room temperature followed by post-curing at elevated temperature to speed up conversion. Epoxy resins were amorphous transparent glasses below glass transitions and hard rubbers above. Despite their high cross-link density, these materials show relatively low Tg’s reflecting the aliphatic nature of fatty acids and the presence of plasticizing “dangling” chains. The structure of the triglyceride starting oils influenced the properties of the resulting materials: the more regular structure of triolein compared to the very heterogeneous structures of soybean and linseed oils seemed to have enhanced some properties of the polymer networks. These epoxy polymers are potentially useful as encapsulating and potting compounds for electronic applications.

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2.
The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. T g’s of the polyesters ranged from ?36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher T g polymers (?17 to 17 °C) than soybean (?25 to 6 °C) and rapeseed (?36 to ?27 °C). Grapeseed oil showed similar properties to soybean oil in terms of T g, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.  相似文献   

3.
Polyols and Polyurethanes from Hydroformylation of Soybean Oil   总被引:10,自引:0,他引:10  
This paper compares physical and mechanical properties of polyurethanes derived via the hydroformylation approach and is a part of our study on the structure–property relationships in polyurethanes created from vegetable oils. The double bonds of soybean oil are first converted to aldehydes through hydroformylation using either rhodium or cobalt as the catalyst. The aldehydes are hydrogenated by Raney nickel to alcohols, forming a triglyceride polyol. The latter is reacted with polymeric MDI to yield the polyurethane. Depending on the degree of conversion, the materials can behave as hard rubbers or rigid plastics. The rhodium-catalyzed reaction afforded a polyol with a 95% conversion, giving rise to a rigid polyurethane, while the cobalt-catalyzed reaction gives a polyol with a 67% conversion, leading to a hard rubber having lower mechanical strengths. Addition of glycerine as a cross-linker systematically improves the properties of the polyurethanes. The polyols are characterized by DSC. The measured properties of polyurethanes include glass transition temperatures, tensile strengths, flexural moduli, and impact strengths.  相似文献   

4.
Polyurethane (PUR) plastic sheets were prepared by reacting hydroxylated polymeric soybean oil (PSbOH) synthesized from autoxidized soybean oil with polyethylene glycol (PEG) in the presence of isophorone diisocyanate (IPDI). FTIR technique was used to identify of chemical reactions. These polyurethanes have different valuable properties, determined by their chemical composition. The effect of stoichiometric balance (i.e., PSbOH/PEG-2000/IPDI weight ratio) on the final properties was evaluated. The polyurethane plastic sheets with the PSbOH/PEG-2000/IPDI weight ratio 1.0/1.0/0.67 and 1.0/0.3/0.3 had excellent mechanical properties indicating elongation at break more than 200%. Increase in IPDI and decrease in PEG weight ratio cause the higher stress–strain value. The properties of the materials were measured by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), stress–strain measurements and FTIR technique.  相似文献   

5.

Graft copolymerization is a distinctive approach to modify the inherently cheap natural fibers (NFs) using different initiators to incorporate synthetic polymer side chains allowing development of novel types of hybrid materials. This method has been widely applied to develop a variety of NFs based adsorbents for decontamination of toxic pollutants from the aqueous environment. However, the development of high-performance adsorbents from NFs is steady challenged by the need to preserve the sustainability during graft modifications and applications. This article critically reviews the progress on modifications of NFs by graft copolymerization of polar monomers on NFs using various initiating methods and their applications in wastewater treatment. Particularly, the applications of the grafted NFs in removal of heavy metal ions, synthetic dyes, oil spills and extraction of precious metals from wastewater are elaborated. The critical challenges to the viability and sustainability of NFs-based adsorbents with respect to functionalization by graft copolymerization and environmental impacts are discussed and the future research directions are also outlined.

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6.
Soybean Oil-Based Photo-Crosslinked Polymer Networks   总被引:1,自引:0,他引:1  
Novel soybean oil-based crosslinked polymer networks were prepared by UV photopolymerization and their mechanical properties were evaluated. Poly(ethylene glycol) diacrylate (PEGDA) and biodegradable poly(ε-caprolactone) diacrylate (PCLDA) were synthesized and used as crosslinking agent to form crosslinked polymer networks by UV-initiated free-radical polymerization with acrylated epoxidized soybean oil (AESO). The synthesis of acrylate end-capped macromers was confirmed using FT-IR and 1H NMR spectroscopic techniques. Photopolymerization time, the composition of reaction mixture, and the type and length of crosslinking agent were changed to obtain crosslinked polymer networks with various mechanical properties. Polymers prepared from AESO and PCL degraded 6% of the initial weight in 24 days in phosphate buffer solution (pH 7.2) containing lipase enzyme. These potentially biodegradable and biocompatible polymers can be used as ecofriendly materials for biomedical and other applications to replace the existing petroleum-based polymers currently used.  相似文献   

7.
The aim of this paper is to provide an update on the ongoing research of our laboratory in the field of polymeric materials derived from biomass components. The first section deals with the oxypropylation of different vegetable or animal biomass residues and the use of the ensuing polyols in different polyurethane formulations. Thus, foams, elastomers, and membranes were obtained and their properties compared favorably with those of equivalent materials prepared from petroleum-based sources. The second section is devoted to furan copolymers and their use in reversibly crosslinked elastomers via the Diels–Alder reaction and in the field of photosensitive materials. The third section describes novel approaches to the surface modification of cellulosic fibers to be employed in composite materials with polymeric matrices, consisting in the use of organometallics and siloxanes as coupling agents. The final two sections are devoted to a brief outline of the role of lignins and vegetable oils as additives in printing inks, varnishes, and paints.  相似文献   

8.
The conjugated soybean oil was synthesized through the isomerization reaction of soybean oil to transformed the structure of linoleic acid into conjugated linoleic acid structure, and Rhodium complexes (RhCl(Pph3)3) was used as catalyst. The efficiency on the conjugation of catalyst RhCl (Pph3)3, tin dichloride dehydrate (SnCl2·2H2O) and triphenylphosphine (Pph3) were evaluated. The results showed when RhCl(Pph3)3, SnCl2·2H2O and Pph3 are 9.25, 9.0 and 13.1 mg in 100 g soybean oil respectively, the highest conversion of conjugation achieved 96%. The free radical copolymerization of conjugated soybean oil with acrylonitrile (AN) and dicyclopentadiene (DCP) was studied. AIBN was used as the initiator. FT-IR and 1H-NMR results indicates that the conjugated soybean oil with AN and DCP did occur free radical copolymerization with the initiator AIBN. The product is light yellow powder. The thermal properties of the soy-based copolymer were investigated by TG and DSC. The initial degradation temperature of polymers is higher then 250 °C.  相似文献   

9.
This paper is a review of the major findings from laboratory studies and field trials conducted in Norway in recent years on the emulsification of oils spilled at sea. Controlled bench-scale and meso-scale basin experiments using a wide spectrum of oils have revealed that both the physico-chemical properties of the oils and the release conditions are fundamental determinants of the rate of emulsion formation, for the rheological properties of the emulsion formed and for the rate of natural dispersion at sea.During the last decade, several series of full-scale field trials with experimental releases of various crude oils have been undertaken in the North Sea and the Norwegian Sea. These have involved both sea surface releases, underwater pipeline leak simulations (release of oil under low pressure and no gas) and underwater blowout simulations (pressurized oil with gas) from 100 and 850 m depth. The field trials have been performed in co-operation with NOFO (Norwegian Clean Seas Association for Operating Companies), individual oil companies, the Norwegian Pollution Control Authority (SFT) and Minerals Management Services (MMS). SINTEF has been responsible for the scientific design and monitoring during these field experiments. The main objectives of the trials have been to study the behaviour of different crude oils spilled under various conditions and to identify the operational and logistical factors associated with different countermeasure techniques.The paper gives examples of data obtained on the emulsification of spilled oil during these field experiments. The empirical data generated from the experimental field trials have been invaluable for the validation and development of numerical models at SINTEF for predicting the spreading, weathering and behaviour of oil released under various conditions. These models are extensively used in contingency planning and contingency analysis of spill scenarios and as operational tools during spill situations and combat operations.  相似文献   

10.
Emission of low molar mass compounds from different polymeric materials was determined and the results from the volatile analysis were applied to predict the degree of degradation and long-term properties, to determine degradation rates and mechanisms, to differentiate between biotic and abiotic degradation and for quality control work. Solid-phase microextraction and solid-phase extraction together with GC-MS were applied to identify and quantify the low molar mass compounds. Volatiles were released and monitored at early stages of degradation before any matrix changes were observed by e.g. SEC, DSC and tensile testing. The analysis of volatiles can thus also be applied to detect small differences between polymeric materials and their susceptibility to degradation. The formation of certain degradation products correlated with the changes taking place in the polymer matrix, these indicator products could, thus, be analysed to rapidly predict the degree of degradation in the polymer matrix and further to predict the long-term properties and remaining lifetime of the product.  相似文献   

11.
Polylactide (PLA) is a major biodegradable polymer, which has received extensive interests over the past decades and holds great potential to replace several petroleum-based polymeric materials. Nevertheless, the inherent brittleness and low impact strength have restricted its invasion to niche markets. In this paper, the authors demonstrate that the entirely bio-sourced blends, namely PLA and castor oil-based polyurethane prepolymer (COPUP), were first melt-compounded in an effort to prepare novel biodegradable materials with an excellent balance of properties. NCO-terminated COPUP was successfully synthesized and subsequently mixed with variable concentration of PLA matrix using melt-compounded by twin-screw extrusion technique. The miscibility, phase morphology, mechanical properties, and thermal resistance of the blends were investigated. During FTIR analysis, it suggests that the interfacial compatibilization between COPUP and PLA phase occurred by the reaction of –NCO group of MDI with terminal hydroxyl group of PLA. DMA analysis showed that COPUP and PLA showed some limited miscibility with shifted glass transition temperature. The morphologies of fracture surface showed a brittle-to-ductile transition owing by the addition of COPUP. The crystallization behavior was studied by differential scanning calorimeter (DSC). The strain at break and notched impact strength of PLA/COPUP blends were increased more than 112–15.4 times elegant of neat PLA; the increase is superior to previous toughening effect by using petroleum-based tougheners. Furthermore, the thermal resistances and melt flow properties of the materials were also examined by analysis of the melt flow index and heat deflection temperature use in the work. With enhanced toughness, the PLA/COPUP blends could be used as replacements for some traditional petroleum-based polymeric materials.  相似文献   

12.
The potential biodegradability of several vegetable oil-based polymers was assessed by respirometry in soil for 60–100 days at temperatures of 30–58°C. Films of soybean oil and linseed oil which were oxidatively polymerized (Co catalyst) on a kraft paper support were 90%–100% mineralized to CO2 after 70 days at 30°C. Mineralization of polymerized tung oil to CO2 was much slower than soy or linseed oils. Mineralization of epoxy resins made from epoxidized soybean oil (ESO) and aliphatic dicarboxylic acids was rapid while mineralization of similar resins made with a triacid (citric) was slower. There was no significant degradation of polyamine/ESO resins after 100 days at 58°C. Mineralization of the available carbon in vegetable oil polyurethanes and cationically polymerized ESO was less than 7.5% after 70 days at 30°C and 25 days at 55°C compared to 100% for soybean oil. From these results, it appears that triglycerides highly cross-linked with non-degradable linkages are not biodegradable to a significant extent while triglycerides cross-linked with hydrolysable bonds such as esters remain biodegradable.  相似文献   

13.
Biodiesel can be a potential alternative to petroleum diesel, but its high production cost has impeded its commercialization in most parts of the world. One of the main drivers for the generation and use of biodiesel is energy security, because this fuel can be produced from locally available resources, thereby reducing the dependence on imported oil. Many countries are now trying to produce biodiesel from plant or vegetable oils. However, the consumption of large amounts of vegetable oils for biodiesel production could result in a shortage in edible oils and cause food prices to soar. Alternatively, the use of animal fat, used frying oils, and waste oils from restaurants as feedstock could be a good strategy to reduce the cost. However, these limited resources might not meet the increasing demand for clean, renewable fuels. Therefore, recent research has been focused the use of residual materials as renewable feedstock in order to lower the cost of producing biodiesel. Microbial oils or single cell oils (SCOs), produced by oleaginous microorganisms have been studied as promising alternatives to vegetable or seed oils. Various types of agro-industrial residues have been suggested as prospective nutritional sources for microbial cultures. Since the most abundant residue from agricultural crops is lignocellulosic biomass (LCB), this byproduct has been given top-priority consideration as a source of biomass for producing biodiesel. But the biological transformation of lignocellulosic materials is complicated due to their crystalline structure. So, pretreatment is required before they can be converted into fermentable sugar. This article compares and scrutinizes the extent to which various microbes can accumulate high levels of lipids as functions of the starting materials and the fermentation conditions. Also, the obstacles associated with the use of LCB are described, along with a potentially viable approach for overcoming the obstacles that currently preclude the commercial production of biodiesel from agricultural biomass.  相似文献   

14.
Biodegradation of polymeric materials affect a wide range of industries, information on degradability can provide fundamental information facilitating design and life-time analysis of materials. Among the methods currently used in testing, traditional gravimetric and respirometric techniques are tailored to readily degradable polymeric materials mostly and polymer blends with biodegradable components, but they are not applicable to the new generation of engineering polymers which are relatively resistant to biodegradation. However, electrochemical impedance spectroscopy (EIS) has been tested for monitoring biodeterioration of high strength materials and the technique has very high sensitivity. A wide range of materials including electronic insulation polyimides, fiber-reinforced polymeric composites (FRPCs) and corrosion protective polyurethane coatings have been successfully measured under inoculation of degradative microorganisms using EIS. In addition, the mechanism of degradation of high strength polymers is mainly due to the presence of plasticizers in the polymer matrices. The information on various methods discussed in this review is intended to illustrate a suite of methods for those who are interested in testing biodeterioration of polymeric materials under different environmental conditions and in selecting appropriate techniques for specific applications.  相似文献   

15.
Novel polymer blends based on completely renewable polymers were reported. Polymer blends based on polylactic acid (PLA) and oxidized and hydroxylated soya bean oil polymers were prepared. Plasticization and mechanical strength effect of the soya bean oil polymers on the PLA were observed. Fracture surface analysis of the polymer blends was carried out by using scanning electron microscopy. The PLA blends showed more amorphous morphologies compared to pure PLA. The blends had better elongation at break in view of the stress–strain measurement. Blend of PLA with the hydroxylated polymeric soya bean oil indicated the slightly antibacterial properties.  相似文献   

16.
This paper identifies and estimates time periods as ‘windows-of-opportunity’ where specific response methods, technologies, equipment, or products are more effective in clean-up operations for several oils. These windows have been estimated utilizing oil weathering and technology performance data as tools to optimize effectiveness in marine oil spill response decision-making. The windows will also provide data for action or no-action alternatives. Crude oils and oil products differ greatly in physical and chemical properties, and these properties tend to change significantly during and after a spill with oil aging (weathering). Such properties have a direct bearing on oil recovery operations, influencing the selection of response methods and technologies applicable for clean up, including their effectiveness and capacity, which can influence the time and cost of operations and the effects on natural resources.The changes and variations in physical and chemical properties over time can be modeled using data from weathering studies of specific oils. When combined with performance data for various equipment and materials, tested over a range of weathering stages of oils, windows-of-opportunity can be estimated for spill response decision-making. Under experimental conditions discussed in this paper, windows-of-opportunity have been identified and estimated for four oils (for which data are available) under a given set of representative environmental conditions. These ‘generic’ windows have been delineated for the general categories of spill response namely: (1) dispersants, (2) in situ burning, (3) booms, (4) skimmers, (5) sorbents, and (6) oil-water separators. To estimate windows-of-opportunity for the above technologies (except booms), the IKU Oil Weathering Model was utilized to predict relationships—with 5 m s−1 wind speed and seawater temperatures of 15°C.The window-of-opportunity for the dispersant (Corexit 9527®) with Alaska North Slope (ANS) oil was estimated from laboratory data to be the first 26 h. A period of ‘reduced’ dispersibility, was estimated to last from 26–120 h. The oil was considered to be no longer dispersible if treated for the first time after 120 h. The most effective time window for dispersing Bonnic Light was 0–2 h, the time period of reduced dispersibility was 2–4 h, and after 4 h the oil was estimated to be no longer dispersible. These windows-of-opportunity are based on the most effective use of a dispersant estimated from laboratory dispersant effectiveness studies using fresh and weathered oils. Laboratory dispersant effectiveness data cannot be directly utilized to predict dispersant performance during spill response, however, laboratory results are of value for estimating viscosity and pour point limitations and for guiding the selection of an appropriate product during contingency planning and response. In addition, the window of opportunity for a dispersant may be lengthened if the dispersant contains an emulsion breaking agent or multiple applications of dispersant are utilized. Therefore, a long-term emulsion breaking effect may increase the effectiveness of a dispersant and lengthen the window-of-opportunity.The window-of-opportunity of in situ burning (based upon time required for an oil to form an emulsion with 50% water content) was estimated to be approximately 0–36 h for ANS oil and 0–1 h for Bonnie Light oil after being spilled. The estimation of windows-of-opportunity for offshore booms is constrained by the fact that many booms available on the market undergo submergence at speeds of less than 2 knots. The data suggest that booms with buoyancy to weight ratios less than 8:1 may submerge at speeds within the envelope in which they could be expected to operate. This submergence is an indication of poor wave conformance, caused by reduction of freeboard and reserve net buoyancy within the range of operation. The windows-of-opportunity for two selected skimming principles (disk and brush), were estimated using modeled oil viscosity data for BCF 17 and BCF 24 in combination with experimental performance data developed as a function of viscosity. These windows were estimated to be within 3–10 h (disk skimmer) and after 10 h (brush skimmer) for BCF 17. Whereas for BCF 24, it is within 2–3 d (disk skimmer) and after 3 d (brush skimmer).For sorbents, an upper viscosity limit for an effective and practical use has in studies been found to be approximately 15,000 cP, which is the viscosity range of some Bunker C oils. Using viscosity data for the relative heavy oils, BCF 17 and BCF 24 (API gravity 17 and 24), the time windows for a sorbent (polyamine flakes) was estimated to be 0–4 and 0–10 d, respectively. With BCF 24, the effectiveness of polyamine flakes, was reduced to 50% after 36 h, although it continued to adsorb for up to 10 d. For BCF 17, the effectiveness of polyamine flakes was reduced to 50% after 12 h, although it continued to adsorb for up to 4 d. The windows-of-opportunity for several centrifuged separators based upon the time period to close the density gap between weathered oils and seawater to less than 0.025 g ml−1 (which is expected to be an end-point for effective use of centrifugal separation technology), were estimated to be 0–18 (ANS) and 0–24 h (Bonnie Light) after the spill. Utilizing the windows-of-opportunity concept, the combined information from a dynamic oil weathering model and a performance technology data base can become a decision-making tool; identifying and defining the windows of effectiveness of different response methods and equipment under given environmental conditions. Specific research and development needs are identified as related to further delineation of windows-of-opportunity.  相似文献   

17.
Graft copolymerization of cellulosic biopolymers with synthetic polymers is of enormous interest because of its application in biofiltration, biosorption, biomedical, biocomposites and various other eco-friendly materials. Synthesis of graft copolymers of methyl acrylate onto mercerized Grewia optiva biofibers using ferrous ammonium sulfate–potassium per sulfate as redox initiator in air was carried out. Different reaction parameters such as amount of solvent, monomer concentration, initiator molar ratio, reaction time and reaction temperature were optimized to get the maximum percentage of grafting. The graft copolymers thus formed were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and differential thermogravimetric techniques. A plausible mechanism for explanation of the graft copolymerization reactions pattern shown is offered. The effect of grafting percentage on the physico–chemical properties of raw as well as grafted Grewia optiva biofibers has also been investigated. The graft copolymers have been found to be more moisture resistant and also showed better chemical and thermal resistance. Green polymer composites were also successfully prepared through compression molding technique by using grafted Grewia optiva biofibers as reinforcement.  相似文献   

18.
In view of bio-inorganic importance, iron and zinc incorporated soybean oil based polymer was prepared by condensation polymerization of oil based fatty amide polyole, sebacic acid, zinc acetate and ferric chloride in a process initiated by sodium ethoxide. Microwave assisted synthesis was used throughout the reaction as it is ecofriendly and requires minimal usage of solvents. Physical techniques such as FT-IR and 1HNMR have been used to establish the structure of the polymers. Standard laboratory methods like acid value, saponification value, iodine value, specific gravity and viscosity were used to study the chemical diversity of each product. Thermo gravimetry/differential thermal analyzer was used to analyse the thermal behavior of polymer. The synthesized compounds were subjected to biological study. The observed fungicidal characteristics of synthesized compounds indicate that these compounds might be promising antifungal agents defining a new class of antimycotics. The polymers were used in preparation of films which can be used as protective packaging material of edible items.  相似文献   

19.
Improvement of mechanical properties of recycled mixed plastic waste is one of the fundamental goals in any recycling process. However, polymer immiscibility makes the development of any effective reprocessing method difficult. In this work, a polymer milling process with liquid CO2 was applied to polymeric mixed waste, obtaining a powder material which was successfully utilized as a matrix for a new composite material. Developed materials have interesting mechanical properties and material performance can easily be improved. Investigations on selected mixtures of PP and PE clearly showed evidence of chemical compatibilization.  相似文献   

20.
Biodegradable nanocomposites comprising of biodegradable polymers and bioactive organically modified layered silicates commonly reveal extremely enhanced mechanical and various other properties when compared to those of virgin polymers. This work was undertaken with a view to preparation of polymer bionanocomposites consisting of biodegradable poly(vinyl alcohol) (PVA) and organo-nanoclay. Cloisite Na+ and ammonium salt of l-isoleucine amino acid was used for the preparation of the novel chiral organo-nanoclay via an intercalation reaction in an aqueous solution. PVA/organo-nanoclay bionanocomposites of various compositions were created through the solution intercalation method by ultrasound-assisted technique. The resulting novel materials were characterized by X-ray diffraction and Fourier transform infrared spectroscopy techniques. Thermogravimetric analysis (TGA) and UV/vis spectroscopy were applied to test the properties of PVA bionanocomposites. TGA indicate that the thermal stability is enhanced distinctly, without a sacrifice in optical clarity. The improvement of thermal properties was attributed to the homogeneous and good dispersion of organo-nanoclay in polymeric matrix and the strong hydrogen bonding between O?CH groups of PVA and the oxygen atoms of silicate layers or carbonyl group as well as OH group of intercalated amino acid. The morphology of the organo-nanoclay and PVA bionanocomposites was examined by scanning electron microscopy and transmission electron microscopy techniques. Uniform distribution of clay due to intimate interaction between clay and polymer appears to be the cause for improved properties.  相似文献   

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