PHOSPHORUS-CONTAINING POLYMERS AND OLIGOMERS

Poly(methyl methacrylate)/Montmorillonite Nanocomposites Prepared with a Novel Reactive Phosphorus–Nitrogen-Containing Monomer of N-(2-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-ylamino)ethyl)-Acrylamide and Its Thermal and Flame Retardant PropertiesGuobo Huang,1Xu Wang,2Zhengdong Fei,2Huading Liang,1Yuyuan Ye11School of Pharmaceutical and Chemical Engineering,Taizhou University,Linhai317000,People’s Republic of China 2College of Chemical Engineering and Materials,Zhejiang University of Technology,Hangzhou310014,People’s Republic of ChinaReceived27June2011;accepted10September2011DOI10.1002/app.35618Published online11December2011in Wiley Online Library().ABSTRACT:A novel reactive phosphorus–nitrogen-con-taining monomer,N-(2-(5,5-dimethyl-1,3,2-dioxaphos-phinyl-2-ylamino)ethyl)-acrylamide(DPEAA),was synthesize and characterized.Flame retardant poly(methyl methacrylate)/organic-modified montmorillonite(PMMA-DPEAA/OMMT)nanocomposites were prepared by in situ polymerization by incorporating methyl methacrylate, DPEAA,and OMMT.The results from X-ray diffraction and transmission electron microscopy(TEM)showed that exfoliated PMMA-DPEAA/OMMT nanocomposites were formed.Thermal stability and flammability properties were investigated by thermogravimetric analysis,cone cal-orimeter,and limiting oxygen index(LOI)tests.The syner-gistic effect of DPEAA and montmorillonite improved thermal stability and reduced significantly the flammabil-ity[including peak heat release rates(PHRR),total heat release,average mass loss rate,etc.].The PHRR of PMMA-DPEAA/OMMT was reduced by about40%compared with pure PMMA.The LOI value of PMMA-DPEAA/ OMMT reached27.3%.The morphology and composition of residues generated after cone calorimeter tests were investi-gated by scanning electronic microscopy(SEM),TEM,and energy dispersive X-ray(EDX).The SEM and TEM images showed that a compact,dense,and uniform intumescent char was formed for PMMA-DPEAA/OMMT nanocompo-sites after combustion.The results of EDX confirmed that the carbon content of the char for PMMA-DPEAA/OMMT nanocomposites increased obviously by the synergistic effect of DPEAA and montmorillonite.V C2011Wiley Periodicals,Inc.J Appl Polym Sci124:5037–5045,2012Key words:clay;flame retardant;nanocompositesINTRODUCTIONPoly(methyl methacrylate)(PMMA)is a typical transparent amorphous polymer and has been widely used in a wide range of fields with several desirable properties such as good flexibility,high strength,and excellent dimension stability.How-ever,PMMA is very flammable and cannot satisfy some applications which require high flame retard-ancy.Incorporating a chemically reactive flame re-tardant monomer into the polymer chain is one of the most efficient methods of improving the flame retardancy of polymer.Some phosphorus-containing components have already been used in the synthesis of several flame retardant step-reaction polymers, e.g.,polyesters,1,2polyurethanes,3and epoxy res-ins.4–6However,phosphorus–nitrogen-containing components used in the synthesis of chain-reaction polymers are much less well developed.7In this arti-cle,a novel reactive phosphorus–nitrogen-containing monomer,N-(2-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-ylamino)ethyl)-acrylamide(DPEAA),was synthe-sized and applied to prepare flame retardancy PMMA.Polymer-layered silicate nanocomposites(PLSN) consisting of continuous polymer matrix reinforced by a few weight percent of intercalated or exfoli-ated layered silicates have drawn more and more attention in recent years due to their unique materials properties.8–17As an important member of such nanocomposites,PLSN exhibit enhanced thermal stability and flame retardancy,reduced gas permeability,and improved physical perform-ance and barrier properties.PLSN exhibit enhanced thermal stability and flame retardancy, reduced gas permeability,and improved physicalCorrespondence to:G.Huang(huangguobo@). Contract grant sponsor:Zhejiang Provincial Natural Science Foundation of China;contract grant number: Y4110026.Contract grant sponsor:Opening Foundation of Zhejiang Provincial Top Key Discipline;contract grant number:20110913.Journal of Applied Polymer Science,Vol.124,5037–5045(2012) V C2011Wiley Periodicals,Inc.performance and barrier properties.Previous researches of the flame retardant properties of PLSN mainly demonstrate a significant decrease in the heat release rate,a change in the char struc-ture,and a decrease in the mass loss rate during combustion in a cone calorimeter.18–26In fact,most of PLSN usually do not extinguish and burn slowly until most of the fuel has been burnt.To further improve flame retarding performance of PLSN,intumescent flame retardant(IFR),as envi-ronmentally friendly halogen-free products,is widely applied in the preparation of flame retard-ant PLSN.27–30The IFR can generate a swollen multicellular thermally stable char during burningwhich insulates the underlying material from the flame action.Previous study showed that the addi-tion of montmorillonite into PMMA improved flame retardancy and reduced the heat release rate.31–33However,little work has been done con-cerning the synergistic effect between IFR and the clay mineral in PMMA nanocomposites.In this article,flame retardant PMMA/montmoril-lonite nanocomposites were prepared by in situ po-lymerization by incorporating methyl methacrylate (MMA),DPEAA,and OMMT.The thermal property and flammability of PMMA/montmorillonite nano-composites were investigated by thermogravimetric analysis(TGA)and cone calorimeter test.The char residue after combustion was also examined by scanning electronic microscopy(SEM),transmission electron microscopy(TEM),and energy dispersive X-ray(EDX).It is anticipated that the combination of montmorillonite and IFR DPEAA could improve the thermal stability and flame retardant of the nanocomposites.EXPERIMENTALMaterialsNeopentyl glycol,acryloyl chloride,MMA,and benzoyl peroxide(BPO)chemically pure(CP)were purchased from Sinopharm Chemical Reagent Co. (Shanghai,China).Phosphoryl trichloride and ethylenediamine(CP)were supplied by Shanghai Chemical Reagent Co.(Shanghai,China).Pristine sodium montmorillonite(Na-MMT),with a cation exchange capacity of$120mequiv./100g,was mined at An’ji,Zhejiang,China and was supplied by Anji Yu Hong Clay Chemical Co.(Zhejiang, China).The OMMT was prepared by ion exchange of Na-MMT and hexadecyl trimethyl ammonium bromide in aqueous solution.2,2-Dimethyl-1,3-propanediol phosphoryl chloride(DPPC)and1N-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-yl)ethane-1,2-diamine(DPEA)were prepared according to the published procedure(Scheme1).34,35Synthesis of DPEAADPEA(0.10mol,20.8g),acryloyl chloride(0.10mol, 9.0g),triethylamine(0.20mol,20.2g),and50mL dried trichloromethane were mixed in a glass flask. The reaction was completed after6h at45 C.The raw product was filtered and purified with methyl alcohol.The purified product(DPEAA)was a white solid(yield:74%).Fourier-transform infrared(FT-IR; KBr,cmÀ1):3190,1728,1478,1269,1224,1068,and 1007.1H NMR(CCl3D,d):7.27(m,1H),6.30–6.27 (m,1H),6.18–6.15(m,1H),5.62–5.60(m,1H),4.22–4.18(m,2H),3.87–3.82(m,2H),3.46–3.45(m,2H), 3.16–3.12(m,2H),1.16(s,3H),and0.93(s,3H).13C NMR(CCl3D,d):166.19,131.24,125.71,77.29,76.78, 41.01,31.81,21.69,and20.82.High-resolution mass spectrometry(HRMS)(ESI):C10H19N2O4P calcd mass(MþH)263.1161,found263.1158.Preparation of PMMA-DPEAAA copolymer of MMA and DPEAA(PMMA-DPEAA)was prepared as follows:in a4-neck round-bottom flask equipped with inlets for refriger-ation,mechanical stirring,and nitrogen,kept in an oil bath at90 C,90g of MMA,10g of DPEAA,and 0.5g of BPO previously dissolved,was added.This solution was stirred mechanically at90 C for30min and then inserted into a mold and kept at80 C for 48h to complete the polymerization process.Finally, the PMMA-DPEAA was kept for6h at120 C to be sure that the entire prepolymer fraction has been converted.The copolymer modified by5wt%and 10wt%DPEAA is denoted by PMMA-DPEAA5 and PMMA-DPEAA10,respectively.Preparation of PMMA-DPEAA/OMMT nanocompositesPMMA-DPEAA/OMMT nanocomposites were pre-pared as follows:first,an appropriate amount of OMMT(5g)was introduced into the matrix of85.5 g of MMA and9.5g of DPEAA monomersunder Scheme1Synthesis of nitrogen-and phosphorus-con-taining monomer of DPEAA.5038HUANG ET AL. Journal of Applied Polymer Science DOI10.1002/appmagnetic stirring for 12h at room temperature.On addition of BPO (0.5g),this solution then was stirred mechanically at 90 C for 30min and inserted into a mold and kept at 80 C for 48h to complete the polymerization process.Finally,the PMMA-DPEAA/OMMT nanocomposites were then obtained by keeping for 6h at 120 C.PMMA filled with 5wt %OMMT is denoted by PMMA/OMMT.Characterization and measurementThe samples of PMMA and PMMA-DPEAA for FT-IR were extracted with acetone for 24h in a Soxhlet extraction apparatus.The FT-IR spectra of com-pound DPEAA and PMMA-DPEAA (30wt %DPEAA)dispersed in potassium bromide discs were recorded with Nicolet (model 5700FT-IR)spectro-photometer,scanning range 400–4000cm À1.1H NMR spectra were recorded by a Bruker Avance III (500MHz)spectrometer in CCl 3D,using tetrame-thylsilane as an internal standard.HRMS was per-formed with a Therm LCQ TM Deca XP plus mass spectrometer coupled to a Waters 2695liquid chro-matograph.Differential scanning calorimeter (DSC)measurements were performed under dry nitrogen by using a DSC 200F3DSC thermal analyzer.All samples of DSC were measured from room tempera-ture to 300 C at a heating rate of 10 C/min with a nitrogen flow of 50mL/min.X-ray diffraction (XRD)patterns were obtained in a Thermo ARL X-TRA dif-fractometer using a CuK-a radiation generator with an intensity of 40mA and a voltage of 40kV.The diffraction patterns were collected within the 2y range of 2–12 using a scanning rate of 0.6 /min.The nanocomposites were examined by TEM using a JEM-1230TEM operating at 80kV.TGA was carried out on a Q600SDT thermogravimetric analyzer.Sam-ple weights were the range of 12–15mg.All TGA samples were measured from 30 C to 600 C at a heating rate of 10 C/min with a nitrogen flow of 100mL/min.The flame retardant characteristics of PMMA-DPEAA,and its nanocomposites were tested using a cone calorimeter (ISQ5660)with a heat flux of 35kW/m 2using a cone radiator.All samples with the dimensions of 10cm Â10cm Â3mmplates were placed in aluminum foil,and then put in a box with the same dimension in the horizontal direction.The limiting oxygen index (LOI)was measured with sheet dimensions of 120Â6.5Â3mm 3according to GB/T 2406-93.The cone data reported here are an average of three replicated measurements.Char residue was examined by using a Hitachi S-4800(II)SEM.EDX measurements were conducted on a Noran Vantage-ESI EDX micro ana-lyzer equipped in the SEM.RESULTS AND DISCUSSIONPreparation and characterization of PMMA-DPEAA As shown in Scheme 2,flame retardant PMMA-DPEAA was prepared by the free radical polymer-ization of MMA and DPEAA.FT-IR spectra of DPEAA,PMMA,and PMMA-DPEAA were pre-sented in Figure 1.In the FT-IR spectrum of DPEAA,the absorption peaks at 3207cm À1(N–H),1569cm À1(C ¼¼C),1220cm À1(P–O),1060cm À1and 1009cm À1(P–O–C),and 948cm À1(P–N)were -pared with the FT-IR spectrum of DPEAA,the char-acteristic peaks of carbon–carbon double bond in DPEAA disappeared from the spectrum of PMMA-DPEAA,demonstrating that the carbon–carbon dou-ble bond on DPEAA had reacted with MMA by free radical polymerization.PMMA-DPEAA showed that several new bands appeared relative to pure PMMA.The band at 3198cm À1and 1224cm À1was corresponding to the stretching band of N–H and P–O,respectively,and the band at 1058cm À1and 1008cm À1was interpreted to the stretching band of P–O.35What mentioned above indicated that a c opoly-mer of MMA and DPEAA had produced by free radical polymerization.PMMA-DPEAA was characterized by 1H NMR as shown in Figure 2.In the 1H NMR spectrum of PMMA-DPEAA,the resonance signals occurringatScheme 2Synthesis ofPMMA-DPEAA.Figure 1FT-IR spectra of DPEAA,PMMA,and PMMA-DPEAA.PMMA-DPEAA/OMMT NANOCOMPOSITES 5039Journal of Applied Polymer Science DOI 10.1002/app1.11,0.94(a,a 0),4.25,3.88(b,b 0)and 3.08,3.45(c,d)ppm were remarkably ascribed to methyl,methylene linked to phosphoric acid ester group,and the mid-dle methylene of DPEAA,respectively.34,35The sig-nals at 3.63(f)and 1.32(h)ppm were assigned to the methyl of MMA.Particularly,the signals at 1.60–1.85ppm (g,i)were caused by the methylene and methenyl groups of PMMA-DPEAA with different combinations of DPEAA and MMA.The appearan-ces of these peaks indicated the random sequences of the chain of PMMA-DPEAA.PMMA,PMMA-DPEAA5and PMMA-DPEAA10were measured by a DSC,and their glass transition temperature (T g )was compared in Figure 3.As shown in Figure 3,only one single glass transition could be detected during heating,proving that the copolymer PMMA-DPEAA was random,which agrees with the 1H NMR results that no obvious microphase separation occurs.The T g of the PMMA-DPEAA10sample was 17 C higher than that of pure PMMA.The monomer of DPEAA with bulky side groups might restrict the chain mobility of PMMA,which led to the increment of the T g of PMMA-DPEAA.In addition,the T g of PMMA-DPEAA increased with the increment of the DPEAA content.Morphology of PMMA-DPEAA/OMMT nanocompositesFigure 4provided that the XRD curves of OMMT,PMMA/OMMT,and PMMA-DPEAA/OMMT.A diffraction peak around 2y ¼4.48 was displayed by OMMT,equaling a d spacing of 1.90nm for the lay-ered silicates in OMMT.PMMA/OMMT showed a basal spacing of 2.98nm.The increased spacing indicated that some PMMA molecular chains were intercalated.However,the characteristic (001)reflec-tion of the layered silicates in the PMMA-DPEAA nanocomposites completely disappeared,indicatingexfoliated silicate layers were dispersed in the PMMA-DPEAA matrix by in situ polymerization.Figure 5showed the TEM photomicrographs of PMMA/OMMT and PMMA-DPEAA/OMMT sam-ples.From the TEM image of PMMA/OMMT,the clay mineral layers consisted of multilayered stacks and intercalated or exfoliated silicate layers can be observed.The TEM image of PMMA-DPEAA/OMMT sample revealed that most of the clay min-eral layers lost their stacking structure and were dis-persed disorderly in the PMMA-DPEAA matrix,which indicated that the clay mineral layers were delaminated.These results further supported by the XRD analysis results for the formation of the exfoli-ated nanocomposites.Thermal propertiesFigure 6showed the TGA thermograms of PMMA,PMMA/OMMT,PMMA-DPEAA,andPMMA-Figure 21H NMR spectrum ofPMMA-DPEAA.Figure 3DSC thermograms of PMMA,PMMA-DPEAA5,andPMMA-DPEAA10.Figure 4X-ray diffraction patterns of OMMT,PMMA/OMMT,and PMMA-DPEAA/OMMT.5040HUANG ET AL.Journal of Applied Polymer Science DOI 10.1002/appDPEAA/OMMT.The corresponding TGA data were presented in Table I.The temperature in which the weight loss is 5wt %is defined as the initial decom-position temperature,which is denoted as T inital .Pure PMMA decomposed at 269 C,leaving negligi-ble char at 500 C.T initial of PMMA/OMMT was 2 C lower than pure PMMA due to the decomposition of the organic modifier.T initial of PMMA-DPEAA10was 19 C higher than PMMA,and the T initial of PMMA-DPEAA was increased with the increment of the DPEAA content,which indicated that DPEAA had a significant effect on the thermal stability of PMMA.On the basis of Figure 6and Table I,T inital of PMMA-DPEAA/OMMT was higher than that of PMMA/OMMT and PMMA-DPEAA10,and the final char for PMMA-DPEAA/OMMT was 4wt %higher than PMMA-DPEAA10,which indicated that the synergistic effect of DPEAA and montmorillonite significantly improved the thermal properties of PMMA.Flame retardant propertiesFigure 7showed that the heat release rate of PMMA,PMMA/OMMT,PMMA-DPEAA5,PMMA-DPEAA10,and PMMA-DPEAA/OMMT at 35kW/m 2.The corresponding cone calorimetry and LOI data were shown in Table II.In comparison to pure PMMA,the peak heat release rates (PHRR)of PMMA/OMMT was 20%lower even though the total heat release (THR),and average mass loss rate (AMLR)remained almost same.The time of ignition (t ign )of PMMA/OMMT was 5s higher than that of pure PMMA,and the LOI value of PMMA/OMMT sample increased to 22.6%.Previous study also showed that the addition of OMMT reduced the flammability of PMMA.31–33For PMMA-DPEAA copolymer s,both the PHRR AHRR and AMLR were reduced with the addition of DPEAA.The PHRR of PMMA-DPEAA5and PMMA-DPEAA10was reduced by 22%and 26%relative to pure PMMA.The THR was reduced by 12%and 15%for PMMA-DPEAA5and PMMA-DPEAA10;the t ign of PMMA-DPEAA blends was longer than that of pure PMMA.In addition,the LOI value of PMMA-DPEAA5and PMMA-DPEAA10was 23.7%andFigure 5TEM images of (a)PMMA/OMMT and (b)PMMA-DPEAA/OMMT.Figure 6TGA curves for PMMA,PMMA/OMMT,PMMA-DPEAA,and PMMA-DPEAA/OMMT.TABLE IData of TGA Thermograms for Various Samples at aHeating Rate of 10°C/min in N 2SampleT initial ( C)Char residue (%)400 C 500 C 600 C PMMA26943.60.70.5PMMA/OMMT 26743.9 2.7 2.6PMMA-DPEAA528148.4 2.1 2.1PMMA-DPEAA1028860.5 4.1 3.9PMMA-DPEAA/OMMT29263.08.17.7T initial ,initial degradation temperature (temperature at 5wt %loss).PMMA-DPEAA/OMMT NANOCOMPOSITES 5041Journal of Applied Polymer Science DOI 10.1002/app25.1%,respectively.These indicated that the phos-phorus–nitrogen-containing monomer DPEAA improved significantly the flame retardant properties of pared with pure PMMA,the PHRR of PMMA-DPEAA/OMMT was reduced by about 40%.For PMMA-DPEAA/OMMT,t ign was longer than that of those of PMMA/OMMT and PMMA-DPEAA10.Meanwhile,the values of PHRR,THR and AMLR of PMMA-DPEAA/OMMT were lower than those of PMMA/OMMT and PMMA-DPEAA10.The LOI value of PMMA-DPEAA/OMMT reached 27.3%and was higher than those of PMMA/OMMT and PMMA-DPEAA10.The improvement of flame retardancy of PMMA-DPEAA/OMMT indicated the synergistic effect between montmorillonite and DPEAA.The similar results were obtained for exfoli-ated ABS/MMT and PA6/MMT nanocomposites with phosphorus–nitrogen-containing flame retardant additive.36,37Figure 8showed the digital photos for the resi-dues of PMMA,PMMA/OMMT,PMMA-DPEAA10,and PMMA-DPEAA/OMMT samples after cone cal-orimeter tests.The digital photos demonstrated that the pure PMMA left almost no residue at the end ofcombustion.The char of PMMA/OMMT was thin and discrete.For the PMMA-DPEAA10sample,the swollen char was observed.For the PMMA-DPEAA/OMMT sample,the char was more rigid,compact,and uniform.The morphologies of the char obtained after cone calorimeter test were examined by SEM,which were shown in Figure 9.A lot of clay mineral layers joined each other and formed a barrier in the residue of PMMA/OMMT.For the char of PMMA-DPEAA10sample,intumescent carbonaceous struc-tures were observed clearly.Residue of PMMA-DPEAA/OMMT showed that many clay mineral layers were dispersed uniformly on the char surface and formed a compact and dense barrier,which could form a better protective shields,and inhibit more effectively the transmission and diffusion of heat more effectively when exposed to flame or heat source.TEM images of the residues after combustion were shown in Figure 10.The TEM image of the res-idues of PMMA/OMMT revealed that most of the clay mineral layers were stacked on top of each other after combustion.However,it was seen clearly that the highly exfoliated clay mineral layers were randomly dispersed in the char from the TEM image of the residues of PMMA-DPEAA/OMMT,which indicated that the clay mineral layers acted as a pro-tective barrier and improved the flame retardant of the nanocomposites.Table III presented the results of element analysis for PMMA/OMMT,PMMA-DPEAA10,and PMMA-DPEAA/OMMT after cone calorimeter tests.As shown in Table III,around 24%phosphorus and 22%carbon still remained in the chars of PMMA-DPEAA10,indicating the excellent carbon-ization of DPEAA.The carbon content of the char for PMMA-DPEAA/OMMT was higher than that of PMMA/OMMT and PMMA-DPEAA10,which indi-cated that the synergistic effect of DPEAA and montmorillonite improved char-forming ability of thenanocomposites.Figure 7Heat release rate of PMMA,PMMA/OMMT,PMMA-DPEAA5,PMMA-DPEAA10,and PMMA-DPEAA/OMMT at 35kW/m 2.TABLE IICone Calorimetry Data for Various Samples at 35kW/m 2Samplet ign (s)PHRR (kW/m 2)THR (MJ/m 2)ASEA (m 2/kg)AMLR (g/s)PMMA26624966116760.86166160.07960.007PMMA/OMMT 3162395686560.96026180.06860.005PMMA-DPEAA53763387675960.75126150.06460.006PMMA-DPEAA104263367665760.73536150.06360.005PMMA-DPEAA/OMMT4862295685460.63366160.05660.004t ign ,time of ignition;PHRR,peak release rate;THR,total heat release;ASEA,aver-age-specific extinction area;AMLR,average mass loss rate.5042HUANG ET AL.Journal of Applied Polymer Science DOI 10.1002/appFigure8Digital photos of the residues after cone calorimeter testing:(a)PMMA,(b)PMMA/OMMT,(c)PMMA-DPEAA10,and(d)PMMA-DPEAA/OMMT.[Color figure can be viewed in the online issue,which is available at.]PMMA-DPEAA/OMMT.Mechanical propertiesTable IV showed that the data for the mechanical properties of PMMA and its -pared with pure PMMA,PMMA/OMMT compo-sites filled with 5wt %showed a 15%increase in tensile strength to 21.4MPa,a 12%increase in elastic modulus to 288.3MPa,little change in elongation at break,which indicated the strength effect of OMMT for PMMA matrix.Tensile tests on PMMA-DPEAA5and PMMA-DPEAA10showed marked reduction of in the tensile strength and elastic modulus compared with pure PMMA.Fortunately,after adding OMMT into PMMA-DPEAA copolymer,the mechanical properties,including tensile strength and elasticmodulus,were to some extent improved compared with PMMA-DPEAA10.Meanwhile,the mechanical properties of PMMA-DPEAA/OMMT nanocompo-sites exhibited almost no deterioration compared with pure PMMA.CONCLUSIONSThe reactive phosphorus–nitrogen-containing mono-mer,DPEAA,was synthesize and characterized.PMMA-DPEAA/OMMT nanocomposites were pre-pared by in situ polymerization by incorporating MMA,DPEAA,and OMMT.The results from XRD and TEM showed that exfoliated PMMA-DPEAA/OMMT nanocomposites were formed.A synergistic effect was found between DPEAA and montmoril-lonite which improved the thermal stability and flame retardancy of pared with pure PMMA,the PHRR of PMMA-DPEAA/OMMT was reduced by about 40%.The LOI value of PMMA-DPEAA/OMMT reached 27.3%.The SEM and TEM images confirmed that a compact,dense,and uni-form intumescent char was formed for PMMA-DPEAA/OMMT nanocomposites after combustion.The EDX analysis results indicated that the carbon content of the char for PMMA-DPEAA/OMMT increased by the synergistic effect of DPEAA and montmorillonite.TABLE IIIThe Results of EDX Analysis of the Residues After Cone Calorimeter TestingSampleMass content (wt %)C O P Si Al Mg PMMA/OMMT 7.9860.1354.4760.88–25.8260.039.4660.172.2760.08PMMA-DPEAA1022.2560.4253.2560.8624.5060.14–––PMMA-DPEAA/OMMT28.8660.1441.5160.8014.4960.1310.6460.203.6660.090.8460.04Figure 10TEM images of the char after cone calorimeter testing:(a)PMMA/OMMT and (b)PMMA-DPEAA/OMMT.TABLE IVMechanical Properties of PMMA and ItsNanocompositesSampleTensile strength (MPa)Elastic modulus (MPa)Elongation at break (%)PMMA18.65256.459.6PMMA/OMMT 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Key to Exercise Unit 1 Chemical Industries1.the Industrial Revolutionanic chemicals3.the contact process4.the Haber process5.synthetic polymers6.intermediates7.artificial fertilizers 8.pesticides (crop protection chemicals)9.synthetic fibers10.pharmaceutical11.research and development12.petrochemicalputers(automatic control equipment)14.capital intensiveSome Chemicals Used In Our Daily LifeUnit 2 Research and Development1.R&D2.ideas and knowledge3.process and products4.fundamental5.applied6.product development7.existing product8.pilot plant9.profitbility10.environmental impact11.energy cost 12.technical support13.process improvement14.effluent treatment15.pharmaceutical16.sufficiently pure17.Reaction18.unreacted material19.by-products20.the product specification21.Product storageUnit 3 Typical Activities of Chemical Engineers1.Mechanical2.electrical3.civil4.scale-upmercial-size6.reactors7.distillation columns8.pumps9.control and instrumentation10.mathematics11.industry12.academia13.steam 14.cooling water15.an economical16.to improve17.P&I Drawings18.Equipment Specification Sheets19.Construction20.capacity and performance21.bottlenecks22.Technical Sales23.new or improved24.engineering methods25.configurationsUnit 4 Sources of Chemicals1.inorganic chemicals2.derive from (originate from)3.petrochemical processes4.Metallic ores5.extraction process6.non-renewable resource7.renewable sources8.energy source9.fermentation process10.selective 11.raw material12.separation and purification13.food industry14.to be wetted15.Key to success16.Crushing and grinding17.Sieving18.Stirring and bubbling19.Surface active agents20.OverflowingUnit 5 Basic Chemicals 1. Ethylene 2. acetic acid 3.4. Polyvinyl acetate5. Emulsion paintUnit 6 Chlor-Alkali and Related Processes 1. Ammonia 2. ammonia absorber 3. NaCl & NH 4OH 4.5. NH 4Cl6. Rotary drier7. Light Na 2CO 3Unit 7 Ammonia, Nitric Acid and Urea 1. kinetically inert 2. some iron compounds 3. exothermic 4. conversion 5. a reasonable speed 6. lower pressures 7. higher temperatures 8.9. energy 10. steam reforming 11. carbon monoxide 12. secondary reformer 13. the shift reaction 14. methane 15. 3:1Unit 8 Petroleum Processing 1. organic chemicals 2. H:C ratios3. high temperature carbonization4. crude tar5. pyrolysis6. poor selectivity7. consumption of hydrogen8. the pilot stage9. surface and underground 10.fluidized bed 11. Biotechnology 12. sulfur speciesUnit 9 PolymersUnit 10 What Is Chemical EngineeringMicroscale (≤10-3m)●Atomic and molecular studies of catalysts●Chemical processing in the manufacture of integrated circuits●Studies of the dynamics of suspensions and microstructured fluidsMesoscale (10-3－102m)●Improving the rate and capacity of separations equipment●Design of injection molding equipment to produce car bumpers madefrom polymers●Designing feedback control systems for bioreactorsMacroscale (>10m)●Operability analysis and control system synthesis for an entire chemicalplant●Mathematical modeling of transport and chemical reactions ofcombustion-generated air pollutants●Manipulating a petroleum reservoir during enhanced oil recoverythrough remote sensing of process data, development and use of dynamicmodels of underground interactions, and selective injection of chemicalsto improve efficiency of recoveryUnit 12 What Do We Mean by Transport Phenomena?1.density2.viscosity3.tube diameter4.Reynolds5.eddiesminar flow7.turbulent flow 8.velocity fluctuations9.solid surface10.ideal fluids11.viscosity12.Prandtl13.fluid dynamicsUnit 13 Unit Operations in Chemical Engineering 1. physical 2. unit operations 3. identical 4. A. D. Little 5. fluid flow6. membrane separation7. crystallization8. filtration9. material balance 10. equilibrium stage model 11. Hydrocyclones 12. Filtration 13. Gravity 14. VaccumUnit 14 Distillation Operations 1. relative volatilities 2. contacting trays 3. reboiler4. an overhead condenser5. reflux6. plates7. packing8.9. rectifying section 10. energy-input requirement 11. overall thermodynamic efficiency 12. tray efficiencies 13. Batch operation 14. composition 15. a rectifying batch 1 < 2 < 3Unit 15 Solvent Extraction, Leaching and Adsorption 1. a liquid solvent 2. solubilities 3. leaching 4. distillation 5. extract 6. raffinate 7. countercurrent 8. a fluid 9. adsorbed phase 10. 400,000 11. original condition 12. total pressure 13. equivalent numbers 14. H + or OH –15. regenerant 16. process flow rates17. deterioration of performance 18. closely similar 19. stationary phase 20. mobile phase21. distribution coefficients 22. selective membranes 23. synthetic24. ambient temperature 25. ultrafiltration26. reverse osmosis (RO).Unit 16 Evaporation, Crystallization and Drying 1. concentrate solutions 2. solids 3. circulation 4. viscosity 5. heat sensitivity 6. heat transfer surfaces 7. the long tube8. multiple-effect evaporators 9.10. condensers 11. supersaturation 12. circulation pump 13. heat exchanger 14. swirl breaker 15. circulating pipe 16. Product17. non-condensable gasUnit 17 Chemical Reaction Engineering1.design2.optimization3.control4.unit operations (UO)5.many disciplines6.kinetics7.thermodynamics,8.fluid mechanics9.microscopic10.chemical reactions 11.more valuable products12.harmless products13.serves the needs14.the chemical reactors15.flowchart16.necessarily17.tail18.each reaction19.temperature and concentrations20.linearUnit 18 Chemical Engineering Modeling1.optimization2.mathematical equations3.time4.experiments5.greater understanding6.empirical approach7.experimental design8.differing process condition9.control systems 10.feeding strategies11.training and education12.definition of problem13.mathematical model14.numerical methods15.tabulated or graphical16.experimental datarmation1.the preliminary economics2.technological changes3.pilot-plant data4.process alternatives5.trade-offs6.Off-design7.Feedstocks 8.optimize9.plant operations10.energy11.bottlenecking12.yield and throughput13.Revamping14.new catalystUnit 19 Introduction to Process Design1. a flowsheet2.control scheme3.process manuals4.profit5.sustainable industrial activities6.waste7.health8.safety9. a reactor10.tradeoffs11.optimizations12.hierarchyUnit 20 Materials Science and Chemical Engineering1.the producing species2.nutrient medium3.fermentation step4.biomass5.biomass separation6.drying agent7.product8.water9.biological purificationUnit 21 Chemical Industry and Environment1.Atmospheric chemistry2.stratospheric ozone depletion3.acid rain4.environmentally friendly products5.biodegradable6.harmful by-product7.efficiently8.power plant emissions 9.different plastics10.recycled or disposed11.acidic waste solutionsanic components13.membrane technology14.biotechnology15.microorganisms。

总763期第二十九期2021年10月河南科技Henan Science and Technology环氧树脂浇注件常见质量问题及原因分析张敬董保莹李永奎陈蕊卢银花（河南平高电气股份有限公司，河南平顶山467001）摘要：浇注件生产过程复杂，工艺控制困难。

浇注件的生产过程容易出现气泡、开裂、缺陷、玻璃化温度不合格等质量问题。

本文就产生这些质量问题的原因一一进行阐述。

在实际生产中，要选择合适的原材料，配合较优的浇注件、嵌件、模具设计，严格进行工艺控制，合理进行装脱模操作，保证浇注件的各项性能指标都能满足要求。

关键词：浇注件；气泡；模具；爆聚中图分类号：TM412文献标识码：A文章编号：1003-5168（2021）29-0063-03 Analysis on Common Quality Problems and Causes of Epoxy Resin Castings ZHANG Jing DONG Baoying LI Yongkui CHEN Rui LU Yinhua（Henan Pinggao Electric Co.,Ltd.,Pingdingshan Henan467001）Abstract:The production process of the casting is complicated and the process control is difficult.The production process of castings is prone to quality problems such as bubbles,cracks,defects,and unqualified glass transition tem⁃perature.This paper explains the reasons for these quality problems one by one.In actual production,it is necessary to select appropriate raw materials,cooperate with better pouring parts,inserts,and mold designs,strictly control the process,and perform reasonable assembly and demolding operations to ensure that the performance indicators of the pouring parts meet the requirements.Keywords:casting parts；bubble；mould；explosive polymerization高压开关设备用环氧浇注绝缘制品要求外观完美，尺寸稳定，机、电、热性能满足产品要求［1-5］。

南开大学硕士学位论文手性硫代磷酰胺催化的环戊酮与查尔酮的不对称Michael加成姓名：***申请学位级别：硕士专业：有机化学指导教师：***2012-05摘要摘要本论文主要研究了手性硫代磷酰胺催化环戊酮与低反应活性Ｍｉｃｈａｅｌ受体一查尔酮的不对称共轭加成反应。

首先从Ｌ．脯氨酸和（足Ｒ）．１，２．二苯基乙二胺出发合成了一系列具有手性四氢吡咯环骨架和１，２．二苯基乙二胺骨架的双功能手性硫代磷酰胺催化剂，作为对照还合成了相应的手性硫脲。

其次以环戊酮与查尔酮的不对称Ｍｉｃｈａｅｌ加成为模型反应，考察了不同结构的手性硫代磷酰胺催化剂的催化活性，并和相应的硫脲催化剂进行了比较。

实验结果表明硫代磷酰胺催化剂表现出了明显优于硫脲催化剂的催化活性。

但是加成产物的非对映和对映选择性很大程度上依赖于催化剂中磷原子上的取代基结构。

就立体选择性而言，其中衍生自Ｌ．脯氨酸、磷原子上含有两个苯氧基催化剂表给出了最好的结果。

在优化反应条件下（２０ｍ０１％催化剂、２０ｔ００１％三乙胺、１０ｍ０１％苯甲酸为添加剂、甲苯作溶剂、２５ｏＣ），取得了９０／１０的非对映选择性和主要非对映体为９２％的对映选择性。

进一步的底物扩展研究表明该催化体系具有较广的底物适用范围，但不足之处是反应的对映选择性具有很强的底物依赖性，取代基的引入会导致对映选择性的明显下降。

关键词：手性硫代磷酰胺，环戊酮，查尔酮，非对映选择性，对映选择性ＡｂｓｔｒａｃｔＡｂｓｔｒａｃｔＩｎｔｈｉｓｔｈｅｓｉｓ，ｗｅｍａｉｎｌｙｆｏｃｕｓｅｄＯｉｌｔｈｅｃｈｉｒａｌｔｈｉｏｐｈｏｓｐｈｏｒａｍｉｄｅｃａｔａｌｙｚｅｄａｓｙｍｍｅｔｒｉｃＭｉｃｈａｅｌａｄｄｉｔｉｏｎｏｆｃｙｃｌｏｐｅｎｔａｎｏｎｅｔｏｌｅｓｓｒｅａｃｔｉｖｅｃｈａｌｃｏｎｅｓ．Ｆｉｒｓｔｌｙ，ａｓｅｒｉｅｓｏｆｃｈｉｒａｌｔｈｉｏｐｈｏｓｐｈｏｒａｍｉｄｅｃａｔａｌｙｓｔｗｅｒｅｓｙｎｔｈｅｓｉｚｅｄｓｔａｒｔｉｎｇｆｒｏｍＬ—ｐｒｏｌｉｎｅａｎｄ（Ｒ，Ｒ）一１，２－ｄｉｐｈｅｎｙｌｅｔｈｙｌｅｎｅｄｉａｍｉｎｅ，ｒｅｓｐｅｃｔｉｖｅｌｙ．Ｆｏｒｃｏｍｐａｒｉｓｏｎ，ｔｈｅｃｏｒｒｅｓｐｏｎｄｉｎｇｔｈｉｏｕｒｅａｃａｔａｌｙｓｔｂｅａｒｉｎｇｔｈｅｓａｍｅｃｈｉｒａｌｓｋｅｌｅｔｏｎｗａｓａｌｓｏｓｙｎｔｈｅｓｉｚｅｄ．Ｓｅｃｏｎｄｌｙ，ｗｉｔｈｔｈｅｓｅｃａｔａｌｙｓｔｓｉｎｈａｎｄ，ｔｈｅｉｒｃａｔａｌｙｔｉｃａｌａｃｔｉｖｉｔｉｅｓｗｅｒｅｖａｌｕａｔｅｄｅｍｐｌｏｙｉｎｇｔｈｅＭｉｃｈａｅｌａｄｄｉｔｉｏｎｏｆｃｙｃｌｏｐｅｎｔａｎｏｎｅｔｏｃｈａｌｃｏｎｅ．Ｔｈｅｅｘｐｅｒｉｍｅｎｔａｌｒｅｓｕｌｔｓｉｎｄｉｃａｔｅｔｈａｔｃｈｉｒａｌｔｈｉｏｐｈｏｓｐｈｏｒａｍｉｄｅｃａｔａｌｙｓｔｓｗｅｒｅｍｏｒｅｅｆｆｉｃｉｅｎｔｔｈａｎｔｈｅｃｏｒｒｅｓｐｏｎｄｉｎｇｔｈｉｏｕｒｅａｓ．Ｍｏｒｅｏｖｅｒ，ｂｏｔｈｔｈｅｄｉａｓｔｅｒｅｏ－ａｎｄｅｎａｎｔｉｏｓｅｌｅｃｔｉｖｉｔｙａｒｅｈｉ曲ｌｙｄｅｐｅｎｄｅｎｔｏｎｔｈｅｓｕｂｓｔｉｔｕｅｎｔｓａｔｔｈｅｐｈｏｓｐｈｏｒｕｓａｔｏｍ．Ｉｎｔｅｒｍｓｏｆｄｉａｓｔｅｒｅｏ．ａｎｄｅｎａｎｔｉｏｓｅｌｅｃｔｉｖｉｔｙ，ｔｈｅＯ，Ｏ—ｄｉｐｈｅｎｙｌｓｕｂｓｔｉｔｕｔｅｄｔｈｉｏｐｈｏｓｐｈｏｒａｍｉｄｅｂｅａｒｉｎｇ（回－ｐｙｒｒｏｌｉｄｉｎｅｓｋｅｌｅｔｏｎｇａｖｅｔｈｅｂｅｓｔｒｅｓｕｌｔｓ．Ｕｎｄｅｒｔｈｅｏｐｔｉｍｉｚｅｄｒｅａｃｔｉｏｎｃｏｎｄｉｔｉｏｎｓ（２０ｍ０１％ｃａｔａｌｙｓｔ，２０ｍ０１％ｔｒｉｅｔｈｙｌａｍｉｎｅ，１０ｍ０１％ｂｅｎｚｏｉｃａｃｉｄａｓｃｏｃａｔａｌｙｓｔ，ｔｏｌｕｅｎｅ，２５ｏＣ），ｔｈｅｄｅｓｉｒｅｄａｄｄｉｔｉｏｎｐｒｏｄｕｃｔｓｗａｓｏｂｔａｉｎｅｄｗｉｔｈｇｏｏｄｄｉａｓｔｅｒｅｏｓｅｌｅｃｔｉｖｉｔｙ（ｔｒａｎｓ／ｃｉｓ：９０／１０）ａｎｄｅｘｃｅｌｌｅｎｔｅｎａｎｔｉｏｓｅｌｅｃｔｉｖｉｔｙ（９２％ｅｅｆｏｒｍａｊｏｒｄｉａｓｔｅｒｅｏｍｅｒ）．Ｆｕｒｔｈｅｒｉｎｖｅｓｔｉｇａｔｉｏｎｒｅｖｅａｌｅｄｔｈａｔｔｈｅｒｅａｃｔｉｏｎｈａｓａｂｒｏａｄａｐｐｌｉｃａｂｉｌｉｔｙｗｉｔｈｒｅｓｐｅｃｔｔｏｃｈａｌｃｏｎｅｓ．Ｈｏｗｅｖｅｒ，ｔｈｅｅｎａｎｔｉｏｓｅｌｅｃｔｉｖｉｔｙｏｆｔｈｅｒｅａｃｔｉｏｎｉｓｇｒｅａｔｌｙｄｅｐｅｎｄｅｎｔｏｎｔｈｅｎａｔｕｒｅｏｆｔｈｅｃｈａｌｃｏｎｅｓｕｂｓｔｒａｔｅｓ．Ｔｈｅｉｎｔｒｏｄｕｃｔｉｏｎｏｆｓｕｂｓｔｉｔｕｅｎｔｏｎｔｈｅｂｅｚｅｎｅｒｉｎｇｓｏｆｔｈｅｃｈａｌｃｏｎｅｒｅｓｕｌｔｅｄｉｎａｎｏｂｖｉｏｕｓｄｅｃｒｅａｓｅｉｎｅｎａｎｔｉｏｓｅｌｅｃｔｉｖｉｔｙ．Ｋｅｙｗｏｒｄｓ：Ｃｈｉｒａｌｔｈｉｏｐｈｏｓｐｈｏｒａｍｉｄｅ，ｃｙｃｌｏｐｅｎｔａｎｏｎｅ，ｃｈａｌｃｏｎｅｓ，ｅｎａｎｔｉｏｓｅｌｅｃｔｉｖｉｔｙ，ｄｉａｓｔｅｒｅｏｓｅｌｅｃｔｉｖｉｔｙＩＩ第一章前言迈克尔加成反应（Ｍｉｃｈａｅｌａｄｄｉｔｉｏｎｒｅａｃｔｉｏｎ）是亲电的共轭体系（电子受体）与亲核的负电性离子（电子给体）进行的共轭加成反应。

CompoundsPhosphorus(V)The most prevalent compounds of phosphorus are derivatives of phosphate (PO 43−), a tetrahedralanion.[35] Phosphate is the conjugate base of phosphoric acid, which is produced on a massive scale for use in fertilisers. Being triprotic, phosphoric acid converts stepwise to three conjugate bases:H 3PO 4 + H 2O ⇌ H 3O + + H 2PO 4− K a1= 7.25×10−3H 2PO 4− + H 2O ⇌ H 3O + + HPO 42− K a2= 6.31×10−8HPO 42− + H 2O ⇌ H 3O + + PO 43− K a3= 3.98×10−13Phosphate exhibits the tendency to form chains and rings with P-O-P bonds. Many polyphosphates are known, including ATP. Polyphosphates arise by dehydration of hydrogen phosphates such as HPO 42− and H 2PO 4−. For example, the industrially important trisodium triphosphate (also knownas sodium tripolyphosphate, STPP) is produced industrially on by the megatonne by this condensation reaction:2 Na 2[(HO)PO 3] + Na[(HO)2PO 2] → Na 5[O 3P-O-P(O)2-O-PO 3] + 2 H 2OPhosphorus pentoxide (P 4O 10) is the acid anhydride of phosphoric acid, but several intermediates between the two are known. This waxy white solid reacts vigorously with water.With metal cations, phosphate forms a variety of salts. These solids are polymeric, featuring P-O-M linkages. When the metal cation has a charge of 2+ or 3+, the salts are generally insoluble, hence they exist as common minerals. Many phosphate salts are derived from hydrogen phosphate (HPO 42−). PCl 5 and PF 5 are common compounds. PF 5 is a colourless gas and the molecules have trigonal bypramidal geometry. PCl 5 is a colourless solid which has an ionic formulation of PCl 4+ PCl 6−, but adopts the trigonal bypramidal geometry when molten or in the vapour phase.[11] PBr 5 is an unstable solid formulated as PBr 4+Br −and PI 5is not known.[11] The pentachloride and pentafluoride are Lewis acids. With fluoride, PF 5 forms PF 6−, an anion that is isoelectronic with SF 6. The most important oxyhalideis phosphorus oxychloride, (POCl 3), which is approximately tetrahedral.Before extensive computer calculations were feasible, it was thought that bonding in phosphorus(V)compounds involved d orbitals. Computer modeling of molecular orbital theory indicates that this bonding involves only s- and p-orbitals.[36]Phosphorus(III)All four symmetrical trihalides are well known: gaseous PF 3, the yellowish liquids PCl 3 and PBr 3, and the solid PI 3. These materials are moisture sensitive, hydrolysing to give phosphorous acid. The trichloride, a common reagent, is produced by chlorination of white phosphorus:P 4 + 6 Cl 2 → 4 PCl 3The trifluoride is produced from the trichloride by halide exchange. PF 3 is toxic because it binds to haemoglobin.Phosphorus(III) oxide, P 4O 6 (also called tetraphosphorus hexoxide) is the anhydride of P(OH)3, the minor tautomer of phosphorous acid. The structure of P 4O 6 is like that of P 4O 10 without the terminal oxide groups.Phosphorus(I) and phosphorus(II)The tetrahedralstructure ofP 4O 10 and P 4S 10.A stable diphosphene , a derivative ofphosphorus(I).These compounds generally feature P-P bonds.[11] Examples include catenated derivatives of phosphine and organophosphines. Compounds containing P=P double bonds have also been observed, although they are rare.Phosphides and phosphinesPhosphides arise by reaction of metals with red phosphorus. The alkali metals (group 1) and alkaline earth metals can form ionic compounds containing the phosphide ion, P3−. These compounds react with water to form phosphine. Other phosphides, for example Na3P7, are known for these reactive metals. With the transition metals as well as the monophosphides there are metal rich phosphides, which are generally hard refractory compounds with a metallic lustre, and phosphorus rich phosphides which are less stable and include semiconductors.[37] Schreibersite is a naturally occurring metal rich phosphide found in meteorites. The structures of the metal rich and phosphorus rich phosphides can be structurally complex.Phosphine (PH3) and its organic derivatives (PR3) are structural analogues with ammonia (NH3) but the bond angles at phosphorus are closer to 90° for phosphine and its organic derivatives. It is an ill-smelling, toxic compound. Phosphorus has an oxidation number of -3 in phosphine. Phosphine is produced by hydrolysis of calcium phosphide, Ca3P2. Unlike ammonia, phosphine is oxidised by air. Phosphine is also far less basic than ammonia. Other phophines are known which contain chains of up to nine phosphorus atoms and have the formula P n H n+2. The highly flammable gas diphosphine (P2H4) is an analogueof hydrazine.OxoacidsPhosphorous oxoacids are extensive, often commercially important, and sometimes structurally complicated. They all have acidic protons bound to oxygen atoms, some have nonacidic protons that are bonded directly to phosphorus and some contain phosphorus - phosphorus bonds.[11] Although many oxoacids of phosphorus are formed, only nine are important, and three of them, hypophosphorous acid, phosphorous acid, and phosphoric acid, are particularly important(See the table).NitridesThe PN molecule is considered unstable, but is a product of crystalline phosphorus nitride decomposition at 1100 K. Similarly, H2PN is considered unstable, and phosphorus nitride halogens like F2PN, Cl2PN, Br2PN, and I2PN oligomerise into cyclic Polyphosphazenes. For example, compounds of the formula (PNCl2)n exist mainly as rings such as the trimer hexachlorophosphazene. The phosphazenes arise by treatment of phosphorus pentachloride with ammonium chloride:PCl5 + NH4Cl → 1/n (NPCl2)n + 4 HCl When the chloride groups are replaced by alkoxide (RO−), a family of polymers is produced with potentially useful properties.[38]SulfidesPhosphorus forms a wide range of sulfides, where the phosphorus can be in P(V), P(III) or other oxidation states. The most famous is the three-fold symmetric P4S3 which is used in strike-anywhere matches. P4S10 and P4O10 have analogous structures.[39] Mixed oxyhalides and oxyhydrides of phosphorus(III) are almost unknown.Organophosphorus compoundsCompounds with P-C and P-O-C bonds are often classified as organophosphorus compounds. They are widely used commercially. The PCl3 serves as a source of P3+ in routes to organophosphorus(III) compounds. For example, it is the precursor to triphenylphosphine:PCl3 + 6 Na + 3 C6H5Cl → P(C6H5)3 + 6 NaClTreatment of phosphorus trihalides with alcohols and phenols gives phosphites, e.g. triphenylphosphite: PCl3 + 3 C6H5OH → P(OC6H5)3 + 3 HClSimilar reactions occur for phosphorus oxychloride, affording triphenylphosphate:OPCl3 + 3 C6H5OH → OP(OC6H5)3 + 3 HCl24 27 28 29 30 31 32CompoundsFluorine has a rich chemistry, encompassing organic and inorganic domains. It combines with metals, nonmetals, metalloids, and most noble gases,and usually assumes an oxidation state of −1.[note10] Fluorine's high electron affinity results in a preference for ionic bonding; when it forms covalent bonds, these are polar, and almost always single.MetalsHydrogenHydrogen and fluorine combine to yield hydrogen fluoride, in which discrete molecules form clusters by hydrogen bonding, resembling water more than hydrogen chloride.[123][124][125] It boils at a much higher temperature than heavier hydrogen halides and unlike them is fully miscible with water.Hydrogen fluoride readily hydrates on contact with water to form aqueous hydrogen fluoride, also known as hydrofluoric acid. Unlike the other hydrohalic acids, which are strong, hydrofluoric acid is a weak acid at low concentrations.However, it can attack glass, something the other acids cannot do.Other reactive nonmetalsBoron trifluoride is planar and possesses an incomplete octet. It functions as a Lewis acid and combineswith Lewis bases like ammonia to form adducts.[132] Carbon tetrafluoride is tetrahedral and inert; itsgroup analogues, silicon and germanium tetrafluoride, are also tetrahedral[133] but behave as Lewis acids. The pnictogens form trifluorides that increase in reactivity and basicity with higher molecular weight, although nitrogen trifluoride resists hydrolysis and is not basic.[136] The pentafluorides of phosphorus, arsenic, and antimony are more reactive than their respective trifluorides, with antimony pentafluoride the strongest neutral Lewis acid known.Chalcogens have diverse fluorides: unstable difluorides have been reported for oxygen (the only known compound with oxygen in an oxidation state of +2), sulfur, and selenium; tetrafluorides and hexafluorides exist for sulfur, selenium, and tellurium. The latter are stabilized by more fluorine atoms and lighter central atoms, so sulfur hexafluoride is especially inert.Chlorine, bromine, and iodine can each form mono-, tri-, and pentafluorides, but only iodine heptafluoride has been characterized amongpossible interhalogen heptafluorides.Many of them are powerful sources of fluorine atoms, and industrial applications using chlorine trifluoride require precautions similar to those using fluorine.Noble gasesThese xenon tetrafluoride crystals were photographed in 1962. The compound's synthesis, as with xenon hexafluoroplatinate, surprised many chemists.Noble gases, having complete electron shells, defied reaction with other elements until 1962 when Neil Bartlett reported synthesis of xenon hexafluoroplatinate;xenon difluoride, tetrafluoride, hexafluoride, and multiple oxyfluorides have been isolated since then. Among other noble gases, krypton formsa difluoride, and radon and fluorine generate a solid suspected to be radon difluoride. Binary fluorides of lighter noble gases are exceptionally unstable: argon and hydrogen fluoride combine under extreme conditions to give argon fluorohydride. Helium and neon have no long-lived fluorides,] and no neon fluoride has ever been observed;helium fluorohydride has been detected for milliseconds at high pressures and low temperatures.Organic compoundsImmiscible layers of colored water (top) and much denser perfluoroheptane (bottom) in a beaker; a goldfish and crab cannot penetrate the boundary; quarters rest at the bottom.Chemical structure of Nafion, a fluoropolymer used in fuel cells and many other applicationsThe carbon–fluorine bond is organic chemistry's strongest, and gives stability to organofluorines. It is almost non-existent in nature, but is used in artificial compounds. Research in this area is usually driven bycommercial applications;the compounds involved are diverse and reflect the complexity inherent in organic chemistry.Discrete moleculesThe substitution of hydrogen atoms in an alkane by progressively more fluorine atoms gradually altersseveral properties: melting and boiling points are lowered, density increases, solubility in hydrocarbonsdecreases and overall stability increases. Perfluorocarbons,[note 16] in which all hydrogen atoms are substituted, are insoluble in most organic solvents, reacting at ambient conditions only with sodium in liquid ammonia.The term perfluorinated compound is used for what would otherwise be a perfluorocarbon if not for the presence of a functional group,[157][note 17] often a carboxylic acid. These compounds share many properties with perfluorocarbons such as stability and hydrophobicity,[159] while the functional group augments their reactivity, enabling them to adhere to surfaces or act as surfactants;[160] Fluorosurfactants, in particular, can lower the surface tension of water more than their hydrocarbon-based analogues. Fluorotelomers, which have some unfluorinated carbon atoms near the functional group, are also regarded as perfluorinated.[159]PolymersPolymers exhibit the same stability increases afforded by fluorine substitution (for hydrogen) in discrete molecules; their melting points generally increase too. Polytetrafluoroethylene (PTFE), the simplestfluoropolymer and perfluoro analogue of polyethylene with structural unit –CF2–, demonstrates this change as expected, but its very high melting point makes it difficult to mold;Various PTFE derivatives are less temperature-tolerant but easier to mold: fluorinated ethylene propylene replaces some fluorine atoms with trifluoromethyl groups, perfluoroalkoxy alkanes do the samewith trifluoromethoxy groups,[162] and Nafion contains perfluoroether side chains capped with sulfonicacid groups. Other fluoropolymers retain some hydrogen atoms; polyvinylidene fluoride has half the fluorine atoms of PTFE and polyvinyl fluoride has a quarter, but both behave much like perfluorinated polymers.1。

Unit 1 Chemical Industry1.Origins of the Chemical IndustryAlthough the use of chemicals dates back to the ancient civilizations, the evolution of what we know as the modern chemical industry started much more recently. It may be considered to have begun during the Industrial Revolution, about 1800, and developed to provide chemicals roe use by other industries. Examples are alkali for soapmaking, bleaching powder for cotton, and silica and sodium carbonate for glassmaking. It will be noted that these are all inorganic chemicals. The organic chemicals industry started in the 1860s with the exploitation of William Henry Perkin’s discovery if the first synthetic dyestuff—mauve. At the start of the twentieth century the emphasis on research on the applied aspects of chemistry in Germany had paid off handsomely, and by 1914 had resulted in the German chemical industry having 75% of the world market in chemicals. This was based on the discovery of new dyestuffs plus the development of both the contact process for sulphuric acid and the Haber process for ammonia. The later required a major technological breakthrough that of being able to carry out chemical reactions under conditions of very high pressure for the first time. The experience gained with this was to stand Germany in good stead, particularly with the rapidly increased demand for nitrogen-based compounds (ammonium salts for fertilizers and nitric acid for explosives manufacture) with the outbreak of world warⅠin 1914. This initiated profound changes which continued during the inter-war years (1918-1939).1．化学工业的起源尽管化学品的使用可以追溯到古代文明时代，我们所谓的现代化学工业的发展却是非常近代（才开始的）。

牛仔洗水对PTT纤维结构和力学性能的影响张磊，左丹英*，易长海，甘厚磊武汉纺织大学，纺织纤维及制品教育部重点实验室，湖北武汉，430073摘要：本文对聚对苯二甲酸丙二醇酯（PTT）短纤进行四种洗水工艺处理，并对处理前后的纤维通过电子单纤维强力仪、红外光谱仪，扫描电子显微镜、X-射线衍射仪进行力学性能和结构的表征。

结果显示，PTT纤维经过四种洗水处理后，纤维的断裂强度和伸长率分别下降，弹性回复率微微下降，纤维的表面均有不同大小坑穴，并且红外分析和XRD分析均表明经洗水处理后，纤维的结晶度均下降，尤其是高锰酸钾处理和双氧水漂洗对纤维力学性能的下降和纤维表面形态的破坏的作用更明显。

关键词：聚对苯二甲酸丙二醇酯（PTT）纤维；牛仔布洗水工艺；力学性能；结构中图分类号：TS195.6 文献标志码：A聚对苯二甲酸丙二醇酯（PTT）是一种新型的聚酯材料，它是由对苯二甲酸( TPA )和1，3-丙二醇( PDO )缩聚而成.。

PTT纤维具有优良的弹性、柔软性及染色等性能，因此在纺织业获得广泛的应用[1]，目前也有研究者进行了PTT纤维牛仔面料的开发，与其他服装不同，牛仔服装需要一系列的后整理，才使得牛仔衣具有“仿旧”效果，后整理中最重要的就洗水[2-3]，但是目前大多数的文献都是研究洗水预处理阶段工艺中碱处理和热处理对PTT结构和性能的影响[4-5]。

对于牛仔洗水来说仅仅考虑脱浆和热处理是远远不够的。

本文采用了常见的四种牛仔洗水工艺（高锰酸钾处理、酶处理、氧漂、氯漂）对PTT纤维进行处理[6]，并对纤维的结构与性能进行了表征，这为PTT纤维牛仔服装洗水的工艺选择与优化奠定了一定的理论基础。

1实验1.1实验原料与药品PTT短纤维，福建海兴材料科技有限公司提供；酸性纤维素酶，双氧水，氢氧化钠，高锰酸钾，草酸，碳酸氢钠，磷酸，次氯酸钠，均为化学纯，购自上海国药集团化学试剂厂。

1.2 PTT纤维洗水处理氧漂处理：配置含1.5gNaOH、65mL30%双氧水的1L去离子水，加入2gPTT纤维，温度95℃~100℃，时间75min，过水3次（80℃），脱水，烘干，备用。