POSS合成与表征

Synthesis and Characterization of Fillers of Controlled Structure Based on Polyhedral Oligomeric Silsesquioxane Cages and Their Use in Reinforcing Siloxane Elastomers

GUIRONG PAN,1,2JAMES E.MARK,1,3DALE W.SCHAEFER1,2

1Polymer Research Center,University of Cincinnati,Cincinnati,Ohio,45221

2Department of Chemical and Materials Engineering,University of Cincinnati,Cincinnati,Ohio,45221-0012

3Department of Chemistry,University of Cincinnati,Cincinnati,Ohio,45221

Received1February2003;revised14April2003;accepted15April2003

ABSTRACT:Four polyhedral oligomeric silsesquioxane(POSS)cages with vinyl groups

were linked to a central siloxane core by hydrosilylation.The goal was to obtain?ller

particles of sizes between those of the POSS cages themselves and the much larger

silica particles typically used to reinforce elastomers.The hydrosilylation reaction was

monitored with Fourier transform infrared spectroscopy and proton nuclear magnetic

resonance,and the resulting structure was con?rmed by mass spectrometry.Simply

blending these POSS-based?llers into silanol-terminated poly(dimethylsiloxane)

(PDMS)had little effect on the mechanical properties,but bonding them to PDMS

provided considerable reinforcement.?2003Wiley Periodicals,Inc.J Polym Sci Part B:

Polym Phys41:3314–3323,2003

Keywords:polyhedral oligomeric silsesquioxane(POSS);MALDI;mass spectrome-

try;siloxane elastomers;nanocomposites;mechanical properties;reinforcement

INTRODUCTION

Although polymer–inorganic composites have been known for decades,they continue to be the focus of worldwide research interest.1Some prop-erties are a combination of those of traditional organic polymers and inorganic compounds, whereas other properties show favorable syner-gistic effects.Moreover,when the size scale of the phases is in the nanometer range,manipulation of the interfacial molecules can be used to adjust the mechanical properties.

A variety of polymers have been used in such composites.Inorganic phases include exfoliated clays,carbon nanotubes,and polyhedral oligo-meric silsesquioxane(POSS)cages.2POSS cages are interesting in part because of their unusual structure,(RSiO3/2)n,where R can represent inert organic groups used to enhance miscibility with polymeric host materials.3,4These molecules have well-de?ned shapes and sizes ranging from 1–3nm.The n?8cage is most common and has been described as the smallest version of colloidal silica,which is used to reinforce elastomers such as polysiloxanes.Making one or more of the R groups reactive permits bonding of the cages to polymers by copolymerization5or grafting onto the chain backbone.6,7Incorporating such POSS cages into polymeric materials has already pro-vided useful property enhancements,such as in-creased glass-transition temperatures,decomposi-tion temperatures,and mechanical strength.2,6,8,9

Correspondence to:D.W.Schaefer(E-mail:dale.schaefer@ https://www.doczj.com/doc/9215441140.html,)

Journal of Polymer Science:Part B:Polymer Physics,Vol.41,3314–3323(2003)?2003Wiley Periodicals,Inc.

3314

Because of the tailorability of POSS molecules,they can also be designed to probe the molecular basis of reinforcement and to establish structure–property relationships that can then be exploited to optimize properties for particular applications.

The primary goal of this study was to explore ?ller particles of sizes between those of the POSS cages themselves and the much larger silica par-ticles typically used to reinforce elastomers. These limits correspond to diameters of about15?for the cages to300?for typical particles of fumed silica.Of course,the?ller size is not the

only issue with respect to reinforcement.The polymer–?ller interface is known to be important, as is the state of aggregation of colloidal?llers. The?rst stage of synthesis of hierarchical POSS structures is reported here with tetrakis(dimeth-ylsilyloxy)silane{[HSi(CH3)2O]4Si(TDSS)}as the multifunctional core.The four hydrogen atoms attached to the silicon atoms can be used in a hydrosilylation reaction to attach four POSS cages that have been monosubstituted with vinyl groups.Extensive effort has been made to use the POSS cubes as building blocks to prepare orga-nic–inorganic nanocomposite materials and pre-cursors.10–12Laine and coworkers13–16developed several routes for linking POSS cubes by chemical reactions that lead to organic tethers(spacers) between the cubes.The resulting materials in-cluded thermoplastic and thermoset methacry-late nanocomposites as well as epoxy resin,hy-drocarbon-linked,amide,and imide-linked nano-composites.

Poly(dimethylsiloxane)(PDMS)was chosen as the matrix because it is by far the most important siloxane elastomer.Two types of PDMS were used. Silanol-terminated PDMS was chosen as an inert version that would not undergo a chemical reaction with vinyl-terminated POSS.In this case,?llers containing one POSS cage(mono-POSS)or four linked POSS cages(tetra-POSS)were physically blended into the elastomer.The other type of PDMS had vinyl terminal groups to which the vinyl-POSS ?llers could be bonded.Reinforcement in the vari-ous types of nanocomposites was characterized with respect to their mechanical properties in simple elongation.

EXPERIMENTAL

Materials

The POSS chosen was an eight-cornered cube with one vinyl substituent and seven isobutyl groups.The material was a white powder with a molecular weight of843.52g/mol and a melting point of213–219°C.The material was supplied by Hybrid Plastic,Inc.Its structure is shown in Scheme1.

The TDSS core material was obtained from Gelest,Inc.The hydrosilylation catalyst was cis-dichlorobis(diethyl sul?de)platinum(II){[(C2H5)2-S]2PtCl2}and was obtained from Sigma–Aldrich;it was dissolved in tetrahydrofuran(THF)to yield a 1mg/mL solution that was stored under nitrogen. Anhydrous toluene was used as a solvent.Sam-ples of vinyl-terminated and silanol-terminated PDMS were obtained from Gelest.The number-average molecular weights were obtained with a Waters746chromatograph and were found to be 14,000and18,000g/mol,respectively.The tetra-ethoxysilane(TEOS)crosslinking agent and the stannous octoate catalyst used in the curing of silanol-terminated PDMS were obtained from Sigma–Aldrich.

Addition of POSS Cages to a Central Core

For the linking of the four POSS cages to TDSS, the hydrosilylation was intentionally starved with respect to SiH groups to ensure that all of these groups were attached to POSS molecules (the molar ratio of TDSS to POSS was1:4.2).This reaction is shown in Scheme2.

The synthesis was carried out in a250-mL, round-bottom?ask equipped with a re?uxing con-denser,a magnetic stirrer,a N2inlet,and a ther-mometer.The?ask was charged with dry N2before 2.2g of POSS,0.1mL of a THF solution of [(C2H5)2S]2PtCl2,and50mL of anhydrous toluene were added.The ingredients were stirred at room temperature for30min,and followed by the addi-tion of0.23mL of TDSS.The resulting mixture was again stirred,subsequently warmed to90°C,and held at that temperature under a stream of dry N2 for33h.Then,volatile components were removed

at Scheme1.Structure of monovinyl-POSS with isobu-tyl substituents(R).

SYNTHESIS AND CHARACTERIZATION OF FILLERS3315

a reduced pressure,and a dark-brown solid was obtained.The following analysis shows that small quantities of mono-POSS and tri-POSS remained.No attempt was made to remove these products.

Preparation of the Composites

Physical Blending of POSS-Based Fillers into PDMS Networks

Various amounts of ?ller particles were blended into silanol-terminated PDMS before end linking.For better mixing,a small portion of anhydrous

THF (amounting to 10wt %of PDMS)was added to dissolve the ?ller before it was mixed with PDMS.The mixture was stirred vigorously,and the solvent was removed at an elevated temperature and then by evacuation.The stannous octoate catalyst and TEOS end-linking agent were then added at room temperature and dispersed completely.The result-ing solution was poured into Te?on molds and put into an oven at 50°C for approximately 10h.The thickness of the resulting ?lms was around 1mm.Pure PDMS ?lms were prepared under the same conditions.The resulting transparent ?lms were consistent with the minimal formation of silica via sol–gel condensation of

TEOS.

Scheme 2.Addition of POSS cages to the TDSS core material through hydrosilylation reaction.

3316PAN,MARK,AND SCHAEFER

Chemical Incorporation of Monovinyl-POSS into PDMS Networks

Vinyl-terminated PDMS was used in this case,and the ?lled networks were formed as shown in Scheme 3.

Speci?cally,the POSS powders (amounting to 5,10,or 20wt %of PDMS)were mixed into uncrosslinked vinyl-PDMS as previously de-scribed.However,in this case,no solvent was used,and the undiluted mixture was stirred vig-orously 48h for good mixing.Then,the desired amount of the catalyst solution was added.The mixture was stirred at approximately 75°C until the small amount of THF from the catalyst solu-tion had evaporated.After the mixture was cooled,TDSS was added and completely dis-persed.This reaction was carried out at 90°C,producing ?lms suitable for the evaluation of the mechanical properties.A pure vinyl-terminated PDMS ?lm was also prepared under the same conditions as a control.The molar ratio of PDMS to TDSS was kept at 0.54:0.33for all the samples.According to Scheme 2,meeting the stoichiomet-ric proportion between silanes and vinyls re-quired 3wt %mono-POSS based on PDMS.Therefore,the ?ller loadings were greater than the stoichiometric proportion in all our chemically

bonded ?lms.Dumbbell-shaped specimens were cut from the ?lms according to Die C of ASTM D 412with a benchmark distance of 25mm for later use in tensile testing.Spectroscopic Measurements

Fourier transform infrared (FTIR)and 1H NMR spectroscopy were used to monitor the hydrosily-lation reaction in the formation of tetra-POSS.FTIR spectra were recorded as a function of time on a PerkinElmer 1600FTIR spectrometer from 450to 4000cm ?1,with 16scans recorded for each spectrum.After each time interval,one or two drops of the sample were removed from the reac-tor by means of a syringe.The samples were dried into ?lms on a KBr plate.1H NMR spectra were obtained at 250.013MHz with a Bruker Ac-250general-purpose spectrometer.

The composition of the ?nal products was in-vestigated with matrix-assisted laser desorption/ionization (MALDI)mass spectrometry (MS).The samples were analyzed with a Bruker Re?ex IV MALDI-TOF mass spectrometer (Bruker Dalton-ics)in the positive-ion mode.The matrix was an-thracene,and silver tri?uoroacetate was used as a cationization reagent.Because the magnitude of a peak in MALDI is not linearly proportional to the concentration,quantitative analyses could not be carried out directly from the heights of the peaks.

Mechanical Properties

Mechanical measurements were made using ten-sile testing and dynamic mechanical analysis.For the former,an Instron 4465tester with comput-erized recording was used at room temperature.The tests were carried out at a crosshead speed of 3mm/min,and an average of at least three mea-surements for each sample was recorded.The dy-namic mechanical properties of the samples were analyzed at 25°C with a TA Instruments 2980dynamic mechanical analyzer operated in the ten-sile strain–sweep mode at a frequency of 1Hz.

RESULTS AND DISCUSSION

FTIR and 1H NMR Analysis

The FTIR spectra of POSS,TDSS,and the ?nal hydrosilylation product are shown in Figure 1.The characteristic stretching vibration peaks of Si O CH A CH 2and Si O H groups are at

1641.9

Scheme 3.Chemical incorporation of POSS cages into PDMS networks.

SYNTHESIS AND CHARACTERIZATION OF FILLERS 3317

and 2186.2cm ?1,respectively.In the product,the peak for Si O H has disappeared completely,and the peak for the vinyl group has nearly disap-peared.The corresponding 1H NMR spectra are shown in Figure 2.The chemical shift of Si O H at approximately 4.72ppm 17,18has almost disap-peared in the ?nal product.The peaks for the chemical shift of vinyl protons around 5.8ppm remain in the ?nal product,but their areas de-crease dramatically.The persistence of vinyl groups is expected because the excess POSS used should leave residual vinyl groups in the ?nal product.Also different from the FTIR spectrum of the ?nal product,a small peak due to the O Si O H group can be detected in the NMR spectra,indi-cating the presence of a small amount of unre-acted Si O H groups.This result has been con-?rmed by the output of MALDI MS,which shows the presence of tri-POSS with one unreacted Si O H left in the ?nal product.The new peak around 5.2might have resulted from the newly formed bonds,Si O CH 2O CH 2O Si O ,but this is-sue needs to be tested by further investigation.Figure 3shows a time sequence of FTIR spec-tra for various stages in the hydrosilylation reac-tion.The characteristic peak of Si O H at 2186.2cm ?1and the peak of O CH A CH 2at 1641.9cm ?1diminish with time.At 31h,the Si O H peak has disappeared completely,and the expected small vinyl peak remains.These results indicate that complete reaction was obtained well before the 33h allowed.MALDI MS Analysis

The molecular weights of POSS (843.52)and TDSS (338)were used to identify the structures of

the compounds from the mass spectrum.Because silver tri?uoroacetate was used as a cationization reagent,the mass spectrum includes peaks with silver adducts,as well as some sodium adducts.Sodium was not added,but it is normally present in trace amounts either on a MALDI plate or in the silver salt.

The positive-ion MALDI mass spectrum of the ?nal product (Fig.4)reveals an ion peak at m /z ?953.43,which can be attributed to unreacted POSS plus Ag.The peak at m /z ?2991.46can be identi?ed as a combination of three POSS mole-cules bound to one TDSS molecule (including the masses of Ag and Na).The amount of this tri-POSS product must be very small because the concentration of unreacted O Si O H groups in the ?nal product was too small to be detected by FTIR.Although there are some other peaks due to the fragments,the signi?cant peak is at m /z ?3821.91,which is the desired structure with four POSS molecules linked to the TDSS core.From this result,it can be estimated that the amount of tetra-POSS is greater than that for mono-POSS because MALDI MS is more sensitive to low-molecular-weight species than high-molec-ular-weight species.Nonbonded Composites

Figure 5shows the results from tensile testing:the engineering stress is plotted against the en-gineering strain for pure silanol-terminated PDMS,2%POSS/PDMS,and 2%tetra-POSS/PDMS.There are no signi?cant differences among these three curves.This result shows that the physical blending of isobutyl-POSS into PDMS does not generate reinforcement.Linking four cages to form tetra-POSS also leads to only a marginal enhancement of elongation.The conclu-sion is that these small particles do not reinforce,at least when they are not bonded to the matrix.There is a possibility that the lack of reinforce-ment is due to the poor miscibility of isobutyl POSS with PDMS,which leads to extensive phase separation.3To test this,the ?ller amount was increased to 5%,and the results are given in Figure 6.Because the amount of POSS is small in this system,increasing it will lead to enhanced susceptibility to phase separation.Both the mod-ulus and elongation of the composite are substan-tially reduced in comparison with those of PDMS,and this suggests that there is aggregation of POSS or interference with PDMS network forma-

tion.

Figure 1.FTIR spectra of POSS,TDSS,and the product:POSS ?TDSS.

3318PAN,MARK,AND SCHAEFER

The dynamic mechanical results for the physi-cally blended composites in Figures 7and 8con-?rm the aforementioned tensile results.The plots of the storage modulus versus the strain ampli-tude for pure PDMS,PDMS with 2%POSS,and PDMS with 2%tetra-POSS are all very similar.Again,there is a signi?cant decrease in the mod-ulus for 5%?lled PDMS,as shown in Figure 8.Chemically Bonded Composites

Quite different results were obtained when the POSS ?llers were partially chemically bonded to the polymer network (Fig.9).Both the ultimate strength (as gauged by the stress at rupture)and the maximum extensibility increase considerably.Figure 10shows the corresponding dynamic me-chanical analysis results.Again,the POSS com-posites show a considerable increase in the low-strain modulus with the POSS loading,and the trend is monotonic.

Probably the most interesting aspect of these materials is the very large dynamic strain soften-ing effect shown in Figure 10.This so-called Payne effect can also be seen in organic rubbers ?lled with carbon black or silica and is tradition-ally attributed to ?ller networking.19In organic rubber,the unfavorable surface energy

associated

Figure 2.

1

H-NMR spectra of POSS,TDSS,and their product:POSS ?TDSS.

SYNTHESIS AND CHARACTERIZATION OF FILLERS 3319

with the dispersed ?ller is relieved by the forma-tion of a physically bonded network of ?ller par-ticles.The rigidity of the bonded network leads to the increased modulus of the composite.The Payne effect (dynamic stress softening)is attrib-uted to that fact that the physically bonded net-work breaks down as the network is strained.The ?ller-networking interpretation of the Payne effect rests on the assumption that the ?ller particles have percolated.Because the per-colation threshold of a random collection of spheres is about 15vol %,we expect a dramatic increase in the Payne effect (de?ned as the stor-age modulus at zero strain divided by the storage

modulus at large strain)at loadings of about 15wt %if the ?ller and polymer have the same density.Although we do not have data for enough loadings to de?nitively ?x the percolation thresh-old,the data in Figure 10suggest that the perco-lation threshold is at or below 10%according to the qualitative differences in the shapes of the 5and 10%curves.The lower percolation threshold could be due to a larger effective ?ller volume fraction caused either by the lower density of POSS compared with that of PDMS or because of fractal aggregation of POSS.

Some con?rmation of the ?ller-networking idea comes from the loss tangent data in Figure 11.Here the loss tangent (the ratio of the loss mod-ulus to the storage modulus)is plotted versus the strain amplitude.In Figure 11,we can observe a substantial peak in the loss tangent in the 10%sample.Kraus 20explained this peak in organic rubbers with the ?ller-networking concept.At a low strain,the strain is insuf?cient to disrupt the ability of the network to reform in its unstrained con?gurations on relaxation of strain,so there is little loss.As the strain amplitude increases,the ?ller particles are not able to recover their un-strained con?guration,and this leads to loss.If the strain amplitude is too high (beyond the peak in Fig.11),however,the network does not have enough time to reform in any con?guration,and this leads to a decrease in the loss.The

maximum

Figure 3.Hydrosilylation reaction monitored with FTIR spectra of the

product.

Figure 4.Positive-ion MALDI mass spectrum of the ?nal product.

3320PAN,MARK,AND SCHAEFER

loss occurs when the amplitude is large enough to destroy the zero-strain con?gurations but not so large that the network cannot recon?gure itself during the zero-strain part of the cycle.The im-plicit timescale in this analysis is the reciprocal of the test frequency,which is 1Hz in our case.This time is to be compared to the time it takes the ?ller to diffuse a distance that depends on the strain amplitude.Because the prefactors are un-known,however,the argument can only be qual-itative.

If these ideas were correct,we would expect that bonding to the network would have a mini-mal effect on reinforcement,contrary to our ob-servations.What network bonding may be doing,however,is not providing reinforcement directly but merely providing the compatibilization needed to ensure full dispersion of POSS in the matrix.Because for loading above 3%there is excess unbonded POSS,it seems that only a tiny fraction of POSS needs to be bonded to alter the

thermodynamics suf?ciently to induce compati-bility.

CONCLUSIONS

Through a study of two levels of the hierarchy of POSS,we have shown that tiny POSS can rein-force silicone rubber,but only when partially bonded to the polymer network.The

bonding,

Figure 5.Stress–strain curves of silanol-terminated PDMS,PDMS blended with 2%POSS,and PDMS blended with 2%

tetra-POSS.

Figure 6.Stress–strain curves of silanol-PDMS and PDMS blended with 2or 5%

tetra-POSS.Figure 7.Strain dependence of the elastic modulus of PDMS,PDMS blended with 2%POSS,and PDMS blended with 2%tetra-POSS

cages.

Figure 8.Strain dependence of the storage modulus of PDMS and PDMS blended with 2or 5%tetra-POSS.

SYNTHESIS AND CHARACTERIZATION OF FILLERS 3321

however,is not the source of reinforcement.Rather,bonding acts as an attractive force be-tween the polymer and the ?ller,leading to in-creased compatibility.Without bonding,POSS phase-separates,leading to,at best,no change in the mechanical properties.If the PDMS network is altered by the chemical incorporation of about 3wt %POSS,however,POSS is dispersed,and substantial reinforcement is possible.

The bonded composite shows a dynamic me-chanical response that is very similar to that of organic rubbers ?lled with colloidal silica:a large Payne effect and a peak in the strain dependence of the loss tangent.These characteristics are the signature of a physically bonded network of ?ller particles.The reinforcement,therefore,is not di-

rectly attributed to the bonds between the ?ller and the matrix.Rather,bonding improves the dispersion of the ?ller,which is necessary if the ?ller network is to form in the ?rst place.The ability to link POSS to the network at just one point is perhaps critical to the enhancement effect because the undecorated POSS dangling from the chain is still capable of forming a ?ller network because it remains incompatible with the PDMS chains.

Some general insight into the role of interfacial linkages can be distilled from our observations.Traditionally,silica is compatibilized with rubber with a silane-coupling agent.Coupling the ?ller to the matrix leads to improved dispersion (good)but also leads to a weaker ?ller network (bad).Our results suggest that optimal reinforcement is achieved with minimum coupling,just enough to ensure dispersion.In this case,the ?ller remains locally incompatible with the matrix,and so there is a strong driving force to form a ?ller network,even though the particles are globally dispersed.

The authors are pleased to acknowledge the ?nancial support provided to J.E.Mark by the National Science Foundation (DMR-0075198)through the Polymers Pro-gram of the Division of Materials Research.The au-thors also thank Stephen Macha for performing the MALDI MS experiments and Elwood Brooks for his help with the 1H NMR

measurements.

Figure 9.Stress–strain curves of vinyl-PDMS and PDMS ?lled with 5,10,or 20%

POSS.

Figure 11.Loss tangent of POSS-?lled samples.Filled symbols represent samples in which POSS is linked to PDMS.Open circles represent samples not chemically linked;in this case,samples with more than 5%POSS are dif?cult to achieve because of the incom-patibility of POSS and

PDMS.

Figure 10.Strain dependence of the storage modulus of vinyl-PDMS with various amounts of chemically linked POSS.

3322PAN,MARK,AND SCHAEFER

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SYNTHESIS AND CHARACTERIZATION OF FILLERS3323

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目录 1. 前言...................................................................... 错误!未定义书签。 1配位化合物 .................................................... 错误!未定义书签。 1. 1配位化合物的组成 .............................. 错误!未定义书签。 1. 2配合物的种类 ...................................... 错误!未定义书签。 2配位化学发展简史 ........................................ 错误!未定义书签。 3配位化学的今天 ...................................... 错误!未定义书签。 2. 实验部分 ............................................................... 错误!未定义书签。 2.1药品................................................................. 错误!未定义书签。 2.2仪器................................................................. 错误!未定义书签。 2.3合成方法 ........................................................ 错误!未定义书签。 3. 结果与讨论 ......................................................... 错误!未定义书签。 3.1 结构分析 ................................................... 错误!未定义书签。 3.2 红外光谱 ................................................... 错误!未定义书签。 3.3 荧光光谱 ................................................... 错误!未定义书签。 4.小结....................................................................... 错误!未定义书签。

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学生根据教材第76页的『交流与讨论』，分小组进行合作学习，交流讨论。 『交流与讨论』乙酸乙酯是一种重要的有机溶剂，也重要的有机化工原料。 依据乙酸乙酯的分子结构特点，运用已学的有机化学知识，推测 怎样从乙烯合成乙酸乙酯，写出在此过程中发生反应的化学方程 式。 [归纳总结] 1. 从乙烯合成乙酸乙酯的合成路线： 2.合成有机物要依据被合成物质的组成和结构特点，选择适合的有机化学反应和起始原料，精心设计并选择合理的合成方法和路线。 [思维拓展] 除上述合成路线外，根据所学过的有机化学知识，还有哪些合成方法和途径呢？ [学生活动] 学生根据教材《苏教版·化学2》第81页的图3－22“制备乙酸乙酯可能的合成路线”，分小组合作，展开讨论。 [归纳总结] 合成路线1： 合成路线2：

铁配合物的制备和表征

X射线单晶衍射：1.配合物晶体数据：

2.配合物的部分键长和键角： 3.配合物晶体结构：

紫外可见分光光度法： 图中实线代表配体H2L1的实验数据，虚线代表相应铁配合物的实验数据。实线在波长为282nm和268 nm处有吸收峰，将其归属为苯环π→π*跃迁。虚线在波长为495nm，340nm和281nm处有吸收峰，现将其进行归属。281nm处的吸收峰为苯环π→π*跃迁；340 nm处的吸收峰为电子由苯环上氧原子的最高占据轨道pπ跃迁到Fe(III)半充满轨道dx2?y2/d z2；495 nm处的吸收峰为电子由苯环上氧原子的pπ轨道跃迁到Fe(III)的d*轨道。

XRD： 普通PAN纤维的XRD谱线在16.84，21.42,23.74和29.06°处都有特征峰。而PAN 纳米纤维的XRD谱线与上述谱线较为相近，但是在22~30°范围内的特征峰有所不同。这说明PAN纳米纤维的结晶特征并未发生显著改变。经过反应后两种纤维的主要特征峰几乎全部消失。这说明改性和铁配位反应具有去晶化作用，使纤维表层的结晶度大为降低。

红外： 配合物Fe1和Fe2在3247cm-1处有强的吸收峰。因配合物Fe2和Fe5的结构中含有炔基，谱图中很明显的能够观察到配合物Fe2和Fe5在ν =2120 cm-1处有振动吸收峰，与配体L2 (ν =2100 cm-1)相比峰波向高波数方向移动约20 cm-1。配合物Fe4的红外谱图中同样能观察到羧酸酯的羰基吸收峰(ν =1731 cm-1)。

常规溶液法：是最常见、最简单的单晶培养方法。通过将金属盐和配体溶于合适溶剂中，静置，待其自然挥发而形成配合物。此方法适用于配体溶解性较好而配合物溶解性较差情况，通常在遇到配体溶解性较差的情况时，采用适当加热的方法于以处理。 扩散法：包括气相扩散法和液相扩散法。 气相扩散法：将金属盐和配体溶于适当的溶剂当中，使惰性易挥发溶剂或者碱性物质扩散其中，以减小配合物的溶解度或者加快反应的速度从而使配合物结晶产生。 液相扩散法：将金属盐和有机配体分别溶于不同的两种溶剂当中，将一种溶液置于另一种溶液之上或者在两种溶液分界面处加入另一种溶剂以减小其扩散速度，使反应物缓慢发生反应，从而使产物结晶产生。 水热/溶剂热法：水热法是指在特制密闭反应容器中（一般是内衬聚四氟乙烯不锈钢反应釜），以水作为溶剂，通过对反应容器加热以制造一个高温高压环境（100-1000℃,1-100MPa），使得通常难溶或者不溶的物质溶解从而重新结晶产生出来。溶剂热法与水热法类似。

聚苯胺的合成及表征

题目（中文）：聚苯胺的合成及表征姓名 xx xxx 学号111111111112222222222 院（系）化学与生命科学 专业、年级 12级化学(3)班（B组） 指导教师xxx职称教授 二○一四年十月

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催化剂制备与表征

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钴(Ⅲ)配合物的制备及表征

基础化学实验I课程小论文题目：钴（Ⅲ）配合物的制备及表征 姓名王一贺学号及专业化学3120000170 姓名徐剑光学号及专业化学3120101744 指导教师曾秀琼 浙江大学化学系 浙江大学化学实验教学中心 2014年 1 月

前言：在水溶液中，电极反应Eθ（Co3+/Co2+）=1.84V，所以在一般情况下，Co(Ⅱ)在水溶液中是稳定的，不易被氧化为Co(Ⅲ)，相反，Co(III)很不稳定，容易氧化水放出氧气（Eθ（Co3+/Co2+）=1.84V >E θ（O2/H2O）=1.229V）。但在有配合剂氨水存在时，由于形成相应的配合物[Co(NH3)6]2+，电极电势E θCo[(NH3)63+/ Co(NH3)62+]=0.1V，因此Co (Ⅱ)很容易被氧化为Co(III)，得到较稳定的Co（Ⅲ）配合物。Co（Ⅲ）可与多种配体配位，能形成多种配合物。 实验方案简述：一、实验中采用H2O2作氧化剂，在大量氨和氯化铵存在下，选择活性炭作为催化剂将Co（Ⅱ）氧化为Co（Ⅲ），来制备三氯化六氨合钴（Ⅲ）配合物，反应式为： 2[Co(H2O)6]Cl2（粉红色）+ 10NH3 +2NH4Cl + H2O2 活性炭 C 2[Co(NH3)6]Cl3（橙黄色）+ 14H2O 将产物溶解在酸性溶液中以除去其中混有的催化剂，抽滤除去活性炭，然后再在浓盐酸存在下使产物晶体析出。 293K时，[Co(NH3)6]Cl3在水中的溶解度为0.26mol·L-1,K不稳=2.2×10-34，在过量强碱存在且煮沸的条件下会按下形式分解： 2[Co(NH3)6]Cl3 + 6NaOH 煮沸 2Co(OH)3 + 12NH3 + 6NaCl 样品中的Co（Ⅲ）用碘量法测定： 2Co(OH)3 + 2I- + 6H+ 2Co2+ + I2 + 6H2O I2 + 2S2O32- S4O62- + 2I- 二、2[Co(en) 2 Cl2]Cl的制备： 2CoCl2·6H2O+4HCl+4en trans- 2[Co(en) 2 Cl2]Cl trans- 2[Co(en) 2 Cl2]Cl?HCl?2H2O △trans- 2[Co(en) 2 Cl2]Cl↓+ HCl+2H2O trans- 2[Co(en) 2 Cl2]Cl △cis- 2[Co(en) 2Cl2]Cl 仪器：100mL锥形瓶，布氏漏斗，量筒，胶头滴管，蒸发皿，恒温水浴，抽滤泵，烘箱，分析天平，台天平，250mL碘量瓶，滴定管，红外光谱仪，烧杯。 药品：H2O2(10%),稀盐酸（3+50），浓氨水（AR），浓盐酸，CoCl2·6H2O（AR），氯化铵（AR），活性炭，冰块，3mol·L-1H2SO4,0.1mol·L-1Na2S2O3,20%的NaOH，0.5%淀粉，6mol·L-1HCl，碘化钾（AR）、、亚硝酸钠（AR）、无水乙醇（AR）、NH4Cl（AR）、乙二胺（AR）。

苏教版化学必修2 专题3 第三单元 人工合成的有机物1 合成简单有机物的方法(同步练习)

（答题时间：25分钟） 一、选择题 1.下列物质反应后可生成纯净的1，2-二溴乙烷的是（） A. 乙烯和溴化氢加成 B. 乙烷和少量的溴蒸气光照 C. 乙烯通入溴的四氯化碳溶液 D. 乙烷通入溴水 **2.从原料和环境两方面考虑，对生产中的化学反应提出原子节约的要求，即尽可能不采用那些对产品的化学组成来说没有必要的原料。现有下列3种合成苯酚的反应路线：其中符合原子节约要求的生产过程是（） A. 只有① B. 只有① C. 只有① D. ①①① 3.以乙烯为有机原料制备乙酸乙酯的合成路线中，最后一步化学反应的反应类型是（） A. 氧化反应 B. 酯化反应 C. 加成反应 D. 水解反应 4.下列反应不能引入羟基的是（） A. 加成反应 B. 取代反应 C. 消去反应 D. 还原反应 *5. （浙江温州检测）具有一个羟基的有机物A 与8 g乙酸充分反应生成了10.2 g 酯，经分析还有2 g 乙酸剩余，则A可能是（） A. C2H5OH C. CH3CH（OH）CHO B. C6H5－CH2－OH D. CH3CH（OH）CH3 二、填空题 *6.（海南高考节选）乙烯是一种重要的化工原料，以乙烯为原料衍生出部分化工产品的反应如下（部分反应条件已略去）： 已知：D的结构简式为，F的结构简式为CH3COOCH2CH2OOCCH3。 请回答下列问题： （1）A的化学名称是________； （2）B和A反应生成C的化学方程式为______________________________________，该反应的类型为________； （3）E的结构简式为__________________________________________________； （4）A生成B的化学方程式为_____________________________________________。 **7.以下是由乙烯合成乙酸乙酯的几种可能的合成路线： （1）分别写出乙烯、乙酸乙酯的结构简式：__________________、__________________。 （2）乙醇和乙醛中含氧官能团的名称分别是：______________、______________。 （3）请写出①、①反应的化学方程式： ①_______________________________________________________________________， ①_______________________________________________________________________， （4）乙酸乙酯在碱性（NaOH）条件下水解的方程式： ________________________________________________________________________。一、选择题

配合物的合成与表征

5-（3-吡啶基）四唑-2-乙酸根与Zn(II)配合物的合成与表征报告 班级：09化学（师范） 学号：150109118 姓名：蔡福东

目录 1. 前言 (1) 1配位化合物 (1) 1. 1配位化合物的组成 (1) 1. 2配合物的种类 (2) 2配位化学发展简史 (2) 3配位化学的今天 (5) 2. 实验部分 (6) 2.1药品 (6) 2.2仪器 (6) 2.3合成方法 (6) 3. 结果与讨论 (6) 3.1 结构分析 (6) 3.2 红外光谱 (6) 3.3 荧光光谱 (7) 4.小结 (8)

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