New polymersupported ioncomplexing agent Designpreparation

2021.33(1) MODERN PLASTICS PROCESSING AND APPLICATIONS20212观代更护Ailfl些物 世r 降解型料物理改研究进展孙浩程I 崔玉磊2王宜迪I 回军I（1.中国石油化丄股份有限公司大连石油化工研究院.辽宁大连116000；2.中国石油化丄股份有限公司胜利油出分公司胜利采油厂•山东东营257000）摘要：综述了可降解塑料的概念、发展及分类，重点介绍了近年來国内外具冇代表性的聚乳酸、聚用基脂肪酸酯两种生物 基可降解塑料物理改性的研究进展，针对改性中存在降解机理不明确、忽略新材料的全生命周期仔理等问题进行了分析•并 对其未来的应用作出了展望。

关键词：生物基可隆解塑料聚乳酸聚轻基脂肪酸酯物理改性DOI ：10. 19690/j.issnl004-3055. 20200166Research Progress on Physical Modification ofBio-Based Degradable PlasticsSun Haocheng 1 Cui Yulei' Wang Yidi 1 Hui Jur?(1.Dalian Research Institute of Petroleum and Petrochemicals ,SINOPEC »Dalian , Liaoning , 116000 ； 2,Shengli Oil Production Plant ,Shengli Oilfield ♦SINOPEC ,Dongying ,Shandong , 257000)Abstract : The concept , development and classification of degradable plastics werereviewed. The research progress of the physical modification of two kinds of bio-based biodegradable plastics at home and abroad in recent year including polylactic acid andpolyhydroxyalkanoate was mainly introduced. The problems existing in the modification , such as the unclear degradation mechanism and the neglect of the whole life cyclemanagement of new materials, were analyzed , and their future development andapplication were prospected.Key words : bio-based degradable plastics ； polylactic acid ； polyhydroxyalkanoate ； physical modification近年来，人们对塑料污染的关注日益增加，对 环境危害的认识逐渐加深。

研究与开发CHINA SYNTHETIC RESIN AND PLASTICS合 成 树 脂 及 塑 料 ， 2022， 39（5）： 13DOI：10.19825/j.issn.1002-1396.2022.05.03*聚丙烯（PP ）具有力学性能优良、加工性能和耐热性能好、化学性能稳定等特点，且原料价格低廉、来源丰富，被广泛应用于日常生活、包装、汽车、农业等领域。

自1957年工业化以来，PP已成为通用树脂中发展最快的品种之一［1-3］。

PP工业发展的关键在于催化剂及相应聚合工艺的发展，而催化剂则是PP发展的核心。

近些年，随着PP需求量的增长，我国的一些大型企业和研究院通过不断努力尝试已研制出性能良好的丙烯聚合催化高活性及高立体定向性丙烯聚合催化剂的合成与性能吴岩松1，高金龙2，丁 伟1，姜 涛2*（1. 东北石油大学 化学化工学院，黑龙江 大庆 163318；2. 天津科技大学 化工与材料学院，天津 300457）摘 要： 以MgCl 2、异辛醇为载体，9,9-双（羟基）甲基芴为内给电子体，苯酐为助析剂，在TiCl 4溶液中进行载钛反应，得到新型丙烯聚合催化剂，并研究了新型丙烯聚合催化剂与2种参比催化剂的元素含量、粒径及分布、催化剂形貌、聚合性能和氢调敏感性。

结果表明：苯酐在TiCl 4载钛过程中原位生成邻苯二甲酸二异辛酯，并与内给电子体复配使用，提高了催化剂活性及聚合物等规指数；3种催化剂的元素含量基本接近，新型丙烯聚合催化剂具有活性高、氢调敏感性好、得到的聚合物粒径分布更加集中且细粉含量更少的优点。

关键词： 丙烯聚合催化剂 颗粒形态 催化剂活性 氢调敏感性 等规指数中图分类号： TQ 325.1+4 文献标志码： B 文章编号： 1002-1396（2022）05-0013-04Synthesis and properties of high activity and stereotactic catalyst for polymerization of propyleneWu Yansong 1，Gao Jinlong 2，Ding Wei 1，Jiang Tao 2（1. School of Chemistry and Chemical Engineering ，Northeast Petroleum University ，Daqing 163318，China ；2. College of Chemical Engineering and Material Science ，Tianjin University of Science & Technology ，Tianjin 300457，China ）Abstract ： Isobutanol and MgCl 2 were used as carriers，9,9-bis （hydroxy ）methyl fluorene as the internal electron donor，and phthalic anhydride as the co-precipitation agent，to carry out the titanium-loading reaction in TiCl 4 solution to obtain a new type of propylene polymerization catalyst. The element content，particle size and distribution，catalyst morphology，polymerization performance and hydrogen sensitivity of the new type of propylene polymerization catalyst and two reference catalysts were studied. The results show that phthalic anhydride in situ forms diisooctyl phthalate，which is used in combination with internal electron donor to improve catalyst activity and polymer isotacticity. The element content of three catalysts is basically similar，and the new propylene polymerization catalyst has the advantages of high catalytic activity，good hydrogen modulation sensitivity，particle size distribution of the obtained polymer more concentrated，and powder content less fine.Keywords ： propylene polymerization catalyst； particle morphology； catalytic activity； hydrogen modulation sensitivity； isotacticity收稿日期： 2022-03-27；修回日期： 2022-06-26。

Biomaterials23(2002)3193–3201Synthesis and characterization of chitosan–poly(acrylic acid)nanoparticlesYong Hu a,Xiqun Jiang a,Yin Ding a,Haixiong Ge a,Yuyan Yuan b,Changzheng Yang a,*a Lab of Mesoscopic Materials,Department of Polymer Science and Engineering,College of Chemistry and Chemical Engineering,Nanjing University,22Hankou Road,Nanjing210093,People’s Republic of Chinab Jiangsu Super-fine Center Powder Science and Technology,People’s Republic of ChinaReceived14August2001;accepted14February2002AbstractChitosan(CS)–poly(acrylic acid)(PAA)complex nanoparticles,which are well dispersed and stable in aqueous solution,have been prepared by template polymerization of acrylic acid(AA)in chitosan solution.The physicochemical properties of nanoparticles were investigated by using size exclusion chromatography,FT-IR,dynamic light scattering,transmission electron microscope and zeta potential.It was found that the molecular weight of PAA in nanoparticles increased with the increase of molecular weight of CS,indicating that the polymerization of acrylic acid in the chitosan solution was a template polymerization.It was also found that the prepared nanoparticles carried a positive charge and showed the size in the range from50to400nm.The surface structure and zeta potential of nanoparticles can be controlled by different preparation processes.The experiment of in vitro silk peptide(SP)release showed that these nanoparticles provided a continuous release of the entrapped SP for10days,and the release behavior was influenced by the pH value of the medium.r2002Elsevier Science Ltd.All rights reserved.Keywords:Chitosan;Poly(acrylic acid);Nanoparticles;Drug delivery;Silk peptide1.IntroductionRecently,polymer nanoparticles have been widely investigated as a carrier for drug delivery[1–3].Among them,much attention has been paid to the nanoparticles made of synthetic biodegradable polymers such as poly-e-caprolactone(PCL)[4,5],polylactide(PLA)[6],and their copolymers[7–9]due to their good biocompat-ibility,biodegradability,and novel drug release beha-vior.However,these nanoparticles are not ideal carriers for hydrophilic drugs like peptides,protein and some anticancer drugs because of their strong hydrophobic property.To improve their hydrophilic property,many different hydrophilic nanoparticles have been developed as hydrophilic drug carriers.Among those hydrophilic systems,poly(ethylene glycol)(PE G)modified polyester nanoparticles are the promising carriers for the hydro-philic drugs due to the hydrophilic property and other outstanding physico-chemical and biological properties of PEG[10–12].But these hydrophobic–hydrophilic nanoparticles have a limitation in their preparation procedure,which requires the use of organic solvents and surfactants as well as sonication or homogenization. Chitosan,a kind of nature polysaccharide,having structural characteristics similar to glycosaminoglycans, is non-toxic and biodegradable[13],which has rendered it widely,applicable in the pharmaceutical and biome-dicalfields[14–16].In the recent years,chitosan micro-spheres and beads have been investigated as drug delivery systems for anticancer drug or protein[17–19]. Many approaches have been developed to prepare the chitosan beads including water in oil method[20,21], emulsion-droplet coalescence technique[22]and spray drying process[23].Usually,these preparation proce-dures are complex and need to use some organic solvents or surfactants.In addition,by these techniques, the beads are not appropriate for the routes of administration;For example,vein injection due to their large size(larger than2m m)[20,21,23].To overcome these drawbacks,many works have been done.Leong et al.[24]reported CS-DNA nanoparticles prepared by coacervation of CS and DNA in acidic*Corresponding author.Tel.:+86-25-331-7807;fax:+86-25-331-7761.E-mail address:czyang@(C.Yang).0142-9612/02/$-see front matter r2002Elsevier Science Ltd.All rights reserved. PII:S0142-9612(02)00071-6solution.The size of the CS-DNA nanoparticles was in the range of100–250nm,and such nanoparticles can protect the encapsulated plasmid DNA from nuclease degradation.Alonso et al.[25]developed a kind of hydrophilic chitosan–polyethylene oxide nanoparticles prepared by the ionic interaction between positively charged CS and negatively charged polymer-tripolypho-sphate(TPP),and the nanoparticles showed a great protein loading capacity and sustained release ability. In the present work,we report a new approach to prepare hydrophilic nanoparticles based on polymeriz-ing acrylic acid into chitosan template in aqueous solution[26].We think that this system has some interesting features:(1)The nanoparticles are obtained spontaneously under very mild conditions without the need of high temperature,organic solvent,surfactant and some other special experimental technology;(2)the nanoparticles have small particle size and positive surface charges,which may improve their stability in the presence of biological cations[27],and is favorable for some drugs due to the interaction with negatively charged biological membranes and site-specific targeting in vivo[28,29];(3)The nanoparticles have pH-depen-dent dissolution behavior.2.Experimental2.1.MaterialsChitosan(Nantong Shuanglin Biological Product Inc.)was refined twice by dissolving it in dilute acetic acid solution,filtered,precipitated with aqueous NaOH, andfinally dried in vacuum at room temperature.The degree of deacetylation was about90%,and the weight average molecular weights of chitosan were40,80,100, 200and300kDa,respectively,determined by visco-metric methods[30].Potassium persulfate(K2S2O8)was recrystallized from distilled water.Acrylic acid(AA) (Shanghai Guanghua Chemical Company)was distilled under reduced pressure in nitrogen atmosphere.Silk peptide powder(SP)was kindly supplied by Nanjing Golden Balei Limited Company(People’s Republic of China)as a model drug.All other reagents were of analytical grade and used without further purification.2.2.Preparation of CS–PAA nanoparticles by polymerizationThe CS–PAA nanoparticles were obtained by poly-merization of AA in CS solution.Chitosan was dissolved in50ml acrylic acid solution in the ratio of 1:1([aminoglucoside units]:[AA],except when otherwise stated)under magnetic stirring.The amount of AA was maintained constantly at3mmol in all experiments. Until the solution became clear,0.1mmol of K2S2O8was added to the solution with continued stirring.The pH value of the system was maintained at about4.0. Then,the polymerization was carried out at701C under a nitrogen stream and magnetic stirring.When the opalescent suspension appeared,the reaction system was cooled,and the opalescent suspension wasfiltered with paperfilter to remove any polymer aggregation.Finally, the residual monomers were removed by dialysis in a buffer solution of pH=4.5for24h using a dialysis membrane bag with a molecular weight cut-off of 10kDa.2.3.Preparation of CS–PAA nanoparticles by dropping methodCS–PAA nanoparticles were also prepared by mixing positively charged CS and negatively charged PAA with dropping method.(a)Adding CS solution into PAA solution.Briefly,1ml0.02%CS solution(CS with a molecular weight being80kDa was dissolved in1%(w/ v)acetic acid solution)was added dropwise into5ml 0.02%PAA(M n=100kDa)aqueous solution under magnetic stirring,the opalescent suspension was formed.The obtained suspension was thenfiltered by paperfilter,thefiltered suspension was incubated in a buffer solution of pH=4.5for24h using a dialysis membrane bag for characterization.(b)Adding PAA solution into CS solution.1ml0.02%PAA (M n=100kDa)solution was added dropwise into5ml 0.02%CS solution(CS with molecular weight80kDa was dissolved in1%(w/v)acetic acid solution)under magnetic stirring.The following procedure was as described in method a.2.4.Preparation of drug loaded CS nanoparticlesThe drug-loaded nanoparticles were prepared by dissolving50mg of SP in50ml CS–PAA nanoparticlate prepared by polymerization of AA in CS solution with the CS molecular weight80kDa and incubated for48h. Then,these nanoparticles were separated from the aqueous phase by ultracentrifugation(Ultra Pro TM80, Du Pont)with50,000rpm at41C for40min.Next,the gained SP loaded CS–PAA nanoparticles were washed by acetone three times,frozen by liquid nitrogen and lyophilized by free dryer system to obtain dried SP loaded CS–PAA nanoparticles.2.5.FT-IR spectrum analysisFT-IR spectra were measured by a Bruke IFS 66V vacuum-type spectrometer to determine the chemical interaction between CS and PAA.The CS–PAA nanoparticles were frozen by liquid nitrogen and lyophilized by free dryer system to obtain dried CS–PAA nanoparticles.These gained CS–PAAY.Hu et al./Biomaterials23(2002)3193–3201 3194nanoparticles were mixed with KBr and pressed to a plate for measurement.2.6.The yields of the CS–PAA nanoparticles and size exclusion chromatography(SEC)characterizationThe nanoparticles were separated from the aqueous phase by ultracentrifugation(Ultra Pro TM80,Du Pont) with50,000rpm at41C for40min.The weight of the sediment nanoparticles was defined as the weight of the resultant nanoparticles.The nanoparticle yields were calculated by the following equation:Nanoparticle yieldð%Þ¼Weight of nanoparticlesWeight of chitosan and monomer fed initiallyÂ100:In order to investigate the molecular weight of PAA in nanoparticles,SE C measurement was carried out on Shimadzu LC-10AD HPLC using Ultrahydrogel120 and500columns and a RID-10A detector.The deionized water was used as eluent and theflow rate was0.5ml minÀ1.The SEC was calibrated with poly (ethylene oxide)standards.For SE C measurement,CS–PAA nanoparticles were dissolved in diluted HCl aqueous solution,and then added NaOH into this system.When the pH value of the above solution was adjusted to9,the solution was separated by ultracen-trifugation at50,000rpm for40min.The supernatant was used for SEC measurement.2.7.Transmission electron microscopyTransmission electron microscopy(TEM)(JEOL TE M-100,Japan)was used to observe the morphology of the CS–PAA nanoparticles.Samples were placed onto copper grill covered with nitrocellulose.They were dried at room temperature,and then were examined using a TEM without being negative stained.2.8.Particle size and zeta potential of CS–PAA nanoparticlesThe mean size and size distribution of the CS–PAA nanoparticles were measured by dynamic light scattering (DLS)(Zetasize;3000HS,Malvern,UK)in buffer solution with different pH values.All DLS measurements were done with a wavelength of 633.0nm at251C with an angle detection of901.Each sample was repeatedly measured3times and the values reported are the mean diameter7SD for two replicate samples.The zeta potential of the CS–PAA nanoparticles were measured on Zetasize3000HS.(Malvern,UK).The samples were diluted with10m m NaCl solution at a pH value of4.5(except when otherwise stated)in order to maintain a constant ionic strength.Each sample was repeatedly measured3times and the values reported are the mean value7SD for two replicate samples.2.9.SP encapsulation efficiency of the nanoparticlesThe SP-loaded CS–PAA nanoparticles were separated from the aqueous suspension medium by ultracentrifu-gation with50,000rpm at41C for40min.The amount of free SP in the clear supertant was measured by fluorescence measurements on LS-50B,(Perkin E lmer) with excitation of274nm and emission of302.4nm.SP encapsulation efficiency(AE)were calculated with the following equation:AE¼Total amount SPÀFree amount SPTotal amount SPÂ100:2.10.In vitro drug release from the nanoparticles Hundred mg SP-loaded CS–PAA nanoparticles were re-dispersed in10ml distilled water and placed in a dialysis membrane bag with a molecular cut-off of10kDa,tied and placed into300ml of water medium with various pH values on sink conditions. The entire system was kept at371C with continuous magnetic stirring.After a predetermined period,5ml of the medium was removed and the amount of SP was analyzed byfluorescence measurement. The released SP was determined by a calibration curve. In order to maintain the original volume,each time, 5ml of the medium was replaced with fresh water. The SP release experiments were repeated three times.3.Results and discussion3.1.Synthesis of CS–PAA nanoparticlesThe CS–PAA nanoparticles were prepared by two methods in our study.One was polymerization of AA in CS solution.Another is mixture of positively charged CS and negatively charged PAA with dropping method. The polymerization of acrylic acid in the presence of chitosan is showed in Scheme1.First,CS was dissolved in AA solution,and then the polymerization of AA was initiated by K2S2O8.When the polymerization of AA reached a certain level,the inter-and intra-molecular linkages occurred between carboxyl groups from PAA and positively charged amino groups of CS.These linkages could make the macromolecular chains of CS rolling up,which was responsible for the formation of the gelation of the CS solution.In this system,at the early stage of the polymerization,there was no or little amount of PAA in the solution,thus the system showed the property as a clear solution.As the polymerizationY.Hu et al./Biomaterials23(2002)3193–32013195time extended,the amount of PAA in the solution increased,and the system changed initially from a clear solution to an opalescent emulsion,indicating the formation of CS–PAA nanoparticles.Ahn et al.[26]had reported that acrylic acid could have undergone template polymerization in CS solution.In our case,we thought that the CS–PAA nanoparticles were also prepared by template polymerization of acrylic acid in chitosan solution using chitosan as the template.As reported by Ferguson,[31]in template polymerization,the presence of template during the polymerization procedure has kinetic and structural effects,which influences the molecular weight of the growing polymer chain.That is to say that the propagation will continue for longer on a higher molecular weight template than on a low molecular weight before termination occurs.In this experiment,we thought that the molecular weight of CS template also influenced the molecular weight of formed PAA.To study it,a series of CS–PAA nanoparticles was synthesized by polymerization of acrylic acid in the solution of chitosan with different molecular weights of 40,80,100,200and 300kDa.All the CS samples have a similar degree of deacetylation of about 90%.The aminoglucoside units of chitosan were equal to the units of AA fed initially.Table 1shows the results of these experiments.From Table 1,it is interestingly found that the molecular weight (M n )of PAA in the CS–PAA nanoparticles increased with the increase of the mole-cular weight of CS,while the yield of CS–PAA nanoparticles was maintained in the range 60–70%.Like in template polymerization,when the PAA reaches a critical molecular weight,the propagation of PAA chains is restricted by the CS template.Thus,it isNH 2NH 2NH 2NH 2CH 2CHCOOH3NH 3NH 3NH 3OOCCHCH 2OOCCHCH2OOCCHCH2OOCCHCH2NH 3NH 3NH 3NH 3OOC OOC OOC OOCPolymerizationNH 3NH 3OOCOOCOOCOOC NH 3NH 3CSCS-PAA nanoparticlesScheme 1.Preparation mechanism of CS–PAA nanoparticles.Table 1The relationship of the molecular weight of CS and PAA Sample no.Molecular weight of CS,M w Polymerization time (h)Molecularweight of PAA,M n Yield of PAA (%)Yield ofnanoparticles (%)140,00023678570.0280,000210878368.63100,000221387262.34200,000245267863.15300,000280267160.0Y.Hu et al./Biomaterials 23(2002)3193–32013196reasonable to conclude that the polymerization of AA in CS solution is a template polymerization.3.2.FT-IR analysisTo investigate the complex formation between PAA and chitosan,FT-IR studies were conducted. Fig.1shows the FT-IR spectra of PAA,CS and CS–PAA nanoparticles prepared by the polymerization of AA in CS solution.For CS–PAA nanoparticles, the intensities of amide band I at1662cmÀ1and amide band II at1586cmÀ1,which can be observed clearly in pure chitosan,decrease dramatically,and two new absorption bands at1731and1628cmÀ1, which can be assigned to the absorption peaks of the carboxyl groups of PAA(the absorption peak of carboxyl groups in pure PAA appears at1740cmÀ1), and the NH3+absorption of CS,respectively,are observed.The broad peaks appeared at2500and 1900cmÀ1also confirmed the presence ofÀNH3+in CS–PAA nanoparticles.Furthermore,the absorption peaks at1532and1414cmÀ1could be assigned to asymmetric and symmetric stretching vibrations of COOÀanion groups.These results indicate that the carboxylic groups of PAA are dissociated into COOÀgroups which complex with protonated amino groups of CS through electrostatic interaction to form the polyelectrolyte complex during the polymerization procedure.3.3.Influence of the ratio of CS/AA on the mean diameter of nanoparticlesThe particle size distributions of CS–PAA nanopar-ticles,prepared by polymerization of AA in CS solution with various CS/AA ratios([aminoglucoside uni-ts]:[AA]),were characterized by DLS at pH4.5.The results are displayed in Fig.2and Table2.It is shown that the diameter of each sample is smaller than300nm. Moreover,the diameter distribution of the nanoparticles is smallest when CS:AA=1:1.This result suggested that the ratio of CS to AA have an influence on the mean particle size.It also can be seen that CS–PAA nanoparticles could be obtained at a different ratio of CS to AA,and the preparation condition of CS–PAA nanoparticles was not very critical on the ratio of CS to AA compared to CS-DNA and CS-TPP systems[24,25]. From the results of zeta potential listed in Table2,it is found that the surfaces of CS–PAA nanoparticles have positive charges of about20–30mV.The positive-charged surface of CS–PAA nanoparticles is common to other CS nanoparticles reported by other authors because of the cationic characteristic of CS.However, it is interesting tofind that as the ratio of CS/AA increases,the zeta potential also increases.It is reason-able that CS is a cationic polysaccharide,when the content of CS(aminoglucoside units)excesses than AA, some of the excessive CS will be absorbed onto the surface of CS–PAA nanoparticles,which will increase 1001000510152025Volume%Particle Diameter (nm)Fig.2.Size distribution of CS–PAA nanoparticles with various CS/PAA ratios(wt/wt)at pH=4.5.Wavelength(cm-1)Fig.1.FT-IR spectra of CS,PAA,and CS–PAA.Table2Mean particle size and zeta potential of CS–PAA complex nanoparticlesSample AA:CS(wt:wt)Mean diameter a(nm)Polydispersity Zeta potential(mV) I1:22507200.32570.046+27.373.5II1:12067220.16570.009+25.373.2III2:12937250.35270.032+23.172.8a Mean diameter was characterized at pH=4.5.Y.Hu et al./Biomaterials23(2002)3193–32013197the surface charges of CS–PAA nanoparticles and resulting in the increase of zeta potential.3.4.Influence of pH value on the mean diameter and morphology of CS–PAA nanoparticlesIn order to investigate the effect of pH values on CS–PAA nanoparticles prepared by polymerizing AA in CS solution,a series of experiments were carried out.The obtained CS–PAA nanoparticles,with CS molecular weight80kDa,were incubated in buffer solution with different pH values(pH=1,2,3,4.5,5.8,7.4,9).Results of these experiments showed that these nanoparticles were stable in distilled water and acidic media in a range of pH values from4.0to7.4but dissolved in a few minutes in0.1n HCl and aggregated quickly at pH values larger than9.Table3shows the result of the mean diameter of the CS–PAA nanoparticles under different pH values.From Table3,it can be seen that, the diameter of the nanoparticles increases with the increase of pH value from4.0to7.4.Fig.3shows the TEM photographs of CS–PAA nanoparticles prepared by template polymerization. All these nanoparticles were incubated in buffers for 48h.The nanoparticles,which were in acetic buffer solution at a pH value of4.5(Fig.3(a)),exhibit solid and consistent spherical shapes,indicating that the CS–PAA nanoparticles have a matrix structure.However these nanoparticles in PBS at a pH of7.4shown in Fig.3(b)exhibit a compact core surrounded by a diffuse and fuzzy coat.These facts can be explained by the following.These CS–PAA nanoparticles were formed by ionic interaction between positively charged chitosan and negatively charged PAA.CS is a kind of weak alkali and PAA is a kind of weak acid.The p K a values of PAAand CS are 4.75and 6.5[26],respectively.Under stronger acidic conditions,such as pH o4.0,most carboxylic groups of PAA are in the form ofÀCOOH. The interaction between NH3+and COOÀin the CS–PAA nanoparticles could be disrupted by the acid of small molecules,which leads to chain stretch of CS and PAA.So the CS–PAA nanoparticles would be dissolved quickly.When the pH value is in the range from4.5to 5.8,CS and PAA are partly ionized.The partly ionized CS and PAA can form compact polyelectrolytes complex by ionic interaction,which results in a matrix structure with solid and consistent spherical shapes. When pH values increased from4.5to7.4,as listed in Table3,the ionized degree of PAA increased,and the charge density of the PAA molecules significantly increased.Thus,the electrostatic repulsive forces of inter-and intra-PAA molecules increased,resulting in the increase of swelling degree of PAA and the increase of the mean size of these CS–PAA nanoparticles.When these CS–PAA nanoparticles were incubated in PBS, (pH=7.4),the morphology of nanoparticles was chan-ged because of the difference of the solubility of CS and PAA.At this pH value,PAA was highly swollen while CS was insoluble,which results in the phase separation of nanoparticles,that is,CS was just physically coated on this nanoparticles.Thus these CS–PAA nanoparti-cles formed the core-shell-like structure as shown in Fig.3(b).On contrary,under extremely basic condition, the COOH groups from PAA were neutralized by OHÀ, and almost all amine groups from CS were in the form of NH2.Thus,the CS–PAA nanoparticles would be destroyed,resulting in an aggregation of CS due to itsTable3The mean diameter of CS–PAA nanoparticles under various pH values pH Value Mean diameter(nm) 4.01757324.52067225.84007467.46257106Fig.3.Electron transmission microphotography of CS–PAA nano-particles at(a)pH=4.5and(b)at pH=7.4.Y.Hu et al./Biomaterials23(2002)3193–3201 3198insolubility in basic solution.These processes can be shown as follows:When pH o4.0,NHþ3ÀCOOÀHþ-NHþ3þCOOHCS-PAA nanoparticles Clear solution:ð1ÞWhen pH>9.0,NHþ3ÀCOOÀOHÀ-NH2þCOOÀþH2OCS-PAA nanoparticles Aggregation:ð2ÞFrom E qs.(1)and(2),it is evident that,to obtain stable nanoparticles,the system should be in suitable pH value.From these results,it could be seen that these nanoparticles are pH-sensitive,which would be good as carriers to load ocular drug because there are different pH values in the alimentary canal.3.5.Influence of different preparation procedures on the morphology of CS–PAA nanoparticlesThe CS–PAA nanoparticles were also synthesized by dropping method.The influence of different preparation procedures on the CS–PAA nanoparticles was investi-gated.Fig.4(a)shows the TEM photograph of CS–PAA nanoparticles prepared by dropping PAA solution into CS aqueous solution.Fig.4(b)shows the nanoparticles obtained by dropping CS aqueous solution into PAA solution.Because many factors influence TEM photo-graph,such as the sample structure,staining condition, in this experiment,all of those nanoparticles are notnegative stained with phosphotungstic acid solution. The difference between the TEM photographs of samples might be mainly conduced by the sample structure.CS–PAA nanoparticles shown in Fig.4(a)have a circular shape consisting of a dark shell and a light core. Fig.4(b)exhibits CS–PAA nanoparticles with a dark, solid and consistent structure.These results indicated that different preparation procedures have significant influence on CS–PAA nanoparticles morphology.In the case of dropping PAA into CS solution,a PAA core was initially generated and a complex coacervate membrane is formed on the surface of PAA core.Thus,the nanoparticles with core-shell structure were formed. The formed CS–PAA complex membrane is so dense that it prevents the CS molecular solution from diffusing into the core to further complex with PAA.When these CS–PAA nanoparticles were dried to the TEM char-acterization,the water,which swelled the PAA cores, was removed off and formed some cavities in the cores. In this region,electron beams could easily pass through the CS–PAA nanoparticles,which resulted in a light region in the TEM photograph.For the CS–PAA complex membrane,which is very dense,it prevents majority of the electron beams passing through it.As a result,the region of CS–PAA complex membrane is dark.Similar structures were also observed by TEM from polystyrene-block-poly(acrylic acid)dissolved in water[32].When dropping CS into PAA solution,CS–PAA nanoparticles with a CS core and a CS–PAA membrane are formed.Because CS does not swell in acidic condition,there are no cavities formed in CS–PAA nanoparticles when they are dried for TEM characterization,thus a dark,solid structure was observed.In addition,similar results were also observed in the chitosan-alginate beads[33].Table4lists the results of mean sizes and zeta potentials of CS–PAA nanoparticles obtained by different preparation procedures described above.As shown in Table4,the preparation procedures have an effect on the CS–PAA nanoparticles size.CS–PAA nanoparticles obtained by template polymerization has the smallest mean diameter.In the case of dropping PAA into CS solution,PAA solution cannot be dispersed homogeneously,and polyelectrolyte complex can be formed instantly,which makes the nanoparticles to have a large size and a broad size distribution.The same happens when CS drops into PAA solution.Inthe Fig.4.Morphology of CS–PAA nanoparticles prepared by different procedure at pH4.5:(a)CS dropping into PAA solution;(b)PAA dropping into CS solution.Y.Hu et al./Biomaterials23(2002)3193–32013199case of template polymerization,since the CS and PAA are homogeneously dispersed in the solution,the smallest and uniform size nanoparticles can be obtained.Interestingly,when CS was dropped into PAA solution,the CS–PAA nanoparticles have negative zeta potential,which is quite different from samples 2and 3.This might be due to the fact that there is excessive PAA in the solution,and that the PAA is negatively charged.Some of the negatively charged PAA molecules were adsorbed onto the surface of CS–PAA nanoparticles,which resulted in the negative zeta potential.These results indicate that the surface structure and the surface charge of these nanoparticles can be adjusted by different preparation processes.3.6.SP releaseIn order to investigate the feasibility of using CS–PAA nanoparticles as hydrophilic drug carriers SP as a model peptide was loaded by CS–PAA nanoparticles prepared by template polymerization.Fig.5shows the release profiles of SP from CS–PAA nanoparticles with an encapsulation efficiency of 82%(7.96%,Wt/Wt)for various time intervals in various pH values release media at 371C.An initial burst release followed by a slow release of SP occurred in pH values of 4.5and 7.4.Moreover,these nanoparticles provided a continuous release of the entrapped peptide for up to 10days.On the other hand,at pH values of 2.0and 3.0,the SP release rate was very fast and about 90%of the loaded SP was released from CS–PAA nanoparticles within 25h.It is obvious from the results that the release of the SP depends on pH values of the release medium.The release profile at a pH of 4.5has the slowest release rate,and at a pH of 2.0,the CS–PAA nanoparticles almost do not have any sustained release property.This can be explained by the fact that the release of the SP depends greatly on the swelling of the nanoparticles.At a pH of 4.5,there is very limited swelling,and the SP entrapped in the nanoparticles cannot be released easily.However,at a pH of 7.4,the nanoparticles are swollen to a great extent,resulting in a fairly fast release of SP comparedwith the nanoparticles at pH of 4.5.This result is also in good agreement with the effect of the pH values on nanoparticles morphology as mentioned above.At strong acidic condition,for example,pH value o 4.0,the nanoparticles will dissolve quickly,which leads to the very fast release effect.These results suggest the possibility to adjust the drug release rate of the CS–PAA nanoparticles by changing the pH values.4.ConclusionThe CS–PAA nanoparticles can be prepared by polymerizing acrylic acid into chitosan template.The remarkable advantage of this system is that it is solely made of hydrophilic polymers:chitosan and poly(acrylic acid),which are non-toxic,and biodegradable.All these CS–PAA nanoparticles are obtained under mild condi-tions without any organic solvents and surfactants.These nanoparticles are stable under acidic and neutral conditions ranging from 4to 8,and aggregate at pH>9.Furthermore,different preparation procedures have a great influence on these CS–PAA nanoparticles.The preliminary results of model drug (silk peptide)loading and release experiments indicate that this system seems to be a very promising vehicle for the administration of hydrophilic drugs,proteins and peptides.Furthermore,due to their pH-sensitive behavior,these CS–PAA nanoparticles are appropriate carriers for the delivery of drugs in the gastric cavity.AcknowledgementsThe authors are thankful to Natural Science Founda-tion of Jiangsu Province,China for the partial financial support of this study.5010015020025030035020406080100S P r e l e a s e d (%)Time (hours)Fig.5.Release profiles of SP from CS–PAA nanoparticles at various pH values at 371C (n ¼3).Table 4Zeta potential of CS–PAA PEC nanoparticles obtained by different procedureSample Mean size a (nm)Zeta potential (mv)1436778À22.273.6235874647.272.8320672225.373.2CS dropping into PAA solution.PAA dropping into CS solution.Free radical polymerization.aMean size was characterized at pH=4.5.Y.Hu et al./Biomaterials 23(2002)3193–32013200。

专业英语accordion 手风琴activation 活化（作用）addition polymer 加成聚合物，加聚物aggravate 加重，恶化agitation 搅拌agrochemical 农药，化肥Alfin catalyst 醇（碱金属）烯催化剂align 排列成行aliphatic 脂肪（族）的alkali metal 碱金属allyl 烯丙基aluminum alkyl 烷基铝amidation 酰胺化（作用）amino 氨基，氨基的amorphous 无定型的，非晶体的anionic 阴（负）离子的antioxidant 抗氧剂antistatic agent 抗静电剂aromatic 芳香（族）的arrangement （空间）排布，排列atactic 无规立构的attraction 引力，吸引backbone 主链，骨干behavior 性能，行为biological 生物（学）的biomedical 生物医学的bond dissociation energy 键断裂能boundary 界限，范围brittle 脆的，易碎的butadiene 丁二烯butyllithium 丁基锂calendering 压延成型calendering 压延carboxyl 羧基carrier 载体catalyst 催化剂，触媒categorization 分类（法）category 种类，类型cation 正[阳]离子cationic 阳（正）离子的centrifuge 离心chain reaction 连锁反应chain termination 链终止char 炭characterize 表征成为…的特征chilled water 冷冻水chlorine 氯（气）coating 涂覆cocatalyst 助催化剂coil 线团coiling 线团状的colligative 依数性colloid 胶体commence 开始，着手common salt 食盐complex 络合物compliance 柔量condensation polymer 缩合聚合物，缩聚物conductive material 导电材料conformation 构象consistency 稠度，粘稠度contaminant 污物contour 外形，轮廓controlled release 控制释放controversy 争论，争议conversion 转化率conversion 转化copolymer 共聚物copolymerization 共聚（合）corrosion inhibitor 缓释剂countercurrent 逆流crosslinking 交联crystal 基体，结晶crystalline 晶体，晶态，结晶的，晶态的crystalline 结晶的crystallinity 结晶性，结晶度crystallite 微晶decomposition 分解defect 缺陷deformability 变形性，变形能力deformation 形变deformation 变形degree of polymerization 聚合度dehydrogenate 使脱氢density 密度depolymerization 解聚deposit 堆积物，沉积depropagation 降解dewater 脱水diacid 二（元）酸diamine 二（元）胺dibasic 二元的dieforming 口模成型diffraction 衍射diffuse 扩散dimension 尺寸dimensional stability 尺寸稳定性dimer 二聚物（体）diol 二（元）醇diolefin 二烯烃disintegrate 分解，分散，分离dislocation 错位，位错dispersant 分散剂dissociate 离解dissolution 溶解dissolve 使…溶解distort 使…变形，扭曲double bond 双键dough （生）面团，揉好的面drug 药品，药物elastic modulus 弹性模量elastomer 弹性体eliminate 消除，打开，除去elongation 伸长率，延伸率entanglement 缠结，纠缠entropy 熵equilibrium 平衡esterification 酯化（作用）evacuate 撤出extrusion 注射成型extrusion 挤出fiber 纤维flame retardant 阻燃剂flexible 柔软的flocculating agent 絮凝剂folded-chain lamella theory 折叠链片晶理论formulation 配方fractionation 分级fragment 碎屑，碎片fringed-micelle theory 缨状微束理论functional group 官能团functional polymer 功能聚合物functionalized polymer 功能聚合物gel 凝胶glass transition temperature 玻璃化温度glassy 玻璃（态）的glassy 玻璃态的glassy state 玻璃态globule 小球，液滴，颗粒growing chain 生长链，活性链gyration 旋转，回旋hardness 硬度heat transfer 热传递heterogeneous 不均匀的，非均匀的hydocy acid 羧基酸hydrogen 氢（气）hydrogen bonding 氢键hydrostatic 流体静力学hydroxyl 烃基hypothetical 假定的，理想的，有前提的ideal 理想的，概念的imagine 想象，推测imbed 嵌入，埋入，包埋imperfect 不完全的improve 增进，改善impurity 杂质indispensable 不了或缺的infrared spectroscopy 红外光谱法ingredient 成分initiation （链）引发initiator 引发剂inorganic polymer 无机聚合物interaction 相互作用interchain 链间的interlink 把…相互连接起来连接intermittent 间歇式的intermolecular (作用于)分子间的intrinsic 固有的ion 离子ion exchange resin 离子交换树脂ionic 离子的ionic polymerization 离子型聚合irradiation 照射，辐射irregularity 不规则性，不均匀的isobutylene 异丁烯isocyanate 异氰酸酯isopropylate 异丙醇金属，异丙氧化金属isotactic 等规立构的isotropic 各项同性的kinetic chain length 动力学链长kinetics 动力学latent 潜在的light scattering 光散射line 衬里，贴面liquid crystal 液晶macromelecule 大分子，高分子matrix 基体，母体，基质，矩阵mean-aquare end-to-end distance 均方末端距mechanical property 力学性能，机械性能mechanism 机理medium 介质中等的，中间的minimise 最小化minimum 最小值，最小的mo(u)lding 模型mobility 流动性mobilize 运动，流动model 模型modify 改性molecular weight 分子量molecular weight distribution 分子量分布molten 熔化的monofunctional 单官能度的monomer 单体morphology 形态（学）moulding 模塑成型neutral 中性的nonelastic 非弹性的nuclear magnetic resonance 核磁共振nuclear track detector 核径迹探测器number average molecular weight 数均分子量occluded 夹杂（带）的olefinic 烯烃的optimum 最佳的，最佳值[点，状态]orient 定向，取向orientation 定向oxonium 氧鎓羊packing 堆砌parameter 参数parison 型柸pattern 花纹，图样式样peculiarity 特性pendant group 侧基performance 性能，特征permeability 渗透性pharmaceutical 药品，药物，药物的，医药的phenyl sodium 苯基钠phenyllithium 苯基锂phosgene 光气，碳酰氯photosensitizer 光敏剂plastics 塑料platelet 片晶polyamide 聚酰胺polybutene 聚丁烯polycondensation 缩（合）聚（合）polydisperse 多分散的polydispersity 多分散性polyesterification 聚酯化（作用）polyethylene 聚乙烯polyfunctional 多官能度的polymer 聚合物【体】，高聚物polymeric 聚合（物）的polypropylene 聚苯烯polystyrene 聚苯乙烯polyvinyl alcohol 聚乙烯醇polyvinylchloride 聚氯乙烯porosity 多孔性，孔隙率positive 正的，阳（性）的powdery 粉状的processing 加工，成型purity 纯度pyrolysis 热解radical 自由基radical polymerization 自由基聚合radius 半径random coil 无规线团random decomposition 无规降解reactent 反应物，试剂reactive 反应性的，活性的reactivity 反应性，活性reactivity ratio 竞聚率real 真是的release 解除，松开repeating unit 重复单元retract 收缩rubber 橡胶rubbery 橡胶态的rupture 断裂saturation 饱和scalp 筛子，筛分seal 密封secondary shaping operation 二次成型sedimentation 沉降（法）segment 链段segment 链段semicrystalline 半晶settle 沉淀，澄清shaping 成型side reaction 副作用simultaneously 同时，同步single bond 单键slastic parameter 弹性指数slurry 淤浆solar energy 太阳能solubility 溶解度solvent 溶剂spacer group 隔离基团sprinkle 喷洒squeeze 挤压srereoregularity 立构规整性【度】stability 稳定性stabilizer 稳定剂statistical 统计的step-growth polymerization 逐步聚合stereoregular 有规立构的，立构规整性的stoichiometric 当量的，化学计算量的strength 强度stretch 拉直，拉长stripping tower 脱单塔subdivide 细分区分substitution 取代，代替surfactant 表面活性剂swell 溶胀swollen 溶胀的synthesis 合成synthesize 合成synthetic 合成的tacky （表面）发粘的,粘连性tanker 油轮，槽车tensile strength 抗张强度terminate （链）终止tertiary 三元的，叔（特）的tetrahydrofuran 四氢呋喃texture 结构，组织thermoforming 热成型thermondynamically 热力学地thermoplastic 热塑性的thermoset 热固性的three-dimensionally ordered 三维有序的titanium tetrachloride 四氯化钛titanium trichloride 三氯化铁torsion 转矩transfer （链）转移，（热）传递triethyloxonium-borofluoride 三乙基硼氟酸羊trimer 三聚物（体）triphenylenthyl potassium 三苯甲基钾ultracentrifugation 超速离心（分离）ultrasonic 超声波uncross-linked 非交联的uniaxial 单轴的unsaturated 不饱和的unzippering 开链urethane 氨基甲酸酯variation 变化，改变vinyl 乙烯基（的）vinyl chloride 氯乙烯vinyl ether 乙烯基醚viscoelastic 黏弹性的viscoelastic state 黏弹态viscofluid state 黏流态viscosity 黏度viscosity average molecular weight 黏均分子量viscous 粘稠的vulcanization 硫化weight average molecular weight 重均分子量X-ray x射线x光yield 产率Young's modulus 杨氏模量。

Process Conditions of Step Polymerization and interfacial polymerization Physical Nature of Polymerization SystemsSeveral considerations are common to all processes for step polymerizations in order to achievehigh molecular weights. One needs to employ a reaction with an absence or at least a minimum of sidereactions, which would limit high conversions. Polymerizations are carried out at high concentrationsto minimize cyclization and maximize the reaction rate. Highpurity reactants in stoichiometric or near-stoichiometric amounts are required. The molecular weight is controlled by the presence of controlled 5 amounts of monofunctional reagents or an excess of one of the bifunctional reagents. Equilibriumconsiderations are also of prime importance. Since many step polymerizations are equilibriumreactions, appropriate means must be employed to displace the equilibrium in the direction of thepolymer product. Distillation of water or other small molecule products from the reaction mixture bysuitable reaction temperatures and reduced pressures are often employed for this purpose.Table 2-8 shows values of some kinetic and thermodynamic characteristics of typical steppolymerizatiosn. These data have implications on the temperature at which polymerization is carriedout. Most step polymerizations proceed at relatively slow rates at ordinary temperatures. Hightemperatures in the range of 150–200 °C and higher are frequently used to obtain reasonablepolymerization rates. Table 2-8 shows that the rate constants are not large even at these temperatures.Typical rate constants are of the order of 10-3 L mol-1s-1. There are a few exceptions of steppolymerizations with significantly larger k values, for example, the polymerization reaction betweenacid halides and alcohols. The need to use higher temperatures can present several problems, includingloss of one or the other reactant by degradation or volatilization. Oxidative degradation of polymer isalso a potential problem in some cases. The use of an inert atmosphere (N2, CO2) can minimizeoxidative degradation.Bulk or mass polymerizations is the simplest process for step polymerizations, since it involves onlythe reactants and whatever catalyst, if any, which is required. There is a minimum of potentialities forcontamination, and product separation is simple. Bulk polymerization is particularly well suited forstep polymerization because high-molecular-weight polymer is not produced until the very last stagesof reaction. This means that the viscosity is relatively low throughout most of the course of thepolymerization and mixing of the reaction mixture is not overly difficult. Thermal control is alsorelatively easy, since the typicaly reaction has both a modest activation energy Ea and enthalpy ofpolymerization ΔH. Although some step polymerizations have moderately high activation energies, forexample, 100.4 kJ mol-1 for the polymerization of sebacic acid and hexamethylene diamine (Table 2-8), the ΔH is still only modestly exothermic. The exact opposite is the case for chain polymerizations,which are generally highly exothermic with high activation energies and where the viscosity increasesmuch more rapidly. Thermal control and mixing present much greater problems in chainpolymerizations.Bulk polymerization is widely used for step polymerizations. Many polymerizations, however, arecarried out in solution with a solvent present to solubilize the reactants, or to allow higher reactiontemperatures to be employed, or as a convenience in moderating the reaction and acting as a carrier.5Different Reactant SystemsFor many step polymerizations there are different combinations of reactants that can be employed to produce the same type of polymer (Table 1-1). Thus the polymerization of a hydroxy acid yields apolymer very similar to (but not the same as) that obtained by reacting a diol and diacid:On the other hand, it is apparent that there are different reactant systems that can yield the exactsame polymer. Thus the use of the diacid chloride or anhydride instead of the diacid in Eq. 2-120would give exactly the same polymer product. The organic chemical aspects of the synthesis ofvarious different polymers by different step polymerization processes have been discussed. Whetherone particular reaction or another is employed to produce a specific polymer depends on severalfactors. These include the availability, ease of purification, and properties (both chemical and physical)of the different reactants and whether one or another reaction is more devoid of destructive side 5 reactions.The ability to obtain high-molecular-weight polymer from a reaction depends on whether theequilibrium is favorable. If the equilibrium is unfavorable as it is in many instances, success dependson the ease with which the polymerization can be driven close to completion. The need for and theease of obtaining and maintaining stoichiometry in a polymerization is an important consideration.The various requirements for producing a high polymer may be resolved in quite different ways fordifferent polymers. One must completely understand each type of polymerization reaction so as toappropriately meet the stringent requirements for the synthesis of high-molecular-weight polymer.Various step polymerizations are described below and serve to illustrate how the characteristics of apolymerization reaction are controlled so as to obtain high polymer.Interfacial PolymerizationMany of the polymers that are produced by the usual high-temperature reactions could be produced at lower temperatures by using the faster Schotten–Baumann reactions of acid chlorides. Thus polyesters and polyamides could be produced by replacing the diacid or dieser reactant by the corresponding diacyl chlorideDescription of ProcessThe rate constants for these reactions are orders of magnitude greater than those for the corresponding reactions of the diacid or diester reactants (Table 2-8). The use of such reactants in a novel low-temperature polymerization technique called interfacial polymerization has been extensively studied. Temperatures in the range 0–50 °C are usually employed. Polymerization of two reactants is carried out at the interface between two liquid phases, each containing one of the reactants (Fig. 2-11). Polyamidation is performed at room temperature by placing an aqueous solution of the diamine on top of an organic phase containing the acid chloride. The reactants diffuse to and undergo polymerization at the interface. The polymer product precipitates and is continuously withdrawn in the form of a continuous film or filament if it has sufficient mechanical strength. Mechanically weak polymers that cannot be removed impede the transport of reactants to the reaction site and the polymerization rate decreases with time. The polymerization rate is usually diffusion-controlled, since the rates of diffusion of reactants to the interface are slower than the rate of reaction of the two functional groups. (This may not be the situation when reactions with small rate constants areemployed.)Interfacial polymerization is mechanistically different from the usual step polymerization in that themonomers diffusing to the interface will react only with polymer chain ends. The reaction rates are sohigh that diacid chloride and diamine monomer molecules will react with the growing polymer chainends before they can penetrate through the polymer film to start the growth of new chains. There isthus a strong tendency to produce highermolecular-weight polymer in the interfacial process comparedto the usual processes. Also, interfacial polymerization does not require overall bulk stoichiometry of 5 the reactants in the two phases. Stoichiometry automatically exists at the interface wherepolymerization proceeds. There is always a supply of both reactants at the interface due to diffusionfrom the organic and aqueous phases. Furthermore, high-molecular-weight polymer is formed at theinterface regardless of the overall percent conversion based on the bulk amounts of the two reactants.The overall percent conversion can be increased by employing a stirred system as a means ofincreasing the total area of reacting interface.Several reaction parameters must be controlled in order for interfacial polymerization to proceedsuccessfully. An inorganic base must be present in the aqueous phase to neutralize the by-producthydrogen chloride. If it were not neutralized the hydrogen chloride would tie up the diamine as itsunreactive amine hydrochloride salt leading to greatly lowered reaction rates. The acid chloride mayundergo hydrolysis to the unreactive acid at high concentrations of the inorganic base or at lowpolymerization rates. Hydrolysis not only decreases the polymerization rate but also greatly limits thepolymer molecular weight, since it converts the diacid chloride into the diacid, which is unreactive atthe temperatures employed in interfacial polymerization. The slower the polymerization rate, thegreater the problem of hydrolysis as the acid chloride will have more time to diffuse through theinterface and into the water layer. Thus acid hydrolysis prevents the use of the interfacial technique forthe synthesis of polyesters from diols, since the reaction is relatively slow (k ~ 10-3 L mol-1 s-1). Thereaction of diacid chlorides and diamines is so fast (k ~ 104–105 L mol-1 s-1) that hydrolysis is usuallycompletely absent.The choice of the organic solvent is very important in controlling the polymer molecular weight,since it appears that the polymerization actually occurs on the organic solvent side of the interface inmost systems. The reason for this is the greater tendency of the diamine to diffuse into the organicsolvent compared to the diffusion of diacid chloride into the aqueous side of the interface. (For somesystems, e.g., the reaction of the disodium salt of a dihydric phenol with a diacid chloride, the exactopposite is the case and polymerization occurs on the aqueous side of the interface.) An organicsolvent that precipitates the high-molecular-weight polymer but not the low-molecular-weightfractions is desirable. Premature precipitation of the polymer will prevent the production of the desiredhigh-molecular-weight product. Thus, for example, xylene and carbon tetrachloride are precipitants forall molecular weights of poly (hexamethylene sebacate), while chloroform is a precipitant only for thehigh-molecularweight polymer. Interfacial polymerization with the former organic solvents wouldyield only low-molecular-weight polymer. The molecular weight distributions observed in interfacialpolymerizations are usually quite different from the most probable distribution. Most interfacialpolymerizations yield distributions broader than the most probable distribution, but narrowerdistributions have also been observed. The differences are probably due to fractionation when thepolymer undergoes precipitation. The effect is dependent on the organic solvent used and thesolubility characteristicsof the polymer.The organic solvent can also affect the polymerization by affecting the diffusion characteristics ofthe reaction system. A solvent that swells the precipitated polymer is desirable to maximize thediffusion of reactants through it to the reaction site. However, the swelling should not decrease the 5 mechanical strength of the polymer below the level that allows it to be continuously removed from theinterface. It has been found that the optimum molar ratio of the two reactants in terms of producing thehighest yield and/or highest molecular weight is not always 1 : 1 and often varies with the organicsolvent. The lower the tendency of the water-soluble reactant to diffuse into the organic phase, thegreater must be its concentration relative to the other reactant’s concentration. The optimum ratio ofconcentrations of the two reactants is that which results in approximately equalizing the rates ofdiffusion of the two reactants to the interface.Fig. 2-11 Interfacial polymerization; removal of polymer film from the interface. From Morgan and Kwolek [1959 a,b] (by permission of Division of Chemical Education, American Chemical Society, Washington, DC and Wiley-Interscience, New York); an original photgraph, from which this figure was drawn, was kindly supplied by Dr. P. W. Morgan.UtilityThe interfacial technique has several advantages. Bulk stoichiometry is not needed to produce high-molecular-weight polymers and fast reactions are used. The low temperatures allow the synthesis ofpolymers that may be unstable at the high temperatures required in the typical step polymerization.The interfacial technique has been extended to many different polymerizations, including theformation of polyamides, polyesters, polyurethanes, polysulfonamides, polycarbonates, and polyureas.However, there are disadvantages to the process, which have limited its commercial utility. Theseinclude the high cost of acid chloride reactants and the large amounts of solvents that must be used andrecovered. Commercial utilization has been limited to some polycarbonates, aliphatic polysulfides, andaromatic polyamides.(Principles of Polymerization（Fourth Edition）. George Odian，John Wiley & Sons, Inc.2004)。

高分子合成英语作文题目，The Synthesis of Polymers。

Polymers, large molecules composed of repeating structural units, play a crucial role in our daily lives. From the plastic bottles we use to the fabrics we wear, polymers are everywhere. The synthesis of polymers, the process of creating these macromolecules, is a fascinating area of study that has revolutionized many industries.Polymers can be synthesized through various methods, each with its own advantages and applications. One common method is polymerization, where monomers, the building blocks of polymers, are chemically bonded together to form long chains or networks. There are two main types of polymerization: addition polymerization and condensation polymerization.Addition polymerization involves the repeated addition of monomers with unsaturated double bonds, such as ethyleneor styrene. In this process, the double bonds break, andthe monomers join together to form a polymer chain. For example, polyethylene, one of the most widely used polymers, is synthesized through addition polymerization of ethylene molecules.Condensation polymerization, on the other hand, occurs when two different monomers react with each other,releasing a small molecule like water or alcohol as a byproduct. This process forms a polymer chain with alternating monomer units. Nylon, a common syntheticpolymer used in textiles, is produced through condensation polymerization of diamines and dicarboxylic acids.Another method of polymer synthesis is by ring-opening polymerization, where cyclic monomers are opened and linked together to form linear polymers. This method is often used to produce biodegradable polymers like polylactic acid (PLA), which is derived from renewable resources such as corn starch.In addition to these methods, scientists arecontinually developing new techniques to synthesize polymers with specific properties and structures. One such technique is controlled/living polymerization, which allows for precise control over the size and structure of the polymer chains. This method is particularly useful in the production of advanced materials for electronics, medicine, and other high-tech industries.The synthesis of polymers has numerous applications across various fields. In the automotive industry, polymers are used to manufacture lightweight and fuel-efficient components, reducing the overall weight of vehicles and improving fuel economy. In the medical field, polymers are used in the production of biocompatible materials for implants and drug delivery systems. In agriculture, polymers are used in the development of crop protection films and controlled-release fertilizers.However, the synthesis of polymers also poses challenges, particularly in terms of environmental sustainability. Many conventional polymers are derived from non-renewable resources like petroleum, leading to concernsabout depletion of natural resources and environmental pollution. In response, researchers are exploring alternative sources of monomers, such as plant-based materials and waste products, to create more eco-friendly polymers.Furthermore, the disposal of polymer waste presents a significant environmental problem. Plastics, in particular, are notorious for their persistence in the environment, taking hundreds of years to decompose. This has led to growing interest in biodegradable polymers, which can break down into harmless compounds under the right conditions.In conclusion, the synthesis of polymers is a complex and versatile field with wide-ranging applications. From everyday items to cutting-edge technologies, polymers have become indispensable in modern society. However, as we continue to rely on these materials, it is essential to explore sustainable methods of polymer synthesis and develop eco-friendly alternatives to minimize environmental impact. Only then can we fully harness the potential ofpolymers while preserving the health of our planet for future generations.。

高分子专业术语中英文比较表加工processing反响性加工reactive processing等离子体加工plasma processing加工性processability熔体流动指数melt [flow] index门尼粘度Mooney index塑化plasticizing增塑作用plasticization内增塑作用internal plasticization外增塑作用external plasticization增塑溶胶plastisol加强reinforcing增容作用compatibilization相容性compatibility相溶性intermiscibility生物相容性biocompatibility血液相容性blood compatibility组织相容性tissue compatibility混炼milling, mixing素炼mastication塑炼plastication过炼dead milled橡胶配合rubber compounding共混blend捏和kneading冷轧cold rolling压延性calenderability压延calendering埋置embedding压片preforming模塑molding模压成型compression molding压缩成型compression forming冲压模塑impact moulding, shock moulding叠模压塑stack moulding复合成型composite molding注射成型injection molding注塑压缩成型injection compression molding射流注塑jet molding无流道冷料注塑runnerless injection molding共注塑coinjection molding气辅注塑gas aided injection molding注塑焊接injection welding传达成型transfer molding树脂传达成型resin transfer molding铸塑cast熔铸fusion casting铸塑成型cast molding单体浇铸monomer casting挤出extrusion共挤出coextrusion多层挤塑multi-layer extrusion共挤吹塑coextrusion blow molding同轴挤塑coaxial extrusion吹胀挤塑blown extrusion挤出吹塑extrusion blow molding挤拉吹塑成型extrusion draw blow molding 反响性挤塑reactive extrusion固相挤出solid-phase extrusion发泡expanding foam后发泡post expansion物剪发泡physical foam化学发泡chemical foam吹塑blow molding多层吹塑multi-layer blow molding拉伸吹塑成型stretch blow molding滚塑rotational moulding反响注射成型reaction injection molding, RIM 真空成型vacuum forming无压成型zero ressure molding真空烧结vacuum sintering真空袋成型vacuum bag molding热成型thermal forming拉伸热成型stretch thermoforming袋模塑bag molding糊塑paste molding镶铸imbedding冲压成型impact molding触压成型impression molding层压资料laminate泡沫塑料成型foam molding包模成型drape molding充气吹胀inflation橡胶胶乳rubber latex胶乳latex高分子胶体polymer colloid生橡胶raw rubber ，crude rubber硬质胶ebonite重生胶reclaimed rubber充油橡胶oil-extended rubber母胶masterbatch交联crosslinking固化cure光固化photo-cure硫化vulcanization后硫化post cure ， post vulcanization自硫[化]bin cure自交联self crosslinking , self curing过硫over cure返硫reversion欠硫under cure动向硫化dynamic vulcanization不均匀硫化heterogeneous vulcanization开始[硫化]效应set-up effect自动硫化self-curing, self-vulcanizing焦烧scorching无压硫化non-pressure cure模压硫化moulding curing常温硫化auto-vulcanization热硫化heat curing蒸汽硫化steam curing微波硫化micro wave curing辐射硫化radiation vulcanization辐射交联radiation crosslinking连续硫化continuous vulcanization无模硫化open vulcanization成纤fiber forming可纺性spinnability纺丝spinning干纺dry spinning湿纺wet spinning干湿法纺丝dry wet spinning干喷湿法纺丝dry jet wet spinning溶液纺丝solution spinning乳液纺丝emulsion spinning乳液闪蒸纺丝法emulsion flash spinning process 发射纺丝jet spinning喷纺成形spray spinning液晶纺丝liquid crystal spinning熔纺melt spinning共混纺丝blended spinning凝胶纺 [ 丝 ]gel spinning反响纺丝reaction spinning静电纺丝electrostatic spinning高压纺丝high-pressure spinning复合纺丝conjugate spinning无纺布non-woven fabrics单丝monofilament, monofil复丝multifilament全取向丝fully oriented yarn中空纤维hollow fiber皮芯纤维sheath core fiber共纺cospinning冷拉伸cold drawing, cold stretching单轴拉伸uniaxial drawing，uniaxial elongation双轴拉伸biaxial drawing多轴拉伸multiaxial drawing皮心效应skin and core effect皮层效应skin effect防缩non-shrink熟成ripening垂挂sag定型sizing起球现象pilling effect捻度twist旦denier特tex纱yarn股strand粘合adhesion反响粘合reaction bonding压敏粘合pressure sensitive adhesion 底漆primer浸渍impregnation浸渍树脂solvent impregnated resin基体matrix聚合物表面活性剂polymeric surfactant 高分子絮凝剂polymeric flocculant预发颗粒pre-expanded bead高分子膜polymeric membraneH-膜H-filmLB 膜Langmuir Blodgett film (LB film)半透膜semipermeable membrane反浸透膜Reverse osmosis membrance多孔膜porous membrane各向异性膜anisotropic membrane正离子互换膜cation exchange membrane 负离子互换膜anionic exchange membrane 吸附树脂polymeric adsorbent增添剂additive固化剂curing agent潜固化剂latent curing agent硫化剂vulcanizing agent给硫剂sulfur donor agent, sulfur donor硫化促使剂vulcanization accelerator硫化活化剂vulcanization activator活化促使剂activating accelerator活化剂activator防焦剂scorch retarder抗硫化返原剂anti-reversion agent塑解剂peptizer偶联剂coupling agent硅烷偶联剂silane coupling agent钛酸酯偶联剂titanate coupling agent铝酸酯偶联剂aluminate coupling agent加强剂reinforcing agent增硬剂hardening agent惰性填料inert filler增塑剂plasticizer辅增塑剂coplasticizer增粘剂tackifier增容剂compatibilizer增塑增容剂plasticizer extender分别剂dispersant agent构造控制剂constitution controller色料colorant荧光增白剂optical bleaching agent抗降解剂antidegradant防老剂anti-aging agent防臭氧剂antiozonant抗龟裂剂anticracking agent抗疲惫剂anti-fatigue agent抗微生物剂biocide防蚀剂anti-corrosion agent光致抗蚀剂photoresist防霉剂antiseptic防腐剂rot resistor防潮剂除臭剂抗氧剂热稳固剂抗静电增添剂抗静电剂紫外线稳固剂紫外光汲取剂光稳固剂光障蔽剂发泡剂物剪发泡剂化学发泡剂脱模剂内脱模剂外脱模剂阻燃剂防火剂烧蚀剂润滑剂润湿剂隔绝剂增韧剂抗冲改性剂消泡剂减阻剂破乳剂粘度改良剂增稠剂阻黏剂洗脱剂附聚剂后办理剂催干剂防结皮剂纺织品整理剂moisture proof agentre-odorantantioxidantheat stabilizerantistatic additiveantistatic agentultraviolet stabilizerultraviolet absorber light stabilizer, photostabilizer light screenerfoaming agentphysical foaming agentchemical foaming agent releasing agentinternal releasing agentexternal releasing agent flame retardantfire retardantablatorlubricantwetting agentseparanttoughening agentimpact modifier antifoaming agentdrag reducerdemulsifierviscosity modifier thickening agent, thickener abhesiveeluantagglomerating agentafter-treating agentdrieranti-skinning agenttextile finishing agent－－－－－－－－－－－－－－－－－－－－－－－高物高化类：构造单元constitutional unit重复构造单元constitutional repeating unit 构型单元configurational unit立构重复单元stereorepeating unit立构规整度tacticity等规度 ,全同立构 [规整 ] 度isotacticity间同度，间同立构 [ 规整 ] 度syndiotacticity无规度，无规立构度atacticity嵌段block规整嵌段regular block非规整嵌段irregular block立构嵌段stereoblock有规立构嵌段isotactic block无规立构嵌段atactic block单体单元monomeric unit二单元组diad三单元组triad四单元组tetrad五单元组pentad无规线团random coil自由连结链freely-jointed chain自由旋转链freely-rotating chain蠕虫状链worm-like chain柔性链flexible chain链柔性chain flexibility刚性链rigid chain棒状链rodlike chain链刚性chain rigidity齐集aggregation齐集体aggregate凝集、齐集coalescence链缠结chain entanglement凝集缠结cohesional entanglement物理缠结physical entanglement拓扑缠结topological entanglement凝集相condensed phase凝集态condensed state凝集过程condensing process临界齐集浓度critical aggregation concentration 线团 - 球粒变换coil-globule transition受限链confined chain受限态confined state物理交联physical crosslinking统计线团statistical coil等效链equivalent chain统计链段statistical segment链段chain segment链构象chain conformation无规线团模型random coil model无规行走模型random walk model自避随机行走模型self avoiding walk model卷曲构象coiled conformation高斯链Gaussian chain无扰尺寸unperturbed dimension扰动尺寸perturbed dimension热力学等效球thermodynamically equivalent sphere近程分子内互相作用short-range intramolecular interaction远程分子内互相作用long-range intramolecular interaction链间互相作用interchain interaction链间距interchain spacing长程有序long range order近程有序short range order展转半径radius of gyration尾端间矢量end-to-end vector链尾端chain end尾端距end-to-end distance无扰尾端距unperturbed end-to-end distance均方根尾端距root-mean-square end-to-end distance挺直长度contour length有关长度persistence length主链；链骨架chain backbone支链branch chain链支化chain branching短支链short-chain branch长支链long-chain branch支化系数branching index支化密度branching density支化度degree of branching交联度degree of crosslinking网络network网络密度network density溶胀swelling均衡溶胀equilibrium swelling分子组装，分子组合molecular assembly自组装self assembly微凝胶microgel凝胶点gel point可逆[性]凝胶reversible gel溶胶 - 凝胶转变sol-gel transformation临界胶束浓度critical micelle concentration， CMC构成非均一性constitutional heterogenity, compositional heterogenity摩尔质量均匀molar mass average数均分子量number-average molecular weight, number-average molar mass重均分子量weight-average molecular weight, weight-average molar massZ 均分子量Z(Zaverage)-average molecular weight, Z-molar mass黏均分子量viscosity-average molecular weight， viscosity-average molar mass表观摩尔质量apparent molar mass表观分子量apparent molecular weight聚合度degree of polymerization动力学链长kinetic chain length单分别性monodispersity临界分子量critical molecular weight分子量散布molecular weight distribution， MWD多分别性指数polydispersity index，PID均匀聚合度average degree of polymerization质量散布函数mass distribution function数目散布函数number distribution function重量散布函数weight distribution function舒尔茨 - 齐姆散布Schulz-Zimm distribution最概然散布most probable distribution对数正态散布logarithmic normal distribution聚合物溶液polymer solution聚合物 - 溶剂互相作用polymer-solvent interaction溶剂热力学性质thermodynamic quality of solvent均方尾端距mean square end to end distance均方旋转半径mean square radius of gyrationθ 温度theta temperatureθ 态theta stateθ 溶剂theta solvent良溶剂good solvent不良溶剂poor solvent位力系数Virial coefficient清除体积excluded volume溶胀因子expansion factor溶胀度degree of swelling弗洛里 - 哈金斯理论Flory-Huggins theory哈金斯公式Huggins equation哈金斯系数Huggins coefficientχ( 互相作用 ) 参数χ-parameter溶度参数solubility parameter摩擦系数frictional coefficient流体力学等效球hydrodynamically equivalent sphere流体力学体积hydrodynamic volume珠- 棒模型bead-rod model球- 簧链模型ball-spring [chain] model流动双折射flow birefringence, streaming birefringence动向光散射dynamic light scattering小角激光光散射low angle laser light scattering沉降均衡sedimentation equilibrium沉降系数sedimentation coefficient沉降速度法sedimentation velocity method沉降均衡法sedimentation equilibrium method相对黏度relative viscosity相对黏度增量relative viscosity increment黏度比viscosity ratio黏数viscosity number[ 乌氏 ] 稀释黏度计[Ubbelohde] dilution viscometer毛细管黏度计capillary viscometer落球黏度计ball viscometer落球黏度ball viscosity本体黏度bulk viscosity比浓黏度reduced viscosity比浓对数黏度inherent viscosity, logarithmic viscosity number 特征黏数intrinsic viscosity, limiting viscosity number黏度函数viscosity function零切变速率黏度zero shear viscosity端基剖析analysis of end group蒸气压浸透法vapor pressure osmometry, VPO辐射的相关弹性散射coherent elastic scattering of radiation折光指数增量refractive index increment瑞利比Rayleigh ratio超瑞利比excess Rayleigh ratio粒子散射函数particle scattering function粒子散射因子particle scattering factor齐姆图Zimm plot散射的非对称性dissymmetry of scattering解偏抖擞用depolarization分级fractionation积淀分级precipitation fractionation萃取分级extraction fractionation色谱分级chromatographic fractionation柱分级column fractionation洗脱分级，淋洗分级elution fractionation热分级thermal fractionation凝胶色谱法gel chromatography摩尔质量清除极限molar mass exclusion limit溶剂梯度洗脱色谱法solvent gradient [elution] chromatography 分子量清除极限molecular weight exclusion limit洗脱体积elution volume普适标定universal calibration加宽函数spreading function链轴chain axis等同周期identity period链重复距离chain repeating distance晶体折叠周期crystalline fold period构象重复单元conformational repeating unit几何等效geometrical equivalence螺旋链helix chain构型无序configurational disorder链取向无序chain orientational disorder构象无序conformational disorder锯齿链zigzag chain双[ 股] 螺旋double stranded helix[ 分子 ] 链大尺度取向global chain orientation结晶聚合物crystalline polymer半结晶聚合物semi-crystalline polymer高分子晶体polymer crystal高分子微晶polymer crystallite结晶度degree of crystallinity, crystallinity高分子 [ 异质 ] 同晶现象macromolecular isomorphism 聚合物形态学morphology of polymer片晶lamella, lamellar crystal轴晶axialite树枝[状]晶体dendrite纤维晶fibrous crystal串晶构造shish-kebab structure球晶spherulite折叠链folded chain链折叠chain folding折叠表面fold surface折叠面fold plane折叠微区fold domain相邻再入模型adjacent re-entry model接线板模型switchboard model缨状微束模型fringed-micelle model折叠链晶体folded-chain crystal平行链晶体parallel-chain crystal伸展链晶体extended-chain crystal球状链晶体globular-chain crystal长周期long period近程构造short-range structure远程构造long-range structure成核作用nucleation分子成核作用molecular nucleation阿夫拉米方程Avrami equation主结晶primary crystallization后期结晶secondary crystallization外延结晶，附生结晶epitaxial crystallization外延晶体生长，附生晶体生长epitaxial growth织构texture液晶态liquid crystal state溶致性液晶lyotopic liquid crystal热致性液晶thermotropic liquid crystal热致性介晶thermotropic mesomorphism近晶相液晶smectic liquid crystal近晶中介相smectic mesophase近晶相smectic phase条带织构banded texture环带球晶ringed spherulite向列相nematic phase盘状相discotic phase解取向disorientation分聚segregation非晶相amorphous phase非晶区amorphous region非晶态amorphous state非晶取向amorphous orientation链段运动segmental motion亚稳态metastable state相分别phase separation亚稳相分别spinodal decompositionbimodal decomposition微相microphase界面相boundary phase相容性compatibility混容性miscibility不相容性incompatibility不混容性immiscibility增容作用compatiibilization最低临界共溶 ( 溶解 ) 温度lower critical solution temperature, LCST 最高临界共溶 ( 溶解 ) 温度upper critical solution temperature , UCST 浓度猝灭concentration quenching激基缔合物荧光excimer fluorescence激基复合物荧光exciplex fluorescence激光共聚焦荧光显微镜laser confocal fluorescence microscopy单轴取向uniaxial orientation双轴取向biaxial orientation, biorientation取向度degree of orientation橡胶态rubber state玻璃态glassy state高弹态elastomeric state黏流态viscous flow state伸长elongation高弹形变high elastic deformation回缩性，弹性复原nerviness拉伸比draw ratio, extension ratio泊松比Poisson's ratio杨氏模量Young's modulus本体模量bulk modulus剪切模量shear modulus法向应力normal stress剪切应力shear stress剪切应变shear strain折服yielding颈缩现象necking折服应力yield stress折服应变yield strain脆性断裂brittle fracture脆性开裂brittle cracking脆- 韧转变brittle ductile transition脆化温度brittleness(brittle) temperature延性破碎ductile fracture冲击强度impact strength拉伸强度tensile strength极限拉伸强度ultimate tensile strength抗撕强度tearing strength曲折强度flexural strength, bending strength 曲折模量bending modulus曲折应变bending strain曲折应力bending stress缩短开裂shrinkage crack剪切强度shear strength剥离强度peeling strength疲惫强度fatigue strength, fatigue resistance 挠曲deflection压缩强度compressive strength压缩永远变形compression set压缩变形compressive deformation压痕硬度indentation hardness洛氏硬度Rockwell hardness布氏硬度Brinell hardness抗刮性scrath resistance断裂力学fracture mechanics力学损坏mechanical failure应力强度因子stress intensity factor断裂伸长elongation at break折服强度yield strength断裂韧性fracture toughness弹性形变elastic deformation弹性滞后elastic hysteresis弹性elasticity弹性模量modulus of elasticity弹性答复elastic recovery不行答复形变irrecoverable deformation裂痕crack银纹craze形变；变形deformation永远变形deformation set节余变形residual deformation节余伸长residual stretch回弹，回弹性resilience延缓形变retarded deformation延缓弹性retarded elasticity可逆形变reversible deformation应力开裂stress cracking应力 - 应变曲线stress strain curve拉伸应变stretching strain拉伸应力弛豫tensile stress relaxation热历史thermal history热缩短thermoshrinking扭辫剖析torsional braid analysis，TBA 应力致白stress whitening应变能strain energy应变张量strain tensor节余应力residual stress应变硬化strain hardening应变融化strain softening电流变液electrorheological fluid假塑性pseudoplastic拉胀性auxiticity牛顿流体Newtonian fluid非牛顿流体non-Newtonian fluid宾汉姆流体Bingham fluid冷流cold flow牛顿剪切黏度Newtonian shear viscosity剪切黏度shear viscosity表观剪切黏度apparent shear viscosity剪切变稀shear thinning触变性thixotropy塑性形变plastic deformation塑性流动plastic flow体积弛豫volume relaxation拉伸黏度extensional viscosity黏弹性viscoelasticity线性黏弹性linear viscoelasticity非线性黏弹性non-linear viscoelasticity蠕变creep弛豫[作用]relaxation弛豫模量relaxation modulus蠕变柔量creep compliance热畸变温度heat distortion temperature弛豫谱relaxation spectrum推延[时间]谱retardation [time] spectrum弛豫时间relaxation time推延时间retardation time动向力学行为dynamic mechanical behavior动向黏弹性dynamic viscoelasticity热- 机械曲线thermo-mechanical curve动向转变dynamic transition储能模量storage modulus消耗模量loss modulus复数模量complex modulus复数柔量complex compliance动向黏度dynamic viscosity复数黏度complex viscosity复数介电常数complex dielectric permittivity介电消耗因子dielectric dissipation factor介电消耗常数dielectric loss constant介电弛豫时间dielectric relaxation time玻璃化转变glass transition玻璃化转变温度glass-transition temperature次级弛豫secondary relaxation次级转变secondary transition次级弛豫温度secondary relaxation temperature开尔文模型Kelvin model麦克斯韦模型Maxwell model时- 温叠加原理time-temperature superposition principle 玻耳兹曼叠加原理Boltzmann superposition principle 平移因子shift factorWLF公式WLF[Williams-Lendel-Ferry] equation融化温度均衡熔点物理老化光老化热老化热氧老化人工老化加快老化计算机模拟分子动力学模拟蒙特卡洛模拟softening temperatureequilibrium melting pointphysical ageingphotoageingthermal ageingthermo-oxidative ageingartificial ageingaccelerated ageingcomputer simulationmolecular dynamics simulation Monte Carlo simulation－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－聚合反响类：单体monomer官能度functionality均匀官能度average functionality双官能［基］单体bifunctional monomer三官能［基］单体trifunctional monomer乙烯基单体vinyl monomer1,1- 亚乙烯基单体，偏［二］代替乙烯单体vinylidene monomer1,2- 亚乙烯基单体，1,2- 二代替乙烯单体vinylene monomer双烯单体，二烯单体diene monomer极性单体polar monomer非极性单体non polar monomer共轭单体conjugated monomer非共轭单体non conjugated monomer活化单体activated monomer官能单体functional monomer大分子单体macromer, macromonomer环状单体cyclic monomer共聚单体comonomer聚合［反响］polymerization均聚反响homopolymerization低聚反响，齐集反响 ( 曾用名 )oligomerization调聚反响telomerization自觉聚合spontaneous polymerization预聚合prepolymerization后聚合post polymerization再聚合repolymerization铸塑聚合 ,浇铸聚合cast polymerization链［式］聚合chain polymerization烯类聚合，乙烯基聚合vinyl polymerization双烯［类］聚合diene polymerization加［成］聚［合］addition polymerization自由基聚合，游离基聚合 ( 曾用名 )free radical polymerization,radical polymerization控制自由基聚合，可控自由基聚合controlled radical polymerization， CRP活性自由基聚合living radical polymerization原子转移自由基聚合atom transfer radical polymerization， ATRP反向原子转移自由基聚合reverse atom transfer radical polymerization ， RATRP 可逆加成断裂链转移reversible addition fragmentation chaintransfer，RAFT氮氧 [ 自由基 ] 调控聚合nitroxide mediated polymerization稳固自由基聚合stable free radical polymerization， FRP自由基异构化聚合free radical isomerization polymerization自由基开环聚合radical ring opening polymerization氧化复原聚合redox polymerization无活性端聚合，死端聚合 ( 曾用名 )dead end polymerization光［致］聚合photo polymerization光引起聚合light initiated polymerization光敏聚合photosensitized polymerization四中心聚合four center polymerization电荷转移聚合charge transfer polymerization辐射引起聚合radiation initiated polymerization热聚合thermal polymerization电解聚合electrolytic polymerization等离子体聚合plasma polymerization易位聚合metathesis polymerization开环易位聚合ring opening metathesis polymerization，ROMP精美聚合precision polymerization环化聚合cyclopolymerization拓扑化学聚合topochemical polymerization均衡聚合equilibrium polymerization离子［型］聚合ionic polymerization辐射离子聚合radiation ion polymerization离子对聚合ion pair polymerization正离子聚合，阳离子聚合cationic polymerization碳正离子聚合carbenium ion polymerization,carbocationic polymerization假正离子聚合pseudo cationic polymerization假正离子活［性］聚合pseudo cationic living polymerization活性正离子聚合living cationic polymerization负离子聚合，阴离子聚合anionic polymerization碳负离子聚合carbanionic polymerization活性负离子聚合living anionic polymerization负离子环化聚合anionic cyclopolymerization负离子电化学聚合anionic electrochemical polymerization负离子异构化聚合anionic isomerization polymerization烯丙基聚合allylic polymerization活［性］聚合living polymerization两性离子聚合zwitterion polymerization齐格勒 - 纳塔聚合Ziegler Natta polymerization配位聚合coordination polymerization配位离子聚合coordinated ionic polymerization配位负离子聚合coordinated anionic polymerization配位正离子聚合coordinated cationic polymerization插入聚合insertion polymerization定向聚合，立构规整聚合stereoregular polymerization, stereospecific polymerization 有规立构聚合tactic polymerization全同立构聚合isospecific polymerization不对称引诱聚合asymmetric induction polymerization不对称选择性聚合asymmetric selective polymerization不对称立体选择性聚合asymmetric stereoselective polymerization对映［体］不对称聚合enantioasymmetric polymerization对映［体］对称聚合enantiosymmetric polymerization异构化聚合isomerization polymerization氢转移聚合hydrogen transfer polymerization基团转移聚合group transfer polymerization，GTP除去聚合elimination polymerization模板聚合matrix polymerization,template polymerization插层聚合intercalation polymerization无催化聚合uncatalyzed polymerization开环聚合ring opening polymerization活性开环聚合living ring opening polymerization不死的聚合immortal polymerization酶聚合作用enzymatic polymerization聚加成反响，逐渐加成聚合 ( 曾用名 )polyaddition偶联聚合coupling polymerization序列聚合sequential polymerization闪发聚合，俗称暴聚flash polymerization氧化聚合oxidative polymerization氧化偶联聚合oxidative coupling polymerization逐渐［增加］聚合step growth polymerization缩聚反响condensation polymerization，polycondensation酯互换型聚合transesterification type polymerization, ester exchange polycondensation自催化缩聚autocatalytic polycondensation均相聚合homogeneous polymerization非均相聚合heterogeneous polymerization相转变聚合phase inversion polymerization本体聚合bulk polymerization, mass polymerization固相聚合solid phase polymerization气相聚合gaseous polymerization,gas phase polymerization吸附聚合adsorption polymerization溶液聚合solution polymerization积淀聚合precipitation polymerization淤浆聚合slurry polymerization悬浮聚合suspension polymerization反相悬浮聚合reversed phase suspension polymerization 珠状聚合bead polymerization, pearl polymerization分别聚合dispersion polymerization反相分别聚合inverse dispersion polymerization种子聚合seeding polymerization乳液聚合emulsion polymerization无乳化剂乳液聚合emulsifier free emulsion polymerization 反相乳液聚合inverse emulsion polymerization微乳液聚合micro emulsion polymerization连续聚合continuous polymerization半连续聚合semicontinuous polymerization分批聚合，间歇聚合batch polymerization原位聚合in situ polymerization均相缩聚homopolycondensation活化缩聚activated polycondensation熔融缩聚melt phase polycondensation固相缩聚solid phase polycondensation体型缩聚three dimensional polycondensation界面聚合interfacial polymerization界面缩聚interfacial polycondensation环加成聚合cycloaddition polymerization环烯聚合cycloalkene polymerization环硅氧烷聚合cyclosiloxane polymerization引起剂initiator引起剂活性activity of initiator聚合催化剂polymerization catalyst自由基引起剂radical initiator偶氮［类］引起剂azo type initiator2,2 ′偶氮二异丁腈2,2'- azobisisobutyronitrile, AIBN过氧化苯甲酰benzoyl peroxide, BPO过硫酸盐引起剂persulphate initiator复合引起系统complex initiation system氧化复原引起剂redox initiator电荷转移复合物，电荷转移络合物charge transfer complex, CTC聚合加快剂，聚合促使剂polymerization accelerator光敏引起剂photoinitiator双官能引起剂bifunctional initiator， difunctional initiator三官能引起剂trifunctional initiator大分子引起剂macroinitiator引起 - 转移剂initiator transfer agent, inifer引起-转移-停止剂initiator transfer agent terminator, iniferter光引起转移停止剂photoiniferter热引起转移停止剂thermoiniferter正离子催化剂cationic catalyst正离子引起剂cationic initiator负离子引起剂ionioic initiator共引起剂coinitiator烷基锂引起剂alkyllithium initiator负离子自由基引起剂anion radical initiator烯醇钠引起剂alfin initiator齐格勒 - 纳塔催化剂Ziegler Natta catalyst过渡金属催化剂transition metal catalyst双组分催化剂bicomponent catalyst后过渡金属催化剂late transition metal catalyst金属络合物催化剂metal complex catalyst［二］茂金属催化剂metallocene catalyst甲基铝氧烷methylaluminoxane, MAOμ 氧桥双金属烷氧化物催化剂bimetallicμ -oxo alkoxides catalyst 双金属催化剂bimetallic catalyst桥基茂金属bridged metallocene限制几何构型茂金属催化剂constrained geometry metallocene catalyst 均相茂金属催化剂homogeneous metallocene catalyst链引起chain initiation热引起thermal initiation染料敏化光引起dye sensitized phtoinitiation电荷转移引起charge transfer initiation引诱期induction period引起剂效率initiator efficiency引诱分解induced decomposition再引起reinitiation链增加chain growth, chain propagation增加链端propagating chain end活性种reactive species活性中心active center连续自由基persistent radical聚合最高温度ceilling temperature of polymerization链停止chain termination双分子停止bimolecular termination初级自由基停止primary radical termination扩散控制停止diffusion controlled termination歧化停止disproportionation termination巧合停止coupling termination单分子停止unimolecular termination自觉停止spontaneous termination停止剂terminator链停止剂chain terminating agent假停止pseudotermination自觉停止self termination自由基捕捉剂radical scavenger旋转光闸法rotating sector method自由基寿命free radical lifetime凝胶效应gel effect自动加快效应autoacceleration effect链转移chain transfer链转移剂chain transfer agent尾咬转移backbitting transfer退化链转移degradation (degradative) chain transfer加成断裂链转移［反响］addition fragmentation chain transfer 链转移常数chain transfer constant①缓聚作用②延缓作用retardation阻聚作用inhibition缓聚剂retarder缓聚剂，阻滞剂retarding agent阻聚剂inhibitor封端［反响］end capping端基terminal group聚合动力学polymerization kinetics聚合热力学polymerization thermodynamics聚合热heat of polymerization共聚合［反响］copolymerization二元共聚合binary copolymerization三元共聚合ternary copolymerization竞聚率reactivity ratio自由基共聚合radical copolymerization离子共聚合ionic copolymerization无规共聚合random copolymerization理想共聚合ideal copolymerization交替共聚合alternating copolymerization恒［组］分共聚合azeotropic copolymerization 接枝共聚合graft copolymerization嵌段共聚合block copolymerization开环共聚合ring opening copolymerization共聚合方程copolymerization equation共缩聚copolycondensation逐渐共聚合step copolymerization同种增加homopropagation自增加self propagation交错增加cross propagation前尾端基效应penultimate effect交错停止cross terminationQ值Q valuee 值e valueQ,e 观点Q, e scheme序列长度散布sequence length distribution侧基反响reaction of pendant group扩链剂，链增加剂chain extender交联crosslinking化学交联chemical crosslinking自交联self crosslinking光交联photocrosslinking交联度degree of crosslinking硫化vulcanization固化curing硫［黄］硫化sulfur vulcanization促使硫化accelerated sulfur vulcanization过氧化物交联peroxide crosslinking无规交联random crosslinking交联密度crosslinking density交联指数crosslinking index解聚depolymerization①降解②退化degradation链断裂chain breaking解聚酶depolymerase细菌降解bacterial degradation生物降解biodegradation化学降解chemical degradation辐射降解断链降解自由基链降解无规降解水解降解热降解热氧化降解光降解光氧化降解力化学降解接枝聚合活化接枝接枝点链支化支化度接枝效率接枝度辐射引诱接枝嵌段聚合radiation degradationchain scission degradationfree radical chain degradation random degradationhydrolytic degradationthermal degradationthermal oxidative degradation photodegradationphoto oxidative degradationmechanochemical degradation graft polymerizationactivation graftinggrafting sitechain branchingdegree of branchingefficiency of graftinggrafting degreeradiation induced grafting block polymerization－－－－－－－－－－－－－－－－－－－－－－－－－－－通用类：高分子macromolecule, polymer超高分子supra polymer天然高分子natural polymer无机高分子inorganic polymer有机高分子organic polymer无机 - 有机高分子inorganic organic polymer金属有机聚合物organometallic polymer元素高分子element polymer高聚物high polymer聚合物polymer低聚物oligomer二聚体dimer三聚体trimer调聚物telomer预聚物prepolymer均聚物homopolymer无规聚合物random polymer无规卷曲聚合物random coiling polymer头- 头聚合物head-to-head polymer头- 尾聚合物head-to-tail polymer尾- 尾聚合物tail-to-tail polymer反式有规聚合物transtactic polymer。

unit1all polymers are built up from bonding together a single kind of repeating unit. At the other extreme ,protein molecules are polyamides in which n amino acide repeat units are bonded together. Although we might still call n the degree of polymerization in this case, it is less usefull,since an amino acid unit might be any one of some 20-odd molecules that are found in proteins. In this case the molecular weight itself,rather than the degree of the polymerization ,is generally used to describe the molecule. When the actual content of individual amino acids is known,it is their sequence that is of special interest to biochemists and molecular biologists.并不是所有的聚合物都是由一个重复单元链接在一起而形成的;在另一个极端的情形中,蛋白质分子是由n个氨基酸重复单元链接在一起形成的聚酰胺;尽管在这个例子中,我们也许仍然把n称为聚合度,但是没有意义,因为一个氨基酸单元也许是在蛋白质中找到的20多个分子中的任意一个;在这种情况下,一般是分子量本身而不是聚合度被用来描述这个分子;当知道了特定的氨基酸分子的实际含量,它们的序列正是生物化学家和分子生物学家特别感兴趣的地方;1,题目：Another striking ...答案：.that quantity low saturation bottom much absorb 2. 乙烯分子带有一个双键,为一种烯烃,它可以通过连锁聚合大量地制造聚乙烯,目前,聚乙烯已经广泛应用于许多技术领域和人们的日常生活中,成为一种不可缺少的材料;Ethylene molecule with a double bond, as a kind of olefins, it can make chain polymerization polyethylene, at present, polyethylene has been widely used in many fields of technology and People's Daily life, become a kind of indispensable materials.Unit31 The polymerization rate may be experimentally followed by measuring the changes in any of several properties of the system such as density,refractive index,viscosity, or light absorption. Density measurements are among the most accurate and sensitive of the techniques. The density increases by 20-25 percent on polymerization for many monomers. In actual practice the volume of the polymerizing system is measured by carrying out the reaction in a dilatometer. This is specially constructed vessel with a capillary tube which allows a highly accurate measurement of small volume changes. It is not uncommon to be able to detect a few hundredths of a percent polymerization by the dilatometer technique. 聚合速率在实验上可以通过测定体系的任一性质的变化而确定,如密度、折射率、黏度、或者吸光性能;密度的测量是这些技术中最准确最敏感的;对许多单体的聚合来说,密度增加了20%-25%;在实际操作中,聚合体系的体积是通过在膨胀计中进行反应测定的;它被专门设计构造了毛细导管,在里面可以对微小体积变化进行高精确度测量;通过膨胀计技术探测聚合过程中万分之几的变化是很常见的;Unti42 合成聚合物在各个领域中起着与日俱增的重要作用,聚合物通常是由单体通过加成聚合与缩合聚合制成的;就世界上的消耗量而论,聚烯烃和乙烯基聚合物居领先地位,聚乙烯、聚丙烯等属聚烯烃,而聚氯乙烯、聚苯乙烯等则为乙烯基聚合物;聚合物可广泛地用作塑料、橡胶、纤维、涂料、粘合剂等The synthetic polymers play an increasingly important role on a range of domains, which are synthesized by monomers through addition polymerization or condensation polymerization. Polyolefin and vinyl polymer have taken the lead in terms of the world consumption. PE, PP, etc. belong to the polyolefin, while PS, PVC etc. belong to the vinyl polymer. Polymers can be widely applied in plastics, rubbers, fibers, coatings, glues and so on.Unit7Ring-opening polymerizations proceed only by ionic mechanisms, the polymerization of cyclic ethers mainly by cationic mechanisms, and the polymerization of lactones andlactones by either a cationic or anionic mechanism. Important initiators for cyclic ethers and lactone polymerization are those derived from aluminum alkyl and zinc alkyl/water systems. It should be pointed out that substitution near the reactive group of the monomer is essential for the individual mechanism that operates effectively in specific cases; for example, epoxides polymerize readily with cationic and anionic initiators, while fluorocarbon epoxides polymerize exclusively by anionic mechanisms.开环聚合反应只能通过离子机理进行,环醚的开环聚合主要通过阳离子机理,而内酯和内酰胺的聚合物是通过阳离子或阴离子机理;对于环醚和内酯型聚合物很重要的引发剂是那些来自于烷基铝和烷基锌/水的体系;应该指出的是对于在活性基团附近有取代的单体,只能由单一机理,这一机理是在特定条件下的有效;1 Polymers can be classified into two main groups, addition polymers and ___condensation__ polymers. This classification is based on whether or not the repeating unit of the polymer contains the same atoms __as____ the monomer. The repeating unit of an addition polymer is identical _with/to____ the monomer, while condensation polymers contain __different/less___ because of formation of __compound/byproduct___ during the polymerization process. The corresponding polymerization processed would then be called addition polymerization and condensation polymerization. As was mentioned earlier, this classification can result ___in__ confusion, since it has been shown in later years that many important types of polymers can be _prepared by both addition and condensation processes. For example, polyesters, polyamides and polyurethanes are usually considered to be _condensation____ polymers, but they can be prepared by addition as well as by condensation reaction. Similarly, polyethylene normally considered an _addition_ polymer, can also be prepared by _condensation_ reaction.2. Answer the following questions in English1 What is chain polymerization Manyolefinicandvinylunsaturatedcompoundsareabletoformchain-likemacromoleculesthrougheliminationofdoublebond.2 Which kinds of monomers can carry out step-growth polymerization processThere are two kinds of monomers could carry out step-growth polymerization process. One ispolyfunctionalmonomers and the other isasinglemonomercontainingbothtypesoffunctional groups.3 What properties of polymers can be based on for measuring the molecular weightThe molecular weight of polymer could be measured based on colligativeproperties, lightscattering, viscosity, ultracentrifugation sedimentation.3. Please write out at least 10 kinds of polymers both in English and in Chinesethe corresponging chemical structure5 In general,head-to-tail addition is considered to be the predominant mode of propagation in all polymerizations;However,when the substitutes on the monomer are small and do not offer appreciable steric hindrance to the approaching radical or do not have a large resonance stabilizing effect,as in the case of fluorine atoms,sizable amounts of head-to-head propagation may occur. The effect of increasing polymerization temperature is to increase the amount of head-to-head placement;Increased temperature leads to less selective more random propagation but the effect is not large. Thus,the head-to-head content in poly vinyl acetate only increases from to percent when the polymerization temperature in increased from 30 to 90 ℃.通常在所有聚合物的链增长中,头-尾加成是主要方式;然而,当单体中的取代基很小对接近的自由基没有空间阻碍或没有较大的共振稳定作用,如氟原子,则有相当量的头头增长发生;提高聚合温度的影响是提高头-头排列的量;温度的提高导致较少的选择更多的无规增长,但影响不大;因而,在聚乙酸乙烯酯中,当聚合温度由30C提高到90C,头-头含量仅由%提高到%;2．Write out an abstract in English for the text in this unitPolymers with different structures present various properties. Usually, polymers are divided into three categories, . plastic, elastomer, fiber with different initial modulus range respectively. Polymers show quite different behaviors due to the different interchain forces in elastomer and fiber. However, with the advent of new techniques and mechanisms to improve the structure of polymers, polymers may be classified and named according to the mechanism, and their properties will largely depend on the structure. 3．Put the following words into Chineseentanglement 纠缠 irregularity 无规 sodium isopropylate异丙醇钠 permeability渗透性crystallite 微晶stoichiomertric balance 当量平衡fractionation分馏法light scattering光散射 matrix 基体 diffraction衍射4．Put the following words into English形态 morphology 酯化 esterification 异氰酸酯isocyanate杂质impurity 二元胺 diamine 转化率change ratio 多分散性polydispersity 力学性能mechanical property 构象conformation 红外光谱法infrared spectroscopy常见聚合物命名1常见杂链和元素有机聚合物类型Polyamide ----聚酰胺. Polyester----聚酯 Poly‘urethane ------聚氨酯 Polysiloxane -------聚硅氧烷Phenol-formaldehyde----酚醛.Urea-formaldehyde-----脲醛Polyureas------聚脲 Polysulfide -----聚硫Polyacetal-------聚缩醛 Polysulfone polysulphone------聚砜 Polyether---------聚醚第五单元Traditional methods of living polymerization are based on ionic, coordination or group transfer mechanisms.活性聚合的传统方法是基于离子,配位或基团转移机理;Ideally, the mechanism of living polymerization involves only initiation and propagation steps.理论上活性聚合的机理只包括引发和增长反应步骤;All chains are initiated at the commencement of polymerization and propagation continues until all monomer is consumed.在聚合反应初期所有的链都被引发,然后增长反应继续下去直到所有的单体都被消耗殆尽;A type of novel techniques for living polymerization, known as living possibly use “controlled” or “mediated” radical polymerization, is developed recently. 最近开发了一种叫做活性自由基聚合的活性聚合新技术;The first demonstration of living radical polymerization and the current definition of the processes can be attributed to Szwarc.第一个活性自由基聚合的证实及目前对这一过程的解释或定义,应该归功于Szwarc;Up to now, several living radical polymerization processes, including atom transfer radical polymerization ATRP, reversible addition-fragmentation chain transfer polymerization RAFT, nitroxide-mediated polymerization NMP, etc., have been reported one after another.到目前为止,一些活性自由基聚合过程,包括原子转移自由基聚合,可逆加成-断裂链转移聚合,硝基氧介导聚合等聚合过程一个接一个被报道;The mechanism of living radical polymerization is quite different not only from that of common radical polymerization but also from that of traditional living polymerization. 活性自由基聚合的机理不仅完全不同于普通自由基聚合机理,也不同于传统的活性聚合机理;It relies on the introduction of a reagent that undergoes reversible termination with the propagating radicals thereby converting them to a following dormant form：活性自由基聚合依赖于向体系中引入一种可以和增长自由基进行可逆终止的试剂,形成休眠种：The specificity in the reversible initiation-termination step is of critical importance in achieving living characteristics.这种特殊的可逆引发-终止反应对于获得分子链活性来说具有决定性的重要意义;This enables the active species concentration to be controlled and thus allows such a condition to be chosen that all chains are able to grow at a similar rate if not simultaneously throughout the polymrization.可逆引发终止使活性中心的浓度能够得以控制;这样就可以来选择适宜的反应条件,使得在整个聚合反应过程中只要没有平行反应所有的分子链都能够以相同的速度增长;This has, in turn, enabled the synthesis of polymers with controlled composition, architecture and molecular weight distribution.这样就可以合成具有可控组成,结构和分子量分布的聚合物;They also provide routes to narrow dispersity end-functional polymers, to high purity block copolymers, and to stars and other more complex architecture.这些还可以提供获得狭窄分布末端功能化聚合物,高纯嵌段共聚物,星型及更复杂结构高分子的合成方法;The first step towards living radical polymerization was taken by Ostu and his colleagues in 1982.活性自由基聚合是Ostu和他的同事于1982年率先开展的;In 1985, this was taken one step further with the development by Solomon et al. of nitroxide-mediated polymerization NMP.1985年,Solomon等对氮氧化物稳定自由基聚合的研究使活性自由基聚合进一步发展;This work was first reported in the patent literature and in conference papers but was not widely recognized until 1993 when Georges et al. applied the method in the synthesis of narrow polydispersity polystyrene.这种方法首先在专利文献和会议论文中报道,但是直到1993年Georges等把这种方法应用在窄分子量分布聚苯乙烯之后,才得以广泛认知;The scope of NMP has been greatly expended and new, more versatile, methods have appeared. NMP的领域已经得到很大的延展,出现了新的更多样化的方法;The most notable methods are atom transfer radical polymerization ATRP and polymerization with reversible addition fragmentation RAFT.最引人注目的方法是原子转移自由基聚合和可逆加成断裂聚合;到2000年,这个领域的论文已经占所有自由基聚合领域论文的三分之一;如图所示;Naturally, the rapid growth of the number of the papers in the field since 1995 ought to be almost totally attributable to development in this area. 、自然地,纸的数量的迅速增长在领域,因为1995在这个区域应该是几乎完全可归属的到发展;UNIT9 Structure and Properties of Polymers 聚合物的结构和性质Most conveniently, polymers are generally subdivided in three categories, namelyviz., plastics, rubbers and fibers. 很方便地,聚合物一般细分为三种类型,就是塑料,橡胶和纤维; In terms of initial elastic modules, rubbers ranging generally between 106 to 107dynes/cm2, represent the lower end of the scale, while fibers with high initial modjulai, of 1010 to 1011dynes/cm2 are situated on the upper end of the scale; plastics, having generally an initial elastic modulus of 108 to 109dynes/cm2, lie in-between. 就初始弹性模量而言,橡胶一般在 6到107达因平方厘米,在尺度的低端, 10到1011达因平方厘米,尺度的高端,而纤维具有高的初始模量, 达到10到1011达因平方厘米,尺度的高端,塑料的弹性模量一般在 8到109达因平方厘米,在尺度的中间As is found in all phases of polymer chemistry, there are many exceptions to this categorization. 正如高分子化学的各个部分都可以看到的那样,在高分子化学的所有阶段,我们都可以发现,这种分类方法有许多例外的情况;An elastomer or rubber results from a polymer having relatively weak interchain forces and high molecular weights. 弹性体是具有相对弱的链之间作用力和高分子量的聚合物; When the molecular chains are “straightened out” or stretched by a process of extension, they do not have sufficient attraction for each other to maintain the oriented state and will retract once the force is released. This is the basis of elastic behavior. 当通过一个拉伸过程将分子链拉直的时候,分子链彼此之间没有足够的相互吸引力来保持其取向状态,作用力一旦解除,将发生收缩;这是弹性行为的基础;However, if the interchain forces are very great, a polymer will make a good fiber. 然而,如果分子链之间的力非常大,聚合物可以用做纤维;Therefore, when the polymer is highly stretched, the oriented chain will come under the influence of the powerful attractive forces and will “crystallize” permanently in a more or less oriented matrix. 因此,当聚合物被高度拉直的时候,取向分子链在不同程度取向的母体中将受强引力的影响而“永久地结晶;These crystallization forces will then act virtually as crosslinks, resulting in a material of high tensile strength and high initial modulus, ., a fiber. 而后,这些结晶力实际上以交联方式作用,产生高拉伸强度和高初始模量的材料,如纤维;Therefore, a potential fiber polymer will not become a fiber unless subjected to a “drawing” process, ., a process resulting in a high degree of intermolecular orientation. 因此,一个可能的潜在的纤维高分子不会变成纤维,除非经历一个拉伸过程, 即, 这导致分子间高度取向的拉伸过程;Crosslinked species are found in all three categories and the process of crosslinking may change the cited characteristics of the categories. 交联的种类在所有三种类型塑料,橡胶,纤维中找到,而交联过程可以改变分类的引用特征;Thus, plastics are known to possesspzes a marked range of deformability in the order of 100 to 200%; they do not exhibit this property when crosslinked, however. 因此,我们熟知塑料具有的形变能力大约在100-200%范围内,然而当交联发生时塑料不能展示这个性能; Rubber, on vulcanization, changes its properties from low modulus, low tensile strength, low hardness, and high elongation to high modulus, high tensile strength, high hardness, and low elongation. 对橡胶而言,硫化可以改变其性质,从低模量,低拉伸强度,低硬度及高拉伸率到高模量,高拉伸强度,高硬度及低拉伸率;Thus, polymers may be classified as noncrosslinked and crosslinked, and this definition agrees generally with the subclassification in thermoplastic and thermoset polymers. 这样,聚合物可以分为非交联和交联的,这个定义与把聚合物细分为热塑性和热固性聚合物相一致; From the mechanistic point of view, however, polymers are properly divided into addition polymers and condensation polymers. Both of these species are found in rubbers, plastics, and fibers. 然而,从反应机理的观点看,聚合物可以分成加聚物和缩聚物;这些种类聚合物在塑料,橡胶和纤维中都可以找得到;In many cases polymers are considered from the mechanistic point of view. Also, the polymer will be named according to its source whenever it is derived from a specific hypothetical monomer, or when it is derived from two or more components which are built randomly into the polymer. 在许多情况下,聚合物可以从反应机理的角度考虑分类; 每当聚合物来自于一个假象单体,或来自于两个或两个以上组成物无规则构建聚合物时,也可以根据聚合物的来源来命名; This classification agrees well with the presently used general practice. 这种分类方法与目前实际情况相符合;When the repeating unit is composed of several monomeric components following each other in a regular fashion, the polymer is commonly named according to its structure. 当重复单元由几个单体组成物规则排布,聚合物通常根据它的结构来命名;It must be borne in mind that, with the advent of Ziegler-Natta mechanisms and new techniques to improve and extend crystallinity, and the closeness of packing of chains, many older data given should be critically considered in relation to the stereoregular and crystalline structure. 必须记住,随着Ziegler-Natta机理,以及提高结晶度和链堆砌紧密度新技术的出现,对许多过去已经得到的关于空间结构和晶体结构旧的资料,应当批判地接受;The properties of polymers are largely dependent on the type and extent of both stereoregularity and crystallinity. As an example, the densities and melting points of atactic and isotactic species are presented in Table . 聚合物的性质主要依靠立体规整性和结晶度的类型和程度;如,无规立构和全同立构物质的密度和熔点展示在表中 ;UNIT11 Functional PolymersFunctional polymers are macromolecules to which chemically functional groups are attached; they have the potential advantages of small molecules with the same functional groups. 功能聚合物是具有化学功能基团的大分子,这些聚合物与具有功能聚合物是具有化学功能基团的大分子, 相同功能基团的小分子一样具有潜在的优点;Their usefulness is related both to the functional groups and to the nature of the polymers whose characteristic properties depend mainly on the extraordinarily large size of the molecules.它们的实用性不仅与功能基团有关,而且与巨大分子尺寸带来的聚合物特性有关;The attachment of functional groups to a polymer is frequently the first step towards the preparation of a functional polymer for a specific use. 把功能基团连接到聚合物上常常是制备特殊用途功能高分子的第一步;However, the proper choice of the polymer is an important factor for successful application. 然而,对成功应用而言,选择适当的聚合物是的一个重要因素;In addition to the synthetic aliphatic and aromatic polymers, a wide range of natural polymers have also been functionalized and used as reactive materials. 除了合成的脂肪组和芳香组聚合物之外,许多天然高分子也被功能化,被用做反应性材料;Inorganic polymers have also been modified with reactive functional groups and used in processes requiring severesi’vi service conditions. 无机聚合物也已经用反应功能基团改性,被用于要求耐用条件的场合;In principle, the active groups may be part of the polymer backbone or linked to a side chain as a pendant group either directly or viavai a space rs’peis group. 理论上讲,活性基团可以是聚合物主链上的一部分,或者直接连接到侧链或通过一个中间基团的侧基;A required active functional group can be introduced onto a polymeric support chain 1 by incorporation during the synthesis of the support itself through polymerization or copolymerization of monomers containing the desired functional groups, 2 by chemical modification of a nonfunctionalized performed support matrix and 3 by a combination of 1 and 2. 所需的活性功能基团可以通过几种方法引入到聚合物主链上, 1在主链的合成过程中,通过聚合或共聚合含有理想功能基团的单体来获得,2通过对已有的非功能化主链进行化学改性的方法,3通过结合1和2来获得;Each of the two approaches has its own advantages and disadvantages, and one approach may be preferred for the preparation of a particular functional polymer when the other would be totally impractical.两种途径中的每一种都有自身的优点和缺点,对特殊功能聚合物的制备而言,当其他方法都无法实现时,所选的方法或许是更合适的;The choice between the two ways to the synthesis of functionalized polymers depends mainly on the required chemical and physical properties of the support for a specific application. 功能聚合物合成的两种方法中,如何选择主要取决于特殊应用要求的主链聚合物的化学和物理性质;Usually the requirements of the individual system must be thoroughly examined in order to take full advantage of each of the preparative techniques. 为了充分利用每种制备方法,必须全面地考察独立体系的要求;Rapid progress in the utilization of functionalized polymeric materials has been noted in the recent past. 近年来,功能化聚合物材料的使用方面有了飞速的发展;Interest in the field is being enhanced due to the possibility of creating systems that combine the unique properties of conventional active moieties and those of high molecular weight polymers. 由于能够制造出来兼有活性官能团特性和高分子量聚合物性能的功能聚合物,所以,人们对功能聚合物这个领域的兴趣与日俱增;The successful utilization of these polymers are based on the physical form, solution behavior, porosity, chemical reactivity and stability of the polymers. 这些聚合物的成功利用,基于功能聚合物的物理形态,溶液行为,空隙率,化学活性及稳定性;The various types of functionalized polymers cover a broad range of chemical applications, including the polymeric reactants, catalysts, carriers, surfactants, stabilizers,ionexchange resins, etc.各种功能化聚合物类型覆盖化学应用的宽广领域,包括聚合物试剂,催化剂, 载体,表面活性剂,稳定剂,离子交换树脂等;In a variety of biological and biomedical fields, such as the pharmaceutical, agriculture, food industry and the like, they have become indispensable materials, especially in controlled release formulation of drugs and agrochemicals. 在生物学及生物医学领域中,如药物,农业,食品工业等, 在生物学及生物医学领域中,如药物,农业,食品工业等,功能聚合物是不可缺少的材料,尤其在药物和农药的控制释放配方上;Besides, these polymers are extensively used as the antioxidants, flame retardants, corrosion inhibitors, flocculating agents, antistatic agents and the other technological applications. 此外,这些聚合物被广泛地用做抗氧化剂,阻燃剂,缓蚀剂, 絮凝剂,抗静电剂及其他技术应用;In addition, the functional polymers possessp’zes broad application prospects in the high technology area as conductive materials, photosensitizers, nuclear track detectors, liquid crystals, the working substances for storage and conversion of solar energy, etc. 另外,功能化聚合物在高科技领域具有广阔的应用前景; 如导电材料,光敏剂,核径迹探测器,液晶,用于太阳能等的转化与储存的工作物质;第十二单元实验室制备氨基树脂氨基树脂是由氨基衍生物和醛在酸性或碱性条件下反应生产得到的其中最重要最具代表性的物质是脲醛树脂和蜜胺树脂; 药品：尿素,福尔马林37%,乙醇,2N NaOH, NaOH溶液,1N标准NaOH溶液,1N标准HCl溶液,冰醋酸,糠醇,三乙醇胺,木粉,磷酸钙,氯化铵, H2SO4溶液,Na 2SO3,1%乙醇百里酚酞指示剂溶液,三聚氰胺,甘油和单羟甲基脲; 装置：烧瓶和烧杯,500ml的三口烧瓶,加热套,机械搅拌器,冷凝器,迪安—斯达克塔分水器,烘箱,广泛试纸,试管,250mL的容量烧瓶,冰浴,10ml 的移液管,滴管,油浴和广口瓶; 酸性条件下制备脲醛树脂：为了证明尿素和甲醛在酸性条件下的迅速反应,将5 g尿素和6 mL福尔马林在试管中混合,振荡试管直到尿素全部溶解;滴加4滴 N H2SO4以调节溶液pH到4,观察析出沉淀所需要的时间,取出部分沉淀并比较此沉淀以及单羟甲基脲样品在水中的溶解性;制备脲醛树脂粘合剂：将600g1mole尿素和137g福尔马林放入500ml三口烧瓶中,并安装好机械搅拌器和回流冷凝器,通过用广泛试纸测定用2NNaOH溶液把混合物PH值调至7~~8,然后将混合物回流2小时;1每隔半小时用下面的方法测定一次混合物中的自由甲醛含量,直到水完全脱除为止;2 当混合物回流2小时后,将迪安—斯达克塔分水器安装在烧瓶和回流冷凝器之间 ;大约有40ml水被蒸馏,用5滴冰醋酸将溶液酸化；将44g糠醇和的三乙醇胺加入到反应混合液中,加热此溶液到90℃并恒温15分钟;将混合物冷却到室温;取出15g的树脂样品和由1g木粉,磷酸钙和氯化铵组成的硬化剂混合 ;将混合物进行室温固化;3将剩下的没有加工硬化剂的树脂放入广口瓶中并提交给实验导师;自由甲醛含量的测定：自由甲醛含量的测定：准备250mL 1N Na2SO3溶液,并中和该溶液,从而使其产生淡蓝色的百里酚酞指示剂溶液;在250ml锥形瓶中加入重为2到3克的树脂样品到100mL的水中,摇晃锥形瓶使锥形瓶内的溶液充分溶解;如果树脂不能溶解,加入乙醇可以帮助溶解;在冰浴中使溶液的温度下降到4℃,加25mL的1M Na2SO3溶液在100mL的烧瓶中,用移液管移取10ml标准的1N HCl溶液到烧瓶中,降温至4℃;加10-15滴百里酚酞指示剂溶剂到样品烧瓶中,调整溶液的颜色至淡蓝色;用冷水冷却以后迅速地转移酸式亚硫酸盐溶液到样品烧瓶中;4滴定溶液到百里酚酞的终点标准1N NaOH 溶液;CH2O+Na2SO3+H2O →CH2OHSO3-Na++NaOH通过中和树脂溶液的HCl溶液的量来测定自由甲醛的百分含量;三聚氰胺甲醛树脂的制备：在一个500ml的配置有机械搅拌器和一个冷凝器的反应器中加入63g 的三聚氰胺和122g的福尔马林37%;混合物回流40分钟;%自由甲醛需要每隔十分钟测定一次;自由甲醛的测定步骤如上所述;样品经过20分钟加热后,在烧瓶和冷凝器间插入一个迪安—斯达克分水器,从而有10mL的水被蒸馏掉;把未固化的样品放入螺丝帽的坛子中,连同固化的树脂一起交给实验指导老师;15单元到目前为止大多数的PVC生产通过悬浮聚合;在这个过程中,氯乙烯单体悬浮液体滴,在连续水相剧烈的搅拌和保护胶体的悬浮剂;使用单体溶自由基引发剂polymeri等自下而上发生在悬浮液滴内,通过一个机制,已被证明相当于本体聚合;商业植物是基于批量反应堆,这增加了支持的大小,多年来;原来的工厂建于1940年代通常由IOOO 加仑反应堆;在1960年代和1950年代这t0 3000一5000加仑和增加随后,在1970年代初,29000加仑反应堆系统开发的胫完全②,t0 44000加仑200立方米的德国公司Huls;目前一些新的工厂正在建造的反应堆由不到isooo加仑容量,有一个批处理大小约25吨单体;小型反应堆通常衬玻璃给光洁度,抵制存款的搁置在墙上;~大反应堆通常的抛光不锈钢;氯乙烯的聚合反应是一个放热反应的能力,移走热量通常试图减少反应时间的限制因素;随着规模的反应堆已经增加了表面积体积比,因此加重这一问题;内部冷却线圈通常不用作吸引存款和很难清洁,从而对产品性能有不利影响;问题通常是克服使用冷冻水或回流冷凝器的装置,通过氯乙烯单体的连续回流;利用其潜热冷却的目的;一个简单的悬浮聚合配方可能包含以下成分:冷水通常是首先向反应堆虽然有时预热;然后添加pH值调节剂紧随其后的是分散剂的形式解决方案;发起者年代立即撒到水相的表面密封反应堆然后撤离前去除氧,因为这可以增加聚合时间,影响产品性能;当引发反应完成乙烯氯化物被指控和加热反应堆的内容开始;反应但真正的,产品分子量的主要控制因素;通常是在50——70 'c导致反应堆压力范围100 - 165 psi;趋势是朝着大的操作只打开关闭反应堆维护或可能偶尔打扫道;”:在这种情况下所有的原料都是负责解决方案或分散体,一般不需要疏散的一步;当达到所需的转换了,通常75%一95%,反应可以如果需要化学short-stopped和剩余的大部分单体恢复;他产品泥浆然后剥下来非常低的残留氯乙烯治疗-水平表示“状态”姆温度升高,在反应堆或类似容器,或接触蒸汽在逆流多平台汽提塔;然后脱水离心法和由此产生的泥浆湿饼乾,多级闪蒸干燥机一般,虽然各种不同的干燥类型使用不同的生产;干燥后,产品是通过某种剥皮屏幕去除无关的大颗粒装袋之前或装载散装油轮;—T 16 Styrene-Butadiene Copolymer第十六单元丁二烯-苯乙烯共聚物合成橡胶工业,以自由基乳液过程为基础,在第二次世界大战期间几乎很快地形成;那时,丁苯橡胶制造的轮胎性能相当优越,使天然橡胶在市场黯然失色;丁苯橡胶的标准制法是组分重量分数组分重量分数丁二烯72 过硫酸钾苯乙烯25 肥皂片十二烷基硫醇水180 混合物在搅拌下50℃加热,每小时转化5%～6%,在转化率达70%～75%时通过加入“终止剂”聚合反应终止,例如对苯二酚大约的重量百分含量,抑制自由基并避免过量支化和微凝胶形成;未反应的丁二烯通过闪蒸去除,苯乙烯在萃取塔中通过蒸汽萃取剥离;在加入抗氧剂后,例如N-甲基-β-萘胺的重量百分含量,加入盐水,其次加入稀释的硫酸或硫酸铝后乳液凝胶;凝胶碎片被洗涤、干燥。