本文選題：共聚合反應(yīng)　切入點(diǎn)：氯乙烯缺陷結(jié)構(gòu)　出處：《河北工業(yè)大學(xué)》2004年碩士論文

【摘要】： 隨著計(jì)算機(jī)技術(shù)的飛速發(fā)展，計(jì)算機(jī)與高分子科學(xué)之間的相互滲透已經(jīng)成為高分子研究的又一亮點(diǎn)。計(jì)算機(jī)模擬既可預(yù)測分子結(jié)構(gòu)行為和宏觀物質(zhì)性質(zhì)，又可深化研究結(jié)果，提高工作效率。本文主要從四個方面研究了計(jì)算機(jī)在高分子科學(xué)上的應(yīng)用，利用可視化程序語言Visual Basic 6.0編制了不同功能的軟件。 第一方面：利用計(jì)算機(jī)，通過截距斜率法、YBR法、JJ法(直線交叉法)、TM法(非線性最小二乘法)和動態(tài)搜索法測算共聚體系競聚率，其中TM法和動態(tài)搜索法獲得比較精確的競聚率結(jié)果。由競聚率的數(shù)據(jù)，，還給出共聚物組成曲線。利用計(jì)算機(jī)，通過共聚積分方程，描繪出共聚反應(yīng)體系隨著聚合轉(zhuǎn)化率的變化，單體組成、共聚體瞬時組成和共聚體平均組成的關(guān)系曲線。此外，還對共聚物鏈段分布和鏈節(jié)分布情況進(jìn)行了模擬，給出了它們的分布曲線。 第二方面：用Monte Carlo法，模擬了聚氯乙烯缺陷結(jié)構(gòu)的產(chǎn)生情況。模擬結(jié)果表明，過高的轉(zhuǎn)化率必然導(dǎo)致形成更多的缺陷結(jié)構(gòu)，使樹脂品質(zhì)下降。建議PVC生產(chǎn)廠家，氯乙烯的轉(zhuǎn)化率以不超過0.85～0.87為宜。 第三方面：利用熱重分析法研究了聚合物的熱分解動力學(xué)。先用三次樣條函數(shù)對熱失重?cái)?shù)據(jù)進(jìn)行了插值和微分，再通過二元回歸求出了它的熱分解動力學(xué)參數(shù)A、n及E，以上便是微商法的求解過程。它具有簡潔、快速等優(yōu)點(diǎn)。通過熱分解動力學(xué)參數(shù)可以綜合地、定量地表征聚合物的熱穩(wěn)定性，并且可確定熱分解速率與溫度之間的關(guān)系，給出熱分解速率的峰值，對實(shí)際應(yīng)用有指導(dǎo)意義。 第四方面：基團(tuán)貢獻(xiàn)法為高分子新產(chǎn)品的開發(fā)研究提供了較好的輔助手段。利用高級編程語言Visual Basic語言編寫的計(jì)算機(jī)軟件，界面可視友好，使用方便，運(yùn)算快速。此方法尤其適用于無定型聚合物，而對分子間具有較強(qiáng)作用力的聚合物，預(yù)測的誤差較大。此外，由于該法僅提供了33種結(jié)構(gòu)單元的有關(guān)參數(shù)，難以組合復(fù)雜結(jié)構(gòu)的高分子，在使用范圍上受到一定限制。 第五方面：利用關(guān)聯(lián)指數(shù)法對聚合物某些性能進(jìn)行了預(yù)測，這些性能包括：摩爾體積，溶解度參數(shù)，表面張力，折光指數(shù)，介電常數(shù)及玻璃化轉(zhuǎn)變溫度等。本文在大量預(yù)測聚合物性能基礎(chǔ)上，把預(yù)測值與實(shí)驗(yàn)值比較，采用相關(guān)系數(shù)和標(biāo)準(zhǔn)偏差評估了預(yù)測過程的精度。本文合成了新型的含氟聚酰亞胺，提出了預(yù)測這類聚酰亞胺玻璃化轉(zhuǎn)變溫度的回歸方程。總的說來，關(guān)聯(lián)指數(shù)法應(yīng)用范圍比基團(tuán)貢獻(xiàn)法廣泛，對聚合物性能的預(yù)測精度也較高，但操作比較繁瑣。
[Abstract]:With the rapid development of computer technology, the mutual penetration between computer and polymer science has become another bright spot in polymer research.Computer simulation can not only predict the molecular structure behavior and macroscopic material properties, but also deepen the research results and improve the working efficiency.In this paper, the application of computer in polymer science is studied from four aspects, and the software with different functions is programmed by the visual program language Visual Basic 6.0.On the one hand, using the computer, the reactivity rate of copolymerization system is calculated by means of intercept slope method and YBR method / JJ method (linear cross method / TM method) and dynamic search method.Among them, TM method and dynamic search method get more accurate results of reactivity rate.Based on the data of reactivity rate, the composition curve of copolymers was given.By using the computer and the integral equation of copolymerization, the relationship curves of the copolymerization reaction system with the polymerization conversion, the monomer composition, the instantaneous composition of the copolymerization and the average composition of the copolymer are described.In addition, the distribution of copolymers was simulated and their distribution curves were given.Second, Monte Carlo method is used to simulate the formation of PVC defect structure.The simulation results show that too high conversion will result in more defective structures and lower resin quality.It is suggested that the conversion rate of vinyl chloride should not exceed 0.85 or 0.87 for PVC manufacturers.Third, thermogravimetric analysis was used to study the thermal decomposition kinetics of polymers.The cubic spline function is first used to interpolate and differentiate the thermogravimetric data, and then the thermal decomposition kinetic parameters An and E are obtained by binary regression. The above is the process of solving the differential quotient method.It has the advantages of simplicity and speed.The thermal stability of the polymer can be quantitatively characterized by the kinetic parameters of thermal decomposition, and the relationship between the thermal decomposition rate and the temperature can be determined. The peak value of the thermal decomposition rate is given, which is of great significance for practical application.The fourth aspect: group contribution method provides a good auxiliary method for the development and research of new polymer products.The computer software written by Visual Basic language has the advantages of friendly interface, convenient use and fast operation.This method is especially suitable for amorphous polymers, and the prediction error is large for polymers with strong intermolecular forces.In addition, it is difficult to combine polymer with complex structure because only 33 kinds of structural elements are provided by the method, and the range of application is limited to a certain extent.Fifth, some properties of polymers were predicted by correlation index method, including molar volume, solubility parameters, surface tension, refractive index, dielectric constant and glass transition temperature.In this paper, based on a large number of predicted polymer properties, the accuracy of the prediction process is evaluated by using the correlation coefficient and standard deviation, comparing the predicted values with the experimental values.A new fluorinated polyimide was synthesized and a regression equation was proposed to predict the glass transition temperature of the polyimide.In general, the correlation index method is more widely used than the group contribution method, and the prediction accuracy of polymer properties is higher, but the operation is more complicated.
【學(xué)位授予單位】：河北工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2004
【分類號】：O631

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