本文選題：陰離子聚合 + 水解聚合��； 參考：《浙江理工大學(xué)》2016年碩士論文

【摘要】：聚酰胺6(PA6)是一種用途廣泛的聚合物材料,作為纖維主要應(yīng)用于紡織服裝、輪胎簾子線等方面,作為五大工程塑料之一,主要應(yīng)用于機(jī)械、化工、通訊等領(lǐng)域。PA6聚合機(jī)理分為水解開環(huán)聚合與陰離子開環(huán)聚合,兩者反應(yīng)條件截然不同,水解聚合為逐步聚合,采用水作為開環(huán)劑,并于聚合后期排水以控制分子量;陰離子聚合為連鎖聚合,須嚴(yán)格控制水、酸在極低的含量。水解聚合為逐步聚合,產(chǎn)物分子鏈端不含活性中心;陰離子聚合為活性聚合,具有反應(yīng)速度快、分子量高的特性。本文結(jié)合水解開環(huán)聚合與陰離子開環(huán)聚合兩種聚合機(jī)理,以熔體流動(dòng)性較好的水解聚合PA6為基體,通過添加己內(nèi)酰胺(CL)單體及陰離子聚合引發(fā)劑與活化劑,在PA6基體熔點(diǎn)以上溫度反應(yīng)得到APA6/HPA6復(fù)合產(chǎn)物。為確定引發(fā)劑與活化劑的用量,以及合適的反應(yīng)溫度與時(shí)間,先后進(jìn)行了靜態(tài)澆鑄與動(dòng)態(tài)混合、常規(guī)工業(yè)澆鑄溫度與目標(biāo)高溫下單純陰離子聚合實(shí)驗(yàn),優(yōu)化得到適合目標(biāo)反應(yīng)的條件。靜態(tài)澆鑄實(shí)驗(yàn)表明,以己內(nèi)酰胺鈉(C10)為引發(fā)劑,雙�；瘍�(nèi)酰胺-1,6-己二胺(C20)為活化劑的陰離子聚合體系在常規(guī)澆鑄溫度(160oС)及相對(duì)較高的溫度(220oС)下均得到了陰離子聚合PA6產(chǎn)物,FT-IR、TGA、DSC等測(cè)試結(jié)果表明該陰離子聚合助劑體系同樣適合較高的反應(yīng)溫度,熱穩(wěn)定性測(cè)試表明CL/C10/C20質(zhì)量比為100/2.0/2.0時(shí),產(chǎn)物小分子失重比例最低,同時(shí)考慮后續(xù)進(jìn)行動(dòng)態(tài)混合時(shí)助劑可能存在的少量熱損失,故同將CL/C10/C20為100/2.5/2.5列為適合比例。采用轉(zhuǎn)矩流變儀混煉平臺(tái)作為動(dòng)態(tài)混合反應(yīng)場(chǎng)所,通過一步加料法混合反應(yīng)得到兩種助劑比例、四種反應(yīng)溫度下的陰離子聚合PA6。FT-IR測(cè)試表明產(chǎn)物具有典型聚酰胺特征峰,可萃取物含量測(cè)試表明單體轉(zhuǎn)化率均在90%左右,熱性能測(cè)試表明產(chǎn)物中含有不同聚合程度組分,100/2.5/2.5比例產(chǎn)物結(jié)晶度較高,單體剩余較少,反應(yīng)溫度過低與過高將影響熔體流動(dòng)性、體系交聯(lián)程度,因而選擇230oС作為目標(biāo)反應(yīng)溫度,反應(yīng)時(shí)間不宜過長(zhǎng),視實(shí)時(shí)扭矩變化而定。按既定助劑比例、溫度進(jìn)行水解聚合PA6熔體中的己內(nèi)酰胺陰離子聚合實(shí)驗(yàn),同樣采用轉(zhuǎn)矩流變儀及一步加料的方式制備水解聚合PA6/陰離子聚合PA6復(fù)合產(chǎn)物。FT-IR測(cè)試表明復(fù)合產(chǎn)物保持聚酰胺的特征峰,DSC測(cè)試表明隨著己內(nèi)酰胺初始含量的增加,復(fù)合產(chǎn)物結(jié)晶度呈下降趨勢(shì),結(jié)晶峰由窄變寬,熔融溫度下降,TGA測(cè)試表明己內(nèi)酰胺含量較高時(shí)存在明顯的三個(gè)熱失重階段,表明陰離子聚合的發(fā)生,可萃取物含量測(cè)試表明隨著己內(nèi)酰胺含量的減小,轉(zhuǎn)化率呈上升趨勢(shì),最高接近50%,相對(duì)黏度測(cè)試表明轉(zhuǎn)化率最高的樣品相對(duì)黏度稍高于空白樣品。推測(cè)聚合體系在轉(zhuǎn)矩流變儀中存在較為嚴(yán)重的熱氧降解,端基含量測(cè)試表明反應(yīng)后空白樣品羧基含量增加,降解產(chǎn)物影響了原本可能進(jìn)行至更高程度的陰離子聚合反應(yīng),引入與己內(nèi)酰胺及PA6相容性較差的線性低密度聚乙烯作為對(duì)照,同時(shí)也對(duì)比了未經(jīng)工業(yè)萃取(含8.88%)的水解聚合PA6作為基體時(shí)的聚合情況,實(shí)時(shí)扭矩變化及反應(yīng)前后己內(nèi)酰胺含量測(cè)試結(jié)果表明,存在熱氧降解的情況下,PA6與PE熔體作為反應(yīng)基體時(shí),己內(nèi)酰胺均未進(jìn)行高聚合程度的反應(yīng),未經(jīng)工業(yè)萃取的水解聚合PA6與對(duì)應(yīng)比例的助劑混合反應(yīng)后,己內(nèi)酰胺參與反應(yīng)比例低于外加己內(nèi)酰胺的體系,從側(cè)面印證了聚合物熱氧降解對(duì)己內(nèi)酰胺陰離子聚合程度的影響。
[Abstract]:Polyamide 6 (PA6) is a widely used polymer material. As a fiber, it is mainly used in textile and clothing, tire cord and other aspects. As one of the five major engineering plastics, the polymerization mechanism of.PA6 is mainly used in mechanical, chemical, communication and other fields, which are divided into hydrolytic open ring polymerization and anionic ring opening polymerization. The reaction conditions are completely different and hydrolyzed. Water is used as an opening agent for polymerization, and water is used as an opening agent, and water is drained to control molecular weight at the later stage of polymerization; anionic polymerization is a chain polymerization which must strictly control water and acid at a very low content. Hydrolysis polymerization is gradually polymerized, the chain end of the product is not containing active center, anions converge to active polymerization, with fast reaction speed and high molecular weight. In this paper, combining the two polymerization mechanisms of hydrolysis open ring polymerization and anionic ring opening polymerization, the APA6/HPA6 composite products are obtained by adding caprolactam (CL) monomer, anionic polymerization initiator and activator by adding caprolactam (CL) monomer and anionic polymerization initiator and activator, to determine the initiator and activator by the two polymerization mechanism of hydrolysis open ring polymerization and anionic ring opening polymerization. Static casting and dynamic mixing were carried out, and the normal industrial casting temperature and the simple anion polymerization under the target high temperature were carried out. The conditions for the target reaction were optimized. The static casting experiment showed that the sodium caprolactam sodium (C10) was used as the initiator, and the diacylated lactam -1,6- hexandiamine (C20) was used as the initiator. The anionic polymerization PA6 products were obtained under the conventional casting temperature (160o) and relatively high temperature (220o). The test results of FT-IR, TGA and DSC showed that the anionic polymerization assistant system was also suitable for higher reaction temperature. The thermal stability test showed that when the mass ratio of CL/C10/C20 was 100/2.0/2.0, it was produced. The weight loss ratio of small molecules is the lowest. At the same time, a small amount of heat loss may exist during the subsequent dynamic mixing, so CL/C10/C20 is the suitable proportion of 100/2.5/2.5. The mixing platform of torque rheometer is used as a dynamic mixing place, and the proportion of two auxiliaries and four kinds of reaction temperatures are obtained by the mixing reaction of one step feeding method. The anionic polymerization PA6.FT-IR test showed that the product had typical peak of polyamide characteristic, and the content test of the extract showed that the conversion rate of the monomer was about 90%. The thermal performance test showed that the product contained different degree of polymerization, the crystallinity of the product of 100/2.5/2.5 was higher, the residue of the monomer was less, the reaction temperature was too low and too high to affect the melting. As the body fluidity and the degree of system crosslinking, 230o is chosen as the target reaction temperature, the reaction time should not be too long, depending on the change of real time torque. The experiment of caprolactam anionic polymerization in the hydrolyzed polymerized PA6 melt is carried out according to the proportion of the established auxiliaries, and the hydrolysis polymerization PA6/ Yin is also prepared by the torque rheometer and one step feeding. The.FT-IR test of the PA6 compound of ionic polymerization showed that the compound product maintained the characteristic peak of polyamide. The DSC test showed that with the increase of the initial content of caprolactam, the crystallinity of the compound product declined, the crystallization peak was narrowed from narrow to the melting temperature, and the melting temperature decreased. The TGA test showed that there were three obvious stages of heat loss when the content of caprolactam was higher. The results showed that the extraction of anionic polymerization showed that with the decrease of the content of caprolactam, the conversion rate was up to 50%, and the relative viscosity test showed that the relative viscosity of the sample with the highest conversion rate was slightly higher than that of the blank sample. The content test showed that the content of the carboxyl group in the blank sample was increased after the reaction, and the degradation products affected the anionic polymerization that might have been higher to a higher degree, and introduced the linear low density polyethylene with poor compatibility with caprolactam and PA6 as the control, and compared the hydrolysis polymerization of PA6 as matrix without industrial extraction (8.88%). The results of polymerization, change of real time torque and the test results of caprolactam content before and after reaction show that when there is thermal oxygen degradation, when PA6 and PE melt are used as reaction matrix, caprolactam does not react to high degree of polymerization, and caprolactam is involved in the reaction without industrial extraction of hydrolytic polymerized PA6 and the corresponding proportions of additives. The effect of thermal degradation of caprolactam on the degree of anionic polymerization of caprolactam was confirmed from the side of the system which was lower than that of caprolactam.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O633.22

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