本文選題：生物基 + 植酸　； 參考：《中北大學》2017年碩士論文

【摘要】：聚丙烯(PP)以其優(yōu)良的物理、化學性能成為現(xiàn)代生活中用途最廣的通用高分子材料。但是PP易燃的特性限制了它在多個領域的應用。近些年,材料的環(huán)保與安全成為人們關注的焦點,因此開發(fā)環(huán)保型阻燃PP一直是研究熱點。以生物基原料制備阻燃劑正好滿足了安全環(huán)保和可持續(xù)的趨勢,相關研究受到了廣泛關注,但是大多數(shù)生物基材料耐熱性能差,應用領域受到限制,而且大多生物基阻燃劑效率較低,無法作為優(yōu)異的阻燃劑使用。因此必須通過物理或化學的方法進行合理的處理,賦予其作為阻燃劑的特性,這也是生物基阻燃技術發(fā)展的必然措施。本文選用具有阻燃作用的植酸和胞嘧啶(Cy)作為原料,分別制備了植酸金屬鹽、植酸哌嗪鹽(PA-Pi)以及三嗪成炭劑CC-Cy,研究了它們作為阻燃劑組分與商品阻燃劑復合使用在PP中的協(xié)同阻燃作用。具體包括以下三部分:1.以具有催化作用的金屬離子鋅(Zn2+)、鎳(Ni2+)、鈷(Co2+)為陽離子分別制備了植酸鋅(PA-Zn)、植酸鎳(PA-Ni)、植酸鈷(PA-Co)等植酸金屬鹽。將其作為協(xié)效劑與商品膨脹型阻燃劑(IFR)復合,通過熔融共混法制備了PP復合材料。研究結果表明,PP復合材料中添加2 wt%PA-Zn和17 wt%IFR可以使氧指數(shù)達到29.2 vol%,比單獨添加19 wt%IFR的氧指數(shù)提高5.1 vol%。同樣添加1 wt%的PA-Ni與17 wt%IFR可以使PP復合材料氧指數(shù)達29.5 vol%,同樣含量的PA-Co則使PP復合材料氧指數(shù)達28.6 vol%,并且兩者均通過了UL-94 V-0級別的測試。這些結果表明,PA-Ni與PA-Co的對阻燃效率的提升作用略優(yōu)于PA-Zn。通過熱失重分析(TGA)、掃描電鏡(SEM)、拉曼(Raman)光譜等分析了阻燃機理,結果發(fā)現(xiàn)植酸金屬鹽有助于提高IFR在高溫下的交聯(lián)度及穩(wěn)定性,提高成炭率。而且植酸金屬鹽的加入改善了炭層質(zhì)量,使殘?zhí)颗蛎洸a(chǎn)生很多褶皺,更好地阻隔氣體和熱量的交換,但是炭層中并未觀察到新結構的形成,故這些植酸金屬鹽應該主要改變了成炭速度和質(zhì)量,因而提高了阻燃效率。2.以哌嗪作為陽離子與植酸反應制備了PA-Pi,將其作為酸源與炭源雙季戊四醇(DPER)復配,通過熔融共混法制備了阻燃PP復合材料。改變阻燃劑體系的復合比例和添加量,發(fā)現(xiàn)總添加量為25 wt%,PA-Pi:DPER為3:1時,PP復合材料的氧指數(shù)為28.1 vol%,達到了UL-94 V-0級別。通過TGA、SEM、Raman光譜等分析了阻燃機理,TGA研究發(fā)現(xiàn)PA-Pi與DPER之間的化學反應比較復雜,前期催化提前降解,后期則促進交聯(lián)成炭。SEM及Raman光譜分析表明,隨著阻燃劑添加量的增加,炭層更完整致密,缺陷明顯減少并且規(guī)整度提高,炭層質(zhì)量變好,因而獲得了更高的阻燃效率。3.采用胞嘧啶與三聚氯氰反應制備了三嗪成炭劑CC-Cy,將其與聚磷酸銨(APP)和雙酚A雙(二苯基磷酸酯)(BDP)組成IFR體系,并用來提高PP的阻燃性能。結果顯示PP中含20 wt%APP與5 wt%CC-Cy可以達到UL-94 V-2級別。而含18 wt%的APP/CC-Cy復合物APP:CC-Cy=4:1)與3 wt%BDP時,PP復合材料就可以達到UL-94 V-0級別,這說明三者間存在明顯的協(xié)同作用,使阻燃效率得到提高。阻燃機理分析表明,APP與CC-Cy的反應促進了殘?zhí)康纳?BDP的加入進一步提高了成炭性能。紅外熱成像發(fā)現(xiàn)BDP可以降低樣品點燃后表面的溫度,而且還發(fā)現(xiàn)BDP不僅在氣相中發(fā)揮作用,同時促進了固相中的成炭反應。APP、CC-Cy、BDP三者之間的良好協(xié)同,促進了有效的保護炭層的形成,提高了阻燃效率。
[Abstract]:Polypropylene (PP) has become the most widely used general polymer material in modern life for its excellent physical and chemical properties. However, the flammability of PP restricts its application in many fields. In recent years, the environmental protection and safety of materials have become the focus of attention. Therefore, the development of environment-friendly flame retardant PP has always been a hot topic. As the flame retardants meet the safety and sustainability trend, the related research has received extensive attention, but most biologically based materials are poor in heat resistance and limited in application fields, and most of the bio-based flame retardants are inefficient and can not be used as excellent flame retardants. Therefore, physical or chemical methods must be used in combination. In this paper, phytic acid and cytosine (Cy) with flame retardancy were used as raw materials to prepare phytic acid metal salts, phytic piperazine salts (PA-Pi) and three azine carbonizing agents, CC-Cy, which were used as flame retardants and flame retardants. The synergistic flame retardancy used in PP is composed of three parts: 1. the zinc phytate (PA-Zn), nickel phytate (PA-Ni), cobalt phytate (PA-Co) and other phytate metal salts are prepared respectively with metal ion zinc (Zn2+) with catalytic action, nickel (Ni2+) and cobalt (Co2+) as cations, respectively, as synergist and commodity expansive flame retardant (IFR). PP composites were prepared by over melt blending. The results showed that the oxygen index reached 29.2 vol% by adding 2 wt%PA-Zn and 17 wt%IFR in the PP composite, and the oxygen index of 19 wt%IFR was increased by 5.1 vol%., and the PA-Ni and 17 wt%IFR of 1 wt% could make the oxygen index of PP composite up to 29.5 vol%. The oxygen index of PP composites reached 28.6 vol% and both passed the test of UL-94 V-0 level. These results showed that the effect of PA-Ni and PA-Co on the improvement of flame retardancy was slightly better than that of PA-Zn. through thermal weight loss analysis (TGA), scanning electron microscopy (SEM), and Raman (Raman) spectroscopy. The results showed that phytate metal salts help to increase IFR. The crosslinking degree and stability at high temperature increase the carbon formation rate. Moreover, the addition of phytic acid improves the quality of the carbon layer, causes the carbon residue to expand and produces many folds, and better obstruct the exchange of gas and heat. However, the formation of the new structure is not observed in the carbon layer, so these phytate metal salts should mainly change the speed and quality of carbon formation. Therefore, the flame retardancy efficiency of.2. was improved by the reaction of piperazine as a cation and phytic acid to prepare PA-Pi, which was used as an acid source and carbon source bis pentaerythritol (DPER), and the flame retardant PP composite was prepared by melt blending. The composite ratio and addition amount of the flame retardant system were changed, and the total addition amount was 25 wt% and PA-Pi:DPER was 3:1, PP composite material was found. The oxygen index of the material was 28.1 vol% and reached the level of UL-94 V-0. The flame retardant mechanism was analyzed by TGA, SEM and Raman spectra. The TGA study found that the chemical reaction between PA-Pi and DPER was more complex, early catalytic degradation, and later promoted cross-linking to carbon.SEM and Raman spectral analysis, and the carbon layer was more complete with the increase of the addition of flame retardant. The defects are obviously reduced and the regularity is improved and the quality of the carbon layer is better. Therefore, a higher flame retardant efficiency.3. is obtained by the reaction of cytosine and cyanuric chloride to prepare the three azimuth carbon forming agent CC-Cy, which is formed with ammonium polyphosphate (APP) and bisphenol A double (two phenyl phosphate) (BDP) as IFR system, and is used to improve the flame retardancy of PP. The results show PP in PP. 20 wt%APP and 5 wt%CC-Cy can reach the level of UL-94 V-2. With the APP/CC-Cy complex of 18 wt%, APP:CC-Cy=4:1) and 3 wt%BDP, the PP composite can reach UL-94 V-0. This shows that there is a significant synergism between the three and the flame retardancy efficiency is improved. The addition of BDP further improves the charcoal performance. Infrared thermal imaging shows that BDP can reduce the temperature of the surface after the sample is ignited. Moreover, it is found that BDP not only plays a role in the gas phase, but also promotes the good CO formation of the carbon forming reaction of the solid phase,.APP, CC-Cy, BDP three, which promotes the formation of the carbon layer effectively and improves the resistance of the carbon layer. Combustion efficiency.
【學位授予單位】：中北大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ325.14

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本文編號：2015865