本文關(guān)鍵詞：硼酸季戊四醇縮聚物改性環(huán)氧樹(shù)脂的性能研究　出處：《中北大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 阻燃劑 硼酸酯 環(huán)氧樹(shù)脂 固化動(dòng)力學(xué)

【摘要】：環(huán)氧樹(shù)脂的力學(xué)性,電絕緣性,粘合性優(yōu)良,而且加工性較為靈活,因此在軍事領(lǐng)域、航空航天領(lǐng)域及民用領(lǐng)域等得到應(yīng)用。然而,環(huán)氧樹(shù)脂的氧指數(shù)低(約19.8),其易燃性,使其應(yīng)用非常有限,因此在一定條件下需要對(duì)環(huán)氧樹(shù)脂阻燃。在阻燃的復(fù)合材料材料中,一般都是采用阻燃劑來(lái)改善材料的阻燃性。目前改性環(huán)氧樹(shù)脂阻燃性能,大多數(shù)使用含鹵阻燃劑、含磷阻燃劑及無(wú)機(jī)阻燃劑,但是無(wú)機(jī)阻燃劑對(duì)環(huán)氧樹(shù)脂所制的復(fù)合材料的力學(xué)性能影響比較大,而含磷阻燃劑、含鹵阻燃劑會(huì)對(duì)環(huán)境造成一定的污染,因此開(kāi)發(fā)新型阻燃劑是勢(shì)在必行。科學(xué)研究證明有機(jī)硼一類的阻燃劑具有阻燃性能好、低毒、低煙等優(yōu)點(diǎn)。本文研究?jī)?nèi)容如下:(1)以硼酸、季戊四醇為原料,經(jīng)脫水縮合反應(yīng),合成了新型的有機(jī)硼阻燃劑-硼酸季戊四醇縮聚物(BP),探討其最佳耐熱性能的合成條件為:硼酸:季戊四醇=1:1,于100℃下反應(yīng)七小時(shí);所得到BP可以溶解于水和乙醇中;BP初始分解溫度368℃,高于大部分高分子的分解溫度,可用于高分子阻燃。由DTG可知最大失重速率的溫度為420.76℃,600℃的殘?zhí)柯蕿?1.5%,分解溫度范圍只有68℃,在較窄的溫度范圍內(nèi)可以生成大量的炭層,有利于阻燃,是一種優(yōu)良的阻燃劑。(2)制備了不同含量的BP/海茵環(huán)氧(EP)樹(shù)脂體系,研究了樹(shù)脂體系的粘度特性和凝聚特性;并制備了BP/EP澆注體固化物,對(duì)其力學(xué)性能進(jìn)行測(cè)試。結(jié)果表明:不同組分的低粘度平臺(tái)的粘度隨著B(niǎo)P的含量增加而增大;在105~125℃之間BP/EP體系有較低的黏度,適合成型操作;在相同的溫度下含BP高的樹(shù)脂體系凝膠時(shí)間更短,計(jì)算得10%BP的反應(yīng)活化能73.33KJ/mol、20%BP反應(yīng)活化能62.89KJ/mol、30%BP反應(yīng)活化能61.03KJ/mol、40%BP反應(yīng)活化能58.89KJ/mol;增加一定BP的用量有利于降低體系的反應(yīng)活化能;BP的加入有效地提高了環(huán)氧樹(shù)脂的沖擊強(qiáng)度,改善了環(huán)氧樹(shù)脂的韌性,同時(shí)BP的加入對(duì)海因環(huán)氧樹(shù)脂的拉伸、彎曲強(qiáng)度的改善效果不明顯。(3)通過(guò)動(dòng)態(tài)DSC對(duì)不同配比的BP/EP樹(shù)脂體系測(cè)試,并推導(dǎo)特征固化溫度,反應(yīng)活化能和固化動(dòng)力學(xué)方程;結(jié)果表明:動(dòng)態(tài)DSC計(jì)算各配方的反應(yīng)活化能,10%反應(yīng)活化能最高為85.51kJ/mol,隨著B(niǎo)P含量的增加,反應(yīng)活化能下降,反應(yīng)活性增加;聯(lián)合Kissinger、Starink和Crane方程建立了BP/EP固化反應(yīng)動(dòng)力學(xué)方程。通過(guò)T-β作圖外推法得到BP/EP各配方的特征固化溫度,制定BP/EP的固化工藝為110℃固化2小時(shí),125℃固化4小時(shí),140℃固化4小時(shí)。(4)對(duì)BP/EP固化體系的阻燃性進(jìn)行探討,結(jié)果表明:阻燃固化劑BP的加入能夠明顯提高固化物的阻燃性能,隨著B(niǎo)P含量的增加,固化物的氧指數(shù)增大,阻燃性能提高,當(dāng)含量為40%時(shí),氧指數(shù)達(dá)到30.5;隨著硼酸季戊四醇縮聚物的的增加,膨脹度減小。通過(guò)對(duì)BP/EP樹(shù)脂TG測(cè)試,10%BP樹(shù)脂固化物在800℃的殘?zhí)柯?8.3%,比沒(méi)有BP的環(huán)氧樹(shù)脂固化物的殘?zhí)柯矢叱?4.4%;且隨著B(niǎo)P含量的增加,固化物的殘?zhí)柯试龃?當(dāng)含量達(dá)到40%時(shí)比沒(méi)有BP的環(huán)氧樹(shù)脂固化物的殘?zhí)柯侍岣吡?20.6%,BP的加入能夠顯著的提高固化物的耐熱性。通過(guò)掃描電鏡觀察BP(40%)/EP的燃燒表面可知,燃燒后的外表面炭層致密,內(nèi)表面為多孔泡沫狀,是一種典型的膨脹型阻燃現(xiàn)象。推測(cè)BP/EP自阻燃體系的阻燃的主要作用機(jī)理為為:形成玻璃體覆蓋層,起隔絕作用的凝聚相阻燃;硼酸脫水吸熱的吸熱阻燃機(jī)理;體系受熱分解產(chǎn)生氨氣,二氧化氮的氣相阻燃機(jī)理。
[Abstract]:The mechanical properties, electrical insulation and adhesion of epoxy resin are excellent, and the machinability is flexible. Therefore, epoxy resin has been applied in military, aerospace and civil fields. However, the oxygen index of epoxy resin is low (about 19.8), and its flammability is very limited, so it needs to be flame-retardant to epoxy resin under certain conditions. In the flame retardant composite materials, flame retardants are generally used to improve the flame retardancy of the material. At present, the properties of modified epoxy resin flame retardant, most of the use of halogen containing flame retardant, flame retardant and inorganic flame retardant, but the mechanical properties of composite material of flame retardant epoxy resin system is relatively large, while the phosphorus containing flame retardant, halogen containing flame retardant can cause the pollution to the environment, so the development of a new type of flame retardant the agent is imperative. It has been proved by scientific research that the flame retardants such as organic boron have the advantages of good flame retardancy, low toxicity, low smoke and so on. The contents of this paper are as follows: (1) with boric acid and pentaerythritol as raw materials by dehydration condensation reaction, organic boron - new flame retardant boric acid polycondensate synthesized pentaerythritol (BP) and explore the optimal synthesis conditions for heat resistance: boric acid: pentaerythritol =1:1, in 100 DEG C for seven hours; the BP can dissolved in water and ethanol; BP initial decomposition temperature is 368 degrees centigrade, the decomposition temperature is higher than most of the polymer, can be used for flame retardant polymer. According to DTG, the maximum weight loss rate is 420.76 C, the carbon residue rate at 600 C is 41.5%, the decomposition temperature range is only 68 centigrade, and a large number of carbon layers can be generated in a narrow temperature range, which is good for flame-retardant and is an excellent flame retardant. (2) different content of BP/ Hai Yin epoxy (EP) resin system has been prepared. The viscosity and agglomeration characteristics of the resin system have been studied, and the solidified material of BP/EP casting body has been prepared, and its mechanical properties have been tested. The results show that the different components of the low viscosity platform viscosity increases with the increase of the content of BP; in 105~125 DEG BP/EP system has low viscosity, suitable for molding operation; at the same temperature with time shorter gel resin system with high BP, 10%BP calculated the reaction activation energy of 73.33KJ/mol and 20%BP activation energy 62.89KJ/mol, 30%BP 61.03KJ/mol 40%BP, the activation energy of the reaction activation energy of 58.89KJ/mol; increase the amount of BP can reduce the activation energy of the reaction system; the addition of BP can effectively improve the impact strength of the epoxy resin, improve the toughness of epoxy resin, while the addition of BP the tensile strength and flexural strength of hydantoin epoxy resins with improved the effect is not obvious. (3) by dynamic DSC BP/EP resin system with different proportion of the test, and is characteristic of curing temperature and curing reaction kinetic equation; the result shows that the dynamic DSC calculate the formula of activation energy, 10% activation energy up to 85.51kJ/mol, with the increase of BP content, the activation energy decreased, the reaction activity increased combined with Kissinger, Starink and Crane; BP/EP equation kinetics equation was established. The characteristic curing temperature of each formula of BP/EP was obtained by T- beta drawing and extrapolation. The curing process of BP/EP was set at 110 C for 2 hours, curing at 125 C for 4 hours, and curing at 140 C for 4 hours. (4) of flame retardant of BP/EP curing system. The results showed that the flame retardant curing agent BP can significantly improve the flame retardant properties of the cured, with the increase of BP content, the oxygen index of curing increases, flame retardant performance, when the content is 40%, the oxygen index reached 30.5; with the increase of boric acid pentaerythritol polycondensation the degree of swelling, decrease. Through the test of BP/EP TG resin, 10%BP resin, carbon residue in 800 C was 28.3%, 74.4% higher than the rate of residual carbon epoxy resin without BP; and with the increase of BP content, carbon residue rate of solidified material increases, when the content reaches 40% carbon residue ratio of cured epoxy resin without the BP rate increased by 220.6%, the addition of BP can improve the heat resistance of the cured markedly. Scanning electron microscope (SEM) was used to observe the combustion surface of BP (40%) /EP. It is known that the carbon layer on the outer surface after combustion is porous, and the inner surface is porous foam, which is a typical intumescent flame retardant phenomenon. It is presumed that the main mechanism of BP/EP self flame retardant system is: forming glass covering layer, flame retarding condensed phase, heat absorbing and flame-retardant mechanism of boric acid dehydration, absorbing gas and flame retardant mechanism of ammonia nitrogen.
【學(xué)位授予單位】：中北大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ323.5

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 劉曉亮;楊波;丁正亞;羅忠富;;硼酸鋅阻燃抑煙PC/ABS的研究[J];合成材料老化與應(yīng)用;2016年01期

2 劉東發(fā);李業(yè)添;潘永紅;劉平;;一種新型有機(jī)硼阻燃劑及其阻燃EVA材料的研究[J];塑料科技;2016年03期

3 齊士成;汪堯雙;韓果;楊震;張孝阿;江盛玲;呂亞非;;碳硼烷雙酚二縮水甘油醚的合成與表征及耐高溫性能研究[J];高分子學(xué)報(bào);2015年08期

4 江蓉;;新型DOPO側(cè)基型環(huán)氧樹(shù)脂的合成及其阻燃性能研究[J];黃山學(xué)院學(xué)報(bào);2015年03期

5 盧林剛;陳英輝;郭楠;楊守生;;膨脹石墨(EG)協(xié)同新型磷系膨脹阻燃環(huán)氧樹(shù)脂的制備及阻燃性能研究[J];高�；瘜W(xué)工程學(xué)報(bào);2015年03期

6 馮海生;李鈴;王會(huì)婭;;新型無(wú)鹵阻燃環(huán)氧樹(shù)脂復(fù)合材料的制備及阻燃性能[J];塑料;2015年01期

7 汪嬌寧;蘇興勇;雅蘭;陸雯婷;陳飛;陳櫻;毛志平;;甲基三硼硅烷對(duì)PET熱性能和阻燃性能的影響[J];工程塑料應(yīng)用;2014年11期

8 張宏坤;王志昂;;新型含磷阻燃劑(PPOHQ)的合成及其在環(huán)氧樹(shù)脂中的應(yīng)用[J];化學(xué)與黏合;2014年05期

9 彭朝陽(yáng);王美曉;羅云慶;劉平;;芳基硼酸衍生物的阻燃性能[J];合成材料老化與應(yīng)用;2014年03期

10 張興宏;閔玉勤;華正江;;含氮雜環(huán)結(jié)構(gòu)的阻燃環(huán)氧樹(shù)脂基電子材料[J];化學(xué)進(jìn)展;2014年06期

相關(guān)碩士學(xué)位論文 前4條

1 田鑫;硼酚醛樹(shù)脂對(duì)環(huán)氧樹(shù)脂的改性及其復(fù)合材料研究[D];中北大學(xué);2016年

2 高玉斌;硼胺絡(luò)合物潛伏型固化劑的合成及環(huán)氧樹(shù)脂體系性能研究[D];華南理工大學(xué);2014年

3 金文琴;新型有機(jī)雜化六方氮化硼及其高性能阻燃雙馬來(lái)酰亞胺樹(shù)脂的研究[D];蘇州大學(xué);2014年

4 馮海偉;磁性磨粒的制備及其導(dǎo)磁性能的研究[D];太原理工大學(xué);2009年

，

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