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摘要
以八甲基环四硅氧烷(单体)和3-缩水甘油丙基甲基硅烷(偶联剂)为原料,以1,3-双(3-缩水甘油氧丙基)-1,1,3,3-四甲基二硅氧烷为封端剂,以四甲基氢氧化铵为催化剂,通过本体聚合法合成环氧改性硅油。通过单因素方法确定了环氧改性硅油的最佳合成工艺条件:单体与偶联剂的摩尔比2:3、催化剂用量0.1%(wt,质量分数,下同)、封端剂用量0.5%、反应温度70℃、反应时间4h,所得产物的环氧值为0.2529mol/100g,黏度为375mPa·s。FT-IR谱图中,910cm-1和3047cm-1处吸收峰归属于产物中的环氧基团;热重分析表明,该环氧改性硅油具有较好的热稳定性。当环氧改性硅油乳液的附着量为1%时,可显著抑制聚丙烯腈(PAN)原丝预氧化过程中出现的粘连问题。
Abstract
Using octamethyl cyclotetrasiloxane (monomer) and 3-glycidyloxypropyl methylsilane (coupling agent) as raw materials,1,3-bis (3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane as a blocking agent and tetramethylammonium hydroxide as a catalyst,an epoxy-modified silicone oil was synthesized by bulk polymerization method.A single factor method was used to determine the optimal synthesis process conditions of epoxy-modified silicone oil,which corresponded to the molar ratio of monomer to coupling agent of 2:3,the amount of catalyst of 0.1wt%,and the capping agent dosage of 0.5wt% at 70℃ for 4h.Under this condition,the epoxy value and viscosity of the as-synthesized epoxy-modified silicone oil was 0.2529mol/100g and 375mPa·s respectively.The absorption peaks at 910cm-1 and 3047cm-1 in the infrared spectrum were attributed to the epoxy group of the as-synthesized silicone oil.Thermogravimetric analysis showed that the as-synthesized epoxy-modified silicone oil had good thermal stability.When the adhesion amount of as-synthesized epoxy-modified silicone oil emulsion was 1wt%,the adhesion problem during the pre-oxidation of PAN could be significantly suppressed.
关键词
环氧改性硅油
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聚丙烯腈
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预氧化
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本体聚合
Key words
epoxy modified silicone oil
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PAN
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pre-oxidation
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bulk polymerization
环氧改性硅油的合成工艺优化及其对PAN原丝预氧化过程的影响[J].
化工新型材料, 2023, 51(1): 113-117 DOI:10.19817/j.cnki.issn1006-3536.2023.01.022
[1] Jasjeet K,Keith M,Shaun S.Producing high-quality precursor polymer and fibers to achieve theoretical strength in carbon fibers:a review[J].J Appl Polym Sci,2016,133(38):43963.
[2] Yusof N,Ismail A F.Post spinning and pyrolysis processes of polyacrylonitrile (PAN)-based carbon fiber and activated carbon fiber:a review[J].J Anal Appl Pyrol,2012,93:1-13.
[3] 高锋,赵江.预氧化过程中张力对聚丙烯腈预氧化纤维微缺陷结构的影响[J].高等学校化学学报,2011,32(12):2711-2713.
[4] Wang S,Chen Z H,Ma W J,et al.Influence of heat treatment on physical-chemical properties of PAN-based carbon fiber[J].Ceram Int,2006,32:291-295.
[5] Naito K,Tanaka Y,Yang J M,et al.Tensile properties of ultrahigh strength PAN-based,ultrahigh modulus pitch-based and high ductility pitch-based carbon fibers[J].Carbon,2008,46(2):189-195.
[6] 李献起,赵洁.功能性聚硅氧烷在织物整理方面的研究进展[J].有机硅材料,2018,32(6):501-505.
[7] 贺福.高性能碳纤维原丝与油剂[J].高科技纤维与应用,2004,29(5):l-5.
[8] 关颖.碳纤维及原丝用油剂研发及应用[J].化工新型材料,2012,40(6):1-4.
[9] 崔晴晴,李同国,赵莹,等.环氧-聚醚端基改性硅油合成与工艺探究[J].化工新型材料,2017(4):221-223.
[10] 李健华.环氧改性碳纤维原丝油剂的合成及其性能研究[D].吉林:吉林化工学院,2020.
[11] 成晓玲,吴士萍,余林,等.一种亲水性嵌段聚醚氨基硅油的制备方法:中国,102617863A[P].2012-08-01.
[12] 郭雅明,李常清,马晓娜,等.硅系油剂对PAN纤维预氧化的影响[J].材料科学与工程学报,2011,29(4):554-558.
[13] 张淑斌,王浩静.氨改性硅油的合成、表征及其在PAN基碳纤维原丝预氧化过程中的作用[J].合成纤维,2010,39(1):17-19.
[14] 申屠鲜艳,胡振羽.氨基硅油的结构分析[J].有机硅材料,2006(5):256-25,279.
[15] 刘瑞云.环氧改性硅油的合成与应用[J].染整技术,2009,31(8):34-36,49,59.
[16] 杨威龙,郭慧君,田晶,等.侧链氨基改性硅油合成条件优化与表征[J].吉林化工学院学报,2019,36(5):89-92.
基金资助
镇江市高等专科学校青年专项课题(GZQNZX2019016)
