烯基聚乙二醇嵌段共聚物的合成及室温固化
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摘要
以聚乙二醇(PEG)为引发剂,三氟化硼乙醚(BF_3·Et_2O)络合物为催化剂,缩水甘油醚(GA)和烯丙基缩水甘油醚(AGE)为共聚单体,通过阳离子开环聚合反应,制备了烯基聚乙二醇嵌段共聚物粘合剂(PEG-PGA-PAGE)。采用红外光谱(FTIR)、核磁共振氢谱(~1HNMR)对产物的结构进行了表征,并以对苯二腈氧化物为固化剂固化合成的粘合剂制备出弹性体。考察了GA、AGE分时间段加和同时加两种不同加料顺序下合成的粘合剂(PEG-PGA-PAGE-1和PEG-PGA-PAGE-2)制备弹性体的力学和热性能。结果表明:粘合剂可实现室温固化,GA、AGE分段加制备的PEG-PGA-PAGE-1固化弹性体的力学性能和耐热性更强,其拉伸强度可达0.948 MPa,断裂伸长率可达89.32%,邵氏硬度可达23.8 Ha,储能模量可达361.05 MPa,玻璃化转变温度(T_g)为–41.85℃,接触角为74°。室温固化提高了弹性体的力学性能,有望应用于复合固体推进剂。
Allyl poly(ethylene glycol) block copolymer(PEG-PGA-PAGE) was synthesized by cationic ring-opening polymerization using polyethylene glycol(PEG) as initiator, BF_3·Et_2O complex as catalyst,glycidyl ether(GA) and allyl glycidyl ether(AGE) as monomers. The product structure was characterized by FTIR and ~1HNMR. The mechanical properties and thermal properties of two elastomers(PEG-PGAPAGE-1 and PEG-PGA-PAGE-2) prepared by curing binders prepared by adding GA and AGE separately and simultaneously with terephthalonitrile oxide were investigated. The results showed that the binder can cure at room temperature, the cured elastomer PEG-PGA-PAGE-1 prepared by subsection addition of GA and AGE had better mechanical properties and thermal properties. Its tensile strength was 0.948 MPa,elongation at break was 89.32%, shaw hardness was 23.8 Ha, storage modulus reached 361.05 MPa, T_g was–41.85 ℃, contact angle was 74°. Room temperature curing improved the mechanical properties, which is expected to be used in composite solid propellants.
Allyl poly(ethylene glycol) block copolymer(PEG-PGA-PAGE) was synthesized by cationic ring-opening polymerization using polyethylene glycol(PEG) as initiator, BF_3·Et_2O complex as catalyst,glycidyl ether(GA) and allyl glycidyl ether(AGE) as monomers. The product structure was characterized by FTIR and ~1HNMR. The mechanical properties and thermal properties of two elastomers(PEG-PGAPAGE-1 and PEG-PGA-PAGE-2) prepared by curing binders prepared by adding GA and AGE separately and simultaneously with terephthalonitrile oxide were investigated. The results showed that the binder can cure at room temperature, the cured elastomer PEG-PGA-PAGE-1 prepared by subsection addition of GA and AGE had better mechanical properties and thermal properties. Its tensile strength was 0.948 MPa,elongation at break was 89.32%, shaw hardness was 23.8 Ha, storage modulus reached 361.05 MPa, T_g was–41.85 ℃, contact angle was 74°. Room temperature curing improved the mechanical properties, which is expected to be used in composite solid propellants.
引文
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[2]Hailu K,Guthausen G,Becker W,et al.In-situ characterization of the cure reaction of HTPB and IPDI by simultaneous NMR and IRmeasurements[J].Polymer Testing,2010,29(4):513-519.
[3]Fan Yaqin(樊亚勤),Xiang Yao(向尧),Lei Yonglin(雷永林),et al.Synthesis of terephthalonnitrile oxides and its curing properties at room temperature[J].Fine Chemicals(精细化工),2017,34(9):1063-1069.
[4]Wang Xiaochuan(王晓川),Shu Yuanjie(舒远杰),Mo Hongchang(莫洪昌),et al.Synthesis and curing of energetic binder triblock alkenyl poly NIMMO[J].Chinese Journal of Explosives&Propellants(火炸药学报),2018,41(6):562-566.
[5]Zhou W Y,Cai J T.Mechanical and dielectric properties of epoxy resin modifieusing reactive liquid rubber(HTPB)[J].Journal of Applied Polymer Science,2012,124(5):4346-4351.
[6]Liu Lei(刘磊),Chen Jing(陈京),Zheng Yuansuo(郑元锁),et al.Study on properties of epoxidized hydroxyl terminated polybutadiene cured at room temperature[J].Journal of Solid Rocket Technology(固体火箭技术),2012,35(6):807-811.
[7]Wang Ligang(王利刚),Li Xiaojiang(李笑江),Yan Qilong(严启龙),et al.Research progress of polyethylene glycol blend systems[J].Chemical Propellants&Polymeric Materials(化学推进剂与高分子材料),2012,10(2):43-47.
[8]Chi M S.Compatibility of cross-linked polymers with plasticizers by glass transition temperature measurement and swelling tests[J].Journal of Polymer Science,Polymer Chemistry Edition,1981,19(7):1767-1779.
[9]Zhang Wanbin(张万斌),Fan Xiaodong(范晓东),Zhu Xiuzhong(朱秀忠).Synthesis and mechanical properties of poly(tetrahydrofuran)-poly(butadiene)-poly(tetrahydrofuran)triblock copolymer[J].Journal of Solid Rocket Technology(固体火箭技术),2015,38(2):251-260.
[10]Fan W W,Fan X D,Tian W,et al.Poly(ethylene glycol)-poly(tetrahydrofuran)-poly(ethylene glycol)triblock copolymer:Synthesis,crystallization behavior and novel morphology[J].Express Polymer Letters,2013,7(5):416-430.
[11]Wang Cundong(汪存东),Luo Yunjun(罗运军),Xia Min(夏敏),et al.Synthesis and characterization of hydroxyl-terminated block copolyether of PTHF-PEO-PTHF[J].Journal of Solid Rocket Technology(固体火箭技术),2011,34(2):202-206.
[12]Weygand C,Bauer E.über die reaktion des hydroxylamins mit enol?thern und acetylenketonen undüber eine neue konstitutiv eindeutige isoxazolsynthese[J].Justus Liebigs Annalen der Chemie,1927,459:123-143.
[13]Hu Hongmei(胡红梅),Yan Changwang(闫长旺),Hou Yibin(侯一斌).Influences of curing factors on the glass transition temperature of polymer[J].Chinese Adhesive(中国胶粘剂),2013,22(9):11-13.
[14]Wang Yulong(王玉龙),Li Zhenzhong(李振中),Bai Jingjing(白静静).Preparation and properties of PCDL/MDI type thermoplastic polyurethane elastomer[J].Engineering Plastics Application(工程塑料应用),2014,11(42):1-2.
[15]Holzworth K,Jia Z,Amirkhizi A V,et al.Effect of isocyanate content on thermal and mechanical properties of polyurea[J].Polymer,2013,54(12):3079-3085.
[16]Liao Mingyi(廖明义),Fan Cheng(范诚),Zhang Xiaojuan(张晓娟),et al.Morphology and properties of polybutadiene/allyl isobutyl polyhedral oligomeric siisesquioxane nanohybrids[J].China Synthetic Rubber Industry(合成橡胶工业),2011,34(5):346-351.
[17]Kissane M,Lawrence S E,Maguire A R,et al.ChemInform abstract:1,3-dipolar cycloadditions of 2-thio-3-chloroacrylamides with nitrile oxides and nitrones[J].ChemInform,2010,41(44),DOI:10.1002/chin.201044144.
[18]Sugium S,Ueno H,Kono M.Process for producing butadiene polymers:US3778424[P].1970-12-11.
[19]Jiang L Y,Xiong C D,Jiang L X,et al.Effect of HA with different grain size range on the crystallization behaviors and mechanical property of HA/PLGA composite[J].Thermochimica Acta,2013,565:52-57.
[20]Yang Taisheng(杨泰生).Research and preparation of superhydrophobic silica thin films by emulsion method[D].Jinan:Shandong Tnstitute of Light Industry(山东轻工业学院),2009.
[21]Jiang L,Wang R,Yang B,et al.Binary cooperative complementary nanoscale interfacial materials[J].Pure and Applied Chemistry,2000,72(1/2):73-81.