特种聚醚的合成
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摘要
聚醚多元醇是制备聚氨酯材料的主要原料之一,对聚氨酯制品的性能有很大的影响。聚氨酯工业的快速发展对特种聚醚多元醇的开发提出了更高的要求,尤其是耐热和阻燃聚醚。本文采用自制的双金属氰化物络合物(DMC)催化剂分别催化环氧丙烷(PO)、环氧氯丙烷(ECH)开环聚合,制备了一系列具有芳香环和杂环结构的端羟基聚醚,并系统研究了反应条件对开环聚合的影响。然后,本文以端羟基聚环氧氯丙烷(PECH)为原料,合成了具有柔顺主链的端环氧基聚醚(ETP),并系统研究了反应条件对环氧化反应的影响。最后,本文以ETP为原料,合成了具有柔顺主链的端环碳酸酯基聚醚(CCP)。主要结论如下:
1.分别以双酚A和三羟乙基异氰脲酸酯(THEIC树脂)为起始剂,采用DMC催化剂合成了具有芳香环和杂环结构的端羟基聚环氧丙烷醚。诱导期随温度和DMC催化剂浓度的提高而减少,温度高于130℃时催化剂易失活,聚合物的分子量与PO/起始剂质量比基本上成正比例关系。
2.分别以双酚A和THEIC树脂为起始剂,采用DMC催化剂合成了具有芳香环和杂环结构的端羟基PECH。ECH与PO相比,前者反应活性较低,反应时需要更高的温度和催化剂浓度。
3.利用端羟基PECH与NaOH进行环氧化反应,制备了柔顺的ETP。在NaOH/PECH摩尔比为3.4:1、水/甲苯体积比3:7、温度为15℃、四丁基溴化铵质量分数为2%、可以较好地制备ETP。NaOH/PECH摩尔比和原料PECH的分子量对副反应有明显的影响。
4.以四丁基溴化铵为催化剂,利用ETP与CO2反应,制备了CCP;利用红外谱图证明了产物中含有端环碳酸酯基。
As one of main raw materials for preparing polyurethane (PU) materials, polyether polyol has great influence on the properties of PU products. The rapid development of PU industry have higher requirement on the exploitation of special polyether polyol, especially heat-resistant and flame-retardant polyether. In this paper, a series of hydroxyl-terminated polyether with aromatic nucleus and heterocycle were prepared by ring-opening polymerization of propylene oxide (PO) and epichlorohydrin (ECH) respectively, using double metal cyanide (DMC) catalyst. And effects of reaction conditions on the polymerization were investigated. Furthermore, epoxy-terminated polyether (ETP) with flexible backbone was synthesized using hydroxyl-terminated polyepichlorohydrin (PECH) as the raw material, and effects of reaction conditions on epoxidation reaction were systematically investigated. Finally, cyclic carbonate-terminated polyether (CCP) with flexible backbone was synthesized using ETP as the raw material. The main results are described as follows:
1. Hydroxyl-terminated poly(propylene oxide)ether with the structure of aromatic nucleus and heterocycle were synthesized with bisphenol A and tri(hydroxyethyl) isocyanurate respectively as initiators, using DMC catalyst. Induce period decreased with the increase of temperature and DMC catalyst concentration, and DMC catalyst was likely to lose catalytic activity when the temperature was higher than 130℃. Furthermore, molecular weight was almost proportional to the mass ratio of PO to initiator.
2. Hydroxyl-terminated PECH with the structure of aromatic nucleus and heterocycle were synthesized with bisphenol A and tri(hydroxyethyl) isocyanurate respectively as initiators, using DMC catalyst. Lower reactivity of ECH compared with PO made it need higher temperature and higher catalyst concentration to be polymerized.
3. Flexible ETP was prepared in by the reaction of hydroxyl-terminated PECH with NaOH. ETP could be well synthesized at 15℃with molar ratio of NaOH to PECH 3.4, volume ratio of water to toluene 3:7 and mass content of tetrabutyl ammonium bromide 2%. Molar ratio of NaOH to PECH and molecular weight of PECH had great influence on side reaction.
4. CPP was prepared by the reaction of ETP with CO2 using tetrabutyl ammonium bromide as catalyst. FTIR was utilized to determine that the outcome had the structure of end cyclic carbonate.
1.分别以双酚A和三羟乙基异氰脲酸酯(THEIC树脂)为起始剂,采用DMC催化剂合成了具有芳香环和杂环结构的端羟基聚环氧丙烷醚。诱导期随温度和DMC催化剂浓度的提高而减少,温度高于130℃时催化剂易失活,聚合物的分子量与PO/起始剂质量比基本上成正比例关系。
2.分别以双酚A和THEIC树脂为起始剂,采用DMC催化剂合成了具有芳香环和杂环结构的端羟基PECH。ECH与PO相比,前者反应活性较低,反应时需要更高的温度和催化剂浓度。
3.利用端羟基PECH与NaOH进行环氧化反应,制备了柔顺的ETP。在NaOH/PECH摩尔比为3.4:1、水/甲苯体积比3:7、温度为15℃、四丁基溴化铵质量分数为2%、可以较好地制备ETP。NaOH/PECH摩尔比和原料PECH的分子量对副反应有明显的影响。
4.以四丁基溴化铵为催化剂,利用ETP与CO2反应,制备了CCP;利用红外谱图证明了产物中含有端环碳酸酯基。
As one of main raw materials for preparing polyurethane (PU) materials, polyether polyol has great influence on the properties of PU products. The rapid development of PU industry have higher requirement on the exploitation of special polyether polyol, especially heat-resistant and flame-retardant polyether. In this paper, a series of hydroxyl-terminated polyether with aromatic nucleus and heterocycle were prepared by ring-opening polymerization of propylene oxide (PO) and epichlorohydrin (ECH) respectively, using double metal cyanide (DMC) catalyst. And effects of reaction conditions on the polymerization were investigated. Furthermore, epoxy-terminated polyether (ETP) with flexible backbone was synthesized using hydroxyl-terminated polyepichlorohydrin (PECH) as the raw material, and effects of reaction conditions on epoxidation reaction were systematically investigated. Finally, cyclic carbonate-terminated polyether (CCP) with flexible backbone was synthesized using ETP as the raw material. The main results are described as follows:
1. Hydroxyl-terminated poly(propylene oxide)ether with the structure of aromatic nucleus and heterocycle were synthesized with bisphenol A and tri(hydroxyethyl) isocyanurate respectively as initiators, using DMC catalyst. Induce period decreased with the increase of temperature and DMC catalyst concentration, and DMC catalyst was likely to lose catalytic activity when the temperature was higher than 130℃. Furthermore, molecular weight was almost proportional to the mass ratio of PO to initiator.
2. Hydroxyl-terminated PECH with the structure of aromatic nucleus and heterocycle were synthesized with bisphenol A and tri(hydroxyethyl) isocyanurate respectively as initiators, using DMC catalyst. Lower reactivity of ECH compared with PO made it need higher temperature and higher catalyst concentration to be polymerized.
3. Flexible ETP was prepared in by the reaction of hydroxyl-terminated PECH with NaOH. ETP could be well synthesized at 15℃with molar ratio of NaOH to PECH 3.4, volume ratio of water to toluene 3:7 and mass content of tetrabutyl ammonium bromide 2%. Molar ratio of NaOH to PECH and molecular weight of PECH had great influence on side reaction.
4. CPP was prepared by the reaction of ETP with CO2 using tetrabutyl ammonium bromide as catalyst. FTIR was utilized to determine that the outcome had the structure of end cyclic carbonate.
引文
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[3]朱吕民,刘益军,聚氨酯泡沫塑料[M],第三版,北京:化学工业出版社.2005.3~4
[4] The General Tire & Rubber Corp, Method of making a polyether using a double metal cyanide complex compound [P], US, US3278457, 1966-10-11
[5]黄亦军,戚国荣,钱锦文,等,Fe-Zn双金属氰化物催化环氧丙烷开环聚合的研究[J],高分子学报,,2001,(2):210~213
[6]徐向阳,周立,聚醚多元醇新型催化剂的技术经济分析[J],化学工业与工程技术,2002,23(1): 16~19
[7]朱吕民,刘益军,聚氨酯泡沫塑料[M],第三版,北京:化学工业出版社.2005.133
[8]朱吕民,刘益军,聚氨酯泡沫塑料[M],第三版,北京:化学工业出版社.2005.198~215
[9]周敬思,梁光兴,王起斌,环氧乙烷与乙二醇生产[M],北京:化学工业出版社. 1979.2~5
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[11]刘晓华,双金属氰化物络合物催化剂的制备,表征及应用,[学位论文]山西:中国科学院山西煤炭化学研究所,2000
[12]潘祖仁,高分子化学[M],第二版,北京:化学工业出版社. 1997.126
[13]张治国,尹红,环氧乙烷和环氧丙烷开环聚合[J],化学进展,2007, 19 (1):145~148
[14] Vandenberg E J, Mechanism Aspects of Epoxide Polymerization Sterenchemical Structure of the Crystalline Polymer from 2,3-epoxybutanes [J], J Polym Sci: B, 1964, 2 (12): 1085~1088
[15] Saegusa R, Ueshima T, A Route to the Controlled Synthesis of polymethyloxirane [J]. Makromol Chem, 1967, 107 (9): 131~134
[16] Inoue S, Control of Polymerization with Metalloporphyrin-discovery and Scope, American Chemical Society, Washington DC, 1992, 194~195
[17] Jacobs C, Dubious Ph, Jér?me R, Synthesis and Characterization of Diblock Copolymers Based on Poly-caprolactone and Poly(L,L or D,L)Lactide by Aluminum Alkoxides [J]. Macromolecular, 1991, 24 (3): 3027~3034
[18] Gonod V J, Llauro M F,Hamaide T, Effect of Butylmagnesium on Polymerization of Styrene with Calixatene-neodymium/butylmagnesium/HMPA Catalyst System [J], Macromol Chem Phys, 2000, 201 (5): 12~16
[19] Hamaide T, Spitz R, Letourneux J P, et al, Heterogeneous Catalysis for Ring-opening Anionic Olige-erization [J], Macromol Symp, 1994, 88 (6): 191~200
[20] Choi Young K, Stevels Willem M, Ankone Mare J, et al, Polymerization of ethylene oxideusing yttrium iso-propoxide [J], Macromol Chem Phys, 1996, 197 (11): 3623~3629
[21] Zheng Y S, Shen Z Q, Zhang Y F, Polymerization of Propylene Oxide by a New Neodymium Complex of Calixarene Derivative [J], Polymer, 2001, 41 (4): 1641~1643
[22] Tsuruta T, A Route to the Controlled Synthesis of polymethyloxirane Oligomers [J], Pure Appl Chem, 1981, 53 (7): 1745~1748
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