一种新型耐高温不饱和聚酯的设计与合成
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摘要
许多应用场合对高分子材料提出了耐高温,高强度的特殊要求。为了改善聚酯高分子材料的耐高温性能,本课题设计用含有饱和六元环结构的环氧环己烷代替二醇与马来酸酐及邻苯二甲酸酐反应,得到耐高温型不饱和聚酯。
以环己二醇和马来酸酐的反应程度,环氧环己烷和苯甲酸的反应程度的大小为依据,探索以环氧环己烷代替二元醇与马来酸酐、邻苯二甲酸酐反应的可行性,确定影响反应程度的因素。通过对影响因素进行正交实验设计,并对实验结果进行极差分析,确定最优的反应条件,并通过红外光谱分析法、核磁共振分析法确定聚合物结构,以及凝胶渗透色谱分析法测定聚合物的分子量及分子量分布。改变原料中不饱和酸酐与饱和酸酐的摩尔比,合成一系列不饱和聚酯树脂。将合成的一系列不饱和聚酯树脂制成纯固化物,并通过热重分析法、差示量热扫描分析法测得纯固化物的耐热指数及玻璃化转变温度；同时将系列不饱和聚酯制成涂料配方,在PC板上喷涂成膜,测定漆膜的硬度,及煮沸前后的附着力。
研究结果显示：环氧环己烷与马来酸酐、苯酐、环己二醇反应合成不饱和聚酯为聚醚嵌段的不饱和聚酯,分子量1200左右,分子量分布1.2。最佳反应条件是：环己二醇与邻苯二甲酸酐、马来酸酐的反应温度为120℃；加入环氧环己烷后的反应温度为100℃；环己二醇与邻苯二甲酸酐、马来酸酐的反应时间为1.5h；环氧环己烷滴加完毕后的反应时间为3h；环氧环己烷的滴加时间为2h；催化剂用量为总质量的0.25%。合成的不饱和聚酯纯固化物耐温性较市场上耐热邻苯型不饱和聚酯树脂亚邦198,进口产品DSM954好,且喷涂而成的漆膜在PC板上有良好的附着力及耐高温高湿性能。
Good tolerance of high temperature and high strength are two criteria physic properties for most polymer materials. In order to have a better understanding of those two properties and produce unsaturated polyester having good ability in standing for high temperature, this thesis applied cyclohexene oxide (with saturated hexatomic ring structure) in stead of menthandiol reacting with maleic anhydride as well as phthalic anhydride.
This thesis determined the feasibility of making unsaturated polyester through reactions between cayclohexene oxide,maleic anhydride and phthalic anhydride. This feasibility study conducted by analyzing the extent of reactions between cyclohexanediol and maleic anhydride, cyclohenxene oxide and benzoic acid, respectively. We designed an Orthogonal Experiment to determine reaction variables. We came to know the optimal experiment conditions by analyzing (Range Analysis method) and adjusting those variables. We also made serials of different unsaturated polyester resins by changing the mole ratios of reactants. These unsaturated polyester resins will be further condensed and purified, and then through thermogravimetric analysis (TGA) and differential scanning calorimetry method, the index of tolerance of high temperature and vitrification temperature will be determined. At the same time, these resins will be coated on the PC sheet to determine the strength of the coating and adhesive attraction pre-and post-boiling point.
This MS thesis research determined optimal experiment conditions as follows: temperature for reaction is 120℃; temperature is 100℃when added cycohenxene oxide; react time of cyclohexanediol and maleic anhydride is 1.5 hours; react time is 3 hours when finished adding cycohenxene oxide, and the adding time is 120 min; catalyst loading is 0.25%; unsaturated polyester resins have better high temperature resistance performance than Yabangl98, DSM954B unsaturated polyester resins. performance on adhesive attraction and tolerance of high temperature and humility.
以环己二醇和马来酸酐的反应程度,环氧环己烷和苯甲酸的反应程度的大小为依据,探索以环氧环己烷代替二元醇与马来酸酐、邻苯二甲酸酐反应的可行性,确定影响反应程度的因素。通过对影响因素进行正交实验设计,并对实验结果进行极差分析,确定最优的反应条件,并通过红外光谱分析法、核磁共振分析法确定聚合物结构,以及凝胶渗透色谱分析法测定聚合物的分子量及分子量分布。改变原料中不饱和酸酐与饱和酸酐的摩尔比,合成一系列不饱和聚酯树脂。将合成的一系列不饱和聚酯树脂制成纯固化物,并通过热重分析法、差示量热扫描分析法测得纯固化物的耐热指数及玻璃化转变温度；同时将系列不饱和聚酯制成涂料配方,在PC板上喷涂成膜,测定漆膜的硬度,及煮沸前后的附着力。
研究结果显示：环氧环己烷与马来酸酐、苯酐、环己二醇反应合成不饱和聚酯为聚醚嵌段的不饱和聚酯,分子量1200左右,分子量分布1.2。最佳反应条件是：环己二醇与邻苯二甲酸酐、马来酸酐的反应温度为120℃；加入环氧环己烷后的反应温度为100℃；环己二醇与邻苯二甲酸酐、马来酸酐的反应时间为1.5h；环氧环己烷滴加完毕后的反应时间为3h；环氧环己烷的滴加时间为2h；催化剂用量为总质量的0.25%。合成的不饱和聚酯纯固化物耐温性较市场上耐热邻苯型不饱和聚酯树脂亚邦198,进口产品DSM954好,且喷涂而成的漆膜在PC板上有良好的附着力及耐高温高湿性能。
Good tolerance of high temperature and high strength are two criteria physic properties for most polymer materials. In order to have a better understanding of those two properties and produce unsaturated polyester having good ability in standing for high temperature, this thesis applied cyclohexene oxide (with saturated hexatomic ring structure) in stead of menthandiol reacting with maleic anhydride as well as phthalic anhydride.
This thesis determined the feasibility of making unsaturated polyester through reactions between cayclohexene oxide,maleic anhydride and phthalic anhydride. This feasibility study conducted by analyzing the extent of reactions between cyclohexanediol and maleic anhydride, cyclohenxene oxide and benzoic acid, respectively. We designed an Orthogonal Experiment to determine reaction variables. We came to know the optimal experiment conditions by analyzing (Range Analysis method) and adjusting those variables. We also made serials of different unsaturated polyester resins by changing the mole ratios of reactants. These unsaturated polyester resins will be further condensed and purified, and then through thermogravimetric analysis (TGA) and differential scanning calorimetry method, the index of tolerance of high temperature and vitrification temperature will be determined. At the same time, these resins will be coated on the PC sheet to determine the strength of the coating and adhesive attraction pre-and post-boiling point.
This MS thesis research determined optimal experiment conditions as follows: temperature for reaction is 120℃; temperature is 100℃when added cycohenxene oxide; react time of cyclohexanediol and maleic anhydride is 1.5 hours; react time is 3 hours when finished adding cycohenxene oxide, and the adding time is 120 min; catalyst loading is 0.25%; unsaturated polyester resins have better high temperature resistance performance than Yabangl98, DSM954B unsaturated polyester resins. performance on adhesive attraction and tolerance of high temperature and humility.
引文
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[3]张小苹.不饱和聚酯树脂及其新发展.玻璃钢,2008,2(no)：23
[4]沈开猷.不饱和聚酯树脂及其应用.北京：化学工业出版社,2005
[5]栢孝达.我国的不饱和聚酯树脂工业.热固性树脂,2001,6(16)：9
[6]韩秀萍,蒋欣,李玉录等.不饱和聚酯树脂的合成研究进展.广东化工,2004,9(no)：26
[7]金离尘,刘春华.聚酯工业的多元化发展.聚酯工业,2008,2(21)：3-6
[8]吴良义,王永红.不饱和聚酯树脂国外近十年研究进展.热固性树脂,2006,6(21)：32-37
[9]盛勤,倪礼忠,周权.浇铸型不饱和聚酯树脂的研究.玻璃钢／复合材料,1997(2)：26-27
[10]Burgueno Rigoberto,Quagliata Mario J,Mohanty Amark K,et al.Load bearing structural components from natural fiber and unsaturated polyester biocom-posites.2004 Society for the Advancement of Material and Process Engineering, 2004
[11]Fang Din,Onishi Tetsuya,Ishigai Koichi,et al.Thermoplastic block copolymers low profile unsaturated polyester compositions containing them,and their moldings with high elastic modulus and impact strength.JP.2005120233,2005-03-12
[12]Owada Fujio.Lightweight fire resistant unsaturated polyester compositions with low viscosity.JP.2005023192,2005-01-27
[13]Hirabayashi Tatsuo.Unsaturated polyester compositions with good hydrolysis resistance and littleshrinkage and their electric packaging materials.JP. 2005015612,2005-01-20
[14]Verdel Nada,Benedejcic Natasa,Bokan Bosiljkov Violeta,et al.Polymer concrete based on unsaturated polyester resins from recycled poly (ethylene-terephthalate).Materiali in Tehnologije,2004,38(1-2):87-92
[15]H S Patel,K K Panchal.Novel unsaturated polyester amideresins based on epoxy resins.Polymer Plastics Technology and Engineering.2004,43(4):1174-1185
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[17]蔡永源.国内外不饱和聚酯技术进展(下).化工新型材料,1998,8(no)：7-11
[18]潘祖仁.高分子化学(第二版).北京：化学工业出版社,2002,19-29
[19]黄志雄,彭永利,秦岩等.热固性树脂复合材料及其应用.北京：化学工业出版社,2007,14-20
[20]成跃祖.不饱和聚酯树脂的合成方法及应用.合成树脂及塑料,1993,2(19)：47-51
[21]郭四虎,李永安,杨直.合成不饱和聚酯树脂的新型催化剂.山西化工,2002,2(22)：9
[22]Signor,Vanlandingham M,Chin J.Effects of ultraviolet radiation exposure on vinylester resins:characterization of chemical, physical and mechanical damage. Polymer Degrade and S tability,2003,79(2):359-368
[23]SakaiW,Sadakane T,Nishimoto W,et al.Photosensitized degradation and cross linking of linear aliphatic polyesters by GPC and ESR. Polymer,2002,43(23): 6231-6238
[24]张庆余,韩孝族,纪奎江.低聚物.北京：科学出版社,1994,120
[25]宫文娟,戚嵘嵘,史子兴.DSC法研究UP树脂及增韧剂改性UP树脂的固化行为.工程塑料应用,2008,12,(36)：51
[26]裴运同.开发轿车在线涂装用耐高温聚酯塑料.中国塑料,2001,2(15)：1-3
[27]李战雄.耐高温聚合物.北京：化学工业出版社,2007
[28]张建国.用环氧环己烷制备不饱和聚酯树脂的研究.湖南化工,1999,29,(5)：38-40
[29]ChenLun,HsingChen,Hsiao,et al.Method for making a heat-resistant reflector for LED display suitable for surface mounting.US.5895302.1999-04-20
[30]Brunelle,DanielJoseph,Jang,et al.Method for preparingloy(1,4-cyclohexanedicar boxylates).US.6084055.2000-07-94
[31]Teranish Tadash,He Shougang,et al.Novel polyesters and production process there of.US.Application,20020042496.2002-24-11
[32]Robert R Burch,Steven R Lustig,Maria Spinu.Synthesis of Cyclic Oligoesters and Their Rapid Polymerization to High molecular Weigh.Macromolecules, 2002,33(50):33-64
[33]应燕,王铁军,杨昌正.1,4-环己烷二甲醇改性聚对苯二甲酸乙二酯结晶行为的研究.高分子材料科学与工程,2000,16(1)：120-123
[34]杨建军,吴明元,查刘生等.癸二酸系聚酯多元醇的合成.合成橡胶工业,1999,07(15)：230-232
[35]GB 7193.2-87,不饱和聚醋树脂酸值测定方法.北京：国家标准局,1987
[36]Kakiuchi H,Tana ka Y.J Org Chem.1966,31(2):405
[37]Tanaka Y,Takeuchl H.Tetrahedron.1968,24(6):433
[38]陈平,王德中.环氧树脂及其应用.北京：化学工业出版社,2004,46-48
[39]曾兆华,杨建文,覃定海等.碱水显影阻焊油墨研究——羧基与环氧基的反应.应用化学,2002,1(19)：18-20
[40]刘艳春,邓剑如等.端羟基聚环氧环己烷的合成.应用化学,2005,22(1)：105-107
[41]房江华,胡富陶.Fe-A1-α,α’-联吡啶催化体系催化马来酸酐与环氧环己烷开环共聚.高分子材料科学与工程,2002,18(5)：66-68
[42]房江华,胡富陶.Fe-Al-α,α’-联吡啶催化体系催化邻苯二甲酸酐与环氧环己烷开环共聚.催化学报,2002,23(1)：88-90
[43]赵之山,林宗基.双环戊二烯改性不饱和聚酯树脂的合成.复合材料学报,1995,12(1)：11-17
[44]J.A安迪.分析化学手册.科学出版社,2003,23-32
[45]泉美治,小川雅弥,加藤俊二等.仪器分析导论.化学工业出版社,2005,34-37
[46]黄小慧,李海霞.双环戊二烯改性不饱和聚酯树脂的研究.精细与专用化学品,2006(1)：23-26
[47]尤勇军,沈澄英.环氧酯生产工艺浅析.山西化工,2007,27(6)：60-62
[48]Rudolf Riesen.Application Handbook Thermal Analysis.东华大学出版社,2009,69-77
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[52]谢美丽,何毅,顾宜等.高填充酸酐固化物／二氧化硅复合材料的研究.热固性树脂,2004,5(19)：11-13
[2]周菊兴,栢孝达.不饱和聚酯树脂.北京：中国建筑工业出版社,1981,1-3
[3]张小苹.不饱和聚酯树脂及其新发展.玻璃钢,2008,2(no)：23
[4]沈开猷.不饱和聚酯树脂及其应用.北京：化学工业出版社,2005
[5]栢孝达.我国的不饱和聚酯树脂工业.热固性树脂,2001,6(16)：9
[6]韩秀萍,蒋欣,李玉录等.不饱和聚酯树脂的合成研究进展.广东化工,2004,9(no)：26
[7]金离尘,刘春华.聚酯工业的多元化发展.聚酯工业,2008,2(21)：3-6
[8]吴良义,王永红.不饱和聚酯树脂国外近十年研究进展.热固性树脂,2006,6(21)：32-37
[9]盛勤,倪礼忠,周权.浇铸型不饱和聚酯树脂的研究.玻璃钢／复合材料,1997(2)：26-27
[10]Burgueno Rigoberto,Quagliata Mario J,Mohanty Amark K,et al.Load bearing structural components from natural fiber and unsaturated polyester biocom-posites.2004 Society for the Advancement of Material and Process Engineering, 2004
[11]Fang Din,Onishi Tetsuya,Ishigai Koichi,et al.Thermoplastic block copolymers low profile unsaturated polyester compositions containing them,and their moldings with high elastic modulus and impact strength.JP.2005120233,2005-03-12
[12]Owada Fujio.Lightweight fire resistant unsaturated polyester compositions with low viscosity.JP.2005023192,2005-01-27
[13]Hirabayashi Tatsuo.Unsaturated polyester compositions with good hydrolysis resistance and littleshrinkage and their electric packaging materials.JP. 2005015612,2005-01-20
[14]Verdel Nada,Benedejcic Natasa,Bokan Bosiljkov Violeta,et al.Polymer concrete based on unsaturated polyester resins from recycled poly (ethylene-terephthalate).Materiali in Tehnologije,2004,38(1-2):87-92
[15]H S Patel,K K Panchal.Novel unsaturated polyester amideresins based on epoxy resins.Polymer Plastics Technology and Engineering.2004,43(4):1174-1185
[16]周菊兴.合成树脂与塑料工艺.北京：化学工业出版社,2001
[17]蔡永源.国内外不饱和聚酯技术进展(下).化工新型材料,1998,8(no)：7-11
[18]潘祖仁.高分子化学(第二版).北京：化学工业出版社,2002,19-29
[19]黄志雄,彭永利,秦岩等.热固性树脂复合材料及其应用.北京：化学工业出版社,2007,14-20
[20]成跃祖.不饱和聚酯树脂的合成方法及应用.合成树脂及塑料,1993,2(19)：47-51
[21]郭四虎,李永安,杨直.合成不饱和聚酯树脂的新型催化剂.山西化工,2002,2(22)：9
[22]Signor,Vanlandingham M,Chin J.Effects of ultraviolet radiation exposure on vinylester resins:characterization of chemical, physical and mechanical damage. Polymer Degrade and S tability,2003,79(2):359-368
[23]SakaiW,Sadakane T,Nishimoto W,et al.Photosensitized degradation and cross linking of linear aliphatic polyesters by GPC and ESR. Polymer,2002,43(23): 6231-6238
[24]张庆余,韩孝族,纪奎江.低聚物.北京：科学出版社,1994,120
[25]宫文娟,戚嵘嵘,史子兴.DSC法研究UP树脂及增韧剂改性UP树脂的固化行为.工程塑料应用,2008,12,(36)：51
[26]裴运同.开发轿车在线涂装用耐高温聚酯塑料.中国塑料,2001,2(15)：1-3
[27]李战雄.耐高温聚合物.北京：化学工业出版社,2007
[28]张建国.用环氧环己烷制备不饱和聚酯树脂的研究.湖南化工,1999,29,(5)：38-40
[29]ChenLun,HsingChen,Hsiao,et al.Method for making a heat-resistant reflector for LED display suitable for surface mounting.US.5895302.1999-04-20
[30]Brunelle,DanielJoseph,Jang,et al.Method for preparingloy(1,4-cyclohexanedicar boxylates).US.6084055.2000-07-94
[31]Teranish Tadash,He Shougang,et al.Novel polyesters and production process there of.US.Application,20020042496.2002-24-11
[32]Robert R Burch,Steven R Lustig,Maria Spinu.Synthesis of Cyclic Oligoesters and Their Rapid Polymerization to High molecular Weigh.Macromolecules, 2002,33(50):33-64
[33]应燕,王铁军,杨昌正.1,4-环己烷二甲醇改性聚对苯二甲酸乙二酯结晶行为的研究.高分子材料科学与工程,2000,16(1)：120-123
[34]杨建军,吴明元,查刘生等.癸二酸系聚酯多元醇的合成.合成橡胶工业,1999,07(15)：230-232
[35]GB 7193.2-87,不饱和聚醋树脂酸值测定方法.北京：国家标准局,1987
[36]Kakiuchi H,Tana ka Y.J Org Chem.1966,31(2):405
[37]Tanaka Y,Takeuchl H.Tetrahedron.1968,24(6):433
[38]陈平,王德中.环氧树脂及其应用.北京：化学工业出版社,2004,46-48
[39]曾兆华,杨建文,覃定海等.碱水显影阻焊油墨研究——羧基与环氧基的反应.应用化学,2002,1(19)：18-20
[40]刘艳春,邓剑如等.端羟基聚环氧环己烷的合成.应用化学,2005,22(1)：105-107
[41]房江华,胡富陶.Fe-A1-α,α’-联吡啶催化体系催化马来酸酐与环氧环己烷开环共聚.高分子材料科学与工程,2002,18(5)：66-68
[42]房江华,胡富陶.Fe-Al-α,α’-联吡啶催化体系催化邻苯二甲酸酐与环氧环己烷开环共聚.催化学报,2002,23(1)：88-90
[43]赵之山,林宗基.双环戊二烯改性不饱和聚酯树脂的合成.复合材料学报,1995,12(1)：11-17
[44]J.A安迪.分析化学手册.科学出版社,2003,23-32
[45]泉美治,小川雅弥,加藤俊二等.仪器分析导论.化学工业出版社,2005,34-37
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