有机硅改性聚氨酯胶粘剂的合成研究
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摘要
聚氨酯(PU)是一种性能优异的高分子材料,因具有优异的机械性能、优良的耐磨性、耐疲劳性而受到广泛的重视。聚二甲基硅氧烷(PDMS)具有优异的介电性,柔韧性,耐低温性和耐候性及较好的疏水性和地表面张力。有机硅改性聚氨酯综合了两种材料的优点,扩大了聚氨酯的应用领域。
本文采用共平衡聚合法合成了侧氨基聚硅氧烷(NH2-PDMS),探讨了最优实验条件;以端羟基聚丁二烯(HTPB)为软段、异佛尔酮二异氰酸酯(IPDI)和3,3′-二氯-4,4′-二苯基甲烷二胺(MOCA)为硬段,羟丙基硅油(HO-PDMS)、自制的侧氨基聚硅氧烷(NH2-PDMS)为改性剂,硅氧烷偶联剂(DB-550)为交联剂,合成了两种不同改性硅氧烷封端的HTPB型聚氨酯,采用L9(34)正交实验方法确定了最佳工艺条件,对反应所得到的胶膜进行了力学性能、吸水率、耐老化测试,用FTIR、SEM、TG对产物进行了表征。
结果表明:合成NH2-PDMS的最优条件为:反应时间为7h,反应温度为120℃,乙醇钾的用量为0.13%,二甲基亚砜的用量为1.0%。
R=2.5、HO-PDMS含量为9%、nMOCA:nDB-550=9:1,采用直接法可以得到力学性能较好的HO-PDMS改性PU;HO-PDMS加入量为9%,此时得到得产品的吸水率较低,耐老化性较优。
R=2.5、NH2-PDMS含量为12%、nMOCA:nDB-550=9:1,采用预聚法可以得到力学性能较好的NH2-PDMS改性PU。NH2-PDMS加入量为12%,此时得到得产品的吸水率较低,耐老化性较优。
TG显示硅氧烷同在等加入量(9%)的情况下,800℃燃烧后,NH2-PDMS改性PU的含碳量比HO-PDMS改性PU的含碳量大,且灰分质量要大。
实验发现,改性PU中加入13X型沸石分子筛可以有效的减少气泡的产生。
Polyurethane (PU) is an important and versatile class of polymer materials. It is attracting significant attention and becoming more and more important as an engineering material, because of its excellent properties such as good mechanical properties, high abrasive resistance, wearability and high impact strength. Polysiloxane (PDMS) has excellent ability such as thermal stability, water resistance, surface property and dielectric property. PDMS modified PU integrated the outstanding performance of two and broadened the application area of PU.
In this paper, (sideamino dimethylsiloxane)NH2-PDMS was synthesized by co- equilibrium methods and the optimum technology condition were obtained. The synthesis of siloxane-urethane block polymers has been carried out from (NH2-PDMS) and oxhydryl end-capped oxhydryl dimethylsiloxane (HO-PDMS) chains, in which isophorone diisocyanate(IPDI), Hydroxyl-terminated polybutadiene (HTPB), 4,4'-methylenebis (2-chloroaniline) (MOCA) andγ-aminopropyl trimethoxysilane were the materials. The optimum technology condition were obtained by three orthogonal experiments and mechanical properties,water absorption and aging-test were tested, the FTIR, TG, DSC,SEM were also used in Characterization.
The result show that: The optimum technology conditions of NH2-PDMS synthesis were as follows: the reaction time was 7h, the reaction temperature was 120℃, the dosage of CH3CH2OK was 0.13% and the dosage of dimethylsulfoxide was 1.0%.
R=2.5, NH2-PDMS=12%, nMOCA:nDB-550=9:1;with the direct method;outstanding performance of NH2-PDMS modified PU can be obtained. When NH2-PDMS content was 12%, Water absorptivity were lower and the aging ability were better.
R=2.5, HO-PDMS=9%, nMOCA:nDB-550 = 9:1;with prepolymer method; outstanding performance of HO-PDMS modified PU can be obtained. When HO-PDMS content was 9%, Water absorptivity were lower and the the aging ability were better.
TG showed that after burning at 800℃in the same PDMS containing,the weight of grayish of NH2-PDMS modified PU are weighter than HO-PDMS modified PU.
Zeolite of 13X can effectively reduce bubble if it were used in modified PU.
本文采用共平衡聚合法合成了侧氨基聚硅氧烷(NH2-PDMS),探讨了最优实验条件;以端羟基聚丁二烯(HTPB)为软段、异佛尔酮二异氰酸酯(IPDI)和3,3′-二氯-4,4′-二苯基甲烷二胺(MOCA)为硬段,羟丙基硅油(HO-PDMS)、自制的侧氨基聚硅氧烷(NH2-PDMS)为改性剂,硅氧烷偶联剂(DB-550)为交联剂,合成了两种不同改性硅氧烷封端的HTPB型聚氨酯,采用L9(34)正交实验方法确定了最佳工艺条件,对反应所得到的胶膜进行了力学性能、吸水率、耐老化测试,用FTIR、SEM、TG对产物进行了表征。
结果表明:合成NH2-PDMS的最优条件为:反应时间为7h,反应温度为120℃,乙醇钾的用量为0.13%,二甲基亚砜的用量为1.0%。
R=2.5、HO-PDMS含量为9%、nMOCA:nDB-550=9:1,采用直接法可以得到力学性能较好的HO-PDMS改性PU;HO-PDMS加入量为9%,此时得到得产品的吸水率较低,耐老化性较优。
R=2.5、NH2-PDMS含量为12%、nMOCA:nDB-550=9:1,采用预聚法可以得到力学性能较好的NH2-PDMS改性PU。NH2-PDMS加入量为12%,此时得到得产品的吸水率较低,耐老化性较优。
TG显示硅氧烷同在等加入量(9%)的情况下,800℃燃烧后,NH2-PDMS改性PU的含碳量比HO-PDMS改性PU的含碳量大,且灰分质量要大。
实验发现,改性PU中加入13X型沸石分子筛可以有效的减少气泡的产生。
Polyurethane (PU) is an important and versatile class of polymer materials. It is attracting significant attention and becoming more and more important as an engineering material, because of its excellent properties such as good mechanical properties, high abrasive resistance, wearability and high impact strength. Polysiloxane (PDMS) has excellent ability such as thermal stability, water resistance, surface property and dielectric property. PDMS modified PU integrated the outstanding performance of two and broadened the application area of PU.
In this paper, (sideamino dimethylsiloxane)NH2-PDMS was synthesized by co- equilibrium methods and the optimum technology condition were obtained. The synthesis of siloxane-urethane block polymers has been carried out from (NH2-PDMS) and oxhydryl end-capped oxhydryl dimethylsiloxane (HO-PDMS) chains, in which isophorone diisocyanate(IPDI), Hydroxyl-terminated polybutadiene (HTPB), 4,4'-methylenebis (2-chloroaniline) (MOCA) andγ-aminopropyl trimethoxysilane were the materials. The optimum technology condition were obtained by three orthogonal experiments and mechanical properties,water absorption and aging-test were tested, the FTIR, TG, DSC,SEM were also used in Characterization.
The result show that: The optimum technology conditions of NH2-PDMS synthesis were as follows: the reaction time was 7h, the reaction temperature was 120℃, the dosage of CH3CH2OK was 0.13% and the dosage of dimethylsulfoxide was 1.0%.
R=2.5, NH2-PDMS=12%, nMOCA:nDB-550=9:1;with the direct method;outstanding performance of NH2-PDMS modified PU can be obtained. When NH2-PDMS content was 12%, Water absorptivity were lower and the aging ability were better.
R=2.5, HO-PDMS=9%, nMOCA:nDB-550 = 9:1;with prepolymer method; outstanding performance of HO-PDMS modified PU can be obtained. When HO-PDMS content was 9%, Water absorptivity were lower and the the aging ability were better.
TG showed that after burning at 800℃in the same PDMS containing,the weight of grayish of NH2-PDMS modified PU are weighter than HO-PDMS modified PU.
Zeolite of 13X can effectively reduce bubble if it were used in modified PU.
引文
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[2] Miller C.E., Edelman P.G., Ratner B.D., et al. Near-infrared spectroscopic analyses of poly(ether urethane urea)block copolymers. Part II: Phase separation[J]. Appl. Spectroscope. 1990, 44:581-586.
[3] Russo R., Thomas E.L. Phase separation in linear and cross-linked polyurethanes[J]. J. Micromole. Sci.Phy.1983, 22:551-573.
[4] Quay J.R.,Sun Z.,Blackwell J., et al. The hard segment unit cell for MDI- BDO- based polyurethane elastomers[J],Polymer 1990,31:1003-1008.
[5] Blackwell J.,Nagarajan M.R., Hoitink T.,The structure of hard segments in polyure- thane[J]. elastomers,Polym.Pre.1980,21:303-304.
[6]傅明源,孙酣经.聚氨酯弹性体及其应用[M].北京:化学工业出版社,2003,5-7.
[7]晨光化工研究院有机硅编写组,有机硅单体及聚合物[M].化学工业出版社.北京,1986: l, 7-10.
[8]吴纪森.有机硅及其应用[M].北京:化学工业出版社,1985:172 -173.
[9]冯圣玉,张洁等.有机硅高分子及其应用[M].北京:化学工业出版社,2004:1, 34-35.
[10]幸松民,王一璐.有机硅合成工艺及产品应用[M].北京:化学工业出版社, 2000, 5,70-74.
[11] Azam Rahimi, Parvin Shokrolahi. Application of inorganic polymeric materials I. polysiloxanes[J]. International Journal of Inorganic Materials, 2001(3):843-847.
[10]余学海,杨昌正,陈雷,会聚硅氧烷共聚物的研究动向[J],功能高分子学报,1991,4 (3):168-180.
[11] Yang C Z,Li C., Cooper SL.Synthesis and characterization of polydimethysiloxane polyurea-urethanes and related zwitterionomers[J]. J. Polym Sci:Polym Phys, 1991, 29:75-86.
[12]徐国强,李荣俊,林绍基.重防腐蚀聚硅氧烷涂料[J].涂料工业,2004,34(8),45-48.
[13]陈景林,罗志臣,李翠莉.Y-128有机硅建筑防水涂料的研制[J].吉林化工学院学报,2004, 21(1):40-41.
[14]杨始燕,汪倩,谢择民.空间级加成型室温硫化硅橡胶粘结剂的研究[J].宇航材料工艺,2000(1):42-45.
[15]郑钦健,李航昱,陈少鹏,等.含氨基聚硅氧烷改性环氧树脂[J].厦门大学学报(自然科学版),2005,44(3):399-402.
[16] Ho Tsung-Han, Wang Chun-Shan. Modification of epoxy resin with siloxane con- taining phenol aralkyl epoxy resin for elect ronic encapsulation application[J]. European Polymer Journal, 2001(37):267-274.
[17]蔡翔,刘侃,苏开第.抗菌整理剂CL的合成与应用性能[J].印染助剂,2000,17(6):22-25.
[18]李俊英,冯圣玉,李天铎.聚硅氧烷季铵盐抗菌整理剂的合成及应用[J].日用化学工业,2003,33(4):249-251.
[19]周建华,张晓镭,赵海萍,等.反应性氨基聚硅氧烷RASI织物柔软剂的制备[J].精细化工,2004,21(3):216-219.
[20]左晶,李临生,丁红梅,等.有机聚硅氧烷在医药中的应用进展[J].化工进展,2005, 24(1):14-20.
[21] Li Lihua, Tu Mei, Mou Shansong, et al. Preparation and blood compatibility of polysiloxane/liquid–crystal composite membranes[J]. Biomaterials, 2001(22):2595- 2599.
[22] Myler S, Davis F., Collyer S D, et al. Sonochemically fabricated microelect rode arrays for biosensors-part II Modification with a polysiloxane coating[J]. Biosensors and Bioelect ronics, 2004(20):408-412.
[23] Jovanovic J, Adnadjevic B, Kicanovic M. The influence of hydrox-yapatite modify- cation on the cross-linking of polydimet hylsiloxane/Hapcomposites[J]. Colloids and Surfaces B: Biointerfaces, 2004(39):181-186.
[24] Yu X.H.,Nagarajan M.R.,Grasel T.G.,et al. Polydimethylsiloxane polyurethaneelastomers:synthesis and propertiesof segmented copolymers and related witterio- nomers[J]. Polym Sci:Polym Phys, 1985,23(11):2319-2338.
[25] Yu X, Nagarajan M R, Li C, et al. Poly(chlorpropylmethyl-dimethylsiloxane) polyure- thane elastomers: synthesis and propertiesof segmented copolymer and related zwitterionomers[J]. J Polym Sci:Polym Physics, 1986 , 24:2681-2701.
[26]陈雷,余学海.聚氰丙基甲基硅氧烷-聚脲嵌段共聚物的结构和性能[J].功能高分子学报,1991,4(1):19-28.
[27]陈雷,朱育平,余学海,等.聚硅氧烷-聚脲嵌段共聚物的形态结构的研究[J].高分子材料科学与工程,1992,(1):45-50.
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