摘要
目前,自组织共混型高分子梯度材料的研究引起越来越多人的关注。由于形成自组织高分子梯度材料的多组分共混物中某组分被接枝具有特定功能的官能团,因而该组分能自发地向材料表面迁移富集,自组织形成梯度结构,从而可得到各种具有特殊功能的材料表面。另外,共混聚合物在静态退火过程中,由于外界因素的影响,也会形成梯度分布的相形态。由于含硅的聚氨酯的表面能比含酯的聚氨酯低,通过控制成膜条件,含硅的聚氨酯在成膜时会发生自组织行为(如自分层),使该类膜的一侧表面具有有机硅本身的耐老化、长寿命、抗污自洁、耐溶剂及防水等优点,而另一侧表面具有聚氨酯的一系列优良特性,且在厚度方向上任一组分浓度从一侧到另一侧变化,从而获得性价比高的含硅的聚氨酯自组织材料。
本工作的主要创新包括以下两点。(1)首次研究了α,ω-二-(4-羟基丁基)聚二甲基硅氧烷与聚已二酸乙二醇酯二醇同时与2,4-甲苯二异氰酸酯反应生成聚氨酯自组织材料。(2)初步研究了热处理对含硅聚氨酯自组织结构表界面性能的影响。
本论文主要研究内容和结论概括为如下几方面。首先,以二甲基二氯硅烷、四氢呋喃和镁粉为原料,碘和碘乙烷为催化剂合成了二-(4-羟基丁基)四甲基二硅氧烷(BHBTMDS),讨论了合成工艺对产率的影响,结果表明,一步法的产率高于两步法;水解过程中需加入18mL水和0.4mL盐酸。二甲基二甲氧基硅烷和BHBTMDS在计量酸和水下进一步反应生成分子量可控的α,ω-二-(4-羟基丁基)聚二甲基硅氧烷(HB-PDMS),讨论了合成条件的影响,结果表明,在80℃下进行反应;甲醇/水的混合物是为了除去低分子量产物。HB-PDMS的分子量通过羟基滴定法来标定,结果表明,HB-PDMS滴定的分子量总是高于设定的分子量。BHBTMDS和HB-PDMS的结构用傅立叶红外光谱和核磁共振来表征。
以已二酸和乙二醇为原料合成了端羟基聚已二酸乙二醇酯,并探讨了端羟丁基聚硅氧烷和端羟基聚已二酸乙二醇酯的表面张力与分子量、温度的关系。从结果上来看,端羟丁基聚硅氧烷和端羟基聚已二酸乙二醇酯的表面张力随着分子量的增大而增大;端羟丁基聚硅氧烷和端羟基聚已二酸乙二醇酯的表面张力随着温度的升高而减少,且呈线性关系。
以HB-PDMS、2,4-甲苯二异氰酸酯和1,4-丁二醇为原料合成了含硅氧烷聚氨酯。以端羟基聚已二酸乙二醇酯、2,4-甲苯二异氰酸酯和1,4-丁二醇为原料合成了含酯聚氨酯,研究了含硅氧烷聚氨酯与含酯聚氨酯性能的不同。结果表明,含硅氧烷聚氨酯和含酯聚氨酯都呈现两个玻璃化温度,表明软段与硬段相分离,这可能是由于软段和硬段的溶解参数相差太大的缘故造成的。含硅聚氨酯和含酯聚氨酯都有两个热分解峰。从接触角和表面自由能的结果上来看,都可以说明PDMS向空气界面迁移。
将HB-PDMS和端羟基聚已二酸乙二醇酯同时与2,4-甲苯二异氰酸酯通过溶液聚合法反应生成含硅的聚氨酯,研究了退火工艺对自组织结构的影响。结果表明,在退火条件下膜可以形成自组织结构。当HB-PDMS和端羟基聚已二酸乙二醇酯按质量比1:3同时与2,4-甲苯二异氰酸酯反应,在室温下以聚四氟乙烯板为成膜基材成膜后,在120℃下随热处理时间增加,膜与基材界面的表面能先迅速降低,然后缓慢降低。经过热处理后,没有改变膜相分离的状况;XPS分析进一步说明了硅向表面迁移。
上述基础研究确定了含硅聚氨酯溶液形成自组织膜的成膜条件,具有学术价值。通过溶液法制备自组织含硅聚合物材料是适应世界环保要求和可持续发展主题的需要。另外,该研究在国内是一片空白,而且国外研究报道也极少。此研究可以填补国内空白。
Gradient polymer blend materials through self-organization have attracted increasing attention of many investigators recently.Due to one component in blends having special functional groups,this component could self-organize to the surface of blend films during film-formation process or annealing process,and accordingly a film surface with special properties is obtained.Silicon-based polyurethanes have much lower surface free energy than easter-based polyurethanes,so self-organization will happen during the film-formation under effects of surface free energy.Finally,a silicon polymer material is obtained.In this material,one surface side exhibits special surface properties,such as anti-aging,long-life,self-cleaning properties, solvent-resistance and water-resistance,whereas,the other surface side shows good properties of polyurethanes.
The creative achievements of this thesis are as follows.(1)It has been studied silicon-based polyurethane and easter-based polyurethane and 2,4-tolyleme diisocyanate reacted to self-organization film.(3)It has been comprehensively discussed that heat-treatment conditions could facilitate structure formation of blend of silicon-based polyurethane and easter-based polyurethane.
The main research contents and conclusions are divided into the following parts. Using ethyl iodide and iodine as catalysts,1,3-bis(4-hydroxybutyl)tetramethyldi—siloxane(BHBTMDS) was directly synthesized from dimethyldichlorosilane, tetrahydrofuran and magnesium powder.And we studied the effects of the synthesis process on rate of production.The results showed that the rate of production of one-step synthesis was higher than two-step synthesis,and we added 18mL H_2O and 0.4mL HCl on the hydrolysis process,α,ω-Bis(4-hydroxybutyl) polydimethylsiloxane(HB-PDMS)with different molecular weight could be prepared through the reaction of 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane and dimethoxydimethylsilane in the presence of a stoichiometric amount of water and hydrochloric acid.We studied the effects of the synthesis condition.The results showed that the reaction was carried at 80℃,and the compound of methanol and water removed the low molecular product.The number molecular weight of these hydroxybutyl-terminated polydimethylsiloxanes could be determined fairly by end group titration method.The number-average molecular weight of an HB-PDMS obtained is higher than the targeted molecular weight.Structures of BHBTMDS and HB-PDMS were characterized by Fourier transform infrared spectroscopy(FT-IR) and high-resolution ~1H NMR
Poly(ethylene-glycol-adipate)diols was directly synthesized from adipic acid and ethanediol.We probed the relation of tension and molecular weight and temperture of HB-PDMS and poly(ethylene-glycol-adipate)diols.The results showed that the tension of HB-PDMS and poly(ethylene-glycol-adipate)diols increase as molecular weight increase.The tensiaon of HB-PDMS and poly(ethylene-glycol-adipate)diols decrease as temperature increase,and they are linear.
Silicon-based polyurethane,based on HB-PDMS,2,4-tolylene diisocyanate, 1,4-butanediol as a chain extender and dibutyltin dilaurate as a catalyzer were synthesized using solution polymerization procedure.Easter-based polyurethane based on poly(ethylene-glycol-adipate)diols,2,4-tolylene diisocyanate(2,4-TDI), 1,4-butanediol as a chain extender and dibutyltin dilaurate as a catalyzer were synthesized using solution polymerization procedure.We studied the different properties between PDMS-based polyurethane and easter-based polyurethane.A complex micro-phase separation of soft segment from the hard segment was demonstrated by DSC.The decomposition of polyurethanes had two steps.The dynamic water contact angles of the sample from the Wilhelmy method indicated that the sample containing polydimethylsiloxane could not be wetted by water.It was suggested that the low surface energy characteristic of PDMS promoted migration to the air-polymer interface to form a predominately PDMS enriched surface.
PDMS-based polyurethane based on poly(ethylene-glycol-adipate)diols and HB-PDMS,2,4-tolylene diisocyanate,1,4-butanediol as a chain extender and dibutyltin dilaurate as a catalyzer was synthesized using solution polymerization procedure,and we studied the effects of annealing process on self-organization.The results showed that under annealing process films could self-organize to material. When teflon was film-formation matix and when the ration of HB-PDMS to poly(ethylene-glycol-adipate)diols was 1:3,the surface free energy in film-teflon in terface of films decreased with enhancing heat-treating 6h at 120℃.The results of XPS showed silicon could move to surface.
In this thesis,the relationship between film-formation conditions and the structure of silicon based-polyurethanes through self-organization has been clarified.The results provide the scientific foundation.The progress of blending in system belongs to green technology.It is worth noting that researchers and ultilizing of renewable resources are compliant with the national objective and sustainable development.
引文
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