This application is directed to novel fluorinated polymers and prepolymers derived from mono-substituted oxetane monomers having fluorinated alkoxymethylene side-chains and the method of making these compositions. The mono-substituted fluorinated oxetane monomers having fluorinated alkoxymethylene side-chains are prepared in high yield by the reaction of a fluorinated alkoxides with either 3-halomethyl-3-methyloxetane premonomers or aryl sulfonate derivative of 3-hydroxymethyl-3-methyloxetane premonomers. Preparation of a mono-substituted 3-bromomethyl-3-methyloxetane premonomer via a simple, high yield process amenable to commercial scaleup is also disclosed. The fluorinated oxetane monomers of this invention can be readily homo/co-polymerized in the presence of a Lewis acid and polyhydroxy compounds to obtain hydroxy-terminated polyether prepolymers having fluorinated alkoxymethylene side chains. Additionally, the fluorinated oxetane monomers can be copolymerized with non-fluorinated monomers such as tetrahydrofuran to give polyether prepolymers with improved hydrocarbon compatibility. These prepolymers are polydisperse and exhibit number average molecular weights from 5,000 to about 50,000. These prepolymers are amorphous oils with primary hydroxy end-groups and thus function efficiently as the soft block for the synthesis of a variety of thermoset/thermoplastic elastomers and plastics having the characteristics of very low surface energy, high hydrophobicity, low glasss transition temperature and low coefficient of friction. The polyurethanes derived from the prepolymers of this invention are elastomeric and, in addition to the above characteristics, exhibit high moisture resistance, high tear strength and excellent adhesion to a variety of substrates.
该申请涉及一种新型的含
氟聚合物和预聚物,其源自于具有含
氟烷氧甲基侧链的单取代
氧杂
环戊烷单体,并且涉及制备这些组合物的方法。这些具有含
氟烷氧甲基侧链的单取代
氟氧杂
环戊烷单体可通过将含
氟烷氧化物与3-卤代
甲基-3-甲
氧基
氧杂
环戊烷预聚物或3-
羟甲基-3-甲
氧基
氧杂
环戊烷预聚物的芳基
磺酸衍
生物反应而高产率制备。此外,还公开了一种简单、高产率的方法,通过该方法可以制备单取代3-
溴甲基-3-甲
氧基
氧杂
环戊烷预聚物,该方法适用于商业规模生产。本发明的含
氟氧杂
环戊烷单体可以在
路易斯酸和多羟化合物的存在下容易地进行同聚/共聚反应,以获得具有含
氟烷氧甲基侧链的羟基终止的聚醚预聚物。此外,含
氟氧杂
环戊烷单体可以与
四氢呋喃等非含
氟单体共聚,以获得具有改善烃类相容性的聚醚预聚物。这些预聚物是多分散的,并且具有5,000至约50,000的数平均分子量。这些预聚物是无定形油状物,具有主要的羟基末端,因此可以有效地作为合成各种热固性/热塑性弹性体和塑料的软块,具有极低的表面能、高疏
水性、低
玻璃转移温度和低摩擦系数的特性。本发明的预聚物衍生的聚
氨酯具有弹性,并且除了上述特性外,还具有高湿度抗性、高撕裂强度和对各种基材的优异粘附性。