Glass fiber reinforced vinyl chloride polymer products and process for their preparation
申请人:THE B.F. GOODRICH COMPANY
公开号:EP0257524A2
公开(公告)日:1988-03-02
Vinyl chloride (VC) resins, particularly poly(vinyl chloride) (PVC) and chlorinated poly(vinyl chloride) (CPVC) are reinforced with glass fibers which have been sized with a particular aminosilane coupling agent and a particularly chracterized basic film former. At the processing temperature of VC resin, containing a stabilizer against degradation during thermoforming, for example in an extruder, or on a mixing mill used to blend the resin with sized glass fibers, a reaction occurs between an aminosilane coupling agent and the VC resin which reaction involves C=C bonds in the homopolymer, provided the polymer film former in the size is more basic than poly(vinyl acetate) ("PVA"). The film former catalyzes the thermal dehydrohalogenation of the VC homopolymer at the fiber-resin interface so as to generate allylic Cl moieties in chains of the homopolymer, which moieties react with the amine groups of the aminosilane. The size is most conveniently coated on the fibers from a sizing solution, dispersion or emulsion containing the coupling agent and film former in which allylic Cl moieties in VC resin chains become covalently bonded to an aminosilane, so that even upon thorough extraction of a GFR VC composite with tetrahydrofuran (THF), sufficient bound VC resin remains so that X-ray photoelectron spectroscopic (XPS) examination indicates that the ratio of total chlorine to total carbon remaining on the surface of the glass fibers, i.e. the ratio of the areas of the "Cl(2p)/C(ls)" peaks, is at least 0.9l.
氯乙烯(VC)树脂,特别是聚氯乙烯(PVC)和氯化聚氯乙烯(CPVC),是用玻璃纤维加固的,玻璃纤维的尺寸是用一种特殊的氨基硅烷偶联剂和一种特殊的铬化碱性成膜剂确定的。在含有防止热成型过程中降解的稳定剂的氯乙烯树脂的加工温度下,例如在挤出机中,或在用于将树脂与一定尺寸的玻璃纤维混合的混炼机上,氨基硅烷偶联剂与氯乙烯树脂之间会发生反应,该反应涉及均聚物中的 C=C 键,条件是聚合物成膜剂的碱性大于聚醋酸乙烯酯("PVA")。成膜剂在纤维-树脂界面上催化 VC 均聚物的热脱氢卤化反应,从而在均聚物链中生成烯丙基 Cl 分子,该分子与氨基硅烷的胺基团发生反应。最方便的方法是将含有偶联剂和成膜剂的上浆溶液、分散体或乳液涂覆在纤维上,在这种情况下,VC 树脂链中的烯丙基 Cl 分子会与氨基硅烷发生共价键合,因此,即使用四氢呋喃(THF)彻底萃取 GFR VC 复合材料,也会残留足够的结合 VC 树脂,从而使 X 射线光电子能谱(XPS)检查显示玻璃纤维表面残留的总氯与总碳之比,即玻璃纤维表面总氯与总碳的面积之比。即 "Cl(2p)/C(ls) "峰的面积比至少为 0.9l。