两性离子型酚醛树脂钻井液降滤失剂的合成与性能

Synthesis and Performance Properties of Amphoteric Phenolic Resin as Filtration Loss Reducer for Drilling Fluids

基于酚醛树脂合成及苯环上取代反应原理,使低分子量的线性酚醛树脂先与二甲胺盐酸盐+甲醛反应,再与碘甲烷反应,制得含碘化亚甲基三甲基铵盐基团的阳离子中间体;使该树脂与羟甲基磺酸钠反应,制得含磺甲基的阴离子中间体;两种中间体在甲醛存在下缩聚,合成了水溶性的两性酚醛树脂。采用正交设计实验方法,根据合成物的阳离子含量、阴离子含量、粘土胶体化率、粘土膨胀率及MMH泥浆和10%盐水浆API滤失量数据,确定了两种中间体和两性树脂的最佳合成条件,得到的两性酚醛树脂(25%～28%水溶液)即为正电胶钻井液降滤失剂DSP 1。在加量为2.0%和2.5%时,DSP 1使0.8%MMH/6.0%膨润土浆的API滤失量由96.2mL分别降至24.6和22.4mL,120℃和150℃滚动16h后的AV和PV变化不大,API滤失量分别为28.8和31.6mL。页岩在2.0%和3.0%DSP 1水溶液中的回收率数据表明,DSP 1具有一定的抑制性。表6。

On the basis of principles of phenolic resin synthesis and of replacing reactions on the benzene ring, a cationic phenolic resin containing group methylenetrimethyl ammonium iodide is obtained by reacting a novalac resin with dimethylamine hydrochloride and formaldehyde at first and with methyl iodide then, an anionic phenolic resin containing sulfomethyl group — with hydroxymethyl sulfonic acid in sodium salt form and a water soluble amphoteric phenolic resin — by polycondensation of the cationic and the anionic phenolic resins at the presence of formaldehyde. Through 3 sets of orthogonalized experiments with 2—3 characteristics from cation or anion content, colloidity of clay, clay swelling, and API fitration loss of MMH mud or 10% salt water mud, the syntheses of cationic, anionic, and amphoteric phenolic resins are optimized and the amphoteric resin in 25—28% aaqueous solution is prepared as fitration loss reducer DSP-1 for positively charged MMH drilling fluid. For 6.0% bentonite/0.8% MMH mud with dosage DSP-1 of 2.0% and 2.5%, the API filtration loss reduces from 96.2 mL to 24.6 and 22.4 mL, respectively, and after rolling at 120℃ or 150℃ in 16 hrs, the AV and PV values change slightly and API filtration loss acounts 28.8 and 31.6 mL, respectively. The data of shale recovery in 2.0% and 3.0% DSP-1 aqueous solutions show that DSP-1 possesses inhibitory property in some extent.