The Synthesis and Evaluation of a High Temperature Nano Micro-Spherical Polymer Plugging Agent
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摘要: 针对目前钻井用柔性封堵剂抗温性弱的问题，开展了抗高温聚合物纳米微球封堵剂的研究。以丙烯酰胺（AM）、对苯乙烯磺酸钠（SSS）、丙烯酸钠（AAS）、丙烯酸十三氟辛酯（TEAC）和1,3,5-三（甲基丙烯酰胺基甲酸酯）苯（B-TMAC）为原料，偶氮异丁氰基甲酰胺（CABN）为引发剂，十二烷基硫醇（TDDM）为分子量调节剂，通过自由基胶束聚合法合成了聚合物纳米微球OPTB。通过正交实验确定了最佳合成条件：反应温度105 ℃、反应时间20 h、反应单体浓度7.5%、CABN浓度0.4%和TDDM浓度1.5%。借助核磁共振光谱仪（1H-NMR）进行了分子结构表征。OPTB的钻井液性能测试结果显示，OPTB对钻井液的流变性能影响较小，滤失造壁性能显著。高温老化后，OPTB的粒径仍呈单分散状态。OPTB的加量达到3.0%时，对纳微米孔隙的封堵率高达90.84%，且可有效减慢井筒内液柱压力向地层传递的速度。采用扫描电镜（ESEM）观测了160 ℃老化16 h前后的OPTB的微观形貌，结果显示 OPTB颗粒呈球形，粒径较均一，高温作用仍有部分颗粒仍保持单分散状态。Abstract: A nano micro-spherical polymer plugging agent OPTB was developed to try to replace the flexible plugging agents presently in use, which have the shortage of low thermal stability. OTPB is a high temperature plugging agent and is synthesized through free radical micellar polymerization with several raw materials such as acrylamide (AM), sodium p-styrene sulfonate (SSS), sodium acrylate (AAS), 1H,1H,2H,2H-perfluorooctyl acrylate (TEAC) and 1,3,5-tris(methacrylamido) benzene (B-TMAC). The polymerization used 1-((cyano-1-methylethyl) azo) formamide as the initiator, and dodecyl mercaptan (TDDM) as the molecular weight regulator. The optimum synthesis conditions were determined through orthogonal experiment, as follows: reaction temperature = 105 ℃, reaction time = 20 h, concentration of the monomeric raw materials = 7.5%, concentration of CABN = 0.4%, and concentration of TDDM = 1.5%. The molecular structure of OPTB was characterized with 1H-NMR. Experiment on the properties of the drilling fluid treated with OPTB showed that OPTB has little effect on the rheology of the drilling fluid, and the quality of the mud cake was significantly improved. After aging at high temperature, the particle size of OPTB is still in a monodisperse state. At a concentration of 3.0%, 90.84% of the nanometer-sized and micron-sized pores can be plugged by OPTB, and this plugging effect can effectively slow down the transmission of the pressure of the fluid column in the wellbore into the formations. The micromorphology of OPTB before and after aging at 160 ℃ for 16 h observed under SEM showed that the particles of OPTB are spherical with narrow size distribution. At elevated temperatures, part of the OPTB particles is still in monodisperse state.
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表 1 L16（45）正交实验
水平 A B C D E 反应温
度/℃反应时
间/h反应单体
浓度/%CABN
浓度/%TDDM
浓度/%1 100 8 5.0 0.2 0.5 2 105 12 7.5 0.4 1.0 3 110 16 10.0 0.6 1.5 4 115 20 12.5 0.8 2.0 
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表 2 L16（45）正交实验结果
实验号 A B C D E 封堵率/% 1# 100 8 5.0 0.2 0.01 87.5 2# 100 12 7.5 0.4 0.02 88.2 3# 100 16 10.0 0.6 0.03 90.3 4# 100 20 12.5 0.8 0.04 91.2 5# 105 8 7.5 0.6 0.04 90.5 6# 105 12 5.0 0.8 0.03 95.0 7# 105 16 12.5 0.2 0.02 93.2 8# 105 20 10.0 0.4 0.01 91.7 9# 110 8 10.0 0.8 0.02 91.4 10# 110 12 12.5 0.6 0.01 84.2 11# 110 16 5.0 0.4 0.04 92.2 12# 110 20 7.5 0.2 0.03 95.8 13# 115 8 12.5 0.4 0.03 95.5 14# 115 12 10.0 0.2 0.04 87.4 15# 115 16 7.5 0.8 0.01 89.9 16# 115 20 5.0 0.6 0.02 87.0 均值1 89.300 91.225 90.425 90.975 88.325 均值2 92.600 88.700 91.100 91.900 89.950 均值3 90.900 91.400 90.200 88.000 94.150 均值4 89.950 91.425 91.025 91.875 90.325 极差（R） 3.300 2.725 0.900 3.900 5.825
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表 3 钻井液流变性能及滤失性能测试结果
OPTB/
%T老化/
℃AV/
mPa·sPV/
mPa·sYP/
PaFLAPI/
mLFLHTHP/
mL0 100 16.0 11.0 5.0 12.6 32.0 120 16.0 11.0 5.0 13.0 32.6 140 15.5 11.0 4.5 14.4 35.0 160 14.5 10.0 4.5 16.8 40.0 180 12.0 8.0 4.0 18.8 60.4 1.0 100 17.5 12.0 5.5 9.2 23.4 120 17.0 12.0 5.0 9.2 24.0 140 16.0 11.0 5.0 9.6 24.8 160 15.0 10.0 5.0 11.8 27.2 180 11.5 8.0 3.5 18.6 58.4 2.0 100 17.5 12.0 5.5 8.6 20.2 120 16.5 11.0 5.5 8.8 21.6 140 16.5 11.0 5.5 9.0 22.4 160 15.5 11.0 4.5 10.8 24.0 180 11.5 8.0 3.5 18.4 58.0 3.0 100 18.5 13.0 5.5 8.0 19.6 120 17.5 12.0 5.5 8.2 20.8 140 17.0 12.0 5.0 8.6 22.0 160 16.0 11.0 5.0 10.0 23.4 180 12.0 8.0 4.0 18.0 57.6 注：磺化钻井液体系：4.0%预水化膨润土浆+0.3%PAC-
HV+1.0%SMC+1.0%SMP-I+1.0%SPNH
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表 4 OPTB对模拟纳微米孔隙地层封堵率的测试结果
OPTB/
%T老化/
℃平均流量/
cm2·s−1渗透率/
10−2 mD封堵率/
%1.0 100 0.1512 39.26 89.84 120 0.2089 54.24 85.96 140 0.3455 89.70 76.79 160 0.4718 122.49 68.30 2.0 100 0.0875 22.72 94.12 120 0.1372 35.62 90.78 140 0.1598 41.49 89.26 160 0.1917 49.77 87.12 3.0 100 0.0500 12.98 96.64 120 0.0916 23.78 93.85 140 0.1251 32.48 91.59 160 0.1364 35.41 90.84 注： 模拟纳微米级孔隙地层的渗透率为386.4×10−2 mD，
磺化钻井液的流量为1.4883 cm2·s−1
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