第21卷第4期油田化學(xué)Vol 21 No 42004年12月25日Oilfield Chemist25Dec,2004文章編號:1000-409x(2004)4033303含氟丙烯酸酯AFSN及其與丙烯酰胺、丙烯酸的共聚物PAMF的合成與共聚物水溶液粘度性能王云芳,孔瑛,楊金榮,辛偉,馮志強(石油大學(xué)華東光學(xué)化工學(xué)院山東東營257061)摘要將將杜邦公司的商品氟表面活性劑 Zonyl FSN含全氟烷基的脂肪醇)與丙烯酰氯AC)等在低溫下反應(yīng)合成了含氟丙烯酸酯AFSN按產(chǎn)物收率和純度確定最佳摩爾比FSN:AC=1:1.05最佳反應(yīng)時間為11~12小時。用IR譜表征了AFSN的結(jié)構(gòu)。將 AFSNAM、AA在水溶液中共聚得到了含氟疏水締合水溶性聚合物PAMF3和PAMF孓混合單體總質(zhì)量中AFSN分別占0.3%和0.5%)PAMF共聚物在水溶液中的增粘性、抗鹽性和耐溫性遠高于超高分子量HPAM。室溫下濃度為1.5g/L的HPAM、PAMF5、PAMF3水溶液不含鹽時粘度分別為520、690、530 mPa s nacl濃度為15g/L時粘度分別為41、410、325mPas粘度下降率分別為92%、40%、38%。1.5L PAME-3水溶液在90℃時保有的粘度高達300mPas而1.5g/ L HPAM水溶液在9o℃時粘度為14mPasPAMF共聚物可望用作耐溫抗鹽的驅(qū)油聚合物。圖5參9。關(guān)鍵詞∶水溶性聚合物丙烯酰胺/丙烯酸/′含氟丙烯酸酯共聚物含氟聚合物浛氟丙烯酸酯冾成水溶液粘度驅(qū)油用聚合物中圖分類號:IE39扛IE357.46文獻標識碼A化學(xué)驅(qū)油技術(shù)是符合我國國情的較經(jīng)濟的提高采收率方法1部分水解聚丙烯酰膠HPM炸為1實驗部分驅(qū)油聚合物已在我國廣泛應(yīng)用但HPAM耐溫抗1.1儀器及試劑鹽能力差2不能用于高溫高鹽油藏。疏水締合水(1)器美國 Varian Unity400型核磁共振溶性聚合物(丙烯酰胺與少量疏水單體的共聚儀3i0 Rad digital division fts-80型紅外光譜儀物}3是為提高耐溫抗鹽性而開發(fā)的一大類驅(qū)油聚 Varian(C3800型色譜儀。合物目前大多數(shù)研究中引入的疏水基團是碳氫基(2試劑 Zonyl FSN氟表面活性劑美國杜邦團。相同碳鏈長度的碳氟基團與碳氫基團相比內(nèi)公司產(chǎn)旵昞丙烯酸過硫酸銨亞硫酸氬鈉氫氧化聚能密度和表面能更低疏水性更強45含氟疏鈉丙烯酰胺均為分析純水單體與丙烯酰胺一般需在含氟表面活性劑存在下1.2FSN丙烯酸釀AFSN合成進行水溶液共聚合含氟表面活性劑不僅價格昂貴,氟表面活性劑FSN)結(jié)構(gòu)式為還可能對共聚物的性能產(chǎn)生不良影響6。本文報道一種含氟單體及其與丙烯酰胺、丙烯酸在水溶液R(CH,CH22CH,CHOH中生成的共聚物該共聚物具有良好的增粘耐溫、其中抗鹽性能。合成YHa中國煤化工y=1-7CNMHG收稿日期200404-22修改日期2004-12-14基金項目國家科技部十五”攻關(guān)項目(2002BA312B05)資助課題作者簡1962-)男副教授頑士從事化學(xué)工程方面研究工作通訊地址257061山東省東營市石油大學(xué)(華東光化學(xué)化工mail:angy(@mail.dpu.edu.cn電話546-8391029334油田化學(xué)2004年R(,,OH+CH2=CHCOCI-2.1.2原料配比對產(chǎn)物收率和純度的影響RA( CH2 2CH,CHao= XCH=CH,+HCI由于氟表面活性劑FSN價格比較貴為使FSNNCH2CH3+HC→NCH2CH3)HCl↓反應(yīng)完全,丙烯酰氯應(yīng)過量。圖2為丙烯酰氯AC與FSN摩爾比對產(chǎn)物AFSN收率和純度的影響在裝有攪拌器、恒壓漏斗、干燥管和溫度計的四由圖2看出AFSN收率在AC、FSN摩爾比為1.05口燒瓶中加入FSN三乙膠及無水乙醚洛劑)在左右時最高,此時產(chǎn)物純度亦趨于穩(wěn)定。當(dāng)AC低溫下(冰浴中)滴加含有丙烯酰氯η的二氯甲烷FSN摩爾比太大時過量的丙烯酰氯發(fā)生聚合反溶液控制反應(yīng)溫度不超過5℃。滴加完畢后使反應(yīng)造成產(chǎn)物后處理困難收率低。應(yīng)溫度緩慢上升到室溫反應(yīng)1~2小時在油浴中加熱到35℃再反應(yīng)7~12小時。將反應(yīng)物放入冰箱冷凍室過夜過濾除去固體濾液用鹽水洗滌2-3收率次用無水硫酸鈉干燥除去溶劑得暗紅色液態(tài)FSN丙烯酸醵AFSN)用色譜分析產(chǎn)物純度1.3共聚物的合成將一定比例的AFSN、AM、AA用去離子水溶解加入NaOH調(diào)溶液pH為9在通氮保護下加熱至50℃加入過硫酸銨、亞硫酸氫鈉引發(fā),反應(yīng)12小時得到膠狀聚合物。取一部分膠狀體烘干粉碎,AC、FSN摩爾比溶解測溶液性能;另一部分用乙醇-水沉淀、洗滌圖2AC、FSN摩爾比對AFSN收率和純度的影響真空烘干用于儀器分析2.1.3反應(yīng)時間對產(chǎn)物收率和純度的影響1.4共聚物粘度測試在AC、FSN摩爾比為1.05的條件下,考察了用NDJ-1型旋轉(zhuǎn)粘度計測定共聚物水溶液的反應(yīng)時間對產(chǎn)物收率和純度的影響結(jié)果見圖3。表觀粘度轉(zhuǎn)速30r/min。由圖3可以看出隨反應(yīng)時間的增加,FSN酯的收2實驗結(jié)果與分析率先增大后減小FSN酯的純度達到一定值后趨于穩(wěn)定。反應(yīng)時間過短時原料反應(yīng)不完全產(chǎn)物收率2.1AFSN的制備和純度不高。隨著反應(yīng)時間的延長原料反應(yīng)逐漸2.1.1AFSN單體的IR光譜分析完全反應(yīng)時間在11~12小時時產(chǎn)物收率和純度AFSN的R譜圖見圖1。圖1中2874cm為達到最大值。反應(yīng)時間過長導(dǎo)致產(chǎn)物聚合使收率CH-的振動峰;727cm-1為C=O的伸縮振動降低。反應(yīng)時間以11~12小時為最佳。峰;1637cm-1為CH2=CH—中雙鍵的伸縮振動峰1199cm1,1240cm-1分別為碳氟基團的對稱和反對稱伸縮振動峰;145cm-1為C-O-C的伸縮振動峰。以上數(shù)據(jù)說明FSN和丙烯酰氯發(fā)生了酯化反應(yīng)生成了丙烯酸FSN酯純度中國煤化工亠CNMHG/3500250016001200圖3反應(yīng)時間對AFSN收率和純度的影響波數(shù)/cm圖1AFSN的IR譜圖2.2三元共聚物PAMF水溶液的性質(zhì)2.2.1礦化度對共聚物水溶液粘度的影響第21卷第4期王云芳孔瑛楊金榮等含氟丙烯酸酯AFSN及其與丙烯酰胺、丙烯酸的共聚物PAMF.335無機鹽主要通過對疏水締合聚合物疏水作用起初下降較慢溫度高于70℃后下降較快90℃時力、靜電作用力的影響改變聚合物分子鏈在溶液中降至300mas此值為90℃時HPAM水溶液粘度的構(gòu)象進而影響溶液的性能。礦化度對部分水解(14mPas肭10.7倍。溫度升高時PAMF共聚物聚丙烯酰胺(HPAM)AFSN含量為0.3%的三元共分子鏈上疏水基團的熱運動加劇使疏水基團周圍聚物PAMF3和AFSN含量為0.5%的三元共聚物的冰山結(jié)構(gòu)發(fā)生改變9削弱疏水締合作用和親水PAMF5水溶液粘度的影響見圖4。AFSN含量指基團的水化作用引起大分子線團收縮水溶液粘度AFSN在3種共聚單體總質(zhì)量中所占的百分率。由下降。圖4可以看出在相同的礦化度條件下PAMF系列三元共聚物水溶液的粘度明顯高于部分水解聚丙烯酰胺HPAM冰溶液的粘度。1500mg/L的HPAM水溶液的粘度隨著溶液中鹽濃度的增大而急劇降PAMF-3低水溶液中不含鹽(NaCl對時粘度為520mPas鹽濃度為15g/L時粘度下降92%只有41 mPa So而1500mg/L的FSN-5和FSN-3水溶液不含鹽時的粘度分別為690mPas和530mPts,鹽濃度為HPAM15g/L時粘度只分別下降40%和38%保留值高達410mPas和325mPas在HPAM水溶液中溫度/℃鹽離子屏蔽了HPAM分子鏈上離子基團的電荷8,圖5溫度對共聚物水溶液粘度的影響削弱了離子基團的靜電排斥作用引起聚合物鏈卷聚合物在溶液中的質(zhì)量濃度為1500mg/物水溶液中鹽使洛劑水的極性增強增加了共聚物3結(jié)論疏水基團間的疏水締合作用水溶液粘度增加的作(1)倉氟表面活性劑FSN和丙烯酰氯反應(yīng)得到用在一定程度上抵消了鹽對水洛液粘度的負面影了FSN丙烯酸酯AHSN由ASNA、MA制得了響因此PAMF共聚物水溶液的粘度受鹽離子濃含氟疏水締合水溶性共聚物PAMF3和PAMF5度的影響相對較小。由圖3可以看到在其他條件(2在相同條件下共聚物PAMF3和PAMF5相同時疏水基團含量較高的PAMF共聚物水溶液水溶液的粘度和抗溫耐鹽能力比HPAM水溶液有的粘度較大較大幅度的提高這類共聚物可望用作三次采油用750驅(qū)油劑。參考文獻PAMF-5[1]岡秦麟,論我國的三次采油技村J].油氣采收率技術(shù)98450PAMF-3[2]姜晨鐘,陳新鋼,章君,等.耐溫抗鹽型聚丙烯酰胺研究進[J]應(yīng)用科技,2000(8)27-28.3]羅開富葉林黃榮華.疏水締合水溶性聚合物的溶液性質(zhì)J]HPAM油田化學(xué),1999(3)286-289[4 ]Zhang YX, Da A H, Butler G B, et al. A fluorine-containing015202hydrophobically associating polymer I synthesis and solutionNaCI質(zhì)量濃度/gLproperties of copolymers of acrylamide and fluorine-containing圖4NaC濃度對3種聚合物水溶液粘度的影響(20℃)中國煤化工olym Sci Part a Polym Chem聚合物在溶液中的質(zhì)量濃度為1500mg/LCNMHG酸酯三元共聚物乳液的研究].高分子學(xué)報2002(5)2.2.2溫度對共聚物水溶液粘度的影響[6]徐鵬何珩羅平亞,表面活性劑對疏水締合聚合物水溶液性質(zhì)粘度均隨遇度升高而下降PMFS水溶液的粘度71,坦有機化學(xué)品越術(shù)手M北原科學(xué)出版社由圖5可以看出HPAM和PAMF5水溶液的啊J].油田化學(xué)2001(3)285-29042油田化學(xué)2004年LPS既可降低高滲透層滲透率,使后續(xù)注入水發(fā)生體系分類探訶J].油田化學(xué)200X4)343—345液流轉(zhuǎn)向進入低滲透層擴大波及體積在一定壓差[21重朝霞林構(gòu)軟,吳亮,交聯(lián)聚合物溶液的粒鷹分機1下LrS還可以在巖心中移動形成段塞驅(qū)替出高[3羅憲波蒲萬芬武海燕,交聯(lián)聚合物溶液的微觀形態(tài)結(jié)構(gòu)研究低滲區(qū)的殘余油提高采收率[J].大慶石油地質(zhì)與開發(fā)20032x5)0參考文獻[4 ]Mack J C, Smith J E. In-depth colloidal dispersion gels improve oilprcovery efficiencey Z ]. SPE/DOE 27780, 1994[Ⅰ]李明遠董朝霞吳肇亮.部分水解聚丙烯酰胺/檸檬酸鋁交聯(lián)Experimental Studies on displacement Efficiency of Linked Polymer Solution in Porous MediaLUO Xian-Bo', PU Wan-Fen', WU Hai-Yan', ZHAO Jin-Zh(1. College of petroleum engineering Southwest Petroleum Institute, Chengdu Sichuan 610500, PR of China 2. College of Natural resourcesnent, Southwest Petroleum Institute Chengdu, Sichuan 610500, PR of China i3. School of Graduate Students SouthwestPetroleum Institute, Chengdu, Sichuan 610500, PR of ChinaAbstract The oicement efficiency of a linked polymer solution( LPS ) is investigated on heterogeneous physical models of twotypes at 60C. The LPS is prepared from HPAM( 300 mg/L),10%AlCit ( 37.5 mg/L), and stabilizer(55 mg/L) in a standardbrine of TSD=1 10 mg/L, Ca2+ 800 mg/L, and Mg+ 200 mg/L and is used in experiments after reaction at 60C in 3 dayswith viscosity of 2.35 mPa s(60C 45 s). The model crude oil used has viscosity 12. 4 mPa s at 60C. The volume of LPSinjected is of 0.5 PV. For the core set of higher permeability ratio( 14.9 against 5. 74 )in profiling/displacing experiments on paralelldouble cores the percentage of LPS entered into the lower permeable coreer(16% against 2%)and the enhancement in oilecovery is higher( 28.5% against 210%), too. For 4 sections with increasing permeability of a plate-like heterogeneous physimodel simulating a five point well net, and the whole model the oil recovery by water flood is of 0%,5.32%,11.70%15.60%, and 32. 62% and the enhancement in oil recovery by 0.5 Pv of Lps injected is of 1.77%,2.34%,4.11%,6.03%and 14.25%( of oil saturated in whole model ) respectively. It is concluded that LPS is capable of indepth permeability adjustingfluid diversion )as well as of oil displacingKeywords: linked polymer solution HPAM/ AlCit/brine system i hetrogeneous physical models i oil displacement efficiencydepth permeability adjustment( fluid diversion(上接第335頁。 continued from p.35)[8]趙東濱馮玉軍羅平亞,NaC對疏水締合聚合物特性粘數(shù)及鏈[9]步懷天楊振忠章云祥·氟碳改性聚丙烯酰胺共聚物的溶液性剛性參數(shù)的影呵J].油田化學(xué)2000(3)260-262質(zhì)J].化學(xué)學(xué)報200260:1707-1710Synthesis of Fluorine-Containing Acrylate AFSN and Copolymers PAMF with High Heat ResistanceSalt Tolerancy and viscosifying Capacity in Aqueous SolutionWANG Yun-Fang KoNG Ying, YANG Jin-Rong, XIN Wei, FENG Zhi-QiangCollege of Chemistry and Chemical Engineering The University of Petroleum, Dongying, Shandong 257061 PR of ChinaAbstract : An F-containing acrylate AFSN is prepared by the way of low temperature reaction of dupond s commercial surfactantZonyl FSN aliphatic alcohols with perfluoroalkyl functionality with acryloyl chloride aC )at the presence of proper reagents and theoptimal AC to FSn molar ratio is established as 1. 05 and the optimal reaction time-11-12 hrs for the highest yield and purity ofreaction product obtained. The structure of AFSN is identified IR-spectrometrically. By copolymerizing AM, AA, and AFSN inaqueous solution, F-containing water soluble hydrophobically associating tercopolymers PAMF-3 and-5 are obtained with massfraction of AFSN in mixed monomer feed being of 0.003 and 0.005. The viscosifying capacity salt tolerancy and heat resistance oftercopolymers PAMF-3 and-5 are significantly higher than that of ultrahiaqueous solutions of HPAM, PAMF-5, and PAMF-3 at 20C is of 520中國煤化工ity of 1. 5 g/L salt freepresence of 15 g NaCl perliter solution--41, 410, and 325 mPa s, that is is decreased by 92%CNMHG1.5 g/L aqueous PAMF-3olution maintains at 90C viscosity as high as 300 mPa s in contract with 14 mPa s for HPAM aqueous solution of the sameconcentration at the same temperature Tercopolymers Pamf are prepared as eor polymers for use in high temperature and highpolymers; taining acrylate; synthesis; aqueous solution viscosity; polymers for Eop polymers; urine containinger soluble polymers acrylamide/acryic acid/fluorine containing acrylate