第54卷第12期化Vol.54 No 122003年12月Journal of Chemical Industry and Engineering ( China )December 2003v∈∈∈∈∈∈∈∈∈qI 研究簡(jiǎn)報(bào)貝NIPAAm的合成路線改進(jìn)及應(yīng)用宋江莉王秀 芬(北京化工大學(xué)可控化學(xué)反應(yīng)科學(xué)與技術(shù)基礎(chǔ)教育部重點(diǎn)實(shí)驗(yàn)室,北京100029 )關(guān)鍵詞N_異丙基丙烯酰胺 合成溫敏中圖分類號(hào)0 633.22文獻(xiàn)標(biāo)識(shí)碼A文章編號(hào)0438-1157 ( 2003) 12- 1787-03IMPROVEMENT ON SYNTHESIZING NIPAAm AND ITS APPLICATIONSONG Jiangli and WANG Xiufen( The Key Laboratory of Science and Technology of Controllable Chemical Reactions , Ministry of Education，Bejing University of Chemical Technology , Bejjing 100029 , China )AbstractNIPAAm is a monomer which can synthesize intelligent polymers sensitive to environment. The methodof synthesizing isopropylacrylamide is improved. The synthesis is noted for its simplicity , low toxicity , high yieldand reproduction as compared with other methods. The melt point , boiling point , IR and NMR spectra of thecompound were determined and compared with standard data and spectra for characterization. Further ，linear p( NIPAAm) and p( NIPAAm ) hydrogel were synthesized by using the NIPAAm and their temperature-sensitivitywere investigated.Keywords isopropylacrylamide , synthesis , temperature-sensitivity提取復(fù)雜,不宜于批量生產(chǎn)，貝 克曼重排合成方法引言會(huì)產(chǎn)生多種N_取代酰胺副產(chǎn)物,選擇性差.報(bào)道聚N_異丙基丙烯酰胺p( NIPAAm)類具有特的異丙胺( IPA )與丙烯酰氯( ACC)合成殊的溫敏性能,其LCST(低臨界溶解溫度)在32NIPAAm101] ,其工藝較復(fù)雜，收率較低,成本C左右,在溫敏薄膜、物料分離、感應(yīng)件、仿生及高.為此,本文對(duì)NIPAAm的合成路線進(jìn)行了改醫(yī)學(xué)等領(lǐng)域具有廣泛的應(yīng)用前景1~4].特別是在物進(jìn)，以期簡(jiǎn)化操作流程,提高產(chǎn)率.并將合成的.質(zhì)的濃縮與分離方面具有很高的工業(yè)應(yīng)用價(jià)值.因NIPAAm用于聚合制成聚合物水凝膠，考察此研究單體N-異丙基丙烯酰胺( NIPAAm)的生產(chǎn)NIPAAm聚合物的溫敏行為.路線就顯得極為重要.NIPAAm合成路線有多種,如胺與不飽和酰氯1實(shí)驗(yàn)部分反應(yīng)、不飽和烯腈或烯胺的N-烷基化反應(yīng)、貝克1.1單體合成操作步驟曼重排反應(yīng)等S6].其中Plat7、金曼蓉8]、陳文稀釋ACC、IPA ,再將稀釋后的ACC溶液滴加明9]等分別報(bào)道了丙烯腈與異丙醇在濃硫酸存在下到IPA溶液中,滴完后于5 C冰水浴攪拌12h.濾NIPAAm的合成方法,該法對(duì)硫酸用量、加料順去沉中國(guó)煤化工,得到NIPAAm粗產(chǎn)序、反應(yīng)階段的溫度及pH值都有要求，后續(xù)分離物.TYHCNMHG針狀結(jié)晶物.正己烷.2002 - 12- 17收到初稿, 2003 -04 - 14收到修改稿.Received date : 2002 -12-17.聯(lián)系人:王秀芬.第一作者:宋江莉，女,26歲,碩士.Corresponding author : WANG Xiufen ，associate professor.E - mail :wxf0062@ yahoo. com. cn1788.化工I學(xué)2003年12月.可反復(fù)使用,每次溶劑損失約15%以內(nèi).應(yīng),影響單體的生成.所以反應(yīng)物濃度控制在0.21.2NIPAAm的交聯(lián)聚合物與線型聚合物的制備(體積比)較好.交聯(lián)聚合物制備:將NIPAAm、N N-亞甲基雙Table 2 Influence of reactant concentration on yield丙烯酰胺以一定比例溶于去離子水中,引發(fā)劑為過(guò)硫酸銨/N N N ,N-四甲基乙二胺, N2保護(hù)下反應(yīng).Reactant: Solven( vol )Yield/%p( NIPAAm)水凝膠室溫下去離子水浸泡48h,每0. 180.30.16.85.6隔幾小時(shí)換一次去離子水,除去未反應(yīng)的單體和0.2086.6雜質(zhì).0.2688. 0線型聚合物的制備:引發(fā)劑為偶氮二異丁腈，0.377.60. 3662.1將NIPAAm溶于叔戊醇中,N2保護(hù)下加入AIBN,60C聚合12h后,蒸發(fā)除去溶劑，分別用丙酮、2.1.2重結(jié)晶溶劑對(duì)產(chǎn)率的影響文獻(xiàn)報(bào)道萃取正己烷提純,得到線型p( NIPAAm ).和提純NIPAAm所用的溶劑有乙醚/正己烷、二甲苯、苯、苯/正己烷混合溶劑,本實(shí)驗(yàn)用正己烷對(duì)2結(jié)果 與討論NIPAAm進(jìn)行重結(jié)晶提純，簡(jiǎn)化了后處理過(guò)程,提2. 1 NIPAAm 單體合成分析純后的產(chǎn)率達(dá)74% (表3 ).2.1.1 反應(yīng)條件對(duì)單體產(chǎn)率的影響 采用ACC與Table 3 Influence of solvent on yield of NIPAAmIPA反應(yīng)的合成路線，生成的鹽酸會(huì)與IPA形成鹽,降低了N-?；俣?為此,加入過(guò)量的IPASolventAmount of NIPAAm/gbenzene/ n-hexane8.4561. 0使介質(zhì)呈中性或弱堿性,提高?；俣群王；a(chǎn)ether/ n-hexane8.3160. 0率,ACC與IPA的比例為1:2(mol)較為適宜.n-hexane10.3該反應(yīng)為放熱反應(yīng),反應(yīng)溫度控制在10 C以內(nèi)有利于反應(yīng)進(jìn)行.在. 上述反應(yīng)條件下進(jìn)-步考察反應(yīng)改進(jìn)后的NIPAAm合成工藝與同類合成方法時(shí)間對(duì)NIPAAm產(chǎn)率的影響,結(jié)果如表1所示.介(產(chǎn)率約58% )及用丙烯腈、異丙醇合成NIPAAm質(zhì)為乙酸乙酯時(shí)反應(yīng)8 h較充分,介質(zhì)為苯時(shí)反應(yīng)的方法(產(chǎn)率61%)相比,產(chǎn)率高(88%)操作12h較充分,繼續(xù)延長(zhǎng)反應(yīng)時(shí)間產(chǎn)率基本無(wú)變化;簡(jiǎn)便.在介質(zhì)的選擇方面,苯、乙酸乙酯均可作為反應(yīng)介2.2結(jié)構(gòu)分 析質(zhì)，所得NIPAAm的產(chǎn)率均達(dá)到80%以上,但由對(duì)合成單體所作的IR譜圖如圖1所示.圖1于乙酸乙酯的介電常數(shù)( ε=6.02 )大于苯的介電中,1455.84、1410.64cm-'為N--CH(CH,)2上常數(shù)( ε=2.283),有利于酰氯的N_酰化,所以乙CH3的對(duì)稱變形振動(dòng)峰, 1550. 16cm-'為NH上的酸乙酯為介質(zhì)的反應(yīng)時(shí)間短、從產(chǎn)率和減小反應(yīng)毒氫特征峰, 1621. 31 cm -1為烯烴C =C伸縮特征峰，性考慮,反應(yīng)介質(zhì)宜采用乙酸乙酯.1657.22 cm-'為羰基C=0振動(dòng)吸收峰,符合Table 1 Relationship of yield and reacting timeNIPAAm分子的紅外特征吸收譜.從該單體的Reacting time/hHNMR譜圖(圖2)可以看到δμ分別為7.5benzene .50.6( N-H),6.2 (2H),5.5( 1H , CH=CH2),4.0benzene67.30(1H,一-CH(CH3)),1.2(6H,2CH,),符合86. 4>12NIPAAm的標(biāo)準(zhǔn)譜圖.綜上分析確認(rèn)所合成的單體ethylacetate60. 76ethy lacetate71. 5為NIPAAm.測(cè)得熔點(diǎn)為61 ~62° (文獻(xiàn)值60 ~863 C中國(guó)煤化工z獻(xiàn)值89 ~92C).熔Note : amount of ACC is 10 ml.程窄MYHCNMHG表2給出了在乙酸乙酯中反應(yīng)物濃度對(duì)產(chǎn)率的2.3NIPAAm交聯(lián)聚合物與線型聚合物的相變影響.實(shí)驗(yàn)觀察到隨著濃度的增大,反應(yīng)逐漸變得分析劇烈、難以控制，而且當(dāng)濃度達(dá)到一定值后產(chǎn)率下將制備的NIPAAm交聯(lián)聚合得到p(NIPAAm)降.分析其原因是由于反應(yīng)物濃度過(guò)大會(huì)加劇副反水凝膠,發(fā)現(xiàn):溫度為30C時(shí),水凝膠達(dá)到溶脹第54卷第12期宋江莉等: NIPAAm的合成路線改進(jìn)及應(yīng)用1789.93結(jié)論70采用改進(jìn)后的工藝合成NIPAAm操作簡(jiǎn)便、重星50復(fù)性好，產(chǎn)率高達(dá)88%，提純后產(chǎn)率仍較高言30(74%),純度好,適于高純度批量生產(chǎn).將其制10成水凝膠和線型聚合物顯示出良好的溫敏性.4000 3500 3000 2500 2000 1500 1000 500wavenumber/cm~ReferencesFig. 1IR spectra of NIPAAmHoffman A S. 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