松香酸封端的二聚脂肪酸/聚乙二醇聚酯的合成及性能表征

第26卷第2期林产化学与工业Vol. 26 No.22006年6月Chemistry and Industry of Forest ProductsJune 2006Preparation and Properties of Dimeric FattyAcid/ Polyethylene Glycol PolyesterTerminated with Rosin A cidFENG Guang-zhu'3 ,CUI Ying-de2* ,LU Kui31 ,QU Hai' ,LI He-ping '( 1. School of Materials Science and Engineering , Northwesterm Polytechnical University , Xi'an 710072 ,China ;2. Zhongkai University of Agriculture and Technology , Guangzhou 510225 , China ; 3. Schoolof Chemistry and Chemical Engineering ,Henan University of Technology , Zhengzhou 450052 , China )Abstract :A new kind of non-ionic polymeric surfactant , the dimeric fatty acid( DFA ) polyethylene gly-FENG Guang zhucol( PEG ) polyester terminated with rosin acid , was prepared with rosin acid and a polyester which wassynthesized from DFA and PEG 400 , and its surface activities were studied. The optimum reaction conditions of esterificationwere as fllows : molar ratio of DFA /PEG 400 1 : 1. 20 ,stannous chloride as the preferable catalyst at amount0. 30 % of DFA ,reaction temperature 200 C , reaction time 6 h , the conversion can reach 98. 11 % . Number-average molecular weight( Mn )ofthe product is 6 135. Weight-average molecular weight( Mw ) of the product is 7 438. The coffcient of distribution of molecularweight( Mw/Mn )is 1. 212 , which indicates a narrow distribution of molecular weight. Orthogonal experiment results of rosinacid terminated reaction of dimeric fatty acid polyethylene glycol polyester showed that optimum reaction conditions were as fol-lows : molar ratio of materials r( DFA/PEG polyester): ( rosin acid)1 : 1. 30 ,dosage of catalyst SnCl2 0. 20 % of polyester ,reaction temperature 215 C. After2.8 h , termnination ratio of the end hydroxyI groups of polyester reached 62. 75 %. Rosin acidterminated DFA/ PEG polyester surfactant has excellent emulsification properties , emulsification stability , power to disperse calci-um soap as well as performances of defoaming and inhibiting foaming.Key words : rosin acid terminated dimeric fatty acid/ polyethylene glycol polyester ;dimeric fatty acid ;rosin acid ;non-ionicpolymeric surfactantCLC number TQ351. 471Document code :AArticle ID 0253 - 2417( 2006 )02 - 0007 -06松香酸封端的二聚脂肪酸/聚乙二醇聚酯的合成及性能表征冯光炷'3 ,崔英德? ,卢奎,渠海’,李和平3(1.西北工业大学材料学院,陕西西安710072 ;2.仲恺农业技术学院,广东广州510225 ;3.河南工业大学化学化工学院,河南郑州450052 )摘要:以妥尔油脂肪酸二聚酸为原料先与聚乙二醇( PEG 400 )缩聚后得到聚酯然后再用松香对聚酯封端制备了松香基聚酯醚型非离子高分子表面活性剂并对其性能进行了研究。聚酯适宜的制备工艺条件减压条件下反应物二聚酸与聚乙二醇的摩尔比为1 : 1.20催化剂SnCl2用量为二聚酸质量的0.30%反应温度200 C ,反应时间6h酯化率达到98. 11 %。产物的数均相对分子质量( Mn )6 135重均相对分子质量( Mw )7 438相对分子质量分布系数( Mw/Mn)为1.212且呈好的窄分布状态。正交试验优化后的松香封端反应的条件为:再补加聚酯质量0.20%的催化剂SnCl2聚酯与松香物质的量之比为1 : 1.30反应温度215 C反应时间2.8h封端率达62.75 %。红外光谱验证了目标产物的存在。性能研究表明产物具有很好的钙皂分散力、消泡和抑泡力、乳化性和乳化稳定性。关键词松香酸封端的二聚脂肪酸聚乙二醇聚酯;二聚脂肪酸松中国煤化工性剂YHCNMHGReceived date 2005 - 10 -26Foundation item河南省自然科学基金资助课题( 051 1021000 )Biography冯光炖1961- )男河南光山人教授主要从事功能高分子材料和表面活性剂的合成与应用研究;E-mail :fgzhu@ 371. net* Correspondence Auther崔英德教授博士生导师主要从事功能高分子材料的研究。林产化学与工业第26卷Dimeric fatty acid( DFA ) was synthesized usually from tall oil fatty acid which has two active carboxylsand long-chain alkyl radical , and its chemical property is similar to fatty acid. Because of its excellent reactionactivity , DFA has been widely used as intermediate in the synthesis of a variety of organic compounds. DFAand its derivatives are safe , nontoxic and uninflammable materials showing many specific physical and chemi-cal properties. Thus they have been widely applied in many fields such as surfactant , paints and coatings , ad-hesives , lubricants , solidified fuel. Rosin is a kind of natural resin with high economic value. As an importantchemical raw material ,it was also widely used in surfactant , paper-making , adhesive , paint , printing ink ,rubber , food and other industries. A serial of surfactants , which is similar to natural fatty acid in structure ,can be synthesized by DFA and rosin acid as reactants. These surfactants have excellent application perfor-mance to benefit human being and ecotype 1.Polymeric surfactant has many excellent application performances , such as emulsification , lime-soapdispersion , solubility enhancement , and so on. These good performances were related to the structure andmolecular weight of polymeric surfactant 2-4 Generally , molecular weight of the DFA/ PEG 400 polyester wascontrolled by adjusting the molar ratio of DFA and PEG 400. The molecular weight became larger when molarratio is closer to 1 ,but the hydrophilic property of polyester is worse' 3-51].In this study , controlling molar ratio of reactants ,a new kind of polyester with appropriate molecularweight , was synthesized by condensation polymerization using DFA and PEG 400 as raw materials , then usingrosin acid to terminate the end-hydroxyls of this polyester in order to adjust the hydrophilic-lipophilic balance( HLB ) of non-ionic polymeric surfactant. This polymeric surfactant has rigid , space sterically hinderedlipophilic groups and hydrophilic polyether chains , therefore this polyester shows composite performance ofaliphatic alcohol surfactant and polyether surfactant , and has good performance in emulsification and emulsionstability , power to disperse calcium soap , defoaming foam and inhibiting foaming , wetting power and solubilityenhancement. It could be used in daily chemical industry , food industry , pesticide industry , metal-processing,etc. It is a non-ionic polymeric surfactant which is low noxious to human being , with good biodegradability andenvironment affinity.1 Materials and methods1.1 MaterialsDFA was purchased from Zhejiang Y ongzai Chemical Industry Corporation. PEG 400 was purchased fromTianjin Bodi Chemical Industry Company. Rosin acid was purchased from Guangxi Wuzhou Pine ChemicalsLtd. Other chemicals are of analytical grade , and they were used without further purification.1.2 Analysis 6]Acid value( AV ) was determined according to GB 12008.5 - 1989 ; Hydroxyl value( HV ) was deter-mined according to GB 12008.3 - 1989 ; Molecular weight of polyester was determined by GPC , using a laserlight-scattering mass detector ( LC10A-Waters 510 , DAWNEOS ) , and the conditions are as follows : chroma-tographie column , SHIM 800p , mobile phase THF ,flow ra中国煤化工Prestige 21 FT-IR wasemployed for IR studies.YHCNMHG1.3 CalculationsER=( AV。-AV )AV。x100 %TR=( HV。-HV )/HV。x100 %o1.4 Determination of surface activitySurface tension and critical micelle concentration( CMC ) were measured by TX- 550A ( Bowing Interna-第2期冯光炷等松香酸封端的二聚脂肪酸聚乙二醇聚酯的合成及性能表征9tional Company ). The performances of defoaming and inhibiting foaming ER- -esterification ratio ,AV,- initialacid value , TR- -termination ratio , HV。- initial hydroxyl value , emulsifying power , power to dispersecalcium soap were measured according to literature'[6. The system of water/ soybean oil was used to measureemulsifying efficiency.2 Experimental2.1 Synthesis of DFA/ PEG polyester 7-81Put PEG intoa 100 mL flask and heated in an oil bath at 110 C for0.5 h to remove water absorbed byPEG. Fixed quantities of DFA and PEG 400 were put into a 100 mL flask , added suitable amount of catalyst.Mixed enough , put flask in an oil bath. Kept mixture reacting under stirring for definite time at 0.097 MPa toobtain the product.Purification of polyesters :3 g product was dissolved in 30 mL acetic ester , using 30 mL salt water toextract water-solubles. Then removed acetic ester in water bath at 85 C , and put product into vacuum dryingoven( 65 9C ,0. 097 MPa ) and vaporized solvent to obtain purification product.2.2 Preparation of rosin acid terminated DFA/PEG polyesterRough rosin should be refined. Rough rosin( 25 g ) and 10 mL hydrochloric acid were added into 100 mLethanol , refluxed about 0.5h at 85 C , then stewed 4h at -5 C. The light-yellow solid product wasobtained after filtering , having acid value 165. 17 mg/g. .Weighed fixed quantities of polyester and rosin acid , put them into 100 mL flask. Controlled the reactiontime , amount of catalyst and molar ratio of the reactants , keeping them in an oil bath and reacting underdefinite temperature for definite time , then the yellow viscous liquid was obtainedf 21.3 Results and discussions3.1 Synthesis conditions of DFA/PEG polyesterMain influencing factors are the kinds and amount of catalysts , reaction time , reaction temperature andratio of reactants. The effects of these factors on synthesis of polyester were studied.3.1.1.Influence of the kind of cata-Table 1 Effects of different catalysts on esterification conversionlystsThe catalysis effect of differentcatalystsamount/%esterification convension/ %colornone063.71fawncatalysts were shown in Table 1 , at tem-0.394.02jet blackperature of reaction 180 C , molar ratio toluene-p-sulfonie acid94.38carmineof reactants 1 : 1. 20 , and reaction timeSnCl293.854 h.It can be showed from Table 1 that using stannous chloride as catalyst , the conversion ratio of product isnot the highest , but the color of product is fawn and the lightest. DFA has double bond which is easy to beoxidized at high temperature. Stannous chloride is a kind of antioxidant which can reduce the incidence rate ofsecondary reaction and increase the ratio of esterification effectively. Meanwhile , stannous chloride is a kind ofacid-catalyst , which can increase the concentration of hydrq中国煤化工, so the speed of wholereaction can be increased effectively. Thus choosing stannoHC N M H Gitable.3.1.2 Influence of amount of catalyst The conditions of experiment are : temperature 180 C , molar ratio ofreactants 1 : 1.20 , reaction time4 h. By analyzing acid value of sample at different times , and calculate thedegree of reaction. The influence of catalysts amount was showed in Table 2.It can be showed in Table 2 , when the amount of catalysts is added to 0.25 %-0.30 % , esterification木产化学与工业第26卷ratio is over 90 %. When amount of catalysts is added further , esterification ratio also reaches more than90 % , but the transparency of product decreases. So the amount of catalyst is 0. 30 % .3.1.3.Infuence of ratio of reactantsUnder the conditions of : amount of catalyst 0. 30 % , temperature200 C , reaction time 4 h , the influence of the ratio of reactants was studied. If PEG was excessive , the endgroup of polyester is mainly hydroxyls.As shown in Table 2 , when molar ratio of reactants is1 : 1. 20 , esterification ratio can reach 96 %. Con-tinuous increase of PEG amount influenced the molecular weight of product , so suitable ratio of reactants is1 : 1.20.3.1. 4 Influence of reaction temperature IncreasingTable 2 Effects of reaction conditions ontemperature can increase the reaction velocity andesterification conversionenhance the rate of conversion. Under the conditions of :reaction conditionsesterification conversion/%0.2080. 62amount of catalyst 0.30 % , molar ratio of reactants0.2589.241 : 1.20 , reaction time 4 h , the influence of reaction0.3090.11temperature can be seen from Table 2.catalyst amount/%0.3584. 390.4082. 85It can be seen from the result that esterification ratio0.5083.46increases with increased reaction temperature. However ，0.7085.38reactants would be decomposed at higher temperature. At_1.0091.0916062.40 .reaction temperature above 200 C , the color of product17083.31would darken obviously , the possible reason is cross-link-18093. 48ing or degradation of reactants or product. So the suitablereaction temp. /C19095.6720096. 02.reaction temperature is 200 C.96.023.1.5 Influence of reaction time According to reaction96. 03kinetics theory , esterification ratio can be enhanced by1 : 1.0091. 39.1 : 1.1093.11increasing reaction time. However , during extended reac-以( DFA): r( PEG )1:1.2096.38tion time , secondary reaction , such as degradation , can1 : 1.3097.21occur , which may influence the performance of product.1 : 1.4096.96Under the conditions of : molar ratio of reactants 1 : 1.20 ,1:1.50.96. 6378.60reaction temperature 200 9C , amount of catalyst 0.30 %，494. 40it can be seen from Table 2 , the reaction rate is highreaction time/h98.11at the beginning of reaction , but after 6h , the reactio898. 7010n rate becomes slow , so the suitable reaction time 0esterification is 6 h.3.2 Synthesis of rosin-terminated DFA/ PEG polyesterAccording to esterification mechanism and some preparatory experiments , factors which afect terminationratio are mainly reaction temperature , amount of catalysis , ratio of reactants and reaction time. These factorshave been studied respectively.3.2.1 Effect of reaction temperature on termination ratio. Under conditions of : molar ratio of reactants 1 :中国煤化工1.50 , amount of catalysis 0.20 % , reaction time 3h , thferent temperatures areshowed in Table 3.Y片CNMHGFrom Table 3，when reaction time is 3 h , the terminated ratio increases with the rising of reactiontemperature , and reaches the maximum at 220 C. When temperature is over 220 C , termination ratio woulddecrease , secondary reaction would increase and the product would darken. So the appropriate temperature of220 C was used in following experiments.第2期冯光炷等松香酸封端的二聚脂肪酸/聚乙二醇聚酯的合成及性能表征113.2.2 Efects of ratio of reactants on termination ratio Temperature 220 C ,amount of catalysis 0. 20 %，reaction time 3 h , the effect of ratio of reactants on esterification conversion of end-hydroxyl is showed inTable 3.It is obvious from Table 3 that termination ratio increases with the amount of rosin increasing. Whenmolar ratio of reactants is 1 : 1. 30 termination ratio reaches the maximum 60.53 % , therefore molar ratio ofreactants 1 : 1. 30 was used for the following experiments.3.2.3 Effect of amount of catalysis on termination ratioTable 3 Effects of reaction conditions onUnder the conditions of : temperature 220 C ,molar ratio oftermination ratioreactants 1 : 1.30 , reaction time 3 h , the results of reactionreaction conditions，termination ratio/%19028. 92at different amounts of catalysis are showed in Table 3.20040.00From Table 3 , the effect of amount of catalysis on the .21055. 30termination ratio is small and unconspicuous ，this is .reaction temp. /C22060. 6923042.64because DFA/ PEG polyester ineluded about 0.30 % of24037.20catalyst SnCl2. When 0. 20 % catalyst SnCl,( 0.20% of1 : 1.1033. 38DFA/PEG polyester amount ) is added to reaction system ,1 : 1.2046. 84termination ratio reaches 60. 65 % , so the amount of cataly- r( DEA/ PEF polyester ):1 : 1.301 : 1.4060. 60sis 0.20 % was used in the following experiments.n( rosin acid )1 : 1.503.2.4 Efct of reaction time on termination ratio Under1:1.10049.05he conditions of : temperature 220 C，molar ratio of0.1038.42reactants 1 : 1. 30 , amount of catalysis 0.20 % , the resultscatalysis amount/%0. 2060. 65of reaction at different times are showed in Table 3.0.3059. 100.40It is obvious from Table 3 that termination ratio reaches23. 57the maximum( 60. 56 % ) when reaction time is 3 h. If the .51. 24time is longer , the ratio of terminated end-hydroxyl decrea-reaction time/h60.5341.50ses since secondary reactions increase.31. 103.2.5Optimum of reaction conditionsOrthogonalexperiment , of four factors and three levels , was designed in order to optimize the reaction conditions. Thefactors are respectively ratio of reactants ,reaction temperature ,reaction time and amount of catalyst. Optimumreaction conditions were as follows molar ratio of materials r( DFA/ PEG polyester ): n( rosin acid)1 : 1.30 ,amount of catalyst SnCl2 0. 20 % of polyester , reaction temperature 215 C , reaction time 2. 8 h. Accordingto optimum reaction conditions , termination ratio of the end hydroxyl group is 62.75 %.3.3 Analysis of product3.3.1 Infrared spectrum analysis of product From infra-Table 4 Molecular weight distribution ofred spectrum it can be seen that 1740 cm- is the charac-DFA/PEG 400 polyesterteristic absorption peak of product , which is the stretchingsamples .MnMwMw/Mnpolyester608877981. 281vibration of C= =O ; the absorption peak at 1100 cm- ' is the .refined polyester613574381.212stretching vibration of C- -O. These informations show that中国煤化工，the product contains ester bond. The vibration of - -0Hpolyethylene glycol ,namely the end hydroxyl is decreased , namely the productTYHCNMHG:id.3.3.2 Analysis of molecular weight of product Polyester and refined polyester were analyzed by GPC , theresult is showed in Table4. It is known that molecular weight of refined polyesters is increasing , showing thatsoluble substances have already been removed. The narrow distribution of molecular weight indicates theimproved effect of refined polyester.12木产化学与工业第26卷3.3.3 Analysis of surface activities The result of measurements of surface activities is showed in Table 5.Interfacial force and CMC of rosin terminated DFA/PEG polyester are lower. It has excellent emulsificationand emulsification stability , power to disperse calcium soap , performance of defoaming and inhibiting foaming.Table 5 Surface activities of rosin acid terminated DFA/ PEG polyesterYemeCMCdefoaming foam inhibitingpower to disperse emulsification poweremulsionitems/(1x10-4N. m-)/( mmol: L-1 )/mmfoaming /scalcium soap/%( soybean oil )/min stability /hproduct30.211.0720.0.1609.625.038. 19186. 03OP-1024.04 Conclusion4.1 The optimum esterification conditions for DFA/PEG polyester are as follows : molar ratio of DFA /PEG400 1 : 1.20 ,amount of catalyst stannous chloride 0. 30 % , reaction temperature 200 C ,reaction time 6h ,esterification ratio can reach 98. 11 %. Number-average molecular weight( Mn ) of the product is6 135 ,thecoefficient of distribution is 1. 212 , showing a narrow distribution of molecular weight.4.2 The suitable synthesis conditions for rosin acid terminated polyester surfactant are as follows :0.20 %catalyst , molar ratio of polyester/rosin 1 : 1. 30 ,reaction temperature 215 C , reaction time 2.8 h , terminationratio can reach 62.75 % .4.3 A new kind of non- ionic polymeric surfactant , rosin acid terminated DF A/ PEG polyester was prepared.The product is a dark yellow viscous oleo liquid , and its interfacial force and CMC are low. It has excellentemulsification property and emulsification stability ; excellent power to disperse calcium soap ; excellentperformance of defoaming foam and inhibiting foaming ; and it has poor foaming property.References :[1周永红,宋湛谦.松香的精细化工利用IV )一 松香类表面活性剂的合成与应用[ J]林产化工通讯,2003 ,37( 1 ):28-32.[2周永红，宋湛谦,许玉芝等.松香季戊四醇酯聚氧乙烯醚的表面活性研究J]林产化学与工业,2004 ,24( 增刊):61-64.[3]金勇,董阳,魏德卿.高分子表面活性剂的合成J]化学进展,2005 ,17( 1 ):151-156.[4 ]王学川, 赵军宁.高分子表面活性剂的合成及其应用进展J]皮革科学与工程,2004 ,14(6):24-30.[5]江龙胶体化学概论[ M]北京:科学出版社,2002 :132.[ 6 ]毛培坤.表面活性剂产品工业分析M]北京:化学工业出版社,2003 396- -474.[ 7 ]O'LENICK Jr , ANTHOINY J. Capped dimer polyesters in personal care applications : US , 6800275[ P ].2004-10-05.[8 ]CUO WEN-XUN , HUANG KAI-XUN. Preparation and properties of poly ( dimer acid-dodecanedioie acid ) copolymer and poly ( dimer acid-tetradecanedioic acid ) copolyme[ J ] Polymer Degradation and Stability , 2004 , 84 :375-381.中国煤化工MHCNMHG