Ishida Shinichiro

Kaneko Katsumasa

Kura Yasuo

Matsui Jiro

A method of molecular weight estimation for the co-condensation resins of phenol-urea­-formaldehyde system was proposed. Samples were prepared by two steps reaction, that is, earlier condensation products of phenol with formaldehyde and urea with formaldehyde were prepared separately and then put together at 80°C. The co-condensation products were fractionated by fractional precipitation with acetone-methanol mixed solvent-water system. Specific volume φ and diffusion coefficient Dᴀ of each fraction were obtained from measurement of solution viscosity and diffusivity. The following relationship between φ and Dᴀ was found to be valid regardless of their heterogeneity,  φ√Dᴀ ＝K.In DMF at 25°C, K is about 3.31 x 10⁻³ regardless of reaction condition. Since the viscosity-diffusion average molecular weight Mvᴅᴀ is proportional to (φ • Dᴀ)⁻¹, it is possible to estimate the molecular weight only from φ or Dᴀ as follows :  M= 43.3 φ⁵ M= 0.17x10⁻¹⁰ Dᴀ -⁵/

石田 真一郎

金子 曽政

Kanazawa University Repository for Academic Resources

１MolecularWeightEstimationofCo-condensationResinofPhenol-Urea-FormaldehydeSystemムyShin-ichiroIsHIDA,＊YasuoKuRA,*＊ＪｉｒｏＭＡｓｕＭＩ**＊andKatsumasaKANEKo＊SynopsisAmethodofmolecularweightestimationfortheco-condensationresmsofphenol-urea-formaldehydesystemwasproposedSampleswerepreparedbytwostepsreaction，ｔｈａｔis，earliercondensationproductsofphenolwithformaldehydeandureawithformaldehydewerepreparedseparatelyandthenputtogetherat80oC、Theco-condensationproductswerefractionatedbyfractionalprecipitationwithacetone-methanolmixedsolvent-watersystem、SpecificvolumeIDanddiffusioncoefIicientDAofeachfractionwereObtainedfrommeasurementofsolutionviscosityanddiffusivity・ＴｈｅｆｏＵｏｗｍｇｒelationShipbetweenpandDAwasfoundtobevalidregardlessoftheirheterOgeneity，901/万丁＝ＫＩｎＤＭＦａｔ２５ｏＣ，Ｋｉｓａｂｏｕｔａ３１×１０－３regardlessofreactioncondition・Smcetheviscosity-diffusionaveragemolecularweightMｧD4isproprtionalto（ID。Ｄ』3)-1,itispossibletoestimatethemolecｕｌａｒｗｅｉｇｈｔｏｎｌｙｆｒｏｍｌＤｏｒＤＡａｓｆｏｌｌCWS：〃＝４３．３９５Ｍ－０．１７×10-ﾕｏＤＡ－５/２ ●１．Introductionlnapreviouspaper1)，itwasrecognizedfrommfraredandnuclearmagneticresonancespectrumthattheco-condensationreactiontakesplaceinphenol-urea-formaldehydesystemanditbecameapparentthattwostepsreactionissuitableforthepreparationoftheco-condensationresinsofhighmolecularｗｅｉｇｈｔｉｎｈｉｇｈｙｉeldsthanonestepreaction・Moreover，someinfOrmationsaboutco-condensationreactionmechanismswereobtainedfromthestandpointofmolecularweightchangeduringthereactionbytheviscosity-diffusionmethod2)．Inthatpaper,however，theaveragemolecularweightofunfractionatedsamplewastreated、Inthispaper，thesampleswerefractionatedandtheSpecificvolumeandthediffusioncoefIicientofeachfractionweremeasure｡、Fromtheresults，amethodofmolecularweight＊Dept・oflndustrialChemistry*＊ＮｏｗｉｎＫｏｒｅａ***NowatNagoyaRubberCo．１金沢大学工学部記要７巻１号１９７３２estimationwasproposed．2．Experimental2.1．MaterialsPhenolwasdistilled・Ureawasrecrystallizedfromwater・Passingthroughacolumnofanionexchangeresms，acidinfOrmalinwasremoved・Acetonewasrefluxedwithpotassiumpermanganateandthendehydratedanddistilled・Methanolanddimethylformamide（DMF）weredistilled．2.2．PreparationofresinsPhenol，formaldehydeandcataIyst（aqueousanⅢnoniaorhydrochloricacid）werechargedinathree-neckedHaskwithareHuxcondenser，astirrerandathermometer・ThereactionwascarriedoutatlOOoCandwascontinuedtillemulsionappeared・Ｏｎｔｈｅｏｔｈｅｒｈａｎｄ，ｔｈｅｍixtureofureaandformaldehydepreviouslycontrolledpHvalueat9byＮＨ４０Ｈｗａｓｒｅａｃｔｅｄｆｏｒ２０ｍｉｎｕｔｅｓａｔ８０ｏＣ、Intothisreactedmixture，thereactionproductofphenolandformaldehydewaspouredAndthentheco-condensationreactionbegan・WecalledthispreparativemethodtwostepsreactionAfter45minutesthereactionsolutionwaspouredintｏｗａｔｅｒｉｎｏｒｄｅｒｔｏｓｔｏｐｒｅａｃｔｉｏｎａｎｄｔｏｔａｋｅｏｆｆｔｈｅｗａｔｅｒｓolublefraction・Ithasbeendiscribedthattheco-condensationresinsresolvedinacetone-methanolmixedsolvent、Thereactionproductswerethenreprecipitatedwiththemixedsolvent-watersystemandtheco-condensationresinswereobtained・ThequantityoｆｒｅａｇｅｎｔｕｓｅｄｉｓＳｈｏｗｎｉｎＴａｂｌｅｌ．TablelQuantitiesofReagentsＳａｍｐｌｅＮｏ．〔Ｐ〕／〔F〕Catalyst（inP-Freaction）〔Ｕ〕／〔F〕10.5/0.5ＮＨ４０ＨＯ５/0.530.5/０．５ＮＨ４０Ｈｑ５/1.520.5/０．５ＮＨ４０ＨＯ､5/１．０４．５/1.ＯＮＨ４０Ｈｑ５/0.550.5/0.5ＮＨ４０ＨＯ５/０．５ＳａｍｐｌｅＮｏ．〔P〕／〔F〕Catalyst（inP-Freaction）〔Ｕ〕／〔F〕71.0/1.ＯＮＨ４０ＨＬＯ/3.061.o/1.0ＮＨ４０Ｈ１.O/1.081.0/ＬＯＮＨ４０ＨＬＯ/6.0101.0/ＬｏＨＣｌ1.0/3.091.0/1.ＯＨＣ１ＬＯ/2.0〔P〕，〔Ｕ〕ａｎｄ〔Ｆ〕ａｒｅｔｈｅｍｏｌｅｏｆｐｈｅｎｏｌ，ureaandformaldehyde，respectively．2.3．FractionationTheresinspreparedwerefractionatedintoseveralfractionsbyfractionalprecipitationusingthemixedsolventassolventandwaterasprecipitant・Themixturewaswarmedtoabout50ｏＣａｎｄｔｈｅｎｃｏｏｌｅｄｓｌｏｗｌｙｔｏｒｏｏｍｔｅｍperatureinordertoensuretheestabliShmentofequilibrium・Thentheprecipitatewasseparatedbycentrifugationat４，０００ｒ・ｐ．ｍ．anddriedunderreducedpressure．２ＩｓＨＩＤＡ・ＫｕＲＡ・ＭＡｓｕＭＩ・ＫＡＮＥＫｏ：Mo1ecularWeightEstimationofCo-condensation３Resinofphenol-Urea-FormaldehydeSystem２．４．ViscosityanddiffusivitymeasurementSincethemixedsolventresolvedtheco-condensationreslnsselectivelyandevaporated●easily,itwasusedinextractionoftheco-condensationresmsfromthereactionproductsandinfractionation・However，mviscosityanddiffusivitymeasurement，ＤＭＦｗａｓｕｓｅｄａｓｔｈｅｓｏｌｖｅｎｔ，becausesomeofthedriedsamplesofhighmolecularweightfractionsbecamemsolubleinthemixedsolventbｕｔｓｏｌｕｂｌｅｉｎＤＭＦ、SolutionviscositywasmeasuredbytheOstwaldtypeviscometer・ThedetermmationofthediffusioncoefIicientwasperformedbyaHitachiTiseliusElectrOphoreticApparatusHTB-2equippedwithaSchlierenopticalsystemandaU-ShapedglasscelLMeasurementswerecarriedoutat25oC・Thereareseveralkindsofaveragediffusioncoefficientsforexample，ＤｍａｎｄＤＡａｓｄｅｆｉｎｅｄｂｅｌｏｗ，、、＝〃02/2/，Ｄ』＝Ａ２/４元Ｈ２ｊ，（１）(２）where”２，ＡａｎｄＨａｒｅｔｈｅｓｅｃｏｎｄｍｏｍｅｎｔ，ｔｈｅａｒｅａａｎｄｔｈｅｍａｘｉｍｕｍｈｉｇｈｔｏｆｔｈｅdiffusioncurve，reSpectively，/isthediffusiontime、Ｄ４ｉｓａｌｓｏｄｅｆｉｎｅｄｂｙｅｑ．(3)，D』＝（Ｚα/zcdDﾎﾞｰ船)2， (３）whereQandDiareweightfractionanddiffusioncoefIicientof卜thcomponent，respectively．2.5．Viscosity-diffusionaveragemolecularweightThespecificvolumeofpolymermolecule，９，，isobtainedfrom胸-25（ )+44（ )。CＰ cＰ (４）100-叩 １００－CIDwhereりspandcarespecificviscosityandConcentration（g/100ｍl)，respectively3)．ThemolecularweightofasphericalmoleculeisgivenbyⅣ昨÷が (５）ＩＤwhereγｉｓｔｈｅｒａｄｉｕｓｏｆｔｈｅｍｏｌｅｃｕｌｅａｎｄｊＶisAvogadro,snumber・TherelationshipbetweenγandDisrepresentedbyeq．(6)，prOposedbyEinstein：ＲＴ１１－●」Ｖ６７Tり｡、 (６）Fromtheseequations，theviscosity￣diffusionaveragemolecularweight,Ｍ,D,ｉｓｏｂｔａｉｎｅｄｂｙＲ３ Ｔ３Ｍｉ,､＝ （７）●１６２，r2｣Ｖ２り｡3，３，，１金沢大学工学部紀要７巻１号１９７３3．ResultsanddiscussionTheresultsofthemolecularweightdeterminationareshowninTable2Table2ResultsofViscosityandDiffusivityMeasurementSample2SamplelFr瀞｡ロ（趾）（駒:::)Ｍ'四Fr識｡ロ（鋤）（鰯:::)MvD』2478013080４４９０３４５０９３０２４６０４５５１４６６９３８８５●●●●●●００１１２２４．５６２．９９２．３６２．２３１．８７２．５２０４６６２８８１７９２０●●●●●●０１１１３２4．６４３．０１２．３６２．２９１．９２２．１３4782022430９９７０４２６０１３２０１５７０１２３４５unfractd．１２３４５unfractd．Sample4Sample34．５５４．５７２．９７２．２８１．８０２．０３2306030000９４９０３９６０１０８０２２４０４．８３３．０２２．６４２．３０１．８７３．３８９２３００６７７２８０２●●●●●●００１１３２1２３４５unfractd．0．７４１．１８１．６０２．１１３．２３１．６４2961011660５３５０２６８０９２０３７５０１２３４５unfractd．Sample6Ｓａｍｐｌｅ５２．８２２．３９１．９８１．７２516032201100３２０21540５９９０３２２０１６２０６９０１５１０１．５６１．９３２．９４４．６３９５８４２８４２８７６８●●●●■●３２１１１１８６４３７２８５０６５６●●●●●●０１２２３２１２３４１２３４５unfractd． unfractd．２．１３ 2．５２１６２０Ｓａｍｐｌｅ８Sample74．７０３．５９２．５３１．８８１．５３２．８２２１１８８３８１７９７０●●●●●●０１１２４２2142011310４３９０１１２０３３０２３５０３４９３９８０５１９２５●●●●●●１１２２４２13320５８００２５００１２５０４４０１４３０１２３４５unfractd．１８７４８２９６１８６３●●●●●●３２２１１２１２３４５unfractd．ＳａｍｐｌｅｌＯSample9４．０５３．２２２．３０１．８６１．４８２．５１０．９８１．１８１．９９３．１９４．４９２．２９1430010300３０００９００４１０１８１０306023201530８００４１０９５０1２３４５unfractd．２．６６２．５０２．０９１．８５１．６５２．１４1．８９２．１２２．５８３．３４４．３５３．００１２３４５unfractd．４ＩｓＨＩＤＡ・ＫｕＲＡ・ＭＡｓｕＭＩ・ＫＡＮＥＫｏ：Mo1ecularWeightEstimationofCo-condensation５Resinofphenol-Urea-FormaldehydeSystemlnthepreviouspaper4)，ｉｔｗａｓＳｈｏｗｎｔｈａｔｅｑ．（８）wasvalidforfractionatedsamplesofalkalicatalizedphenolicresin．９１/-万＝Ｋ、 (８）InthecaseofaheterOgeneoussystem,ｉｔｉｓｒｅａｓｏｎａｂｌｅｔｏｕｓｅＤＡａｓｄｅｆｉｎｅｄｉｎｅｑ．（３）ｉｎｓｔｅａｄｏｆＤａｓｉｎｅｑ．（８）．Ifthenextequationforahomogeneoussystemisapplicabletoaheterogeneoussystem，ｐｚ－ＫＤｆ化，sincePisweightaveragevalue，thefollowingequationarevalidＰ－ｚｃ'９`/Ｚｃ，＝ＫＺｃｉＤ`脆/ｚｃｉ＝ＫＤＡｋ－Ｋ(皿/zc四一弦)遡臘．Ｉｆｂ＝一弘ｉｎｅｑ．（11)，ｅｑ．（12）isObtained・ｚｗ/ｚｃ←(皿/皿D`-兇)識，Ｐ'/万７－Ｋ．(９）(10）(11）(12）薫蕊I,=TgJ豆ｉｉ地liH.:｡｝,麟､!:r小…｡ご゜ろｅＣｅＣ○蕊 ①の－％Ｍ,､△＝(K'/K）Ｄ』 (15）５金沢大学工学部紀要７巻１号１９７３６WhereＫ'＝Ｒ３Ｔ３/162元Ｗ２り０３．UsingＫ＝3.31×10-3,）7。＝0.7729ｃ、ｐ・（ｉｎＤＭＦａｔ２５｡C)，ｅｑ．（14）ａｎｄ（15）aretransformedintoeq．（16）ａｎｄ（17)．Table3ComparisonofM,ａｎｄｌＶＤ４ｗｉｔｈＭの△Ｓａｍｐｌｅｌ Sample2FractionjV},ＤＡ Ｍ９Ｄ ｊＭＤＡＮｏ． FractionＭｖＤＡ ＭＤ ＭＤＡＮＯ．1２３４５unfractd．4782022430９９７０４２６０１３２０１５７０9323010720３１７０２７５０１１３０１９００5208019330８０３０３８６０１２５０１６２０１２３４５unfractd．2478013080４４９０３４５０９３０２４６０8565010300３２００２３８０９９０４４４０2970012250４１４０３１６０９２０２７３０Ｓａｍｐｌｅ３ Sample4１２３４５unfractd．2961011660５３５０２６８０９２０３７５０11335010930５５７０２７８０９８０１９１３０3609011240５２５０２６３０９００４９４０１２３４５unfractd．2306030000９４９０３９６０１０８０２２４０845308669010070２６５０８１０１５１０302603865010130３９１０１０９０２２１０Sample5 Sample6１２３４５unfractd．21540５９９０３２２０１６２０６９０１５１０22390２５１０１０００６９０４８０１０２０23400５５９０２８６０１５１０７００１５３０１２３４516032201100３２０771033601310６５０559032801150３８０unfractdl620 1880１６８０Ｓａｍｐｌｅ７ Ｓａｍｐｌｅ８１２３４５unfractd．13320５８００２５００１２５０４４０１４３０39420６０２０２０８０９２０５８０２９３０15790５７８０２４００１１５０４５０１５９０１２３４５unfractd．2142011310４３９０１１２０３３０２３５０9910025890４４９０１０００３６０７７５０2792013100４４５０１１２０３４０２９００Ｓａｍｐｌｅ９ ＳａｍｐｌｅｌＯ１２３４５unfractd．306023201530８００４１０９５０580041901740９４０5301940346025901590８３０4201090１２３４５unfractd．1430010300３０００９００４１０１８１０4706014970２８１０９７０３１０４３１０1788011240３０５０９３０４２０２１４０６ＩｓＨＩＤＡ・ＫｕＲＡ・ＭＡｓｕＭＩ・ＫＡＮＥＫｏ：Mo1ecularWeightEstimationofCo-condensation７Resinofphenol-Urea-FormaldehydeSystemMD4（＝Ｍｐ）-43.3Ｐ５ （16）一弘Ｍｉ'､』（＝MD4）＝0.17×10-1OＤＡ (17）InordertodiStinguishthesethreekindsofMiのA,ｔｈｅｍolecularweightscalculatedbyeq．（16）and（17）aresymbolizedMDandMDA，reSPeCtiVely・ＴｈｅｒｅｓｕｌｔｓａｒｅｓｈｏｗｎｉｎＴａｂｌｅ３，Ｆｉｇ．２ａｎｄＦｉｇ．３．ハZDAShowsagoodagreementwithM,DAregardlessofreactionconditioｎｓＯｎｔｈｅｏｔｈｅｒｈａｎｄ，thereissomewhatdifferencebet-wｅｅｎＭのａｎｄＭｉ,D』．ItisbecauseMpisprOportionaltoｐ５ｉｎｅｑ．（14)．However，thesolutionofthesphericalmoleculehasnopropertywhichdependsremar-kablyonthemolecularweightandonecaneasilymeasurethesolutionviscosity，therefore，ｅｑ．(16）isusefulfortheestimationofthemolecularweightofsphe-ricalmoleculessuchastheco-condensationreｓｉｎｌｎｔhesecases，theintrinsicviscosity〔り〕ｉｓｇｉｖｅｎａｓｆｏｌｌｏｗｓ：ｏ鋤の〉 ｓｑｍｐｌｅＮｏ．４．５０ ｏ●Ｃｅの①のｅｅｅ２３４５６７８９０１ｏｅｅｅ０５４５ゴロンニヮ。０謎：ろ.０2.5０２０．３０．４０５０６ｏ７ＩｏｇＬＰＦｉｇ､２．PlotsoflogMj,Ｄ４ｖｓ・10gpforallsamples（Solidlineisobtainedfromeq．（16)）sompleNo．４５ｏ●ｏ①①①①ｅｅｅ２３４５６７８９０１０５４３コロン三つ。5０〔り〕＝〃/100＝ＩＤ/40.（18）2.5Ｆｒｏｍｅｑ．（16）ａｎｄ（18)．thenextequationisvalid．ＴＢＯＯ２０．４０．６ｌ０ｇＤＡ＋ｅFig.3.PlotsoflogMm4vs・logD4forallsamples（Solidlineisobtainedfromeq．（17)）〔り〕=1.28×10-2Ｍ０％.(19)WhentheintrinsicviscosityisprOｐｏｒｔｉｏｎａｌｔｏｔｈｅａ－ｔｈｐｏｗｅｒｏｆｔｈｅｍolecularweight，theviscosityaveragemolecularweiｇｈｔＭｍｓｇｉｖｅｎｂｙM－(皿川畑)1'三 (20）７８ 金沢大学工学部紀要７巻１号１９７３Ｍ,D4wasprevious1ydennedasfo110ws5）：Ｍｎ`-(ｚＱＭ(…)｡/(z``MXzα)`． (21）ＳｉｎｃｅＭ『ａｎｄＭＵｉｈａｖｅｔｈｅｓａｍｅａｖｅｒａｇｅｗｈｅｎα＝％，ｉｔｉｓｒｅａｓｏｎａｂｌｅｔｏａｄＯｐｔＤ４ａｔｔｈｅｉntroductionoftherelationshipbetweenviscosityandmolecularweig11t．4．ConclusionInthispaper，thefractionationoftheco-condensationresinsofphenol-urea-fOrmaldehydesystembyfractionalprecipitationandthedeterminationoftheviscosity-diffUsionaveragemolecularweightfromthespecificvolumeandthediffusioncoefIicienｔｉｎＤＭＦａｒｅｐｅｒｆＯｒｍｅｄ・Fromtheresults，thefollowingconclusionsareobtained、1）Thefollowmgequationisvalidregardlessofreactionconditions，Ｗ-万万＝ＫＩｎＤＭＦｓｏｌｖｅｎｔａｔ２５ｏＣ，Ｋｉｓ３．３１×１０－３．２）TherelationShipbetweenIDandMｏｒＤＡａｎｄＭａｒｅｏｂｔａｉｎｅｄａｓｆｏｌｌｏｗｓ：Ｐ＝0.4707Ｍ％、Ａ＝0.4915×１０－４Ｍ一発、Fromtheseequations，ｔｈｅｍo]ecularweightscanbeestimated，Ｍ＝43.39,5,一弘Ｍ－０．１７×１０－１０，４．AcknowIedgementThedeterminationofthediffusioncoefIicientwerecarriedoutwithFACOM230-35inKanazawaUniversity・ＷｅａｒｅｖｅｒｙｇｒａｔｅｆＵｌｔｏｔｈｅｓｔａｆｆｏｆｔhecomputercenter．ReferenceShin-ichirolSHIDA，YasuoKURAandKatsumasaKANEKO,Ｊ・Ｃｈｅｍ・SOC、Japan，ＩｎｄＣｈｅｍ．Sec､，ワ3，１２０６（1970)．Shin-ichirolSHIDA,Ｊ・Ｃｈｅｍ・ＳＯＣ・Japan,Ind・Che、．Ｓec・'70,1206（1967)．KatsumasaKANEKO,Ｊ・Ｃｈｅｍ､SOC・Japan，Ind､Che、．Ｓec､，４４，４７１（1941)．KatsumasaKANEKOandHiroshiSUDA,Ｊ・Ｃｈｅｍ､SOC・Japan,ＩｎｄＣｈｅｍ.Ｓec､，４９，２６（1946)．（RecievedSept､20,1972）1）2）3）4）８

Molecular Weight Estimation of Co-condensation Resin of Phenol-Urea-Formaldehyde System

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Molecular Weight Estimation of Co-condensation Resin of Phenol-Urea-Formaldehyde System

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