jp062794341994PRODUCTION OF LACTIDES制备丙交酯.docx

jp062794341994PRODUCTION OF LACTIDES制备丙交酯.docx

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jp062794341994PRODUCTIONOFLACTIDES制备丙交酯

PATENTABSTRACTSOFJAPAN

（11）Publicationnumber:

06-279434

（43）Dateofpublicationofapplication:

04.10.1994

（51）Int.Cl.

C07D319/12

//C07B61/00

（21）Applicationnumber:

05-065201

（71）Applicant:

DAINIPPONINK&CHEMINC

（22）Dateoffiling:

24.03.1993

（72）Inventor:

KUBOTAKAZUOMI

MURAKAMIYOICHI

（54）PRODUCTIONOFLACTIDES

（57）Abstract:

PURPOSE:

Toobtainamesoform-contg.lactidecompound,i.e.,alactidecompoundcapableofregulatingitsopticalpuritybyonlythermaldecompositionofahydroxyacid-basedoligomerusing,ascatalyst,analkalimetalsalt（andtin,zincorsalt（s）thereof）.

CONSTITUTION:

Usinganalkalimetalsalt（esp.pref.,lithiumsalt,sodiumsaltorpotassiumsalt）ascatalyst,ahydroxyacidoligomer（pref.anoligomermadeupof1500-3500hydroxyacidunits）isthermallydecomposedunderheatingatakettletemperatureof150-200°Catareducedpressureofpref.5-15Torrtoobtaintheobjectivemesoform-contg.lactidecompound.Thiscatalystmaybeacombinationofanalkalimetalsaltwithoneofgroups4-15metal（s）and/orsaltthereof（themetalbeingpref.tin,zinc,salt（s）thereof）.Thehydroxyacidise.g.lacticacid,hydroxybutyricacid,hydroxyvalericacid,hydroxycaproicacid,2-hydroxy-2-methylbutyrlicacid.Themesoform-contg.lactidesareusefulasrawmaterialsforbiodegradablepolymers.

CLAIMS

[Claim（s）]

[Claim1]Amanufacturingmethodofthemesoobjectcontentlactideperformingapyrolysisofhydroxyacidsystemoligomerbymakingalkalimetalsaltintoacatalyst.

[Claim2]Themanufacturingmethodaccordingtoclaim1whichusestogethermetalofperiodictable4group-15groups,and/oritssaltwithalkalimetalsaltasacatalyst.

[Claim3]Themanufacturingmethodaccordingtoclaim1or2inwhichmetalusedtogetherand/oritssaltaremetalofperiodictable12group-15groups,and/oritssalt.

[Claim4]Themanufacturingmethodaccordingtoclaim1or2whosealkalimetalsaltislithiumsalt,sodiumsalt,andpotassiumsaltandinwhichmetalof12toperiodictable15groupand/oritssaltaretin,zinc,and/oritssalt.

DETAILEDDESCRIPTION

[DetailedDescriptionoftheInvention]

[0001]

[IndustrialApplication]Thisinventionrelatestothemanufacturingmethodofmesoobjectcontentlactideusefulasabiodegradablepolymerrawmaterialcharacterizedbymakingthethermaldecompositionreactionofhydroxyacidsystemoligomerperformunderalkali-metal-saltcatalystexistence.

[0002]

[DescriptionofthePriorArt]Itisknownthathydroxyacidsystemoligomerwillgenerateadimerizationthing,i.e.,lactide,byathermaldecompositionreaction.Theselactideisthecompoundswhichattractattentionasarawmaterialofbiodegradablepolymerinrecentyears.WhenL-lactideorD-lactidemanufacturedfromL-hydroxyacidorD-hydroxyacidisused,itisknownthatthecrystallinityofthepolymerobtainedistoohighandshapingofpolymerisdifficult.Therefore,itisimportantforpolymermanufacturetolowertheopticalpurityoflactidemoderatelyandtosuppressthecrystallinityofpolymerlow.

[0003]Aboutmanufactureofthelactidebythethermaldecompositionreactionofhydroxyacidoligomer,manyexamplesofresearcharepubliclyknown.Forexample,atGermanJP,1083275,B,theyareaperiodictableIVgroup,Vgroup,oraVIIIgroup（withthepresentnotation,4groups）.Thewaythemethodofmakingacatalystthemetaloffivegroups,eightgroups,ninegroups,tengroups,14groups,and15groupsoritscompoundmakestinanditscompoundacatalystbyGermanJP,3708915,Bagainisindicated.AtitaniumtetraalkoxidecatalystisusedinGermanJP,1234703,BandthezincoxidecatalystisusedinGermanJP,250413,B.

[0004]However,eachofthesepubliclyknownmethodshassetthechiefaimtoonlykeeptheopticalpurityofthelactideobtainedhigh,andisnotthemethodsofnotnecessarilysatisfyingfromaviewpointofopticalpurityadjustmentofhavingbeensuitableforpolymermanufacture.

[0005]

[Problem（s）tobeSolvedbytheInvention]Althoughthemanufacturingmethodoflactideisfundamentalartindispensabletobiodegradationstudentpolymermanufacture,thepointwhichshouldbeimprovedinrespectofopticalpurityfromthesituationdescribedsofarisleftbehind.Now,thecomplicatedmethodoftheopticalpurityadjustmentforpolymermanufacturemixinganotheropticalactivitylactideseparatelycompoundedtolactidewithhighopticalactivityacquiredbytheabove-mentionedmethod,ormixingopticallyinactivelactideistaken.

[0006]thisinventionpersoncametofindoutthemanufacturingmethodofthelactidewhichmakesitpossibletoadjusttheopticalpurityofgenerationlactideifneededinthecaseoflactidemanufacture,asaresultofinquiringwholeheartedlyforthepurposeofthisimprovement.Thatis,anobjectofthisinventionistoprovidethemanufacturingmethodofthelactidewhichcanadjustopticalpurity.

[0007]

[MeansforSolvingtheProblem]Ifthisinventionpersonsmanufacturethelactidebyapyrolysisofhydroxyacidsystemoligomer,usingalkalimetalsaltasacatalystasaresultofinquiringwholeheartedlyinviewofsuchtheactualcondition,Itfindsoutthatanopticallyinactivemesoobjectcanbemadetogeneratecomparativelysomuchcomparedwiththeconventionalmanufacturingmethodduringareaction,andcametocompletethisinvention.Namely,thisinventionrelatestoamanufacturingmethodofthemesoobjectcontentlactideperformingapyrolysisofhydroxyacidsystemoligomerbymakingalkalimetalsaltintoacatalyst.

[0008]Althougheachalkalimetalsaltusedasacatalystisusedforthisinvention,especiallylithiumsalt,sodiumsalt,andpotassiumsaltareusedpreferably.Forexample,lithiumcarbonate,alithiumchloride,alithiumbromide,lithiumiodide,Lithiumhydroxide,lithiumsulfate,alithiumnitrate,lithiumphosphorate,lithiumacetate,Propionicacidlithium,butanoicacidlithium,isobutyricacidlithium,valeric-acidlithium,Isovalericacidlithium,caproicacidlithium,lithiumenanthate,caprylicacidlithium,octanoicacidlithium（2-ethylhexanoicacidlithium）,laurylacidlithium,pulmiticacidlithium,lithiumstearate,oleicacidlithium,lithiumoxalate[0009]Malonicacidlithium,succinicacidlithium,glutaricacidlithium,adipicacidlithium,Pimelicacidlithium,subericacidlithium,azelaicacidlithium,Sebacicacidlithium,lithiumbenzoate,alpha-naphthoicacidlithium,beta-naphthoicacidlithium,glycolicacidlithium,lacticacidlithium,lithiumtartrate,Lithiumsaltoforganicacid,suchaslithiummandelate,benzilicacidlithium,andlithiumsalicylate,orinorganicacid,Sodiumcarbonate,sodiumbicarbonate,sodiumchloride,asodiumbromide,Sodiumiodide,sodiumhydroxide,sodiumsulfate,sodiumnitrate,sodiumphosphate,sodiumacetate,sodiumpropionate,sodiumbutyrate,isobutyricacidsodium,valeric-acidsodium,isovalericacidsodium,[0010]Sodiumcaproate,sodiumenanthate,sodiumcaprylate,Sodiumoctanoate（2-ethylhexanoicacidsodium）,laurylacidsodium,Pulmiticacidsodium,sodiumstearate,sodiumoleate,Aspecificoxalate,malonicacidsodium,sodiumsuccinate,glutaricacidsodium,Adipicacidsodium,pimelicacidsodium,subericacidsodium,Azelaicacidsodium,sebacicacidsodium,sodiumbenzoate,Sodiumsaltoforganicacid,suchasalpha-naphthoicacidsodium,beta-naphthoicacidsodium,sodiumglycolate,sodiumlactate,sodiumtartrate,sodiummandelate,benzilicacidsodium,andsodiumsalicylate,orinorganicacid,[0011]Potassiumcarbonate,potassiumbicarbonate,potassiumchloride,potassiumbromide,potassiumiodide,Apotassiumhydrate,potassiumsulfate,potassiumnitrate,potassiumphosphate,potassiumacetate,Potassiumpropionate,butanoicacidpotassium,isobutyricacidpotassium,potassiumvalerate,Isovalericacidpotassium,caproicacidpotassium,potassiumenanthate,caprylicacidpotassium,Octanoicacidpotassium（2-ethylhexanoicacidpotassium）,laurylacidpotassium,Pulmiticacidpotassium,potassiumstearate,oleicacidpotassium,Apotassiumoxalate,malonicacidpotassium,pottassiumsuccinate,glutaricacidpotassium,adipicacidpotassium,pimelicacidpotassium,subericacidpotassium,azelaicacidpotassium,sebacicacidpotassium,potassiumbenzoate,alpha-naphthoicacidpotassium,[0012]Althoughpotassiumsaltoforganicacid,suchasbeta-naphthoicacidpotassium,glycolicacidpotassium,lacticacidpotassium,potassiumtartrate,sodiumpotassiumtartrate,potassiummandelate,benzilicacidpotassium,andpotassiumsalicylate,orinorganicacidismentioned,Asaltofalltheisomerscanbeincludedaboutasaltinwhichahydrate,anopticalisomer,andastereoisomericformexistaboutasaltwhichformsahydrate.Carbonateofthismetalandahydrogencarbonatearepreferredatapointthatonlycarbondioxidewithoutcorrosivenessisemittedatareactionofacatalystandlacticacidsystemoligomeralsoespeciallyamongthesesalts.

[0013]Althoughmetalofperiodictable4group-15groupsand/oritssaltwereoftenconventionallyusedforacatalystofapyrolysisofhydroxyacidsystemoligomer,whenthesewereusedasacatalyst,evenifitusedany,aphenomenonwhichistoolowwasseen.then--asthecatalyst,thisinventionpersons,--alkalimetalsalt--metaloffourtoperiodictable15group,and/oritssalt--preferably,Byusingtogetherinmetalofperiodictable12group-15groups,and/oritssalt,ageneratedamountofamesoobjectcouldbechanged,andwhenadjustmentofopticalpuritychangedakindandthemixtureratioofacatalyst,itfoundoutthatitcouldcarryouteasily.

[0014]Althoughmeta