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Chithunzi chojambulidwa chomwe chikuwonetsa masilaidi atatu nthawi imodzi. Gwiritsani ntchito mabatani a Yapitayi ndi Yotsatira kuti mudutse masilaidi atatu nthawi imodzi, kapena gwiritsani ntchito mabatani otsetsereka kumapeto kuti mudutse masilaidi atatu nthawi imodzi.
Kupanga zinthu zowonjezera kukusintha momwe ofufuza ndi akatswiri opanga mafakitale amapangira ndi kupanga zida zamankhwala kuti akwaniritse zosowa zawo. Mu pepalali, tikupereka chitsanzo choyamba cha reactor yoyenda yomwe imapangidwa ndi ultrasonic additive manufacturing (UAM) lamination ya pepala lolimba lachitsulo lokhala ndi zigawo zolumikizirana mwachindunji ndi zinthu zomverera. Ukadaulo wa UAM sumangogonjetsa zolepheretsa zambiri zomwe zimagwirizana ndi kupanga zowonjezera za ma reactor a mankhwala, komanso umakulitsa kwambiri mphamvu za zida zotere. Ma compounds angapo ofunikira a 1,4-dissubstituted 1,2,3-triazole apangidwa bwino ndikukonzedwa bwino ndi Cu-mediated 1,3-dipolar Huisgen cycloaddition reaction pogwiritsa ntchito UAM chemistry facility. Pogwiritsa ntchito mawonekedwe apadera a UAM ndi continuous flow processing, chipangizochi chimatha kuyambitsa zochitika zomwe zikuchitika komanso kupereka ndemanga yeniyeni kuti ziwunikire ndikukonza zochitikazo.
Chifukwa cha ubwino wake waukulu kuposa wofanana nawo, kayendedwe ka kayendedwe ka madzi ndi gawo lofunika komanso lokulirakulira m'masukulu ndi m'mafakitale chifukwa cha kuthekera kwake kowonjezera kusankha ndi kugwira ntchito bwino kwa kapangidwe ka mankhwala. Izi zimayambira pakupanga mamolekyu osavuta achilengedwe1 mpaka mankhwala ophatikizika2,3 ndi zinthu zachilengedwe4,5,6. Kupitilira 50% ya zochita m'mafakitale abwino a mankhwala ndi mankhwala zimatha kupindula ndi kayendedwe kopitilira7.
M'zaka zaposachedwapa, pakhala chizolowezi chowonjezeka cha magulu omwe akufuna kusintha magalasi achikhalidwe kapena zida zamagetsi zoyendera ndi "ma reactor" a mankhwala osinthika8. Kapangidwe kake kobwerezabwereza, kupanga mwachangu, ndi kuthekera kwa magawo atatu (3D) kwa njira izi ndizothandiza kwa iwo omwe akufuna kusintha zida zawo kuti zigwirizane ndi machitidwe enaake, zida, kapena mikhalidwe. Mpaka pano, ntchitoyi yayang'ana kwambiri kugwiritsa ntchito njira zosindikizira za 3D zochokera ku polymer monga stereolithography (SL)9,10,11, Fused Deposition Modeling (FDM)8,12,13,14 ndi inkjet printing7,15. , 16. Kusowa kudalirika ndi kuthekera kwa zida zotere kuchita machitidwe/kusanthula kwamitundu yosiyanasiyana ya mankhwala17, 18, 19, 20 ndi chinthu chachikulu chomwe chimalepheretsa kugwiritsa ntchito AM m'munda uno17, 18, 19, 20.
Chifukwa cha kuchuluka kwa kugwiritsa ntchito mankhwala oyendera ndi makhalidwe abwino okhudzana ndi AM, njira zabwino ziyenera kufufuzidwa zomwe zingathandize ogwiritsa ntchito kupanga mitsempha yoyendera ndi mankhwala abwino komanso luso lowunikira. Njirazi ziyenera kulola ogwiritsa ntchito kusankha kuchokera kuzinthu zosiyanasiyana zamphamvu kapena zogwira ntchito zomwe zingagwiritsidwe ntchito pansi pa mikhalidwe yosiyanasiyana yowunikira, komanso kuthandizira mitundu yosiyanasiyana ya zotsatira zowunikira kuchokera ku chipangizocho kuti athe kuyang'anira ndikuwongolera zomwe zimachitika.
Njira imodzi yopangira zowonjezera zomwe zingagwiritsidwe ntchito popanga ma reactor a mankhwala apadera ndi Ultrasonic Additive Manufacturing (UAM). Njira yopangira ma sheet olimba iyi imagwiritsa ntchito ma vibration a ultrasonic ku ma foil achitsulo owonda kuti azilumikize pamodzi wosanjikiza ndi wosanjikiza ndi kutentha kochepa komanso kuchuluka kwa pulasitiki 21, 22, 23. Mosiyana ndi ukadaulo wina wa AM, UAM imatha kuphatikizidwa mwachindunji ndi kupanga kochotsa, komwe kumadziwika kuti njira yopangira yosakanizidwa, momwe kugayira kwa periodic in-situ numeral control (CNC) kapena kukonza laser kumatsimikiza mawonekedwe a wosanjikiza wa zinthu zomangiriridwa 24, 25. Izi zikutanthauza kuti wogwiritsa ntchito samangokhala ndi mavuto okhudzana ndi kuchotsa zinthu zomangira zotsalira kuchokera ku ngalande zazing'ono zamadzimadzi, zomwe nthawi zambiri zimakhala mu ufa ndi makina amadzimadzi AM26,27,28. Ufulu wa kapangidwe kameneka umakhudzanso kusankha zipangizo zomwe zilipo - UAM imatha kulumikiza kuphatikiza kwa zinthu zofanana ndi kutentha ndi zosiyana mu gawo limodzi la njira. Kusankha kuphatikiza kwa zinthu kupitirira njira yosungunula kumatanthauza kuti zofunikira zamakina ndi mankhwala za ntchito zinazake zitha kukwaniritsidwa bwino. Kuwonjezera pa kugwirizana kolimba, chinthu china chomwe chimachitika ndi kugwirizana kwa ultrasound ndi kusinthasintha kwakukulu kwa zinthu zapulasitiki pa kutentha kochepa 29,30,31,32,33. Mbali yapadera ya UAM iyi imalola zinthu zamakanika/zotentha kuyikidwa pakati pa zigawo zachitsulo popanda kuwonongeka. Masensa ophatikizidwa a UAM angathandize kupereka chidziwitso cha nthawi yeniyeni kuchokera ku chipangizocho kupita kwa wogwiritsa ntchito kudzera mu kusanthula kophatikizidwa.
Ntchito yakale ya olemba32 inasonyeza kuthekera kwa njira ya UAM kupanga mapangidwe achitsulo a 3D microfluidic okhala ndi mphamvu zomvera zomwe zili mkati. Chipangizochi ndi chongoyang'anira chokha. Nkhaniyi ikupereka chitsanzo choyamba cha reactor ya microfluidic chemical yopangidwa ndi UAM, chipangizo chogwira ntchito chomwe sichimangolamulira komanso chimayambitsa kupanga mankhwala ndi zinthu zolumikizirana bwino. Chipangizochi chimaphatikiza zabwino zingapo zokhudzana ndi ukadaulo wa UAM popanga zida za mankhwala za 3D, monga: kuthekera kosintha kapangidwe kathunthu ka 3D mwachindunji kuchokera ku chitsanzo chothandizidwa ndi kompyuta (CAD) kukhala chinthu; kupanga zinthu zambiri kuphatikiza kutentha kwambiri ndi zinthu zolumikizira, komanso masensa otentha omwe ali mkati mwachindunji pakati pa mitsinje ya reactant kuti azilamulira molondola komanso kuyang'anira kutentha kwa reaction. Kuti awonetse magwiridwe antchito a reactor, laibulale ya mankhwala ofunikira a 1,4-dissubstituted 1,2,3-triazole opangidwa ndi mankhwala adapangidwa ndi 1,3-dipolar Huisgen cycloaddition ya mkuwa. Ntchitoyi ikuwonetsa momwe kugwiritsa ntchito sayansi ya zinthu ndi kapangidwe kothandizidwa ndi makompyuta kungatsegule mwayi watsopano ndi mwayi wa chemistry kudzera mu kafukufuku wosiyanasiyana.
Zosungunulira zonse ndi ma reagents zinagulidwa kuchokera ku Sigma-Aldrich, Alfa Aesar, TCI, kapena Fischer Scientific ndipo zinagwiritsidwa ntchito popanda kuyeretsa kale. Ma spectra a 1H ndi 13C NMR omwe adalembedwa pa 400 ndi 100 MHz, motsatana, adapezeka pa spectrometer ya JEOL ECS-400 400 MHz kapena Bruker Avance II 400 MHz spectrometer yokhala ndi CDCl3 kapena (CD3)2SO ngati zosungunulira. Ma reaction onse adachitika pogwiritsa ntchito nsanja ya Uniqsis FlowSyn flow chemistry.
UAM idagwiritsidwa ntchito popanga zipangizo zonse mu kafukufukuyu. Ukadaulowu unapangidwa mu 1999 ndipo tsatanetsatane wake waukadaulo, magawo ogwirira ntchito ndi chitukuko kuyambira pomwe idapangidwa zitha kuphunziridwa pogwiritsa ntchito zinthu zotsatirazi34,35,36,37. Chipangizochi (Chithunzi 1) chinagwiritsidwa ntchito pogwiritsa ntchito makina olemera a 9 kW SonicLayer 4000® UAM (Fabrisonic, Ohio, USA). Zipangizo zomwe zinasankhidwa pa chipangizo choyendera madzi zinali Cu-110 ndi Al 6061. Cu-110 ili ndi mkuwa wambiri (wosachepera 99.9% mkuwa), zomwe zimapangitsa kuti ikhale yoyenera kuchita zinthu zomwe zimayambitsidwa ndi mkuwa ndipo motero imagwiritsidwa ntchito ngati "gawo logwira ntchito mkati mwa microreactor. Al 6061 O imagwiritsidwa ntchito ngati "zinthu zambiri". , komanso gawo lolumikizana lomwe limagwiritsidwa ntchito posanthula; kuphatikiza kwa zigawo zothandizira za alloy ndi mkhalidwe wophatikizidwa ndi gawo la Cu-110. lapezeka kuti ndi lokhazikika pamankhwala ndi ma reagents omwe amagwiritsidwa ntchito pantchitoyi. Al 6061 O kuphatikiza ndi Cu-110 kumaonedwanso kuti ndi kuphatikiza kwa zinthu zogwirizana ndi UAM ndipo chifukwa chake ndi chinthu choyenera pa kafukufukuyu38,42. Zipangizozi zalembedwa mu Gome 1 pansipa.
Masitepe opangira reactor (1) 6061 aluminiyamu alloy substrate (2) Kupanga njira yotsika kuchokera ku foil yamkuwa (3) Kuyika ma thermocouple pakati pa zigawo (4) Njira yapamwamba (5) Kulowa ndi kutuluka (6) Reactor ya Monolithic.
Malingaliro a kapangidwe ka njira yamadzimadzi ndi kugwiritsa ntchito njira yopotoka kuti muwonjezere mtunda womwe madziwo amayenda mkati mwa chip pomwe mukusunga kukula kwa chip komwe kungathe kuyendetsedwa. Kuwonjezeka kwa mtunda kumeneku ndikofunikira kuti muwonjezere nthawi yolumikizirana ndi catalyst ndikupereka zokolola zabwino kwambiri. Ma chips amagwiritsa ntchito ma bend a 90° kumapeto kwa njira yowongoka kuti apangitse kusakanikirana kosasunthika mkati mwa chipangizocho44 ndikuwonjezera nthawi yolumikizirana yamadzimadzi ndi pamwamba (catalyst). Kuti muwonjezere kusakaniza komwe kungatheke, kapangidwe ka reactor kamaphatikizapo ma inlet awiri a reactant ophatikizidwa mu Y-connection asanalowe mu gawo la mixing coil. Khomo lachitatu, lomwe limadutsa pakati pa residence yake, likuphatikizidwa mu dongosolo la ma multi-stage synthesis reactions amtsogolo.
Ma channel onse ali ndi mawonekedwe a sikweya (opanda ma angles ofooka), zomwe zimachitika chifukwa cha CNC milling yomwe imagwiritsidwa ntchito popanga mawonekedwe a channel. Miyeso ya channel imasankhidwa kuti ipereke volumetric yield yapamwamba (ya microreactor), koma yaying'ono mokwanira kuti ithandize kuyanjana ndi pamwamba (ma catalysts) pazakumwa zambiri zomwe zilimo. Kukula koyenera kumadalira zomwe olemba adakumana nazo kale ndi zida zochitira zinthu zachitsulo-zamadzimadzi. Miyeso yamkati ya channel yomaliza inali 750 µm x 750 µm ndipo voliyumu yonse ya reactor inali 1 ml. Cholumikizira chomangidwa mkati (1/4″-28 UNF thread) chimaphatikizidwa mu kapangidwe kake kuti chilolere kulumikizana mosavuta kwa chipangizocho ndi zida zamakemikolo oyenda. Kukula kwa channel kumachepetsedwa ndi makulidwe a foil, mawonekedwe ake amakaniko, ndi magawo omangirira omwe amagwiritsidwa ntchito ndi ma ultrasonic. Pa mulifupi winawake wazinthu zomwe zaperekedwa, zinthuzo "zidzagwera" mu channel yomwe idapangidwa. Pakadali pano palibe chitsanzo chenicheni cha kuwerengera kumeneku, kotero m'lifupi mwa njira yayikulu ya chinthu ndi kapangidwe kake kamatsimikiziridwa mwa kuyesa, momwemo m'lifupi mwa 750 µm sichidzapangitsa kuti chigwe.
Mawonekedwe (sikweya) a njirayo amatsimikiziridwa pogwiritsa ntchito chodulira sikweya. Mawonekedwe ndi kukula kwa njirayo zitha kusinthidwa pamakina a CNC pogwiritsa ntchito zida zosiyanasiyana zodulira kuti mupeze kuchuluka kwa kayendedwe ndi mawonekedwe osiyanasiyana. Chitsanzo chopanga njira yokhotakhota yokhala ndi chida cha 125 µm chingapezeke mu Monaghan45. Pamene gawo la foil likugwiritsidwa ntchito mosalala, kugwiritsa ntchito zinthu za foil ku njirayo kudzakhala ndi malo osalala (sikweya). Mu ntchitoyi, mawonekedwe a sikweya adagwiritsidwa ntchito kusunga kufanana kwa njirayo.
Pakangoyimitsidwa pang'ono kupanga, masensa otenthetsera a thermocouple (mtundu K) amamangidwa mwachindunji mu chipangizocho pakati pa magulu a channel apamwamba ndi otsika (Chithunzi 1 - gawo 3). Ma thermocouple awa amatha kuwongolera kusintha kwa kutentha kuyambira -200 mpaka 1350 °C.
Njira yoyika zitsulo imachitika ndi nyanga ya UAM pogwiritsa ntchito zojambulazo zachitsulo 25.4 mm mulifupi ndi makulidwe a 150 microns. Zigawo za zojambulazo zimalumikizidwa mu mndandanda wa mizere yoyandikana kuti ziphimbe malo onse omangira; kukula kwa zinthu zomwe zasungidwa kumakhala kwakukulu kuposa chinthu chomaliza chifukwa njira yochotsera imapanga mawonekedwe oyera omaliza. Makina a CNC amagwiritsidwa ntchito popanga mawonekedwe akunja ndi amkati a zidazo, zomwe zimapangitsa kuti zida ndi njira zigwirizane ndi zida zosankhidwa ndi magawo a njira ya CNC (mu chitsanzo ichi, pafupifupi 1.6 µm Ra). Kupopera kosalekeza kwa zinthu za ultrasonic ndi makina opitilira nthawi zonse kumagwiritsidwa ntchito panthawi yonse yopanga chipangizocho kuti zitsimikizire kuti kulondola kwa miyeso kukusungidwa ndipo gawo lomalizidwa likukwaniritsa mulingo wolondola wa CNC. M'lifupi mwa njira yomwe imagwiritsidwa ntchito pa chipangizochi ndi yaying'ono mokwanira kuti zitsimikizire kuti zinthu za zojambulazo "sizikugwa" mu njira yamadzimadzi, kotero njirayo ili ndi gawo lozungulira lalikulu. Mipata yomwe ingakhalepo muzinthu za zojambulazo ndi magawo a njira ya UAM idatsimikiziridwa mwa kuyesa ndi mnzake wopanga (Fabrisonic LLC, USA).
Kafukufuku wasonyeza kuti pa malo olumikizirana 46, 47 a UAM compound palibe kufalikira kwakukulu kwa zinthu popanda kutentha kwina, kotero pa zipangizo zomwe zili mu ntchitoyi, gawo la Cu-110 limakhalabe losiyana ndi gawo la Al 6061 ndipo limasintha kwambiri.
Ikani chowongolera kuthamanga kwa mpweya (BPR) chomwe chimayang'aniridwa kale pa 250 psi (1724 kPa) pansi pa reactor ndikupopera madzi kudzera mu reactor pa liwiro la 0.1 mpaka 1 ml min-1. Kuthamanga kwa reactor kunayang'aniridwa pogwiritsa ntchito FlowSyn pressure transducer yomwe idamangidwa mu system kuti zitsimikizire kuti system ikhoza kusunga kuthamanga kokhazikika. Kuchuluka kwa kutentha komwe kungachitike mu flow reactor kunayesedwa pofufuza kusiyana kulikonse pakati pa thermocouples zomwe zidamangidwa mu reactor ndi thermocouples zomwe zidamangidwa mu heating plate ya FlowSyn chip. Izi zimachitika mwa kusintha kutentha kwa hotplate komwe kudakonzedwa pakati pa 100 ndi 150 °C mu 25 °C increments ndikuyang'anira kusiyana kulikonse pakati pa kutentha komwe kudakonzedwa ndi komwe kudalembedwa. Izi zidachitika pogwiritsa ntchito tc-08 data logger (PicoTech, Cambridge, UK) ndi pulogalamu ya PicoLog yomwe ili nayo.
Mikhalidwe ya cycloaddition reaction ya phenylacetylene ndi iodoethane imakonzedwa bwino (Scheme 1-Cycloaddition of phenylacetylene ndi iodoethane, Scheme 1-Cycloaddition of phenylacetylene ndi iodoethane). Kukonza kumeneku kunachitika pogwiritsa ntchito njira yonse yopangira zoyeserera (DOE), pogwiritsa ntchito kutentha ndi nthawi yokhazikika ngati zosintha pamene akukonza chiŵerengero cha alkyne:azide pa 1:2.
Mayankho osiyana a sodium azide (0.25 M, 4:1 DMF:H2O), iodoethane (0.25 M, DMF), ndi phenylacetylene (0.125 M, DMF) adakonzedwa. Aliquot ya 1.5 ml ya yankho lililonse idasakanizidwa ndikupopedwa kudzera mu reactor pamlingo wofunikira wa kuyenda ndi kutentha. Yankho la chitsanzocho linatengedwa ngati chiŵerengero cha dera lapamwamba la triazole product ku zinthu zoyambira za phenylacetylene ndipo linatsimikiziridwa pogwiritsa ntchito high performance liquid chromatography (HPLC). Kuti ayese bwino, mayankho onse adatengedwa nthawi yomweyo pambuyo poti chisakanizo cha reaction chachoka mu reactor. Ma parameter ranges omwe adasankhidwa kuti akonzedwe akuwonetsedwa mu Table 2.
Zitsanzo zonse zinasanthulidwa pogwiritsa ntchito njira ya Chromaster HPLC (VWR, PA, USA) yokhala ndi quaternary pump, column oven, variable wavelength UV detector ndi autosampler. Column inali Equivalence 5 C18 (VWR, PA, USA), 4.6 x 100 mm, 5 µm particle size, yosungidwa pa 40°C. Soluble inali isocratic methanol:water 50:50 pa flow rate ya 1.5 ml·min-1. Voliyumu ya jakisoni inali 5 μl ndipo wavelength ya detector inali 254 nm. % peak area ya DOE sample inawerengedwa kuchokera ku peak a residual alkyne ndi triazole products zokha. Kuyambitsa kwa starting tool kumathandiza kuzindikira peaks yoyenera.
Kuphatikiza zotsatira za kusanthula kwa reactor ndi pulogalamu ya MODDE DOE (Umetrics, Malmö, Sweden) kunalola kusanthula bwino momwe zinthu zilili komanso kudziwa momwe zinthu zilili bwino pa cycloaddition iyi. Kuyendetsa chowongolera chomangidwa mkati ndikusankha mawu onse ofunikira kumapanga mndandanda wa zinthu zomwe zimapangidwa kuti ziwonjezere malo oyambira a chinthucho ndikuchepetsa malo oyambira a acetylene feedstock.
Kusungunuka kwa mkuwa pamwamba pa chipinda chothandizira kunachitika pogwiritsa ntchito yankho la hydrogen peroxide (36%) lomwe limayenda m'chipinda chothandizira (kuchuluka kwa madzi = 0.4 ml min-1, nthawi yokhazikika = mphindi 2.5) lisanapangidwe laibulale iliyonse ya triazole.
Pamene mikhalidwe yabwino kwambiri yapezeka, idagwiritsidwa ntchito pamitundu yosiyanasiyana ya acetylene ndi haloalkane derivatives kuti ilole kuti pakhale laibulale yaying'ono yopangira zinthu, motero kukhazikitsa kuthekera kogwiritsa ntchito mikhalidwe iyi pamitundu yambiri ya ma reagents (Chithunzi 1). 2).
Konzani njira zosiyana za sodium azide (0.25 M, 4:1 DMF:H2O), haloalkanes (0.25 M, DMF), ndi alkynes (0.125 M, DMF). Ma quots a 3 ml a yankho lililonse adasakanizidwa ndikupopedwa kudzera mu reactor pa liwiro la 75 µl/min ndi kutentha kwa 150°C. Voliyumu yonse idasonkhanitsidwa mu vial ndikuchepetsedwa ndi 10 ml ya ethyl acetate. Njira yoyezera idatsukidwa ndi 3 x 10 ml ya madzi. Zigawo zamadzi zidaphatikizidwa ndikuchotsedwa ndi 10 ml ya ethyl acetate, kenako zigawo za organic zidaphatikizidwa, kutsukidwa ndi 3 × 10 ml ya brine, kuumitsidwa pa MgSO 4 ndikusefedwa, kenako solvent idachotsedwa mu vacuo. Zitsanzo zidayeretsedwa ndi silica gel column chromatography pogwiritsa ntchito ethyl acetate musanayesedwe ndi kuphatikiza kwa HPLC, 1H NMR, 13C NMR ndi high resolution mass spectrometry (HR-MS).
Ma spectra onse adapezeka pogwiritsa ntchito Thermofischer Precision Orbitrap mass spectrometer yokhala ndi ESI ngati gwero la ionization. Zitsanzo zonse zidakonzedwa pogwiritsa ntchito acetonitrile ngati solvent.
Kusanthula kwa TLC kunachitika pa mbale za silica zokhala ndi substrate ya aluminiyamu. Ma mbalewo adawonetsedwa ndi kuwala kwa UV (254 nm) kapena utoto wa vanillin ndi kutentha.
Zitsanzo zonse zinasanthulidwa pogwiritsa ntchito makina a VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) okhala ndi choyezera zinthu zokha, pampu ya binary yokhala ndi uvuni wa column ndi choyezera kutalika kwa mafunde chimodzi. Chipinda cha ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland) chinagwiritsidwa ntchito.
Majakisoni (5 µl) anapangidwa mwachindunji kuchokera ku chisakanizo cha crude reaction chochepetsedwa (1:10 dilution) ndipo anawunikidwa ndi madzi:methanol (50:50 kapena 70:30), kupatula zitsanzo zina pogwiritsa ntchito njira yosungunulira ya 70:30 (yomwe imatchedwa nyenyezi nambala ) pamlingo woyenda wa 1.5 ml/min. Mzatiwo unasungidwa pa 40°C. Kutalika kwa kutalika kwa chowunikira ndi 254 nm.
Malo okwana % ya chiŵerengero cha zitsanzo anawerengedwa kuchokera ku malo okwana 100 a alkyne yotsala, chinthu cha triazole chokha, ndipo kuyambitsidwa kwa zinthu zoyambira kunapangitsa kuti zitheke kuzindikira 100 ofanana.
Zitsanzo zonse zinasanthulidwa pogwiritsa ntchito Thermo iCAP 6000 ICP-OES. Miyezo yonse yoyezera inakonzedwa pogwiritsa ntchito yankho la 1000 ppm Cu mu 2% nitric acid (SPEX Certi Prep). Miyezo yonse inakonzedwa mu yankho la 5% DMF ndi 2% HNO3, ndipo zitsanzo zonse zinachepetsedwa ka 20 ndi yankho la chitsanzo la DMF-HNO3.
UAM imagwiritsa ntchito ultrasonic metal welding ngati njira yolumikizira chitsulo chomwe chimagwiritsidwa ntchito popanga msonkhano womaliza. Ultrasonic metal welding imagwiritsa ntchito chida chachitsulo chogwedezeka (chotchedwa nyanga kapena ultrasound horn) kuti ikani mphamvu pa foil/gawo lolumikizidwa kale kuti ligwirizane/ligwirizane kale mwa kugwedeza zinthuzo. Pa ntchito yopitilira, sonotrode ili ndi mawonekedwe a cylindrical ndipo imazungulira pamwamba pa zinthuzo, ndikumamatira malo onse. Pamene kupanikizika ndi kugwedezeka zimagwiritsidwa ntchito, ma oxides pamwamba pa zinthuzo amatha kusweka. Kupanikizika kosalekeza ndi kugwedezeka kungayambitse kuwonongeka kwa kukhwima kwa zinthuzo 36. Kukhudzana kwambiri ndi kutentha ndi kupanikizika komwe kumachitika pamalopo kumabweretsa mgwirizano wolimba pamalumikizidwe azinthuzo; kungathandizenso kulimbitsa mgwirizano mwa kusintha mphamvu ya pamwamba48. Mtundu wa njira yolumikizira umathetsa mavuto ambiri okhudzana ndi kutentha kosinthasintha komanso zotsatira za kutentha kwambiri zomwe zatchulidwa muukadaulo wina wowonjezera wopanga. Izi zimalola kulumikizana mwachindunji (monga popanda kusintha pamwamba, zodzaza kapena zomatira) za zigawo zingapo za zinthu zosiyanasiyana kukhala kapangidwe kamodzi kogwirizana.
Chinthu chachiwiri chabwino cha CAM ndi kuchuluka kwa pulasitiki komwe kumachitika m'zinthu zachitsulo ngakhale kutentha kochepa, mwachitsanzo pansi pa malo osungunuka a zinthu zachitsulo. Kuphatikiza kwa kugwedezeka kwa ma ultrasound ndi kupanikizika kumayambitsa kuchuluka kwa kusamuka kwa malire a tirigu m'deralo ndi kubwezeretsanso popanda kutentha kwakukulu komwe kumagwirizanitsidwa ndi zinthu zambiri. Pakupangidwa kwa msonkhano womaliza, chodabwitsachi chingagwiritsidwe ntchito kuyika zinthu zogwira ntchito komanso zosagwira ntchito pakati pa zigawo za zojambulazo zachitsulo, gawo ndi gawo. Zinthu monga ulusi wowala 49, reinforcement 46, zamagetsi 50 ndi thermocouples (ntchitoyi) zaphatikizidwa bwino mu kapangidwe ka UAM kuti apange magulu ogwirira ntchito komanso osagwira ntchito.
Mu ntchitoyi, mphamvu zosiyanasiyana zomangira zinthu ndi mphamvu zolumikizirana za UAM zinagwiritsidwa ntchito popanga microreactor yoyenera yowongolera kutentha kwa catalytic.
Poyerekeza ndi palladium (Pd) ndi zinthu zina zogwiritsidwa ntchito kwambiri zachitsulo, Cu catalysis ili ndi zabwino zingapo: (i) Pazachuma, Cu ndi yotsika mtengo kuposa zitsulo zina zambiri zomwe zimagwiritsidwa ntchito mu catalysis ndipo motero ndi njira yokongola kwa makampani opanga mankhwala (ii) mitundu yosiyanasiyana ya Cu-catalyzed cross-coupling reactions ikukula ndipo ikuwoneka kuti ikugwirizana pang'ono ndi njira za Pd51, 52, 53 (iii) Cu-catalyzed reactions imagwira ntchito bwino popanda ma ligand ena. Ma ligand awa nthawi zambiri amakhala osavuta kupanga komanso otsika mtengo. ngati mukufuna, pomwe omwe amagwiritsidwa ntchito mu Pd chemistry nthawi zambiri amakhala ovuta, okwera mtengo, komanso ogwirizana ndi mpweya (iv) Cu, yomwe imadziwika bwino chifukwa cha kuthekera kwake kogwirizanitsa ma alkynes mu kapangidwe, monga Sonogashira's bimetallic catalyzed coupling ndi cycloaddition ndi azides (click chemistry) (v) Cu ikhozanso kulimbikitsa arylation ya ma nucleophiles ena mu Ullmann-type reactions.
Posachedwapa, zitsanzo za kusintha kwa zinthu zonsezi pamaso pa Cu(0) zawonetsedwa. Izi makamaka chifukwa cha makampani opanga mankhwala komanso chidwi chomwe chikukulirakulira pakubwezeretsa ndikugwiritsanso ntchito zinthu zoyambitsa zitsulo55,56.
Kachitidwe ka 1,3-dipolar cycloaddition pakati pa acetylene ndi azide ku 1,2,3-triazole, komwe kadaperekedwa koyamba ndi Huisgen m'ma 1960, kamaonedwa kuti ndi kachitidwe kowonetsera mgwirizano. Zidutswa za triazole 1,2,3 zomwe zapezeka ndizofunika kwambiri ngati mankhwala ophera mankhwala chifukwa cha kugwiritsidwa ntchito kwawo m'thupi komanso mankhwala osiyanasiyana 58.
Kachitidwe kameneka kanalandira chidwi chatsopano pamene Sharpless ndi ena adayambitsa lingaliro la "click chemistry"59. Mawu akuti "click chemistry" amagwiritsidwa ntchito pofotokoza gulu lamphamvu komanso losankha la machitidwe opangira mwachangu mankhwala atsopano ndi malaibulale ophatikizana pogwiritsa ntchito heteroatomic bonding (CXC)60. Kukongola kwa machitidwewa kumachitika chifukwa cha zokolola zambiri zomwe zimagwirizanitsidwa nawo. mikhalidwe ndi yosavuta, kukana mpweya ndi madzi, ndipo kulekanitsidwa kwa zinthu ndikosavuta61.
Kachitidwe ka 1,3-dipole Huisgen cycloaddition sikagwera mu gulu la "click chemistry". Komabe, Medal ndi Sharpless adawonetsa kuti chochitika ichi cholumikizira azide-alkyne chimadutsa 107-108 pamaso pa Cu(I) poyerekeza ndi kufulumira kwakukulu kwa liwiro la 1,3-dipolar cycloaddition 62,63. Njira yotsogola iyi yochitira zinthu siifuna kuteteza magulu kapena mikhalidwe yovuta yochitira zinthu ndipo imapereka kusintha kwathunthu ndi kusankha ku 1,4-dissubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) pakapita nthawi (Chithunzi 3).
Zotsatira za isometric za Huisgen cycloadditions zachikhalidwe ndi zamkuwa. Ma Huisgen cycloadditions a Cu(I)-catalyzed Huisgen amapereka 1,4-dissubstituted 1,2,3-triazoles okha, pomwe ma Huisgen cycloadditions omwe amapangidwa ndi kutentha nthawi zambiri amapereka 1,4- ndi 1,5-triazoles chisakanizo cha 1:1 cha azole stereoisomers.
Ma protocol ambiri amakhudza kuchepetsa magwero okhazikika a Cu(II), monga kuchepetsa CuSO4 kapena Cu(II)/Cu(0) compound pamodzi ndi sodium salts. Poyerekeza ndi ma catalyzed reactions ena achitsulo, kugwiritsa ntchito Cu(I) kuli ndi ubwino waukulu wokhala wotsika mtengo komanso wosavuta kugwiritsa ntchito.
Kafukufuku wa kinetic ndi isotopic wochitidwa ndi Worrell et al. 65 wasonyeza kuti pankhani ya ma terminal alkynes, ma equivalents awiri a mkuwa amakhudzidwa pakuyambitsa reactivity ya molekyulu iliyonse yokhudzana ndi azide. Njira yomwe ikuperekedwayi imapitilira kudzera mu mphete yachitsulo yamkuwa yokhala ndi ziwalo zisanu ndi chimodzi yopangidwa ndi mgwirizano wa azide ndi acetylide yamkuwa yokhala ndi σ-bonded ndi mkuwa wokhala ndi π ngati ligand yokhazikika ya donor. Ma copper triazolyl derivatives amapangidwa chifukwa cha kufupika kwa mphete kutsatiridwa ndi kuwonongeka kwa proton kuti apange zinthu za triazole ndikutseka kayendedwe ka catalytic.
Ngakhale ubwino wa zipangizo zamagetsi zoyendera madzi zalembedwa bwino, pakhala chikhumbo chophatikiza zida zowunikira mu machitidwe awa kuti ziwunikire njira yeniyeni mu situ66,67. UAM yatsimikizira kukhala njira yoyenera yopangira ndi kupanga ma reactor ovuta kwambiri a 3D flow kuchokera ku zinthu zoyendetsera kutentha zomwe zimagwira ntchito molimbika komanso zomwe zimayendetsedwa ndi zinthu zowunikira mwachindunji (Chithunzi 4).
Choyatsira madzi cha aluminiyamu-mkuwa chopangidwa ndi ultrasonic additive manufacturing (UAM) chokhala ndi kapangidwe ka njira yamkati yovuta, ma thermocouple omangidwa mkati ndi chipinda chothandizira kuchitapo kanthu. Kuti muwone njira zamkati mwa madzi, chitsanzo chowonekera chopangidwa pogwiritsa ntchito stereolithography chikuwonetsedwanso.
Kuti zitsimikizidwe kuti ma reactor apangidwa kuti agwiritsidwe ntchito mtsogolo, ma solvents ayenera kutenthedwa bwino pamwamba pa kutentha kwawo; amayesedwa ndi kupanikizika ndi kutentha. Kuyesedwa kwa kupanikizika kunasonyeza kuti dongosololi limasunga kupanikizika kokhazikika komanso kosalekeza ngakhale pa kupanikizika kwakukulu mu dongosololi (1.7 MPa). Mayeso a hydrostatic adachitika kutentha kwa chipinda pogwiritsa ntchito H2O ngati madzi.
Kulumikiza thermocouple yomangidwa mkati (Chithunzi 1) ku deta ya kutentha kunawonetsa kuti kutentha kwa thermocouple kunali 6 °C (± 1 °C) pansi pa kutentha komwe kunakonzedwa mu dongosolo la FlowSyn. Kawirikawiri, kuwonjezeka kwa kutentha kwa 10°C kumawirikiza kawiri kuchuluka kwa reaction rate, kotero kusiyana kwa kutentha kwa madigiri ochepa chabe kungasinthe kwambiri reaction rate. Kusiyana kumeneku kumachitika chifukwa cha kutayika kwa kutentha mu RPV yonse chifukwa cha kutentha kwakukulu kwa zinthu zomwe zimagwiritsidwa ntchito popanga. Kutentha kumeneku kumakhala kosalekeza ndipo chifukwa chake kumatha kuganiziridwa pokhazikitsa zida kuti zitsimikizire kuti kutentha kolondola kwafikiridwa ndikuyesedwa panthawi ya reaction. Chifukwa chake, chida ichi chowunikira pa intaneti chimapangitsa kuti kutentha kwa reaction kuyende bwino ndipo kumathandizira kukonza bwino njira ndikukula kwa mikhalidwe yabwino. Masensa awa angagwiritsidwenso ntchito kuzindikira zochitika za exothermic ndikuletsa zochitika zothawa m'makina akuluakulu.
Reactor yomwe yaperekedwa mu pepalali ndi chitsanzo choyamba cha kugwiritsa ntchito ukadaulo wa UAM popanga ma reactor a mankhwala ndipo ikufotokoza zoletsa zazikulu zingapo zomwe zikugwirizana ndi kusindikiza kwa AM/3D kwa zida izi, monga: (i) Kuthana ndi mavuto omwe adziwika okhudzana ndi kukonza mkuwa kapena aluminiyamu (ii) kukonza bwino njira zamkati poyerekeza ndi njira zosungunulira ufa (PBF) monga kusungunulira laser (SLM)25,69 Kuyenda bwino kwa zinthu ndi kapangidwe koyipa ka pamwamba26 (iii) kutentha kochepa kwa processing, komwe kumathandiza masensa olumikizira mwachindunji, zomwe sizingatheke muukadaulo wa ufa, (v) kuthana ndi zovuta zamakaniko komanso kukhudzidwa kwa zigawo zochokera ku polima ku zinthu zosiyanasiyana zachilengedwe17,19.
Kugwira ntchito kwa reactor kunawonetsedwa ndi mndandanda wa machitidwe a alkinazide cycloaddition omwe amathandizidwa ndi mkuwa pansi pa mikhalidwe yopitilira kuyenda (Chithunzi 2). Reactor ya mkuwa yosindikizidwa ndi ultrasonic yomwe yawonetsedwa pa chithunzi 4 idalumikizidwa ndi njira yogulitsira ndipo idagwiritsidwa ntchito popanga laibulale ya azide ya ma 1,4-dissubstituted 1,2,3-triazoles osiyanasiyana pogwiritsa ntchito kutentha komwe kumayendetsedwa ndi acetylene ndi alkyl group halides pamaso pa sodium chloride (Chithunzi 3). Kugwiritsa ntchito njira yopitilira kuyenda kumachepetsa mavuto achitetezo omwe angabuke mu njira zamagulu, popeza izi zimapangitsa kuti azide izikhala yogwira ntchito komanso yoopsa [317], [318]. Poyamba, reaction idakonzedwa kuti igwirizane ndi phenylacetylene ndi iodoethane (Chiwembu 1 - Cycloaddition ya phenylacetylene ndi iodoethane) (onani Chithunzi 5).
(Kumwamba kumanzere) Chithunzi cha momwe zinthu zimakhalira chomwe chimagwiritsidwa ntchito pophatikiza 3DP reactor mu flow system (kumtunda kumanja) chopezeka kuchokera ku scheme yokonzedwa (yotsika) ya Huisgen 57 cycloaddition scheme pakati pa phenylacetylene ndi iodoethane kuti zitheke bwino komanso kuwonetsa magawo okonzedwa bwino a kusintha kwa reaction.
Mwa kuwongolera nthawi yokhala ya ma reactants mu gawo lothandizira la reactor ndikuyang'anira mosamala kutentha kwa reaction ndi sensa ya thermocouple yolumikizidwa mwachindunji, momwe zinthu zimachitikira zimatha kukonzedwa mwachangu komanso molondola ndi nthawi yochepa komanso zinthu. Zinapezeka mwachangu kuti kusintha kwakukulu kunapezeka pogwiritsa ntchito nthawi yokhala ya mphindi 15 komanso kutentha kwa reaction kwa 150°C. Zitha kuwoneka kuchokera ku coefficient plot ya pulogalamu ya MODDE kuti nthawi yokhala ndi kutentha kwa reaction ndi momwe zimachitikira zimaonedwa kuti ndizofunikira kwambiri pa chitsanzo. Kuyendetsa optimizer yomangidwa mkati pogwiritsa ntchito zinthu zosankhidwazi kumapanga mikhalidwe yochitira yomwe idapangidwa kuti iwonjezere madera okhala ndi zinthu zambiri pomwe ikuchepetsa madera okhala ndi zinthu zoyambira. Kukonza kumeneku kunapereka kusintha kwa 53% kwa chinthu cha triazole, komwe kunafanana ndendende ndi zomwe chitsanzocho chinaneneratu za 54%.