I-Synthesis and Characterization of Butane Sulfonate Cellulose Ether Water Reducer

I-Microcrystalline cellulose (MCC) enezinga eliqondile le-polymerization etholwe yi-acid hydrolysis ye-cellulose kakotini pulp yasetshenziswa njengento eluhlaza. Ngaphansi kokusebenza kwe-sodium hydroxide, yaphendulwa nge-1,4-butane sultone (BS) ukuze kutholwe i-cellulose butyl sulfonate (SBC) yokunciphisa amanzi ene-solubility enhle yamanzi yathuthukiswa. Isakhiwo somkhiqizo sibonakala nge-infrared spectroscopy (FT-IR), i-nuclear magnetic resonance spectroscopy (NMR), i-scanning electron microscopy (SEM), i-X-ray diffraction (XRD) nezinye izindlela zokuhlaziya, kanye neziqu ze-polymerization, isilinganiso sezinto ezingavuthiwe, kanye nokusabela kwe-MCC kwaphenywa. Imithelela yezimo zezinqubo zokwenziwa ezifana nezinga lokushisa, isikhathi sokusabela, nohlobo lwe-ejenti yokumisa okwesikhashana ekusebenzeni kokunciphisa amanzi komkhiqizo. Imiphumela ibonisa ukuthi: uma idigri ye-polymerization yezinto ezingavuthiwe ze-MCC zingama-45, isilinganiso sesisindo sama-reactants sithi: AGU (cellulose glucoside unit): n (NaOH): n (BS) = 1.0: 2.1: 2.2, The i-ejenti yokumisa i-isopropanol, isikhathi sokuvula sezinto ezingavuthiwe ekamelweni lokushisa ngamahora angu-2, futhi isikhathi sokuhlanganiswa somkhiqizo singamahora angu-5. Uma izinga lokushisa lingu-80°C, umkhiqizo otholiwe unezinga eliphezulu kakhulu lokushintsha amaqembu e-butanesulfonic acid, futhi umkhiqizo unokusebenza okungcono kakhulu kokunciphisa amanzi.

Amagama angukhiye:i-cellulose; i-cellulose butylsulfonate; i-ejenti yokunciphisa amanzi; ukusebenza kokunciphisa amanzi

1,Isingeniso

I-concrete superplasticizer ingenye yezingxenye ezibalulekile zikakhonkolo wesimanje. Kungenxa yokubukeka kwe-ejenti yokunciphisa amanzi ukuthi ukusebenza okuphezulu, ukuqina okuhle kanye namandla aphezulu okukhonkolo kungaqinisekiswa. Izinciphisi zamanzi ezisebenza kahle kakhulu okwamanje ezisetshenziswa kakhulu zihlanganisa lezi zigaba ezilandelayo: i-naphthalene-based water reducer (SNF), i-sulfonated melamine resin-based water-reducer (SMF), i-sulfamate-based water-reducer (ASP), i-modified Lignosulfonate superplasticizer ( ML), kanye ne-polycarboxylate superplasticizer (PC), okwamanje okucwaningwa ngayo kakhulu. Ukuhlaziya inqubo yokuhlanganiswa kwezinciphisi zamanzi, iningi lezinciphisi zamanzi ze-condensate zangaphambilini zisebenzisa i-formaldehyde enephunga elinamandla njengempahla eluhlaza yokusabela kwe-polycondensation, futhi inqubo ye-sulfonation ngokuvamile yenziwa nge-acid evuthayo eyi-sulfuric eshisa kakhulu noma i-sulfuric acid egxilile. Lokhu kuzodala imiphumela engemihle neze kubasebenzi nasezindaweni ezizungezile, futhi kuzophinde kukhiqize inani elikhulu lensalela yemfucuza kanye noketshezi olulahlwayo, olungayingeni intuthuko esimeme; noma kunjalo, nakuba ama-polycarboxylate anciphisa amanzi anezinzuzo zokulahlekelwa okuncane kukakhonkolo ngokuhamba kwesikhathi, umthamo ophansi, ukugeleza okuhle Kunezinzuzo zokuminyana okuphezulu futhi azikho izinto ezinobuthi ezifana ne-formaldehyde, kodwa kunzima ukuyikhuthaza e-China ngenxa yokuphakama okuphezulu. intengo. Kusukela ekuhlaziyweni komthombo wezinto zokusetshenziswa, akunzima ukuthola ukuthi iningi lalezi zinciphisi zamanzi ezibalwe ngenhla zihlanganiswa ngokusekelwe emikhiqizweni ye-petrochemical/by-products, kuyilapho i-petroleum, njengensiza engavuseleleki, iyanda futhi iyancipha. intengo yawo ilokhu ikhuphuka njalo. Ngakho-ke, indlela yokusebenzisa izinsiza zemvelo ezishibhile nezichichimayo ezivuselelekayo njengezinto ezingavuthiwe ukuze kuthuthukiswe ama-superplasticizer kakhonkolo amasha asebenza kahle sekuyisiqondiso esibalulekile socwaningo sama-superplasticizers kakhonkolo.

I-Cellulose iyi-macromolecule eqondile eyakhiwe ngokuxhuma i-D-glucopyranose eminingi namabhondi e-β-(1-4) e-glycosidic. Kunamaqembu amathathu e-hydroxyl eringini ngayinye ye-glucopyranosyl. Ukwelashwa okufanele kungathola ukusabela okuthile. Kuleli phepha, i-cellulose kakotini i-pulp yasetshenziswa njengento yokuqala eluhlaza, futhi ngemva kwe-acid hydrolysis ukuthola i-microcrystalline cellulose enezinga elifanele le-polymerization, yasebenza nge-sodium hydroxide futhi yasabela nge-1,4-butane sultone ukulungisa i-butyl sulfonate Acid. i-cellulose ether superplasticizer, kanye nezici ezinethonya zokusabela ngakunye kwaxoxwa ngakho.

2. Isivivinyo

2.1 Izinto ezisetshenziswayo

I-Cellulose Cotton Pulp, i-polymerization degree 576, i-Xinjiang Aoyang Technology Co., Ltd.; I-1,4-butane sultone (BS), ibanga lezimboni, ekhiqizwa yi-Shanghai Jiachen Chemical Co., Ltd.; 52.5R usimende ojwayelekile wasePortland, e-Urumqi Ihlinzekwe yifekthri kasimende; Isihlabathi esijwayelekile sase-China ISO, esikhiqizwe yi-Xiamen Ace Ou Standard Sand Co., Ltd.; i-sodium hydroxide, i-hydrochloric acid, i-isopropanol, i-anhydrous methanol, i-ethyl acetate, i-n-butanol, i-petroleum ether, njll., zonke zihlanzekile ngokohlaziyo, zitholakala ngokuthengisa.

2.2 Indlela yokuhlola

Kala inani elithile le-pulp kakotini bese uyigaya kahle, uyifake ebhodleleni elinezintamo ezintathu, ufake i-concentration ethile ye-dilute hydrochloric acid, ugovuze ukushisa futhi ukhiphe i-hydrolyze isikhathi esithile, upholile ekamelweni lokushisa, ukuhlunga, Geza ngamanzi kuze kube yilapho ungathathi hlangothi, futhi uvale ukoma ku-50 ° C ukuze uthole Ngemva kokuba nezinto zokusetshenziswa ze-microcrystalline cellulose ezinamadigri ahlukene e-polymerization, linganisa izinga labo le-polymerization ngokusho kwezincwadi, ulibeke ebhodleleni lokuphendula elinentamo ezintathu, ulimise nge i-ejenti yokumisa izikhathi ezingu-10 ubukhulu bayo, engeza inani elithile le-sodium hydroxide isixazululo samanzi ngaphansi kokugqugquzela, Govuza futhi wenze kusebenze ekamelweni lokushisa isikhathi esithile, engeza inani elibaliwe le-1,4-butane sultone (BS), ukushisa emazingeni okushisa okusabela, sabela ekushiseni okungaguquki isikhathi esithile, pholisa umkhiqizo ngokwezinga lokushisa elilingana negumbi, futhi uthole umkhiqizo ongahluziwe ngokumunca. Hlanza ngamanzi ne-methanol izikhathi ezi-3, bese uhlunga ngokumunca ukuze uthole umkhiqizo wokugcina, okuyi-cellulose butylsulfonate water reducer (SBC).

2.3 Ukuhlaziywa komkhiqizo kanye nokuhlukaniswa kwezinhlamvu

2.3.1 Ukunqunywa kokuqukethwe kwesibabule somkhiqizo nokubalwa kwezinga lokushintshwa

I-FLASHEA-PE2400 elemental analyzer yasetshenziswa ukwenza ukuhlaziya okuyisisekelo kumkhiqizo wokunciphisa amanzi we-cellulose butyl sulfonate omisiwe ukuze kutholwe okuqukethwe kwesibabule.

2.3.2 Ukunqunywa kwamanzi odaka

Kukalwe ngokuya ngo-6.5 ku-GB8076-2008. Okungukuthi, qala ngokukala ingxube yesihlabathi samanzi/usimende/esijwayelekile kusihloli se-NLD-3 sikasimende se-fluidity tester lapho ububanzi bokunwetshwa bungu-(180±2)mm. usimende, isilinganiso esilinganisiwe sokusetshenziswa kwamanzi singama-230g), bese wengeza i-ejenti yokunciphisa amanzi enesisindo esingu-1% wesisindo sikasimende emanzini, ngokuya nge-simende/i-ejenti yokunciphisa amanzi/amanzi ajwayelekile/isihlabathi esijwayelekile=450g/4.5g/ 230 g/ Isilinganiso esingu-1350 g sifakwa kumxube wosimende we-JJ-5 bese sinyakaziswa ngokulinganayo, futhi ububanzi obunwetshiwe bodaka kumshini wokuhlola uketshezi olunodaka luyalinganiswa, okuwuketshezi olukalwa olukasimende.

2.3.3 Ukwakheka Komkhiqizo

Isampula iphawulwe nge-FT-IR kusetshenziswa i-EQUINOX 55 yohlobo lwe-Fourier transform infrared spectrometer ye-Bruker Company; i-spectrum ye-H NMR yesampula ibonakaliswe yi-INOVA ZAB-HS plough superconducting nuclear magnetic resonance instrument ye-Varian Company; I-morphology yomkhiqizo yabonwa ngaphansi kwe-microscope; Ukuhlaziywa kwe-XRD kwenziwa kusampula kusetshenziswa i-X-ray diffractometer ye-MAC Company M18XHF22-SRA.

3. Imiphumela kanye nengxoxo

3.1 Imiphumela yabalingiswa

3.1.1 Imiphumela yezinhlamvu ze-FT-IR

Ukuhlaziywa kwe-infrared kwenziwa ku-cellulose ye-microcrystalline eluhlaza enezinga le-polymerization Dp=45 kanye nomkhiqizo we-SBC ohlanganiswe kusuka kule nto eluhlaza. Njengoba iziqongo zokumunca ze-SC ne-SH zibuthakathaka kakhulu, azifanele ukukhonjwa, kuyilapho i-S=O inenani eliphakeme lokumunca eliqinile. Ngakho-ke, kungakhathaliseki ukuthi kukhona iqembu le-sulfonic acid esakhiweni samangqamuzana kunganqunywa ngokuqinisekisa ukuba khona kwe-S=O peak. Ngokusobala, ku-spectrum ye-cellulose, kukhona ukuphakama okunamandla kokumuncwa kwenani lamagagasi angu-3344 cm-1, okubangelwa ukuphakama kokudlidliza kwe-hydroxyl ku-cellulose; ukuphakama kokumunca okunamandla kunani legagasi elingu-2923 cm-1 ukuphakama kokudlidliza okunwebekayo kwe-methylene (-CH2). Ukudlidliza okuphezulu; uchungechunge lwamabhendi akhiwe ngo-1031, 1051, 1114, kanye no-1165cm-1 abonisa ukuphakama kokumuncwa kwe-hydroxyl stretching vibration kanye nenani eliphakeme lokumuncwa le-ether bond (COC) ukudlidliza okugobayo; inombolo yegagasi 1646cm-1 ikhombisa i-hydrogen eyakhiwe yi-hydroxyl namanzi amahhala Isilinganiso esiphezulu sokumuncwa kwebhondi; ibhande le-1432 ~ 1318cm-1 libonisa ukuba khona kwe-cellulose crystal structure. Ku-spectrum ye-IR ye-SBC, ukuqina kwebhendi 1432 ~ 1318cm-1 kuncipha; kuyilapho ukuqina kokumuncwa kwe-absorption ku-1653 cm-1 kukhuphuka, okubonisa ukuthi ikhono lokwakha izibopho ze-hydrogen liqiniswa; I-1040, 605cm-1 ibonakala iziqongo zokumuncwa ezinamandla, futhi lezi ezimbili aziboniswa kububanzi obuyi-infrared we-cellulose, eyokuqala iwuphawu lokumunca eliphakeme lesibopho se-S=O, futhi lokhu kwakamuva kuwuphawu lokumuncwa okuphezulu kwe-SO bond. Ngokusekelwe ekuhlaziyweni okungenhla, kungabonakala ukuthi ngemva kokusabela kwe-etherification ye-cellulose, kunamaqembu e-sulfonic acid e-chain chain yayo.

3.1.2 H NMR imiphumela yezinhlamvu

I-spectrum ye-H NMR ye-cellulose butyl sulfonate ingabonakala: ngaphakathi kwe-γ=1.74~2.92 kukhona ukushintshwa kwamakhemikhali e-hydrogen proton ye-cyclobutyl, futhi ngaphakathi kuka-γ=3.33~4.52 kuneyunithi ye-cellulose anhydroglucose Ukushintshwa kwamakhemikhali e-oxygen proton ku-γ=4.52 ~6 ukushintshwa kwamakhemikhali eproton ye-methylene eqenjini le-butylsulfonic acid exhunywe kumoya-mpilo, futhi akukho ukuphakama kokuthi γ=6~7, okubonisa ukuthi umkhiqizo awuwona Amanye ama-proton akhona.

3.1.3 Imiphumela yezinhlamvu ze-SEM

Ukubonwa kwe-SEM ye-cellulose ukotini uginindela, i-microcrystalline cellulose kanye nomkhiqizo we-cellulose butylsulfonate. Ngokuhlaziya imiphumela yokuhlaziywa kwe-SEM ye-cellulose ukotini ukhuni, i-microcrystalline cellulose kanye nomkhiqizo we-cellulose butanesulfonate (SBC), kutholakala ukuthi i-microcrystalline cellulose etholwe ngemva kwe-hydrolysis nge-HCL ingashintsha kakhulu ukwakheka kwe-cellulose fibers. Isakhiwo esine-fibrous sacekelwa phansi, futhi kwatholakala izinhlayiya ezinhle ze-cellulose ezihlanganisiwe. I-SBC etholwe ngokuqhubeka nokusabela nge-BS yayingenawo ukwakheka kwe-fibrous futhi ngokuyisisekelo yaguqulwa yaba isakhiwo se-amorphous, esasizuzisa ekuhlakazweni kwayo emanzini.

3.1.4 Imiphumela yezinhlamvu ze-XRD

I-crystallinity ye-cellulose kanye nokuphuma kwayo kubhekisela kumaphesenti esifunda se-crystalline esakhiwe isakhiwo seyunithi ye-cellulose ngokuphelele. Lapho i-cellulose kanye nokuphuma kwayo kungena ukusabela kwamakhemikhali, izibopho ze-hydrogen ku-molecule naphakathi kwama-molecule ziyabhujiswa, futhi isifunda se-crystalline sizoba isifunda se-amorphous, ngaleyo ndlela sinciphise i-crystallinity. Ngakho-ke, ushintsho ku-crystallinity ngaphambi nangemva kokusabela kuyisilinganiso se-cellulose Enye yezindlela zokubamba iqhaza ekuphenduleni noma cha. Ukuhlaziywa kwe-XRD kwenziwa ku-microcrystalline cellulose kanye nomkhiqizo we-cellulose butanesulfonate. Kungabonakala ngokuqhathanisa ukuthi ngemva kwe-etherification, i-crystallinity ishintsha ngokuyisisekelo, futhi umkhiqizo uguqule ngokuphelele isakhiwo se-amorphous, ukuze uhlakazwe emanzini.

3.2 Umthelela wezinga le-polymerization yezinto zokusetshenziswa ekusebenzeni kokunciphisa amanzi komkhiqizo

I-fluidity yodaka ikhombisa ngokuqondile ukusebenza kokunciphisa amanzi komkhiqizo, futhi okuqukethwe kwesibabule komkhiqizo kungenye yezinto ezibaluleke kakhulu ezithinta uketshezi lodaka. I-fluidity yodaka ikala ukusebenza kokunciphisa amanzi komkhiqizo.

Ngemva kokushintsha izimo zokusabela kwe-hydrolysis ukuze ulungiselele i-MCC enamazinga ahlukene e-polymerization, ngokwendlela engenhla, khetha inqubo ethile yokuhlanganisa ukuze ulungise imikhiqizo ye-SBC, ulinganise okuqukethwe kwesibabule ukubala idigri yokushintsha umkhiqizo, bese wengeza imikhiqizo ye-SBC emanzini. /usimende/uhlelo olujwayelekile lokuhlanganisa isihlabathi Kala uketshezi lodaka.

Kungabonakala emiphumeleni yokuhlola ukuthi ngaphakathi kwebanga locwaningo, lapho idigri ye-polymerization ye-microcrystalline cellulose impahla eluhlaza iphezulu, okuqukethwe kwesibabule (i-substitution degree) yomkhiqizo kanye nokumanzi kodaka kuphansi. Lokhu kungenxa yokuthi: isisindo samangqamuzana wempahla eluhlaza sincane, esivumela ukuxuba okufanayo kwempahla eluhlaza kanye nokungena kwe-etherification agent, ngaleyo ndlela kuthuthukiswe izinga le-etherification yomkhiqizo. Kodwa-ke, izinga lokunciphisa amanzi lomkhiqizo alikhuphuki ngendlela eqondile kanye nokwehla kwezinga le-polymerization yezinto zokusetshenziswa. Imiphumela yokuhlola ibonisa ukuthi uketshezi olunodaka lwengxube yodaka lukasimende oluxutshwe ne-SBC olulungiswe ngokusebenzisa i-microcrystalline cellulose enezinga le-polymerization Dp<96 (isisindo samangqamuzana<15552) sikhulu kuno-180 mm (okungaphezu kwalokho ngaphandle kwesinciphisi samanzi) . i-benchmark fluidity), ebonisa ukuthi i-SBC ingalungiswa ngokusebenzisa i-cellulose enesisindo se-molecular esingaphansi kuka-15552, futhi izinga elithile lokunciphisa amanzi lingatholakala; I-SBC ilungiswa ngokusebenzisa i-microcrystalline cellulose enezinga le-polymerization engu-45 (isisindo samangqamuzana: 7290), futhi yengezwe engxube yekhonkrithi , uketshezi olulinganisiwe lodaka likhulu kakhulu, ngakho-ke kubhekwa ukuthi i-cellulose enezinga le-polymerization. ezingaba ngu-45 ezifanele kakhulu ukulungiswa kwe-SBC; lapho izinga le-polymerization yezinto zokusetshenziswa likhulu kunama-45, i-fluidity yodaka iyancipha kancane kancane, okusho ukuthi izinga lokunciphisa amanzi liyancipha. Lokhu kungenxa yokuthi lapho isisindo samangqamuzana sikhulu, ngakolunye uhlangothi, i-viscosity yesistimu yengxube izokhula, ukufana kokuhlakazeka kukasimende kuzobe kubi, futhi ukuhlakazeka kokhonkolo kuzohamba kancane, okuzothinta umphumela wokuhlakazeka; ngakolunye uhlangothi, lapho isisindo samangqamuzana sikhulu, Ama-macromolecules e-superplasticizer aku-conformation yekhoyili engahleliwe, okunzima kakhulu ukuyikhanga ebusweni bezinhlayiya zikasimende. Kodwa lapho izinga le-polymerization yezinto eziluhlaza lingaphansi kwama-45, nakuba okuqukethwe kwesibabule (i-substitution degree) yomkhiqizo kukhulu kakhulu, i-fluidity yengxube yodaka nayo iqala ukwehla, kodwa ukwehla kuncane kakhulu. Isizathu siwukuthi lapho isisindo samangqamuzana we-ejenti yokunciphisa amanzi sisincane, nakuba ukusabalalisa kwamangqamuzana kulula futhi kunokumanzisa okuhle, ukusheshisa kwe-adsorption kwe-molecule kukhulu kunaleyo ye-molecule, futhi uchungechunge lokuthutha emanzini lufushane kakhulu, futhi ukungqubuzana phakathi kwezinhlayiya kukhulu, okuyingozi kukhonkolo. Umphumela wokuhlakazeka awumuhle njengalowo wokunciphisa amanzi onesisindo samangqamuzana amakhulu. Ngakho-ke, kubaluleke kakhulu ukulawula kahle isisindo samangqamuzana obuso bezingulube (ingxenye ye-cellulose) ukuthuthukisa ukusebenza kokunciphisa amanzi.

3.3 Umthelela wezimo zokusabela ekusebenzeni kokunciphisa amanzi komkhiqizo

Kutholwa ngokuhlolwa ukuthi ngaphezu kwezinga le-polymerization ye-MCC, isilinganiso sama-reactants, izinga lokushisa lokusabela, ukwenziwa kusebenze kwezinto zokusetshenziswa, isikhathi sokuhlanganiswa komkhiqizo, kanye nohlobo lwe-ejenti yokumisa okwesikhashana konke kuthinta ukusebenza kokunciphisa amanzi komkhiqizo.

3.3.1 Isilinganiso sokusabela

(1) Umthamo we-BS

Ngaphansi kwezimo ezinqunywe amanye amapharamitha wenqubo (izinga le-polymerization ye-MCC ngu-45, n(MCC):n(NaOH)=1:2.1, i-ejenti emisiwe yi-isopropanol, isikhathi sokuvula se-cellulose ekamelweni lokushisa ngu-2h, Izinga lokushisa lokuhlanganisa lingu-80°C, kanti isikhathi sokuhlanganisa singu-5h), ukuze kuphenywe umthelela wenani le-etherification agent 1,4-butane sultone (BS) ngezinga lokushintshwa kwamaqembu e-butanesulfonic acid omkhiqizo kanye nokumanzi komkhiqizo. udaka.

Kungabonakala ukuthi njengoba inani le-BS likhula, izinga lokufakwa esikhundleni kwamaqembu e-butanesulfonic acid kanye ne-fluidity yodaka landa kakhulu. Uma isilinganiso se-BS kuya ku-MCC sifinyelela ku-2.2:1, uketshezi lwe-DS nodaka kufinyelela phezulu. inani, kubhekwa ukuthi ukusebenza kokunciphisa amanzi kungcono kakhulu ngalesi sikhathi. Inani le-BS laqhubeka nokukhula, futhi kokubili izinga lokushintshwa kanye nokugeleza kodaka kwaqala ukwehla. Lokhu kungenxa yokuthi uma i-BS idlulele, i-BS izosabela nge-NaOH ukuze ikhiqize i-HO-(CH2)4SO3Na. Ngakho-ke, leli phepha likhetha isilinganiso esiphezulu se-BS ukuya ku-MCC njengo-2.2:1.

(2) Umthamo we-NaOH

Ngaphansi kwezimo ezinqunywe amanye amapharamitha wenqubo (izinga le-polymerization ye-MCC ngu-45, n(BS):n(MCC)=2.2:1. I-ejenti emisiwe yi-isopropanol, isikhathi sokuvula se-cellulose ekamelweni lokushisa ngu-2h, Izinga lokushisa le-synthesis lingu-80°C, kanti isikhathi sokuhlanganisa singu-5h), ukuze kuphenywe umthelela wenani le-sodium hydroxide ngezinga lokushintshwa kwamaqembu e-butanesulfonic acid emkhiqizweni kanye nokumanzi kodaka.

Kungabonakala ukuthi, ngokukhuphuka kwenani lokunciphisa, izinga lokushintshwa kwe-SBC likhula ngokushesha, futhi liqala ukwehla ngemva kokufinyelela inani eliphakeme kakhulu. Lokhu kungenxa yokuthi, lapho okuqukethwe kwe-NaOH kuphezulu, kunezisekelo eziningi zamahhala ohlelweni, futhi amathuba okusabela ohlangothini ayanda, okuholela ekuhlanganyeleni kwama-etherification (BS) amaningi abambe iqhaza ekuphenduleni okusemaceleni, ngaleyo ndlela kunciphisa izinga lokushintshwa kwe-sulfonic. amaqembu acid emkhiqizweni. Emazingeni okushisa aphezulu, ukuba khona kwe-NaOH eningi kakhulu kuzophinde kunciphise i-cellulose, futhi ukusebenza kokunciphisa amanzi komkhiqizo kuzothinteka ngezinga eliphansi le-polymerization. Ngokwemiphumela yokuhlola, lapho isilinganiso se-molar ye-NaOH ku-MCC sicishe sibe ngu-2.1, izinga lokushintsha likhulu kakhulu, ngakho leli phepha linquma ukuthi isilinganiso se-molar ye-NaOH kuya ku-MCC ngu-2.1:1.0.

3.3.2 Umthelela wezinga lokushisa elisabelayo ekusebenzeni komkhiqizo okwehlisa amanzi

Ngaphansi kwezimo ezinqunywe amanye amapharamitha enqubo (izinga le-polymerization ye-MCC ngu-45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, i-ejenti emisiwe yi-isopropanol, futhi isikhathi sokwenza kusebenze I-cellulose ekamelweni lokushisa ngu-2h Isikhathi se-5h), ithonya lokushisa lokusabela kwe-synthesis ngezinga lokushintshwa kwamaqembu e-butanesulfonic acid emkhiqizweni.

Kungabonakala ukuthi njengoba izinga lokushisa lokusabela likhuphuka, i-sulfonic acid substitution degree DS ye-SBC iyanda kancane kancane, kodwa lapho izinga lokushisa lokusabela lidlula u-80 °C, i-DS ibonisa ukwehla. Ukusabela kwe-etherification phakathi kwe-1,4-butane sultone ne-cellulose kuwukusabela kwe-endothermic, futhi ukwandisa izinga lokushisa lokusabela kunenzuzo ekuphenduleni phakathi kwe-etherifying agent kanye neqembu le-cellulose hydroxyl, kodwa ngokwanda kwezinga lokushisa, umphumela we-NaOH ne-cellulose uyakhula kancane kancane. . Iba namandla, ibangele ukuba i-cellulose yehle futhi iwe, okuholela ekwehleni kwesisindo samangqamuzana e-cellulose kanye nokukhiqizwa koshukela omncane wamangqamuzana. Ukusabela kwalawa ma-molecule amancane ane-etherifying agent kulula, futhi ama-ejenti e-etherifying amaningi azosetshenziswa, okuthinta izinga lokushintshwa komkhiqizo. Ngakho-ke, le thesis ibheka ukuthi izinga lokushisa elifaneleka kakhulu lokusabela kwe-etherification ye-BS ne-cellulose ngu-80℃.

3.3.3 Umthelela wesikhathi sokusabela ekusebenzeni komkhiqizo wokunciphisa amanzi

Isikhathi sokuphendula sihlukaniswe ngokuvula izinga lokushisa legumbi lezinto ezingavuthiwe kanye nesikhathi sokushisa esiqhubekayo semikhiqizo.

(1) Isikhathi sokwenza kusebenze izinga lokushisa legumbi lezinto ezingavuthiwe

Ngaphansi kwezimo zenqubo ezilungile ezingenhla (i-MCC degree of polymerization ngu-45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, i-ejenti emisiwe yi-isopropanol, izinga lokushisa lokusabela kwe-synthesis ngu-80°C, umkhiqizo Isikhathi sokuhlanganisa izinga lokushisa njalo 5h), phenya umthelela wesikhathi sokwenza kusebenze izinga lokushisa ekamelweni ngezinga lokushintshwa kweqembu le-butanesulfonic acid.

Kungabonakala ukuthi izinga lokushintshwa kweqembu le-butanesulfonic acid lomkhiqizo we-SBC liyakhuphuka kuqala bese lehla ngokwandisa isikhathi sokwenza kusebenze. Isizathu sokuhlaziya singase sibe ukuthi ngokunyuka kwesikhathi sesenzo se-NaOH, ukuwohloka kwe-cellulose kubi kakhulu. Yehlisa isisindo samangqamuzana e-cellulose ukuze ukhiqize ushukela wamangqamuzana amancane. Ukusabela kwalawa ma-molecule amancane ane-etherifying agent kulula, futhi ama-ejenti e-etherifying amaningi azosetshenziswa, okuthinta izinga lokushintshwa komkhiqizo. Ngakho-ke, leli phepha libheka ukuthi isikhathi sokwenza kusebenze izinga lokushisa legumbi lezinto zokusetshenziswa ngu-2h.

(2) Isikhathi sokuhlanganiswa komkhiqizo

Ngaphansi kwezimo zenqubo ezilungile ezingenhla, umthelela wesikhathi sokwenza kusebenze kuzinga lokushisa legumbi ngezinga lokushintshwa kweqembu le-butanesulfonic acid lomkhiqizo uye waphenywa. Kungabonakala ukuthi ngokunwetshwa kwesikhathi sokuphendula, izinga lokushintsha likhuphuka kuqala, kodwa lapho isikhathi sokusabela sifinyelela ku-5h, i-DS ikhombisa ukwehla. Lokhu kuhlobene nesisekelo samahhala esikhona ekuphenduleni kwe-etherification ye-cellulose. Emazingeni okushisa aphezulu, ukwandiswa kwesikhathi sokuphendula kuholela ekwandeni kwezinga le-alkali hydrolysis ye-cellulose, ukufinyezwa kweketango lamangqamuzana e-cellulose, ukwehla kwesisindo samangqamuzana omkhiqizo, kanye nokwenyuka kokusabela okuseceleni, okuholela ekutheni esikhundleni. idigri iyancipha. Kulesi sivivinyo, isikhathi esifanelekile sokuhlanganiswa amahora angu-5.

3.3.4 Umthelela wohlobo lwe-ejenti emisiwe ekusebenzeni kokunciphisa amanzi komkhiqizo.

Ngaphansi kwezimo ezilungile zenqubo (i-MCC polymerization degree ngu-45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, isikhathi sokwenza kusebenze kwezinto ezingavuthiwe ekamelweni lokushisa ngu-2h, isikhathi sokuhlanganisa izinga lokushisa esingaguquki yemikhiqizo ingu-5h, futhi izinga lokushisa lokusabela kokuhlanganiswa ngu-80 ℃), ngokulandelanayo khetha i-isopropanol, i-ethanol, i-n-butanol, i-ethyl acetate ne-petroleum ether njengama-ejenti amisiwe, futhi uxoxe ngethonya lazo ekusebenzeni kokunciphisa amanzi komkhiqizo.

Ngokusobala, i-isopropanol, i-n-butanol ne-ethyl acetate zonke zingasetshenziswa njenge-ejenti emisiwe kulokhu kusabela kwe-etherification. Indima ye-ejenti emisiwe, ngaphezu kokuhlakaza ama-reactants, ingalawula izinga lokushisa lokusabela. Iphuzu elibilayo le-isopropanol lingu-82.3 ° C, ngakho-ke isopropanol isetshenziswa njenge-ejenti yokumisa, izinga lokushisa lesistimu lingalawulwa eduze nezinga lokushisa elihle lokusabela, kanye nezinga lokushintshanisa amaqembu e-butanesulfonic acid emkhiqizweni kanye nokumanzi udaka luphakeme kakhulu; kuyilapho indawo yokubilisa ye-ethanol iphakeme kakhulu Iphansi, izinga lokushisa lokusabela alihlangabezani nezidingo, izinga lokushintshwa kwamaqembu e-butanesulfonic acid emkhiqizweni kanye ne-fluidity ye-mortar iphansi; I-petroleum ether ingase ibambe iqhaza ekuphenduleni, ngakho-ke awukho umkhiqizo ohlakaziwe ongatholakala.

4 Isiphetho

(1) Ukusebenzisa i-cotton pulp njengento yokuqala eluhlaza,I-microcrystalline cellulose (MCC)nge-degree efanelekile ye-polymerization yalungiswa, yasebenza yi-NaOH, futhi yasabela nge-1,4-butane sultone ukuze kulungiswe amanzi e-butylsulfonic acid Cellulose ether, okungukuthi, isinciphisi samanzi esisekelwe ku-cellulose. Isakhiwo somkhiqizo sasibonakaliswe, futhi kwatholakala ukuthi ngemva kokusabela kwe-etherification ye-cellulose, kwakukhona amaqembu e-sulfonic acid ku-chain yayo yamangqamuzana, eyayiguqukile yaba isakhiwo se-amorphous, futhi umkhiqizo wokunciphisa amanzi wawune-solubility enhle yamanzi;

(2) Ngokuhlola, kutholakala ukuthi lapho izinga le-polymerization ye-microcrystalline cellulose ingu-45, ukusebenza kokunciphisa amanzi komkhiqizo otholiwe kungcono kakhulu; ngaphansi kwesimo sokuthi izinga le-polymerization yezinto zokusetshenziswa linqunywa, isilinganiso sama-reactants ngu-n(MCC):n(NaOH):n( BS)=1:2.1:2.2, isikhathi sokwenza kusebenze kwezinto zokusetshenziswa kuzinga lokushisa legumbi ngu 2h, izinga lokushisa lokwenziwa komkhiqizo ngu-80°C, kanti isikhathi sokuhlanganisa singu-5h. Ukusebenza kwamanzi kuhle kakhulu.