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. Ukwakheka komkhiqizo bekubonakala nge-infrared spectroscopy (FT-IR), i-nuclear magnetic resonance spectroscopy (NMR), i-electron microscopy (SEM), i-X-ray diffraction (XRD) nezinye izindlela zokuhlaziya, kanye nedigri ye-polymerization, isilinganiso sempahla eluhlaza, 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: lapho izinga le-polymerization ye-MCC ye-raw material ingu-45, isilinganiso sesisindo sama-reactants yi-AGU (cellulose glucoside unit): n (NaOH): n (BS) = 1.0: 2.1: 2.2, I-ejenti yokumisa i-isopropanol, isikhathi sokusebenza se-synthesis ye-synthesis ngesikhathi sokushisa komkhiqizo we-synthesis eluhlaza. 5 h. 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 ezisetshenziswa kakhulu njengamanje ezisetshenziswa kakhulu ngokuyinhloko 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 esebenzayo (PC) okwamanje, okuyiyona esebenzayo okwamanje. 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; Nokho, nakuba i-polycarboxylate yokunciphisa amanzi inezinzuzo zokulahlekelwa okuncane kokhonkolo ngokuhamba kwesikhathi, umthamo ophansi, ukugeleza okuhle Kunezinzuzo zokuminyana okuphezulu futhi azikho izinto ezinobuthi ezifana ne-formaldehyde, kodwa kunzima ukuyikhuthaza e-China ngenxa yentengo ephezulu. Kusukela ekuhlaziyweni komthombo wezinto zokusetshenziswa, akunzima ukuthola ukuthi iningi lezinciphisi zamanzi ezibalwe ngenhla zihlanganiswa ngokusekelwe emikhiqizweni ye-petrochemical / by-products, kuyilapho i-petroleum, njengensiza engavuseleleki, iyanda futhi intengo yayo 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 i-pulp kakotini yasetshenziswa njengento yokuqala eluhlaza, futhi ngemva kwe-acid hydrolysis ukuze kutholwe i-microcrystalline cellulose enezinga elifanele le-polymerization, yacushwa yi-sodium hydroxide futhi yasabela nge-1,4-butane sultone ukuze kulungiswe i-butyl sulfonate Acid cellulose ether superplasticizer, futhi izici ezithonya zokusabela ngakunye zaxoxwa.

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 ugaya kahle, ulifake ebhodleleni elinezintamo ezintathu, engeza i-concentration ethile ye-dilute hydrochloric acid, ugovuze ukushisa futhi ukhiphe i-hydrolyze isikhathi esithile, uphole ekamelweni lokushisa, ukuhlunga, ugeze ngamanzi kuze kube yilapho ungathathi hlangothi, futhi u-vacuum wome ku-50 ° C ukuze uthole Ngemva kokuba ne-microcrystalline cellulose degree of polymer degree, faka i-polymer degree ye-polymer ezincwadini ezihlukahlukene, faka i-polymer degree ye-polymer. ebhodleleni lokuphendula elinezintamo ezintathu, yimise nge-ejenti yokumisa izikhathi ezingu-10 ubukhulu bayo, engeza inani elithile lesisombululo se-sodium hydroxide yamanzi ngaphansi kokugqugquzela, Govuza futhi usebenze ekamelweni lokushisa isikhathi esithile, engeza inani elibaliwe le-1,4-butane sultone (BS), ukushisa kuze kufike ekushiseni okuphendulayo, thola ngesikhathi sokushisa kwegumbi, ukupholisa umkhiqizo isikhathi esithile, upholise umkhiqizo ngesikhathi esithile. ukuhlunga. 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, ukusetshenziswa kwamanzi okulinganiselwe kungama-230g), bese wengeza i-ejenti yokunciphisa amanzi enesisindo esingu-1% wesisindo sikasimende emanzini, ngokusho kwe-simende/i-ejenti yokunciphisa amanzi/amanzi avamile/isihlabathi esivamile = 450g/4.5g/230 g/ Isilinganiso esingu-1350 g sifakwa ku-JJ-5 we-mixer enwetshiwe nodaka olunwetshiwe. Kukalwa kumhloli we-motar fluidity, okuyi-motar fluidity elinganisiwe.

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 kukhona iyunithi ye-cellulose anhydroglucose Ukushintshwa kwamakhemikhali e-oksijini proton ku-γ=4.52 ~ 6 umoya-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 kulungiswe i-MCC enamazinga ahlukene e-polymerization, ngokwendlela engenhla, khetha inqubo ethile yokuhlanganisa ukuze ulungise imikhiqizo ye-SBC, ulinganise okuqukethwe kwesibabule ukuze ubale idigri yokushintsha umkhiqizo, bese wengeza imikhiqizo ye-SBC ohlelweni lwamanzi/usimende/ 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 ilungiselelwe ngokusebenzisa i-cellulose ye-microcrystalline enezinga le-polymerization ye-45 (isisindo samangqamuzana: 7290), futhi yengezwe ingxube yekhonkrithi , i-fluidity elinganisiwe yodaka inkulu kakhulu, ngakho-ke kubhekwa ukuthi i-cellulose enezinga le-polymerization engaba ngu-45 ifaneleka 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 e-ejenti yokunciphisa amanzi sisincane, nakuba ukusakazeka kwamangqamuzana kulula futhi kunokumanzisa okuhle, ukushesha kwe-adsorption kwe-molecule kukhulu kunaleyo ye-molecule, futhi iketango lokuthutha amanzi lifushane 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 (idigri ye-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 le-synthesis lingu-80°C, kanye nesikhathi sokuhlanganiswa kwe-ether ye-ether), ukuze kuphenywe inani le-ether ye-ether). I-1,4-butane sultone (BS) ngezinga lokufaka esikhundleni samaqembu e-butanesulfonic acid yomkhiqizo kanye nokumanzi kodaka.

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 yokumisa i-isopropanol, isikhathi sokusebenza se-cellulose ekamelweni lokushisa ngu-2h, izinga lokushisa lokuhlanganiswa ngu-80 ° C, kanye nesikhathi sokuhlanganisa isikhathi se-5h), ukuphenya inani le-hydroxide degree ye-sodium substitution. amaqembu e-butanesulfonic acid emkhiqizweni kanye ne-fluidity yodaka.

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 ekutheni ama-etherification agents (BS) amaningi abambe iqhaza ekuphenduleni okuseceleni, ngaleyo ndlela kunciphisa izinga lokushintshwa kwamaqembu e-sulfonic 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 wenqubo (izinga le-polymerization ye-MCC ngu-45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, i-ejenti yokumisa i-isopropanol, futhi isikhathi sokwenza kusebenze kwe-cellulose ekamelweni lokushisa ngu-2h. Isikhathi 5h), umthelela we-synthesis yezinga lokushisa lomkhiqizo we-acid substitution kwaba ukusabela kwe-acid substitution. kuphenywe.

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 ukukhulisa 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 (idigri ye-MCC ye-polymerization ngu-45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, i-ejenti emisiwe yi-isopropanol, izinga lokushisa lokusabela kokuhlanganiswa ngu-80°C, umkhiqizo Isikhathi sokuhlanganisa izinga lokushisa elingu-5h), phenya umthelela wesikhathi sokusebenza kwe-asidi yegumbi kodwa i-asidi yeqembu isebenze.

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 ekufakweni 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 sokuhlanganiswa kwezinga lokushisa esingaguquki semikhiqizo ngu-5h, kanye nezinga lokushisa lokuphendula lokuhlangana elingu-80 ℃), ngokulandelanayo, i-isoltano, i-epronoltanoltano, ngokulandelana i-acetate ne-petroleum ether njengama-ejenti amisiwe, futhi baxoxe ngomthelela wabo ekusebenzeni komkhiqizo okwehlisa amanzi.

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 i-isopropanol isetshenziswa njenge-ejenti yokumisa, izinga lokushisa lesistimu lingalawulwa eduze nezinga lokushisa elihle lokusabela, kanye nezinga lokushintshwa kwamaqembu e-butanesulfonic acid emkhiqizweni kanye ne-fluidity ye-mortar iphakeme ngokuqhathaniswa; 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 idigri ye-polymerization yezinto zokusetshenziswa inqunywa, isilinganiso sama-reactants ngu-n(MCC):n(NaOH):n( BS)=1:2.1:2.2, isikhathi sokwenza kusebenze kwezinto ezingavuthiwe ekamelweni lokushisa ngu-2h, izinga lokushisa lokuhlanganiswa komkhiqizo ngu-80°C, futhi isikhathi sokuhlanganisa singu-5h. Ukusebenza kwamanzi kuhle kakhulu.