Ukwenziwa kanye Nokuchazwa Kwe-Butane Sulfonate Cellulose Ether Water Reducer

I-microcrystalline cellulose (MCC) enezinga elithile le-polymerization etholwe yi-acid hydrolysis ye-cellulose cotton pulp yasetshenziswa njengezinto zokusetshenziswa. Ngaphansi kokusebenza kwe-sodium hydroxide, yaphendulwa nge-1,4-butane sultone (BS) ukuze kutholakale i-cellulose butyl sulfonate (SBC) water reducer ene-water solubility enhle yathuthukiswa. Isakhiwo somkhiqizo sabonakala 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 nezinga le-polymerization, isilinganiso sezinto zokusetshenziswa, kanye nokusabela kwe-MCC kwahlolwa. Imiphumela yezimo zenqubo yokwenziwa njengokushisa, isikhathi sokusabela, kanye nohlobo lwe-agent yokumisa ekusebenzeni kokunciphisa amanzi komkhiqizo. Imiphumela ikhombisa ukuthi: uma izinga lokupholimitha le-MCC yezinto zokusetshenziswa lingama-45, isilinganiso sobuningi bama-reactants yilesi: AGU (iyunithi ye-cellulose glucoside): n (NaOH): n (BS) = 1.0: 2.1: 2.2, I-ejenti yokumisa yi-isopropanol, isikhathi sokusebenza kwezinto zokusetshenziswa ekushiseni kwegumbi singamahora ama-2, kanti isikhathi sokwenziwa komkhiqizo singamahora ama-5. Uma izinga lokushisa lingama-80°C, umkhiqizo otholiwe unezinga eliphakeme kakhulu lokufaka esikhundleni amaqembu e-butanesulfonic acid, futhi umkhiqizo unamandla okunciphisa amanzi kangcono kakhulu.

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

1、Isingeniso

I-superplasticizer yekhonkrithi ingenye yezingxenye ezibalulekile zekhonkrithi yesimanje. Kungenxa yokubonakala kwe-ejenti yokunciphisa amanzi ukuthi ukusebenza kahle okuphezulu, ukuqina okuhle kanye nokuqina okuphezulu kwekhonkrithi kungaqinisekiswa. Izinciphisi zamanzi ezisebenzayo kakhulu ezisetshenziswa kabanzi njengamanje zifaka phakathi izigaba 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 ecwaningwa kakhulu. Ukuhlaziya inqubo yokwenziwa kwezinciphisi zamanzi, iningi lezinciphisi zamanzi zendabuko zangaphambilini zisebenzisa i-formaldehyde enephunga elinamandla elinamandla njengezinto zokusetshenziswa zokusabela kwe-polycondensation, futhi inqubo ye-sulfonation ngokuvamile yenziwa nge-sulfuric acid ebola kakhulu noma i-sulfuric acid egxilile. Lokhu kuzobangela imiphumela emibi ngokungenakugwenywa kubasebenzi kanye nendawo ezungezile, futhi kuzophinde kukhiqize inani elikhulu lezinsalela zemfucuza kanye noketshezi lwemfucuza, okungavumeli intuthuko eqhubekayo; noma kunjalo, yize ama-polycarboxylate water reducer anezinzuzo zokulahlekelwa okuncane kwekhonkrithi ngokuhamba kwesikhathi, umthamo ophansi, ukugeleza okuhle. Inezinzuzo zokuminyana okuphezulu kanye nokungabi nezinto ezinobuthi njenge-formaldehyde, kodwa kunzima ukuyikhuthaza eShayina ngenxa yentengo ephezulu. Kusukela ekuhlaziyweni komthombo wezinto zokusetshenziswa, akunzima ukuthola ukuthi iningi lama-reducer amanzi ashiwo ngenhla lenziwa ngokusekelwe emikhiqizweni/imikhiqizo ye-petrochemical, kuyilapho i-petroleum, njengomthombo ongavuseleleki, iyanda kakhulu futhi intengo yayo ikhuphuka njalo. Ngakho-ke, indlela yokusebenzisa izinsiza zemvelo ezishibhile neziningi ezivuselelekayo njengezinto zokusetshenziswa ukuthuthukisa ama-superplasticizer amasha ekhonkrithi asebenza kahle kakhulu isibe isiqondiso esibalulekile socwaningo lwama-superplasticizer ekhonkrithi.

I-Cellulose iyi-macromolecule eqondile eyakhiwe ngokuxhumanisa i-D-glucopyranose eminingi nezibopho ze-β-(1-4) glycosidic. Kunamaqembu amathathu e-hydroxyl ering ngayinye ye-glucopyranosyl. Ukwelashwa okufanele kungathola ukusabela okuthile. Kuleli phepha, i-cellulose cotton pulp yasetshenziswa njengezinto zokuqala zokusetshenziswa, futhi ngemva kwe-acid hydrolysis ukuthola i-microcrystalline cellulose enezinga elifanele le-polymerization, yavuselelwa yi-sodium hydroxide futhi yasabela nge-1,4-butane sultone ukulungiselela i-butyl sulfonate I-Acid cellulose ether superplasticizer, futhi kwaxoxwa ngezinto ezithonya ukusabela ngakunye.

2. Ukuhlolwa

2.1 Izinto zokusetshenziswa

I-Cellulose cotton pulp, i-polymerization degree 576, i-Xinjiang Aoyang Technology Co., Ltd.; i-sultone engu-1,4-butane (BS), izinga lezimboni, ekhiqizwe yi-Shanghai Jiachen Chemical Co., Ltd.; i-52.5R ejwayelekile ye-Portland cement, i-Urumqi Ehlinzekwe yifektri yesamente; isihlabathi esijwayelekile se-ISO saseShayina, ekhiqizwe 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., konke kuhlanzekile ngokuhlaziya, kuyatholakala kwezentengiselwano.

2.2 Indlela yokuhlola

Kala inani elithile le-pulp kakotini bese uyigaya kahle, uyifake ebhodleleni elinezintamo ezintathu, engeza ukuhlushwa okuthile kwe-hydrochloric acid encibilikisiwe, uvuselele ukuze ufudumale bese uyi-hydrolyze isikhathi esithile, uphole kuze kufike ekushiseni kwegumbi, ukuhlunga, ugeze ngamanzi kuze kube yilapho kungathathi hlangothi, bese womisa nge-vacuum ku-50°C ukuze uthole Ngemva kokusebenzisa izinto zokusetshenziswa ze-microcrystalline cellulose ezinamazinga ahlukene e-polymerization, kala izinga lazo le-polymerization ngokwezincwadi, ulifake ebhodleleni le-reaction elinezintamo ezintathu, ulimise nge-agent yokumisa izikhathi eziyi-10 ubukhulu balo, engeza inani elithile lesisombululo samanzi se-sodium hydroxide ngaphansi kokuxuba, Hlanganisa bese uvuselela ekushiseni kwegumbi isikhathi esithile, engeza inani elibalwe le-sultone engu-1,4-butane (BS), ufudumale kuze kufike ekushiseni kokusabela, uphendule ekushiseni okulinganayo isikhathi esithile, upholise umkhiqizo ekushiseni kwegumbi, bese uthola umkhiqizo ongahluziwe ngokuwuhlunga. Hlanza ngamanzi ne-methanol izikhathi ezintathu, bese uhlunga ngokumunca ukuze uthole umkhiqizo wokugcina, okungukuthi i-cellulose butylsulfonate water reducer (SBC).

2.3 Ukuhlaziywa komkhiqizo kanye nokuhlukaniswa kwawo

2.3.1 Ukunqunywa kokuqukethwe kwesibabule somkhiqizo kanye nokubalwa kwezinga lokushintshaniswa

I-FLASHEA-PE2400 elemental analyzer yasetshenziswa ukwenza ukuhlaziywa kwe-elemental kumkhiqizo wokunciphisa amanzi we-cellulose butyl sulfonate owomile ukuze kutholakale okuqukethwe kwe-sulfur.

2.3.2 Ukunqunywa kokugeleza kodaka

Kukalwe ngokwe-6.5 ku-GB8076-2008. Okusho ukuthi, qala ulinganise ingxube yesihlabathi samanzi/isamente/ejwayelekile ku-NLD-3 cement mortar tester lapho ububanzi bokunwebeka buyi-(180±2)mm. cement, ukusetshenziswa kwamanzi okulinganiselwe okulinganisiwe kungu-230g), bese ufaka i-ejenti yokunciphisa amanzi enobunzima obungu-1% wesisindo sesimende emanzini, ngokwe-cement/ejenti yokunciphisa amanzi/amanzi ajwayelekile/isihlabathi esijwayelekile=450g/4.5g/230 g/ Isilinganiso esingu-1350 g sifakwa ku-JJ-5 cement mortar mixer bese sivuselelwa ngokulinganayo, bese kulinganiswa ububanzi obubanzi besihlabathi ku-cement mortar tester, okuyi-cement mortar elinganisiwe.

2.3.3 Ukuchazwa Komkhiqizo

Isampula yachazwa nge-FT-IR kusetshenziswa i-EQUINOX 55 type Fourier transform infrared spectrometer yeBruker Company; i-H NMR spectrum yesampula yachazwa nge-INOVA ZAB-HS plow superconducting nuclear magnetic resonance instrument yeVarian Company; I-morphology yomkhiqizo yabonwa ngaphansi kwe-microscope; Ukuhlaziywa kwe-XRD kwenziwa esampula ngokusebenzisa i-X-ray diffractometer ye-MAC Company M18XHF22-SRA.

3. Imiphumela kanye nengxoxo

3.1 Imiphumela yokubhala izinhlamvu

3.1.1 Imiphumela yokuchaza i-FT-IR

Ukuhlaziywa kwe-infrared kwenziwe ku-cellulose yezinto zokusetshenziswa ezingavuthiwe enezinga le-polymerization Dp=45 kanye nomkhiqizo i-SBC owenziwe kusukela kule nto eluhlaza. Njengoba iziqongo zokumunca ze-SC ne-SH zibuthakathaka kakhulu, azifaneleki ukuhlonza, kuyilapho i-S=O inesiqongo sokumunca esinamandla. Ngakho-ke, ukuthi ngabe kukhona iqembu le-sulfonic acid esakhiweni sama-molecule kunganqunywa ngokuqinisekisa ukuthi kukhona isiqongo se-S=O. Ngokusobala, ku-spectrum ye-cellulose, kukhona isiqongo sokumunca esinamandla enombolweni yamagagasi engu-3344 cm-1, okubangelwa isiqongo sokumunca sokunwebeka kwe-hydroxyl ku-cellulose; isiqongo sokumunca esinamandla enombolweni yamagagasi engu-2923 cm-1 isiqongo sokumunca sokunwebeka se-methylene (-CH2). Isiqongo sokudlidliza; uchungechunge lwamabhande akhiwe yi-1031, 1051, 1114, kanye ne-1165cm-1 lubonisa isiqongo sokumunca sokunwebeka kwe-hydroxyl kanye nesiqongo sokumunca sokugoba kwe-ether bond (COC); Inombolo yamagagasi engu-1646cm-1 ibonisa i-hydrogen eyakhiwe yi-hydroxyl kanye namanzi akhululekile. I-bond absorption peak; i-band engu-1432~1318cm-1 ibonisa ukuba khona kwesakhiwo sekristalu ye-cellulose. Ku-spectrum ye-IR ye-SBC, amandla e-band engu-1432~1318cm-1 ayancipha; kuyilapho amandla e-absorption peak ku-1653 cm-1 enyuka, okubonisa ukuthi ikhono lokwakha izibopho ze-hydrogen liyaqiniswa; ama-Absorption peak angu-1040, 605cm-1 abonakala enamandla kakhulu, futhi lawa amabili awabonakali ku-spectrum ye-infrared ye-cellulose, eyokuqala iyi-characteristic absorption peak ye-S=O bond, kanti eyokugcina iyi-characteristic absorption peak ye-SO bond. Ngokusekelwe ekuhlaziyweni okungenhla, kungabonakala ukuthi ngemva kokusabela kwe-etherification kwe-cellulose, kunezinhlobo ze-sulfonic acid ku-chain yayo yama-molecule.

3.1.2 Imiphumela yokuchaza i-H NMR

I-H NMR spectrum ye-cellulose butyl sulfonate ingabonakala: ngaphakathi kwe-γ=1.74~2.92 kukhona ukushintsha kwamakhemikhali e-hydrogen proton kwe-cyclobutyl, kanti ngaphakathi kwe-γ=3.33~4.52 kukhona iyunithi ye-cellulose anhydroglucose. Ukushintsha kwamakhemikhali e-oxygen proton ku-γ=4.52~6 kungukushintsha kwamakhemikhali e-methylene proton eqenjini le-butylsulfonic acid elixhunywe ku-oxygen, futhi akukho ukuphakama ku-γ=6~7, okubonisa ukuthi umkhiqizo awukho Amanye ama-proton akhona.

3.1.3 Imiphumela yokuchaza i-SEM

Ukubonwa kwe-SEM kwe-cellulose cotton pulp, i-microcrystalline cellulose kanye ne-cellulose butylsulfonate yomkhiqizo. Ngokuhlaziya imiphumela yokuhlaziywa kwe-SEM ye-cellulose cotton pulp, i-microcrystalline cellulose kanye ne-product cellulose butanesulfonate (SBC), kutholakale ukuthi i-microcrystalline cellulose etholakale ngemuva kwe-hydrolysis nge-HCL ingashintsha kakhulu isakhiwo se-cellulose fibers. Isakhiwo se-fibrous sabhujiswa, kwatholakala izinhlayiya ze-cellulose ezincane ezihlanganisiwe. I-SBC etholakale ngokuqhubeka nokusabela ne-BS yayingenaso isakhiwo se-fibrous futhi ngokuyisisekelo yaguqulwa yaba isakhiwo esingenasimo, esasizuzisa ekuncibilikeni kwayo emanzini.

3.1.4 Imiphumela yokuchaza i-XRD

Ukwakheka kwekristalu ye-cellulose kanye nezinto eziphuma kuyo kubhekisela kumaphesenti esifunda sekristalu esakhiwe yisakhiwo seyunithi ye-cellulose kuyo yonke. Lapho i-cellulose kanye nezinto eziphuma kuyo zithola ukusabela kwamakhemikhali, izibopho ze-hydrogen ku-molecule naphakathi kwama-molecule ziyabhujiswa, futhi isifunda sekristalu sizoba isifunda esingaguquki, ngaleyo ndlela sinciphise ukwakheka kwekristalu. Ngakho-ke, ushintsho kukristalu ngaphambi nangemva kokusabela luyisilinganiso se-cellulose Enye yezindlela zokubamba iqhaza empendulweni noma cha. Ukuhlaziywa kwe-XRD kwenziwa ku-cellulose ye-microcrystalline kanye ne-cellulose butanesulfonate yomkhiqizo. Kungabonakala ngokuqhathanisa ukuthi ngemva kokufakelwa kwe-ether, ukwakheka kwekristalu kuyashintsha ngokuyisisekelo, futhi umkhiqizo usuguquke ngokuphelele waba yisakhiwo esingaguquki, ukuze uncibilike emanzini.

3.2 Umphumela wezinga lokupholimitha kwezinto zokusetshenziswa ekusebenzeni komkhiqizo okunciphisa amanzi

Ukugeleza kodaka kubonisa ngqo ukusebenza komkhiqizo okunciphisa amanzi, kanti okuqukethwe yisibabule komkhiqizo kungenye yezinto ezibaluleke kakhulu ezithinta ukugeleza kodaka. Ukugeleza kodaka kulinganisa ukusebenza komkhiqizo okunciphisa amanzi.

Ngemva kokushintsha izimo zokusabela kwe-hydrolysis ukuze kulungiselelwe i-MCC enamazinga ahlukene e-polymerization, ngokwendlela engenhla, khetha inqubo ethile yokwenziwa ukuze kulungiselelwe imikhiqizo ye-SBC, ulinganise okuqukethwe kwesulfure ukuze ubale izinga lokufakwa komkhiqizo, bese ufaka imikhiqizo ye-SBC ohlelweni lokuxuba isihlabathi lwamanzi/usimende/olujwayelekile. Kala ukugeleza kodaka.

Kungabonakala emiphumeleni yokuhlola ukuthi ngaphakathi kobubanzi bocwaningo, lapho izinga le-polymerization lezinto zokusetshenziswa ze-microcrystalline cellulose liphezulu, okuqukethwe kwe-sulfur (izinga lokufaka esikhundleni) komkhiqizo kanye nokugeleza kodaka kuphansi. Lokhu kungenxa yokuthi: isisindo sama-molecule sezinto zokusetshenziswa sincane, okuhambisana nokuhlanganiswa okufanayo kwezinto zokusetshenziswa kanye nokungena kwe-etherification agent, ngaleyo ndlela kuthuthukiswe izinga le-etherification yomkhiqizo. Kodwa-ke, izinga lokunciphisa amanzi omkhiqizo alikhuphuki ngendlela eqondile ngokuncipha kwezinga le-polymerization yezinto zokusetshenziswa. Imiphumela yokuhlola ikhombisa ukuthi ukugeleza kodaka kwengxube ye-cement mortar exutshwe ne-SBC elungiselelwe ngokusebenzisa i-microcrystalline cellulose enezinga le-polymerization Dp<96 (isisindo sama-molecule<15552) sikhulu kune-180 mm (okukhulu kunalokho ngaphandle kokunciphisa amanzi). ukugeleza kokulinganisa), okubonisa ukuthi i-SBC ingalungiswa ngokusebenzisa i-cellulose enesisindo sama-molecule esingaphansi kwe-15552, futhi izinga elithile lokunciphisa amanzi lingatholakala; I-SBC ilungiswa ngokusebenzisa i-microcrystalline cellulose enezinga le-polymerization elingu-45 (isisindo sama-molecule: 7290), futhi ingezwe engxubeni yekhonkrithi, ukugeleza okulinganisiwe kodaka kukhulu kakhulu, ngakho-ke kubhekwa ukuthi i-cellulose enezinga le-polymerization elingu-45 ifaneleka kakhulu ekulungiseleleni i-SBC; lapho izinga le-polymerization lezinto zokusetshenziswa lingaphezu kuka-45, ukugeleza kodaka kwehla kancane kancane, okusho ukuthi izinga lokunciphisa amanzi liyancipha. Lokhu kungenxa yokuthi lapho isisindo sama-molecule sikhulu, ngakolunye uhlangothi, i-viscosity yesistimu yokuxuba izokwanda, ukufana kokuhlakazeka kwesimende kuzowohloka, futhi ukuhlakazeka kukhonkrithi kuzohamba kancane, okuzothinta umphumela wokuhlakazeka; ngakolunye uhlangothi, lapho isisindo sama-molecule sikhulu, ama-macromolecule e-superplasticizer asesimweni se-coil esingahleliwe, okunzima ukumunca ebusweni bezinhlayiya zesimende. Kodwa uma izinga lokupholimitha kwezinto zokusetshenziswa lingaphansi kuka-45, yize okuqukethwe yi-sulfur (izinga lokufaka esikhundleni) komkhiqizo kukhulu kakhulu, ukugeleza kwengxube ye-mortar nakho kuqala ukwehla, kodwa ukwehla kuncane kakhulu. Isizathu ukuthi lapho isisindo sama-molecule se-ejenti yokunciphisa amanzi sincane, yize ukusabalala kwama-molecule kulula futhi kunokumanzi okuhle, ukushesha kokumuncwa kwe-molecule kukhulu kune-molecule, futhi uchungechunge lokuthuthwa kwamanzi lufushane kakhulu, kanti ukungqubuzana phakathi kwezinhlayiya kukhulu, okulimaza ukhonkolo. Umphumela wokuhlakazeka awumuhle njengowokunciphisa amanzi onesisindo sama-molecule esikhulu. Ngakho-ke, kubaluleke kakhulu ukulawula kahle isisindo sama-molecule sobuso bengulube (ingxenye ye-cellulose) ukuze kuthuthukiswe ukusebenza kokunciphisa amanzi.

3.3 Umphumela wezimo zokusabela ekusebenzeni komkhiqizo okunciphisa amanzi

Kutholakale ngokuhlolwa ukuthi ngaphezu kwezinga lokupholishwa kwe-MCC, isilinganiso sama-reactants, izinga lokushisa lokusabela, ukusebenza kwezinto zokusetshenziswa, isikhathi sokwenziwa komkhiqizo, kanye nohlobo lwe-ejenti yokumisa konke kuthinta ukusebenza komkhiqizo okunciphisa amanzi.

3.3.1 Isilinganiso se-Reactant

(1) Umthamo we-BS

Ngaphansi kwezimo ezinqunywe yiminye imingcele yenqubo (izinga lokupholimitha kwe-MCC lingu-45, n(MCC):n(NaOH)=1:2.1, i-ejenti yokumisa yi-isopropanol, isikhathi sokusebenza kwe-cellulose ekushiseni kwegumbi singamahora ama-2, izinga lokushisa lokwenziwa lingu-80°C, kanye nesikhathi sokwenziwa singamahora ama-5), ukuphenya umphumela wenani le-etherification agent engu-1,4-butane sultone (BS) ezingeni lokufakwa esikhundleni kwamaqembu e-butanesulfonic acid omkhiqizo kanye nokugeleza kodaka.

Kungabonakala ukuthi njengoba inani le-BS landa, izinga lokushintshana kwamaqembu e-butanesulfonic acid kanye nokugeleza kodaka kuyanda kakhulu. Lapho isilinganiso se-BS ku-MCC sifinyelela ku-2.2:1, ukugeleza kwe-DS kanye nodaka kufinyelela inani eliphezulu kakhulu, kubhekwa ukuthi ukusebenza okunciphisa amanzi kungcono kakhulu ngalesi sikhathi. Inani le-BS laqhubeka nokukhula, futhi kokubili izinga lokushintshana kanye nokugeleza kodaka kwaqala ukwehla. Lokhu kungenxa yokuthi lapho i-BS ingaphezu kwamandla, i-BS izosabela ne-NaOH ukuze ikhiqize i-HO-(CH2)4SO3Na. Ngakho-ke, leli phepha likhetha isilinganiso sezinto ezibonakalayo se-BS ku-MCC njengo-2.2:1.

(2) Umthamo we-NaOH

Ngaphansi kwezimo ezinqunywe yiminye imingcele yenqubo (izinga lokupholimitha kwe-MCC lingu-45, n(BS):n(MCC)=2.2:1. I-ejenti yokumisa yi-isopropanol, isikhathi sokusebenza kwe-cellulose ekushiseni kwegumbi singamahora ama-2, izinga lokushisa lokwenziwa lingu-80°C, kanye nesikhathi sokwenziwa singamahora ama-5), ukuphenya umphumela wenani le-sodium hydroxide ezingeni lokufakwa esikhundleni kwamaqembu e-butanesulfonic acid kumkhiqizo kanye nokugeleza kodaka.

Kungabonakala ukuthi, ngokwanda kwenani lokunciphisa, izinga lokushintsha i-SBC liyanda ngokushesha, futhi liqala ukwehla ngemva kokufinyelela inani eliphakeme kakhulu. Lokhu kungenxa yokuthi, lapho okuqukethwe yi-NaOH kuphezulu, kunezisekelo eziningi zamahhala ohlelweni, futhi amathuba okusabela okungekuhle ayanda, okuholela ekutheni ama-etherification agents amaningi (BS) ahlanganyele ekuphenduleni okungekuhle, ngaleyo ndlela kuncishiswe izinga lokushintsha amaqembu e-sulfonic acid kumkhiqizo. Ezingeni lokushisa eliphakeme, ukuba khona kwe-NaOH eningi kakhulu kuzophinde kunciphise i-cellulose, futhi ukusebenza komkhiqizo okunciphisa amanzi kuzothinteka ngezinga eliphansi le-polymerization. Ngokusho kwemiphumela yokuhlola, lapho isilinganiso se-molar se-NaOH kuya ku-MCC singaba ngu-2.1, izinga lokushintsha lilikhulu kunawo wonke, ngakho-ke leli phepha linquma ukuthi isilinganiso se-molar se-NaOH kuya ku-MCC singu-2.1:1.0.

3.3.2 Umphumela wokushisa kokusabela ekusebenzeni kokunciphisa amanzi komkhiqizo

Ngaphansi kwezimo ezinqunywe yiminye imingcele yenqubo (izinga lokupholimitha kwe-MCC lingu-45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, i-ejenti yokumisa yi-isopropanol, kanti isikhathi sokusebenza kwe-cellulose ekushiseni kwegumbi singamahora ama-2. Isikhathi samahora ama-5), ithonya lokushisa lokusabela kokwenziwa ezingeni lokufakwa esikhundleni kwamaqembu e-butanesulfonic acid kumkhiqizo lihlolisisiwe.

Kungabonakala ukuthi njengoba izinga lokushisa lokusabela likhuphuka, izinga lokufaka esikhundleni se-sulfonic acid DS ye-SBC liyanda kancane kancane, kodwa lapho izinga lokushisa lokusabela lidlula u-80 °C, i-DS ikhombisa umkhuba wokwehla. Ukusabela kwe-etherification phakathi kwe-1,4-butane sultone ne-cellulose kuyimpendulo ye-endothermic, futhi ukwandisa izinga lokushisa lokusabela kuzuzisa ekusabeleni phakathi kwe-etherifying agent neqembu le-cellulose hydroxyl, kodwa ngokwanda kwezinga lokushisa, umphumela we-NaOH ne-cellulose uyanda kancane kancane. Uba namandla, okwenza i-cellulose yonakale futhi iwe, okuholela ekunciphiseni isisindo sama-molecule se-cellulose kanye nokukhiqizwa koshukela omncane wama-molecule. Ukusabela kwama-molecule amancane anjalo anama-etherifying agent kulula kakhulu, futhi kuzosetshenziswa ama-etherifying agent amaningi, okuthinta izinga lokufaka esikhundleni somkhiqizo. Ngakho-ke, le ngqikithi ibheka ukuthi izinga lokushisa lokusabela elifanele kakhulu lokusabela kwe-etherification kwe-BS ne-cellulose lingu-80℃.

3.3.3 Umphumela wesikhathi sokusabela ekusebenzeni kokunciphisa amanzi komkhiqizo

Isikhathi sokusabela sihlukaniswe ngokuthi ukusebenza kwezinga lokushisa legumbi lezinto zokusetshenziswa kanye nesikhathi sokuhlanganiswa kwezinga lokushisa eliqhubekayo lemikhiqizo.

(1) Isikhathi sokuvuselela izinga lokushisa legumbi lezinto zokusetshenziswa

Ngaphansi kwezimo zenqubo ezifanele kakhulu ezingenhla (izinga le-MCC le-polymerization lingu-45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, i-suspending agent yi-isopropanol, izinga lokushisa lokusabela kokwenziwa lingu-80°C, isikhathi sokwenziwa kokushisa okuhlala njalo komkhiqizo singu-5h), phenya ithonya lesikhathi sokusebenza kokushisa kwegumbi ezingeni lokushintsha iqembu le-butanesulfonic acid lomkhiqizo.

Kungabonakala ukuthi izinga lokushintshaniswa kweqembu le-butanesulfonic acid lomkhiqizo i-SBC liyanda kuqala bese lincipha ngokwelulwa kwesikhathi sokusebenza. Isizathu sokuhlaziya singase sibe ukuthi ngokwanda kwesikhathi sokusebenza se-NaOH, ukuwohloka kwe-cellulose kubi kakhulu. Nciphisa isisindo sama-molecule se-cellulose ukuze ukhiqize ushukela omncane wama-molecule. Ukusabela kwama-molecule amancane anjalo ngama-etherifying agents kulula kakhulu, futhi kuzosetshenziswa ama-etherifying agents amaningi, okuthinta izinga lokushintshaniswa komkhiqizo. Ngakho-ke, leli phepha libheka ukuthi isikhathi sokusebenza kwegumbi lezinto zokusetshenziswa zokusetshenziswa singamahora ama-2.

(2) Isikhathi sokuhlanganiswa komkhiqizo

Ngaphansi kwezimo zenqubo ezifanele kakhulu ezingenhla, kuhlolwe umphumela wesikhathi sokusebenza ekamelweni lokushisa ngezinga lokushintsha iqembu le-butanesulfonic acid lomkhiqizo. Kungabonakala ukuthi ngokwelulwa kwesikhathi sokusabela, izinga lokushintsha liqala ukwanda, kodwa lapho isikhathi sokusabela sifika kumahora ama-5, i-DS ikhombisa umkhuba wokwehla. Lokhu kuhlobene nesisekelo samahhala esikhona ekusabeleni kwe-etherification kwe-cellulose. Emazingeni okushisa aphezulu, ukwelulwa kwesikhathi sokusabela kuholela ekwandeni kwezinga le-alkali hydrolysis ye-cellulose, ukufinyezwa kwe-cellulose molecular chain, ukwehla kwesisindo sama-molecule somkhiqizo, kanye nokwanda kwe-side reactions, okuholela ekwehleni kwezinga lokushintsha. Kulesi sivivinyo, isikhathi esifanele sokwenziwa singamahora ama-5.

3.3.4 Umphumela wohlobo lwe-ejenti yokumisa ekusebenzeni komkhiqizo okunciphisa amanzi

Ngaphansi kwezimo zenqubo ezifanele (izinga le-polymerization le-MCC lingu-45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, isikhathi sokusebenza kwezinto zokusetshenziswa ekushiseni kwegumbi singamahora ama-2, isikhathi sokwenziwa kwezinga lokushisa elihlala njalo lemikhiqizo singamahora ama-5, kanye nezinga lokushisa lokusabela kokwenziwa lingama-80 ℃), ngokulandelana khetha i-isopropanol, i-ethanol, i-n-butanol, i-ethyl acetate kanye ne-petroleum ether njengezinto ezimisayo, bese uxoxa ngethonya lazo ekusebenzeni komkhiqizo okunciphisa amanzi.

Ngokusobala, i-isopropanol, i-n-butanol kanye ne-ethyl acetate konke kungasetshenziswa njenge-ejenti yokumisa kulokhu kusabela kwe-etherification. Indima ye-ejenti yokumisa, ngaphezu kokuhlakaza ama-reactants, ingalawula izinga lokushisa lokusabela. Indawo yokubilisa ye-isopropanol ingu-82.3°C, ngakho-ke i-isopropanol isetshenziswa njenge-ejenti yokumisa, izinga lokushisa lesistimu lingalawulwa eduze kwezinga lokushisa lokusabela elihle kakhulu, kanye nezinga lokushintshana kwamaqembu e-butanesulfonic acid kumkhiqizo kanye nokugeleza kodaka kuphakeme kakhulu; kuyilapho izinga lokubila le-ethanol liphezulu kakhulu. Izinga lokushisa lokusabela alihlangabezani nezidingo, izinga lokushintshana kwamaqembu e-butanesulfonic acid kumkhiqizo kanye nokugeleza kodaka kuphansi; i-petroleum ether ingabamba iqhaza ekusabeleni, ngakho-ke akukho mkhiqizo ohlakazekile ongatholakala.

4 Isiphetho

(1) Ukusebenzisa i-pulp kakotini njengezinto zokuqala zokusetshenziswa,i-microcrystalline cellulose (MCC)ngesilinganiso esifanele se-polymerization yalungiswa, yasebenza yi-NaOH, futhi yasabela nge-sultone engu-1,4-butane ukuze kulungiswe i-butylsulfonic acid encibilikayo emanzini i-Cellulose ether, okungukuthi, i-cellulose-based water reducer. Isakhiwo somkhiqizo sachazwa, futhi kwatholakala ukuthi ngemva kokusabela kwe-etherification kwe-cellulose, kwakukhona amaqembu e-sulfonic acid ku-chain yayo yama-molecule, ayeseguqukile aba yisakhiwo esingaguquki, futhi umkhiqizo we-water reducer wawunokuncibilika okuhle kwamanzi;

(2) Ngokusebenzisa izivivinyo, kutholakale ukuthi uma izinga lokupholisha i-microcrystalline cellulose lingu-45, ukusebenza komkhiqizo otholakele okunciphisa amanzi kungcono kakhulu; ngaphansi kwesimo sokuthi izinga lokupholisha izinto zokusetshenziswa linqunywa, isilinganiso sama-reactants ngu-n(MCC):n(NaOH):n(BS)=1:2.1:2.2, isikhathi sokusebenza kwezinto zokusetshenziswa ekushiseni kwegumbi singamahora ama-2, izinga lokushisa lokwenziwa komkhiqizo lingu-80°C, kanti isikhathi sokwenziwa singamahora ama-5. Ukusebenza kwamanzi kungcono kakhulu.