Indlela yokwenza i-Cellulose ether?

I-cellulose ether iwuhlobo lokuphuma kwe-cellulose olutholakala ngokuguqulwa kwe-etherification ye-cellulose. Isetshenziswa kabanzi ngenxa yokuqina kwayo okuhle kakhulu, i-emulsification, ukumiswa, ukwakheka kwefilimu, i-colloid evikelayo, ukugcinwa komswakama, kanye nezakhiwo zokunamathela. Idlala indima ebalulekile ekuthuthukisweni komnotho kazwelonke ocwaningweni lwesayensi kanye nemikhakha yezimboni efana nokudla, imithi, ukwenza amaphepha, okokugcotshwa, izinto zokwakha, ukubuyiswa kukawoyela, izindwangu kanye nezingxenye ze-elekthronikhi. Kuleli phepha, inqubekelaphambili yocwaningo yokuguqulwa kwe-etherification ye-cellulose iyabuyekezwa.

I-Celluloseetheriyi-polymer ephilayo eningi kakhulu ngokwemvelo. Iyavuseleleka, iluhlaza futhi ihambisana ne-biocompatible. Kuyimpahla ebalulekile eyisisekelo yobunjiniyela bamakhemikhali. Ngokusho kwezingxenye ezihlukile ze-molecule etholwe ekuphenduleni kwe-etherification, ingahlukaniswa ibe ama-ether awodwa futhi axutshwe. i-cellulose ama-ethers.Lapha thina ibuyekeza inqubekelaphambili yocwaningo ekuhlanganisweni kwama-ether awodwa, okuhlanganisa ama-alkyl ether, ama-hydroxyalkyl ether, ama-carboxyalkyl ether, nama-ether axubile.

Amagama angukhiye: i-cellulose ether, i-etherification, i-ether eyodwa, i-ether exubile, ukuqhubeka kocwaningo

1.Ukusabela kwe-Etherification ye-cellulose

Ukusabela kwe-etherification ye-cellulose ether iwumphumela obaluleke kakhulu we-cellulose derivatization reaction.I-Etherification ye-cellulose iwuchungechunge lwezinto eziphuma kuzo ezikhiqizwa ukusabela kwamaqembu e-hydroxyl kumaketanga e-cellulose yamangqamuzana ane-alkylating agents ngaphansi kwezimo ze-alkali. Kunezinhlobo eziningi zemikhiqizo ye-cellulose ether, engahlukaniswa ibe i-ether eyodwa kanye nama-ether axubile ngokuya ngezingxenye ezihlukile zama-molecule atholwe ekuphenduleni kwe-etherification. Ama-ether awodwa angahlukaniswa abe ama-alkyl ether, ama-hydroxyalkyl ether kanye nama-carboxyalkyl ether, futhi ama-ether axubile abhekisela kuma-ether anamaqembu amabili noma ngaphezulu axhunywe esakhiweni samangqamuzana. Phakathi kwemikhiqizo ye-cellulose ether, i-carboxymethyl cellulose (CMC), i-hydroxyethyl cellulose (HEC), i-hydroxypropyl cellulose (HPC), i-hydroxypropyl methyl cellulose (HPMC) imelwe, phakathi kwayo Eminye imikhiqizo idayiswe.

2.Ukwenziwa kwe-cellulose ether

2.1 Ukuhlanganiswa kwe-ether eyodwa

Ama-ether awodwa ahlanganisa i-alkyl ethers (njenge-ethyl cellulose, i-propyl cellulose, i-phenyl cellulose, i-cyanoethyl cellulose, njll.), ama-hydroxyalkyl ethers (afana ne-hydroxymethyl cellulose, i-hydroxyethyl cellulose, njll. njll.).

2.1.1 Ukuhlanganiswa kwe-alkyl ethers

U-Berglund et al uqale waphatha i-cellulose ngesisombululo se-NaOH esifakwe nge-ethyl chloride, wabe esengeza i-methyl chloride ekushiseni okungama-65.°C ku90°C kanye nengcindezi ye-3bar ukuya ku-15bar, futhi yasabela ukukhiqiza i-methyl cellulose ether. Le ndlela ingasebenza kahle kakhulu Ukuthola ama-ethers e-methyl cellulose ancibilika emanzini anamazinga ahlukene okushintsha.

I-Ethylcellulose iyimbudumbudu emhlophe ye-thermoplastic noma impushana. Izimpahla ezijwayelekile ziqukethe u-44%~49% we-ethoxy. Incibilika kuzincibilikisi eziningi eziphilayo, ezingancibiliki emanzini. i-pulp noma ama-linter kakotini ane-40% ~ 50% ye-sodium hydroxide aqueous solution, kanye ne-alkalized cellulose yafakwa ethoxylated ne-ethyl chloride ukukhiqiza i-ethyl cellulose. kuhlanganiswe ngempumelelo i-ethyl cellulose (EC) enokuqukethwe kwe-ethoxy okungu-43.98% ngendlela yesinyathelo esisodwa ngokusabela i-cellulose nge-ethyl chloride eyeqile ne-sodium hydroxide, kusetshenziswa i-toluene njenge-diluent. I-Toluene isetshenziswe njenge-diluent ocwaningweni. Ngesikhathi sokusabela kwe-etherification, ayikwazi nje ukukhuthaza ukusabalalisa kwe-ethyl chloride ku-alkali cellulose, kodwa futhi ichithe i-ethyl cellulose efakwe kakhulu esikhundleni. Ngesikhathi sokusabela, ingxenye engaphenduliwe ingadalulwa ngokuqhubekayo, okwenza i-ejenti ye-etherification Kulula ukuyihlasela, ukuze ukusabela kwe-ethylation kushintshe ukusuka kokungafani kuye kokufana, kanye nokusatshalaliswa kwezinto ezingaphansi komkhiqizo kufane kakhulu.

isebenzise i-ethyl bromide njenge-etherification agent kanye ne-tetrahydrofuran njenge-diluent ukuze ihlanganise i-ethyl cellulose (EC), futhi ibonise ukwakheka komkhiqizo nge-infrared spectroscopy, i-nuclear magnetic resonance kanye ne-gel permeation chromatography. Kubalwa ukuthi izinga lokushintshaniswa kwe-ethyl cellulose ehlanganisiwe licishe libe ngu-2.5, ukusatshalaliswa kwesisindo samangqamuzana kuncane, futhi kunokuncibilika okuhle kuzinyibilikisi zemvelo.

I-cyanoethyl cellulose (CEC) ngokusebenzisa izindlela ezilinganayo futhi ezihlukile zisebenzisa i-cellulose enamazinga ahlukene we-polymerization njengezinto zokusetshenziswa, futhi yalungisa izinto eziminyene ze-CEC zolwelwesi ngokusakazwa kwesixazululo nokucindezela okushisayo. Ama-membrane e-CEC anezimbotshana alungiswa ngobuchwepheshe bokuhlukaniswa kwesigaba se-solvent-induced (NIPS), kanye ne-barium titanate/cyanoethyl cellulose (BT/CEC) i-nanocomposite membrane materials yalungiselelwa ubuchwepheshe be-NIPS, futhi izakhiwo nezakhiwo zabo zafundwa.

wasebenzisa isincibilikisi se-cellulose esizithuthukisayo (isixazululo se-alkali/urea) njengendlela yokusabela ukuze ihlanganise ngokulinganayo i-cyanoethyl cellulose (CEC) ene-acrylonitrile njenge-etherification agent, futhi yenza ucwaningo ngesakhiwo, izakhiwo kanye nokusetshenziswa komkhiqizo. funda ngokujulile. Futhi ngokulawula izimo zokusabela ezihlukene, uchungechunge lwama-CEC anamanani e-DS asukela ku-0.26 kuya ku-1.81 lungatholakala.

2.1.2 Ukuhlanganiswa kwe-hydroxyalkyl ethers

U-Fan Junlin et al ulungiselele i-hydroxyethyl cellulose (HEC) ku-reactor engu-500 L esebenzisa ukotini ocolisisiwe njengempahla eluhlaza kanye no-87.7% we-isopropanol-amanzi njenge-solvent nge-alkalization yesinyathelo esisodwa, ukungathathi hlangothi kwesinyathelo ngesinyathelo kanye ne-etherification yesinyathelo ngesinyathelo. . Imiphumela yabonisa ukuthi i-hydroxyethyl cellulose (HEC) elungisiwe ine-molar substitution MS ye-2.2-2.9, efinyelela izinga elifanayo lekhwalithi njengomkhiqizo wezinga lezohwebo we-Dows 250 HEC ngokufaka i-molar esikhundleni se-2.2-2.4. Ukusebenzisa i-HEC ekukhiqizeni upende we-latex kungathuthukisa ukwakheka kwefilimu nokulinganisa izakhiwo zopende we-latex.

U-Liu Dan nabanye baxoxe ngokulungiswa kwe-quaternary ammonium salt cationic hydroxyethyl cellulose ngendlela eyomile kancane ye-hydroxyethyl cellulose (HEC) kanye ne-2,3-epoxypropyltrimethylammonium chloride (GTA) ngaphansi kwesenzo se-alkali catalysis. izimo ze-ether. Umphumela wokwengeza i-cationic hydroxyethyl cellulose ether ephepheni uye waphenywa. Imiphumela yokuhlola ibonisa ukuthi: ku-pulp yokhuni oluqinile olu-bleached, lapho idigri yokufaka esikhundleni se-cationic hydroxyethyl cellulose ether ingu-0.26, inani lokugcinwa likhuphuka ngo-9%, futhi izinga lokuhlunga amanzi likhuphuka ngo-14%; ku-pulp yokhuni oluqinile oluxutshwe, lapho Uma inani le-cationic hydroxyethyl cellulose ether lingu-0.08% we-pulp fiber, linomthelela obalulekile wokuqinisa ephepheni; lapho izinga lokushintshwa kwe-cationic cellulose ether likhulu, kukhulu ukuminyana kweshaje ye-cationic, kanye nomphumela oqinisayo.

I-Zhanhong isebenzisa indlela yokwenziwa kwesigaba soketshezi ukuze kulungiswe i-hydroxyethyl cellulose enevelu ye-viscosity engu-5.×104mPa·s noma ngaphezulu kanye nenani lomlotha elingaphansi kuka-0.3% ngenqubo yezinyathelo ezimbili ze-alkalization kanye ne-etherification. Kusetshenziswe izindlela ezimbili ze-alkalization. Indlela yokuqala ukusebenzisa i-acetone njenge-diluent. I-cellulose eluhlaza isekelwe ngokuqondile ekuhlanganiseni okuthile kwesisombululo samanzi se-sodium hydroxide. Ngemva kokwenziwa kwe-basification reaction, i-ejenti ye-etherification iyengezwa ukuze yenze ngokuqondile ukusabela kwe-etherification. Indlela yesibili ukuthi impahla eluhlaza ye-cellulose yenziwa i-alkali kusisombululo esinamanzi se-sodium hydroxide ne-urea, futhi i-alkali cellulose elungiswe ngale ndlela kufanele incinywe ukuze kukhishwe i-lye eyeqile ngaphambi kokusabela kwe-etherification. Imiphumela yokuhlola ibonisa ukuthi izici ezifana nenani elikhethiwe le-diluent, inani le-ethylene oxide elengeziwe, isikhathi se-alkalization, izinga lokushisa nesikhathi sokusabela kokuqala, nezinga lokushisa nesikhathi sokusabela kwesibili konke kunethonya elikhulu ekusebenzeni. yomkhiqizo.

Xu Qin et al. kwenziwe i-etherification reaction ye-alkali cellulose ne-propylene oxide, kanye ne-synthesized hydroxypropyl cellulose (HPC) enedigri ephansi yokufaka esikhundleni ngendlela yesigaba esiqinile segesi. Imiphumela yengxenye enkulu ye-propylene oxide, isilinganiso sokuminyanisa kanye nezinga lokushisa le-etherification ngezinga le-etherification ye-HPC kanye nokusetshenziswa ngempumelelo kwe-propylene oxide kwacwaningwa. Imiphumela yabonisa ukuthi izimo ezinhle zokuhlanganisa ze-HPC kwakuyingxenyana ye-propylene oxide mass 20% (isilinganiso sobuningi ku-cellulose), i-alkali cellulose extrusion ratio 3.0, kanye nezinga lokushisa le-etherification 60.°C. Ukuhlolwa kwesakhiwo se-HPC nge-nuclear magnetic resonance kubonisa ukuthi idigri ye-etherification ye-HPC ingu-0.23, izinga lokusebenzisa elisebenzayo le-propylene oxide lingu-41.51%, futhi iketango lamangqamuzana e-cellulose lixhunywe ngempumelelo namaqembu e-hydroxypropyl.

Kong Xingjie et al. kulungiswe i-hydroxypropyl cellulose ngoketshezi lwe-ionic njengesincibilikizi ukuze kubonakale ukusabela okulinganayo kwe-cellulose ukuze kuqashelwe ukulawulwa kwenqubo yokusabela kanye nemikhiqizo. Ngesikhathi sokuhlolwa, i-synthetic imidazole phosphate ionic liquid 1, 3-diethylimidazole diethyl phosphate yasetshenziselwa ukuhlakaza i-microcrystalline cellulose, kanye ne-hydroxypropyl cellulose yatholakala ngokusebenzisa i-alkalization, i-etherification, i-acidification, nokugeza.

2.1.3 Ukuhlanganiswa kwe-carboxyalkyl ethers

I-carboxymethyl cellulose ejwayelekile kakhulu i-carboxymethyl cellulose (CMC). Isixazululo esinamanzi se-carboxymethyl cellulose sinemisebenzi yokuqina, ukwenza ifilimu, ukubopha, ukugcinwa kwamanzi, ukuvikelwa kwe-colloid, i-emulsification kanye nokumiswa, futhi isetshenziswa kabanzi ekuwasheni. Imithi, ukudla, umuthi wokuxubha amazinyo, izindwangu, ukuphrinta nokudaya, ukwenza amaphepha, uphethiloli, izimayini, imithi, izitsha zobumba, izinto zikagesi, irabha, upende, izibulala-zinambuzane, izimonyo, isikhumba, amapulasitiki nokumba uwoyela, njll.

Ngo-1918, u-E. Jansen waseJalimane wasungula indlela yokuhlanganisa i-carboxymethyl cellulose. Ngo-1940, imboni yaseKalle ye-German IG Farbeninaustrie Company yaqaphela ukukhiqizwa kwezimboni. Ngo-1947, i-Wyandotle Chemical Company yase-United States yathuthukisa ngempumelelo inqubo yokukhiqiza eqhubekayo. izwe lami laqala ukufakwa ekukhiqizweni kwezimboni ze-CMC e-Shanghai Celluloid Factory ngo-1958. I-Carboxymethyl cellulose iyi-ether ye-cellulose ekhiqizwa ukotini ocolisisiwe ngaphansi kwesenzo se-sodium hydroxide ne-chloroacetic acid. Izindlela zayo zokukhiqiza ezimbonini zingahlukaniswa zibe izigaba ezimbili: indlela esekelwe emanzini kanye nendlela esekelwe ku-solvent ngokusho kwemidiya ehlukene ye-etherification. Inqubo yokusebenzisa amanzi njengendlela yokusabela ibizwa ngokuthi indlela ye-water medium, futhi inqubo equkethe i-solvent ephilayo endaweni yokusabela ibizwa ngokuthi indlela ye-solvent.

Ngokujula kocwaningo kanye nokuthuthuka kobuchwepheshe, izimo zokusabela ezintsha ziye zasetshenziswa ekuhlanganiseni kwe-carboxymethyl cellulose, futhi uhlelo olusha lwe-solvent lunomthelela omkhulu enqubweni yokusabela noma ikhwalithi yomkhiqizo. Olaru et al. ithole ukuthi ukusabela kwe-carboxymethylation ye-cellulose usebenzisa uhlelo oluxubile lwe-ethanol-acetone lungcono kune-ethanol noma i-acetone yodwa. Nicholson et al. Kuhlelo, i-CMC enezinga eliphansi lokushintshwa yalungiswa. U-Philipp et al ulungiselele i-CMC esikhundleni sayo I-N-methylmorpholine-N oxide ne-N, N, N dimethylacetamide/lithium chloride solvent systems ngokulandelanayo. Cai et al. yakha indlela yokulungiselela i-CMC ohlelweni lwe-NaOH/urea solvent. Ramos et al. isebenzise i-DMSO/tetrabutylammonium fluoride ionic liquid system njengesixazululi ku-carboxymethylate impahla eluhlaza ye-cellulose ecolisisiwe kusuka kukotini ne-sisal, futhi yathola umkhiqizo we-CMC onedigri yokufaka esikhundleni esiphezulu esifinyelela ku-2.17. U-Chen Jinghuan et al. wasebenzisa cellulose nge high uginindela lokuhlushwa (20%) njengoba impahla eluhlaza, sodium hydroxide kanye acrylamide njengoba reagents ukuguqulwa, kwenziwe carboxyethylation ukuguqulwa ukusabela ngesikhathi esimisiwe kanye lokushisa, futhi ekugcineni wathola carboxyethyl base cellulose. Okuqukethwe kwe-carboxyethyl yomkhiqizo oshintshiwe kungalawulwa ngokushintsha inani le-sodium hydroxide ne-acrylamide.

2.2 Ukuhlanganiswa kwama-ether axubile

IHydroxypropyl methyl cellulose ether iwuhlobo lwe-non-polar cellulose ether encibilika emanzini abandayo atholakala ku-cellulose yemvelo ngokwenziwa kwe-alkalization nokuguqulwa kwe-etherification. I-alkalized nesisombululo se-sodium hydroxide futhi yengeza inani elithile Lenani le-isopropanol ne-toluene solvent, i-etherification agent eyamukelayo i-methyl chloride ne-propylene oxide.

UDai Mingyun et al. isebenzise i-hydroxyethyl cellulose (HEC) njengomgogodla we-hydrophilic polymer, futhi yaxhunyelelwa i-hydrophobizing agent butyl glycidyl ether (BGE) kumgogodla ngokusabela kwe-etherification ukuze kulungiswe iqembu le-hydrophobic butyl. Izinga lokushintshwa kweqembu, ukuze libe nenani elifanele lebhalansi ye-hydrophilic-lipophilic, kanye ne-2-hydroxy-3-butoxypropyl hydroxyethyl cellulose (HBPEC) ephendula izinga lokushisa; kulungiswa impahla ephendula izinga lokushisa Izinto zokusebenza ezisekelwe ku-cellulose zinikeza indlela entsha yokusetshenziswa kwezinto ezisebenzayo emkhakheni wokukhululwa okuqhubekayo kwezidakamizwa kanye ne-biology.

U-Chen Yangming nabanye basebenzisa i-hydroxyethyl cellulose njengento eluhlaza, futhi ohlelweni lwesisombululo se-isopropanol, bangeze inani elincane le-Na2B4O7 ku-reactant yokusabela kwe-homogeneous ukuze balungiselele i-ether exubile ye-hydroxyethyl carboxymethyl cellulose. Umkhiqizo uyashesha emanzini, futhi I-viscosity izinzile.

U-Wang Peng usebenzisa ukotini ocolisisiwe we-cellulose wemvelo njengento eyisisekelo eluhlaza, futhi usebenzisa inqubo ye-etherification eyisinyathelo esisodwa ukukhiqiza i-carboxymethyl hydroxypropyl cellulose ngokusabela okufanayo, i-viscosity ephezulu, ukumelana ne-asidi enhle kanye nokumelana nosawoti ngokusebenzisa ukusabela kwe-alkalization kanye ne-etherification Inhlanganisela ye-ether. Isebenzisa inqubo ye-etherification enesinyathelo esisodwa, i-carboxymethyl hydroxypropyl cellulose inokumelana nosawoti okuhle, ukumelana ne-asidi kanye nokuncibilika. Ngokushintsha amanani ahlobene e-propylene oxide ne-chloroacetic acid, imikhiqizo enokuqukethwe okuhlukile kwe-carboxymethyl kanye ne-hydroxypropyl ingalungiswa. Imiphumela yokuhlolwa ibonisa ukuthi i-carboxymethyl hydroxypropyl cellulose ekhiqizwa indlela yesinyathelo esisodwa inomjikelezo omfushane wokukhiqiza, ukusetshenziswa kwe-solvent ephansi, futhi umkhiqizo unokumelana okuhle kakhulu nosawoti we-monovalent kanye ne-divalent kanye nokuphikiswa okuhle kwe-asidi. Uma iqhathaniswa neminye imikhiqizo ye-cellulose ether, inokuncintisana okunamandla emkhakheni wokuhlola ukudla nowoyela.

IHydroxypropylmethylcellulose (HPMC) iwuhlobo oluguquguqukayo kakhulu futhi olusebenza kahle kakhulu phakathi kwazo zonke izinhlobo ze-cellulose, futhi iphinde ibe ngummeleli ojwayelekile wokuhweba phakathi kwama-ether axubile. Ngo-1927, i-hydroxypropylmethylcellulose (HPMC) yahlanganiswa ngempumelelo futhi yahlukaniswa. Ngo-1938, i-Dow Chemical Co. yase-United States yabona ukukhiqizwa kwezimboni kwe-methyl cellulose futhi yakha uphawu lokuhweba olwaziwayo "Methocel". Ukukhiqizwa kwezimboni ezinkulu ze-hydroxypropyl methylcellulose kwaqala e-United States ngo-1948. Inqubo yokukhiqiza ye-HPMC ingahlukaniswa ngezigaba ezimbili: indlela yesigaba segesi kanye nendlela yesigaba se-liquid. Njengamanje, amazwe athuthukile njengeYurophu, iMelika kanye neJapan asebenzisa kakhulu inqubo yesigaba segesi, futhi ukukhiqizwa kwasekhaya kwe-HPMC kusekelwe ikakhulukazi kwinqubo yesigaba soketshezi.

U-Zhang Shuangjian kanye nabanye abacwengisise impushana kakotini njengento eluhlaza, bayenza i-alkali nge-sodium hydroxide ekuphenduleni i-toluene ephakathi nendawo ne-isopropanol, bayifake etherifying agent propylene oxide ne-methyl chloride, basabela futhi balungiselela uhlobo olusheshayo lwe-hydroxypropyl methyl alcohol base cellulose ether.

3. I-Outlook

I-Cellulose iyinto ebalulekile yamakhemikhali namakhemikhali eluhlaza ecebile ngezinsiza, eluhlaza futhi ehambisana nemvelo, futhi evuselelekayo. Okuphuma kokunye kokuguqulwa kwe-cellulose etherification kusebenza kahle kakhulu, ukusetshenziswa okubanzi nemiphumela emihle kakhulu yokusetshenziswa, futhi kuhlangabezana nezidingo zomnotho kazwelonke ngezinga elikhulu. Futhi izidingo zokuthuthukiswa komphakathi, ngenqubekelaphambili yezobuchwepheshe eqhubekayo kanye nokufezekiswa kokuhweba esikhathini esizayo, uma izinto zokwenziwa zokwenziwa nezindlela zokwenziwa zokuphuma kwe-cellulose zingathuthukiswa kakhulu, zizosetshenziswa ngokugcwele futhi zibone uhla olubanzi lwezinhlelo zokusebenza. Inani.