Synthesis uye Hunhu hweButane Sulfonate Cellulose Ether Mvura Reducer

Microcrystalline cellulose (MCC) ine dhigirii chaiyo yepolymerization yakawanikwa neacid hydrolysis ye cellulose donje pulp yakashandiswa seyakagadzirwa. Pasi pekushandiswa kwe sodium hydroxide, yakaitwa ne 1,4-butane sultone (BS) kuti iwane A cellulose butyl sulfonate (SBC) inoderedza mvura ine yakanaka solubility yemvura yakagadzirwa. Chimiro chechigadzirwa chairatidzirwa ne infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD) nedzimwe nzira dzekuongorora, uye dhigirii repolymerization, raw material ratio, uye maitiro eMCC akaongororwa. Mhedzisiro yemamiriro ekugadzira maitiro senge tembiricha, nguva yekuita, uye mhando yekumisa mumiriri pakuita kwekudzikisa mvura kwechigadzirwa. Mhedzisiro yacho inoratidza kuti: kana dhigirii repolymerization yeMCC 45, chiyero chehuwandu hweanogadzirisa ndeichi: AGU (cellulose glucoside unit): n (NaOH): n (BS) = 1.0: 2.1: 2.2, The kumisa mumiriri ndeye isopropanol, iyo activation nguva yeyakaomeswa pamhepo tembiricha ndeye 2 h, uye nguva yekugadzira yechigadzirwa ndeye 5 h. Kana tembiricha iri 80 ° C, chigadzirwa chakawanikwa chine dhigirii yepamusoro yekutsiviwa kwemapoka ebutanesulfonic acid, uye chigadzirwa chine yakanyanya kunaka yekudzikisa mvura.

Mazwi akakosha:cellulose; cellulose butylsulfonate; mvura inoderedza mumiririri; mvura kuderedza kushanda

1,Nhanganyaya

Concrete superplasticizer ndechimwe chezvinhu zvakakosha zvekongiri yemazuva ano. Izvo chaizvo nekuda kwekuonekwa kwemvura inodzikisa agent iyo yakanyanya kushanda, yakanaka kusimba uye kunyange yakakwirira simba rekongiri inogona kuvimbiswa. Izvo zvino kushandiswa zvakanyanya-kunyanya kushandiswa kwemvura zvinoderedza zvinonyanya kusanganisira zvinotevera: naphthalene-based water reducer (SNF), sulfonated melamine resin-based water-reducer (SMF), sulfamate-based water-reducer (ASP), yakagadziridzwa Lignosulfonate superplasticizer ( ML), uye polycarboxylate superplasticizer (PC), iyo parizvino iri kuongororwa zvakanyanya. Kuongorora maitiro ekugadzira ezvidzikisiri zvemvura, mazhinji ekare ekare echinyakare condensate anoderedza mvura anoshandisa formaldehyde ine yakasimba pungent hwema seyakabikwa yepolycondensation reaction, uye iyo sulfonation process inowanzoitwa ine corrosive fuming sulfuric acid kana concentrated sulfuric acid. Izvi zvinozokonzera mhedzisiro yakaipa kune vashandi uye nharaunda yakapoteredza, uye ichaitawo huwandu hukuru hwemarara emarara uye tsvina yemvura, iyo isingakodzeri kubudirira kwakasimba; zvisinei, kunyange zvazvo polycarboxylate mvura inoderedza ine zvakanakira kurasikirwa kudiki kwekongiri nekufamba kwenguva, yakaderera dosage, yakanaka kuyerera Iine zvakanakira yakakwira density uye isina chepfu zvinhu zvakaita se formaldehyde, asi zvakaoma kuisimudzira muChina nekuda kweiyo yakakwirira. mutengo. Kubva pakuongororwa kwekwakabva zvinhu zvakasvibirira, hazvina kuoma kuwana kuti mazhinji eaya ataurwa pamusoro apa anoderedza mvura anogadzirwa zvichibva pane petrochemical zvigadzirwa / ne-zvigadzirwa, nepo petroleum, sechinhu chisingadzokerikezve, chiri kuramba chichishomeka. mutengo wayo uri kuramba uchikwira. Naizvozvo, mashandisiro ekushandisa zvakachipa uye akawanda echisikigo anogona kudzokororwa zviwanikwa semidziyo mitsva yekugadzira nyowani yepamusoro-inoshanda kongiri superplasticizers yave yakakosha yekutsvagisa nzira yekongiri superplasticizers.

Cellulose is linear macromolecule inoumbwa nekubatanidza D-glucopyranose yakawanda ne β-(1-4) glycosidic bonds. Kune matatu mapoka emahydroxyl pane yega yega glucopyranosyl ring. Kurapa kwakakodzera kunogona kuwana imwe reactivity. Mupepa iri, cellulose donje pulp yakashandiswa seyekutanga mbishi, uye mushure measidhi hydrolysis kuti iwane microcrystalline cellulose ine dhigirii yakakodzera yepolymerization, yakagadziriswa nesodium hydroxide uye yakaitwa ne1,4-butane sultone kugadzira butyl sulfonate Acid. cellulose ether superplasticizer, uye zvinhu zvinofurira zvega rega rega zvakakurukurwa.

2. Kuedza

2.1 Raw zvinhu

Cellulose donje pulp, polymerization dhigirii 576, Xinjiang Aoyang Technology Co., Ltd.; 1,4-butane sultone (BS), giredhi yeindasitiri, yakagadzirwa neShanghai Jiachen Chemical Co., Ltd.; 52.5R yakajairwa Portland simende, Urumqi Inopihwa nefekitori simende; China ISO yakajairika jecha, yakagadzirwa na Xiamen Ace Ou Standard Sand Co., Ltd.; sodium hydroxide, hydrochloric acid, isopropanol, anhydrous methanol, ethyl acetate, n-butanol, petroleum ether, nezvimwewo, zvose zvakachena, zvinotengeswa.

2.2 Nzira yekuedza

Weresa huremu hwedonje pulp woikuya nemazvo, woiisa mubhodhoro remitsipa mitatu, wowedzera imwe denderedzwa re dilute hydrochloric acid, kurudzira kupisa uye hydrolyze kweimwe nguva yenguva, inotonhorera kusvika kukamuri tembiricha, sefa, geza nemvura kusvika kwaurerekera, uye vacuum yakaoma pa50 ° C kuti uwane Mushure mekuva ne microcrystalline cellulose raw materials ine madhigirii akasiyana epolymerization, yera dhigirii yavo yepolymerization maererano nezvinyorwa, zviise mubhodhoro rekuita katatu, rimise ne. inomisa mumiriri kanokwana kagumi kuwanda kwayo, wedzera imwe chiyero chesodium hydroxide aqueous solution pasi pekubvongodza, Gadzirisa uye shandisa patembiricha yekamuri kweimwe nguva yenguva, wedzera huwandu hwakaverengerwa hwe1,4-butane sultone (BS), kupisa. kune reaction tembiricha, ita painogara tembiricha kwenguva yakati rebei, tonhodza chigadzirwa kusvika patembiricha yekamuri, uye tora crude chigadzirwa nekusefa. Shamba nemvura uye methanol ka3, uye sefa nekusveta kuti uwane chigadzirwa chekupedzisira, chinonzi cellulose butylsulfonate water reducer (SBC).

2.3 Kuongororwa kwechigadzirwa uye maitiro

2.3.1 Kutemerwa kwechigadzirwa sarufa zvirimo uye kuverenga kwedhigirii rekutsiva

Iyo FLASHEA-PE2400 elemental analyzer yakashandiswa kuita ongororo yekutanga pane yakaomeswa cellulose butyl sulfonate mvura inoderedza chigadzirwa kuona iyo sulfur yemukati.

2.3.2 Kuona kuyerera kwedhaka

Yakayerwa zvinoenderana ne6.5 muGB8076-2008. Ndiko kuti, tanga kuyera mvura / simende / yakajairwa jecha musanganiswa paNLD-3 simende dhaka fluidity tester kana dhayamita yekuwedzera iri (180±2) mm. simende, iyo yakayerwa bhenji mashandisirwo emvura i230g), wobva wawedzera mvura yekudzikisa mvura ine huremu hunosvika 1% yesamende kumvura, zvinoenderana nesamende/mvura yekudzikisa mvura/standard mvura/standard jecha=450g/4.5g/ 230 g/ Reshiyo ye1350 g inoiswa muJJ-5 simende musanganisi wedhaka uye yakasimudzwa zvakaenzana, uye yakawedzera dhayamita yedhaka pane yevhu fluidity tester inoyerwa, inova yakayerwa dhaka fluidity.

2.3.3 Chigadzirwa Chimiro

Sample yairatidzwa neFT-IR ichishandisa EQUINOX 55 mhando yeFourier inoshandura infrared spectrometer yeBruker Company; iyo H NMR spectrum yemuenzaniso yakaratidzwa neINOVA ZAB-HS gejo superconducting nuclear magnetic resonance instrument yeVarian Company; The morphology yechigadzirwa yakaonekwa pasi pe microscope; Ongororo yeXRD yakaitwa pasample nekushandisa X-ray diffractometer yeMAC Company M18XHF22-SRA.

3. Migumisiro uye nhaurirano

3.1 Maitiro ehunhu

3.1.1 FT-IR maitiro ekuita

Ongororo ye infrared yakaitwa pane yakabikwa microcrystalline cellulose ine dhigirii repolymerization Dp = 45 uye chigadzirwa SBC chakagadzirwa kubva kune iyi mbishi. Sezvo nhongonya dzeSC neSH dzisina kusimba, hadzina kukodzera kuzivikanwa, nepo S=O ine peak yakasimba yekunyura. Naizvozvo, kana paine sulfonic acid boka muchimiro chemolecular inogona kutsanangurwa nekusimbisa kuvepo kweiyo S = O peak. Zviripachena, mune cellulose spectrum, kune yakasimba kunyura peak pane wave nhamba ye 3344 cm-1, iyo inofungidzirwa kune iyo hydroxyl inotambanudza vibration peak mu cellulose; iyo yakanyanya kunyura peak pane wave nhamba ye2923 cm-1 ndiyo inotambanudzira vibration peak yemethylene (-CH2). Vibration peak; nhevedzano yemabhendi anoumbwa ne1031, 1051, 1114, uye 1165cm-1 anoratidza kunyudzwa kwepamusoro pehydroxyl inotambanudza vibration uye iyo yekunyudza peak ye ether bond (COC) bending vibration; iyo wave nhamba 1646cm-1 inoratidza iyo haidrojeni yakaumbwa nehydroxyl uye yemahara mvura Iyo bond absorption peak; iyo bhendi ye1432 ~ 1318cm-1 inoratidza kuvepo kweiyo cellulose crystal chimiro. Mune IR spectrum yeSBC, kusimba kwebhendi 1432 ~ 1318cm-1 kunopera simba; nepo kusimba kwekunyura kwepamusoro pa 1653 cm-1 kunowedzera, zvichiratidza kuti kukwanisa kuumba hydrogen bonds kunosimbiswa; 1040. Kubva pane ongororo iri pamusoro, zvinogona kuonekwa kuti mushure mekuita kwe etherification ye cellulose, kune mapoka e sulfonic acid mumaketani ayo e-molecular.

3.1.2 H NMR maitiro ehunhu

Iyo H NMR spectrum ye cellulose butyl sulfonate inogona kuonekwa: mukati me γ = 1.74 ~ 2.92 ndiyo hydrogen proton kemikari kuchinja kwe cyclobutyl, uye mukati me γ = 3.33 ~ 4.52 ndiyo cellulose anhydroglucose unit Kuchinja kwekemikari ye oxygen proton mu γ = 4.52 ~6 ndiko kuchinja kwemakemikari emethylene proton muboka rebutylsulfonic acid rakabatana neokisijeni, uye hapana peak pa γ = 6 ~ 7, zvichiratidza kuti chigadzirwa hachisi Mamwe mapurotoni aripo.

3.1.3 SEM maitiro ehunhu

SEM yekucherechedza cellulose donje pulp, microcrystalline cellulose uye chigadzirwa cellulose butylsulfonate. Nekuongorora iyo SEM yekuongorora mhedzisiro ye cellulose donje pulp, microcrystalline cellulose uye chigadzirwa cellulose butanesulfonate (SBC), zvinoonekwa kuti iyo microcrystalline cellulose inowanikwa mushure me hydrolysis neHCL inogona kushandura zvakanyanya chimiro che cellulose fiber. Iyo fibrous chimiro chakaparadzwa, uye yakanaka agglomerated cellulose particles yakawanikwa. Iyo SBC yakawanikwa nekuwedzera kuita neBS yakanga isina chimiro chefibrous uye yakashandurwa kuita chimiro cheamorphous, icho chaibatsira pakuparara kwayo mumvura.

3.1.4 XRD maitiro emhedzisiro

Iyo crystallinity ye cellulose uye zvinobva mairi inoreva chikamu cheiyo crystalline dunhu rakaumbwa ne cellulose unit chimiro mune yese. Kana cellulose nezvinobuda pairi kuita kemikari kuita, zvisungo zvehydrogen mumorekuru uye pakati pemamorekuru zvinoparadzwa, uye nharaunda yecrystalline ichava dunhu reamorphous, nekudaro ichidzikisa kuchena. Nokudaro, shanduko yekristallinity isati yasvika uye mushure mekuita chiyero che cellulose Imwe yemaitiro ekutora chikamu mumhinduro kana kwete. XRD ongororo yakaitwa pamicrocrystalline cellulose uye chigadzirwa cellulose butanesulfonate. Inogona kuonekwa nekuenzanisa kuti mushure me etherification, crystallinity inoshanduka zvakanyanya, uye chigadzirwa chacho chakashandurwa zvachose kuva chimiro cheamorphous, kuitira kuti chigone kunyungudutswa mumvura.

3.2 Mhedzisiro yedhigirii repolymerization yezvigadzirwa pamvura inoderedza kuita kwechigadzirwa.

Iyo fluidity yedhaka inoratidzira zvakananga kushanda kwemvura-kuderedza kwechigadzirwa, uye sulfuri yezvinyorwa zvechigadzirwa ndechimwe chezvinhu zvakakosha zvinokanganisa kusvibiswa kwedhaka. Iyo fluidity yevhu inoyera kudzikisa mvura kwechigadzirwa.

Mushure mekushandura mamiriro ekuita hydrolysis kugadzirira MCC ine madhigirii akasiyana epolymerization, zvinoenderana neiyo nzira iri pamusoro, sarudza imwe nzira yekugadzira kugadzirira zvigadzirwa zveSBC, kuyera sarufa yemukati kuverenga iyo chigadzirwa chinotsiva dhigirii, uye kuwedzera zvigadzirwa zveSBC kumvura. /cement/standard jecha mixing system Yera kuyerera kwedhaka.

Inogona kuonekwa kubva mumigumisiro yekuedza iyo mukati mekutsvaga kwekutsvaga, apo dhigirii yepolymerization ye microcrystalline cellulose raw material yakakwira, sulfur content (inotsiva dhigirii) yechigadzirwa uye fluidity yedhaka yakaderera. Izvi zvinodaro nekuti: huremu hwemamorekuru hweiyo mbishi idiki, iyo inobatsira kune yunifomu kusanganiswa kwezvinhu zvakasvibiswa Uye kupinda kweiyo etherification agent, nekudaro inovandudza dhigirii reetherification yechigadzirwa. Nekudaro, mwero wekudzikisa mvura yechigadzirwa hausimuke mumutsara wakatwasuka nekudzikira kwedhigirii repolymerization yezvigadzirwa. Migumisiro yekuedza inoratidza kuti dhaka remvura yemusanganiswa wesamende yakasanganiswa neSBC yakagadzirirwa nekushandisa microcrystalline cellulose ine dhigirii yepolymerization Dp<96 (molecular weight<15552) yakakura kudarika 180 mm (iyo yakakura kudarika iyo isina mvura inoderedza) . benchmark fluidity), zvichiratidza kuti SBC inogona kugadzirwa nekushandisa cellulose ine huremu hwemamorekuru isingasviki 15552, uye imwe chiyero chekudzikisa mvura inogona kuwanikwa; SBC inogadzirwa nekushandisa microcrystalline cellulose ine dhigirii yepolymerization ye45 (molecular uremu: 7290), uye yakawedzerwa kune musanganiswa wekongiri, iyo yakayerwa fluidity yedhaka ndiyo yakakura, saka inofungidzirwa kuti cellulose ine chidimbu chepolymerization. pamusoro pe45 inonyanya kukodzera kugadzirira kweSBC; apo dhigirii yepolymerization yezvinhu zvakasvibirira yakakura kudarika 45, kunyunguduka kwevhu kunoderera zvishoma nezvishoma, izvo zvinoreva kuti mvura inoderedza chiyero inoderera. Izvi zvinodaro nekuti kana huremu hwemamorekuru hwakakura, kune rumwe rutivi, viscosity yemusanganiswa system ichawedzera, kupararira kufanana kwesimende kuchave kwakaderera, uye kupararira mukongiri kunononoka, izvo zvinokanganisa kupararira mhedzisiro; nerumwe rutivi, kana huremu hwemamorekuru hwakakura, Iwo macromolecules e superplasticizer ari mune isina kujairika coil conformation, iyo inonetsa kushambadza pamusoro pemasimende esimende. Asi kana dhigirii yepolymerization yezvigadzirwa zvisingasviki makumi mana nemashanu, kunyange zvazvo sulfur yemukati (inotsiva dhigirii) yechigadzirwa yakakura, mvura yemusanganiswa wedhaka inotanga kuderera, asi kuderera kuduku zvikuru. Chikonzero ndechekuti kana huremu hwemamorekuru emvura inodzikisa mumiriri idiki, kunyangwe kupararira kwema molecular kuri nyore uye kuine kunyorova kwakanaka, kukurumidza kweadsorption kwemorekuru kwakakura kupfuura iyo yemamorekuru, uye cheni yekutakura mvura ipfupi kwazvo. uye kupesana pakati pezvikamu zvakakura, izvo zvinokuvadza kune kongiri. The dispersion effect haina kunaka seyechidzikisiso chemvura chine huremu hombe hwemamorekuru. Naizvozvo, zvakakosha kudzora nemazvo huremu hwema molecular yenguruve face (cellulose segment) kuvandudza mashandiro emvura inoderedza.

3.3 Mhedzisiro yemamiriro ekuita pane mvura-kudzikisa kuita kwechigadzirwa

Inowanikwa kuburikidza nekuyedza kuti mukuwedzera kune dhigirii repolymerization yeMCC, chiyero chezvinoita, tembiricha yekuita, activation yezvakagadzirwa, chigadzirwa synthesis nguva, uye mhando yekumisa mumiriri zvese zvinokanganisa kuita-kudzikisa mvura kwechigadzirwa.

3.3.1 Reactant ratio

(1) Chiyero cheBS

Pasi pemamiriro akatemerwa nemamwe maparamita ekuita (chiyero chepolymerization yeMCC 45, n(MCC):n(NaOH) = 1:2.1, iyo inomisa mumiriri ndeye isopropanol, iyo activation nguva ye cellulose pamhepo tembiricha ndeye 2h, iyo synthesis tembiricha i80 ° C, uye synthesis nguva 5h), kuongorora mhedzisiro yehuwandu hweetherification agent 1,4-butane sultone (BS) padanho rekutsiva butanesulfonic acid mapoka echigadzirwa uye kuyerera kwechigadzirwa. dhaka.

Zvinogona kuonekwa kuti sezvo huwandu hweBS hunowedzera, dhigirii yekutsiviwa kweboka rebutanesulfonic acid uye fluidity yedhaka inowedzera zvakanyanya. Kana chiyero cheBS kune MCC chasvika 2.2: 1, iyo fluidity yeDS uye dhaka inosvika pakakwirira. kukosha, inofungidzirwa kuti mvura-inoderedza kushanda ndiyo yakanakisisa panguva ino. Kukosha kweBS kwakaramba kuchiwedzera, uye zvose dhigirii yekutsiviwa uye fluidity yevhu yakatanga kuderera. Izvi zvinodaro nekuti kana BS yakawandisa, BS ichaita neNaOH kugadzira HO-(CH2)4SO3Na. Naizvozvo, bepa rino rinosarudza yakaringana zvinhu reshiyo yeBS kune MCC se2.2:1.

(2) Chiyero cheNaOH

Pasi pemamiriro ezvinhu akatemerwa nemamwe maitiro ekugadzirisa (dhigirii yepolymerization yeMCC ndeye 45, n (BS): n (MCC) = 2.2: 1. Mushonga unomisa ndeye isopropanol, nguva yekushandiswa kwe cellulose pakupisa kwekamuri ndeye 2h, iyo synthesis tembiricha i80 ° C, uye synthesis nguva 5h), kuongorora mhedzisiro yehuwandu hwesodium hydroxide padanho rekutsiviwa kwemapoka ebutanesulfonic acid muchigadzirwa uye kuyerera kwedhaka.

Zvinogona kuonekwa kuti, nekuwedzera kwehuwandu hwekuderedza, dhigirii yekutsiviwa kweSBC inowedzera nokukurumidza, uye inotanga kuderera mushure mokusvika pamutengo wepamusoro. Izvi zvinodaro nekuti, kana iyo NaOH yemukati yakakwira, kune akawanda akawandisa mabhesi emahara muhurongwa, uye mukana wekuita kwedivi kunowedzera, zvichikonzera kuti mamwe etherification agents (BS) atore chikamu mukuita kwedivi, nekudaro kuderedza dhigirii rekutsiva sulfonic. asidhi mapoka muchigadzirwa. Pakupisa kwepamusoro, kuvapo kweNaOH yakawandisa kuchaderedzawo cellulose, uye mvura inoderedza kushanda kwechigadzirwa ichakanganiswa pachidimbu chepolymerization. Maererano nemigumisiro yekuedza, kana chiyero chemolar cheNaOH kuMCC chinenge 2.1, dhigirii yekutsiva ndiyo yakakura, saka bepa rino rinotarisa kuti molar ratio yeNaOH kuMCC i2.1: 1.0.

3.3.2 Mhedzisiro yetembiricha yekuita pane chigadzirwa chinoderedza kuita kwemvura

Pasi pemamiriro akatemerwa nemamwe maparameter ekuita (dhigirii repolymerization yeMCC i45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, iyo inomisa mumiririri is isopropanol, uye activation nguva ye cellulose pakamuri tembiricha ndeye 2h Nguva 5h), pesvedzero ye synthesis reaction tembiricha pane dhigirii rekutsinhanisa mapoka ebutanesulfonic acid muchigadzirwa akaongororwa.

Zvinogona kuonekwa kuti sezvo tembiricha yekuita ichiwedzera, sulfonic acid inotsiva dhigirii DS yeSBC zvishoma nezvishoma inowedzera, asi kana tembiricha yekupindura ikadarika 80 °C, DS inoratidza kudzikira. Iyo etherification reaction pakati pe1,4-butane sultone uye cellulose ndeye endothermic reaction, uye kuwedzera kupisa kwekuita kunobatsira kuita pakati peetherifying agent uye cellulose hydroxyl boka, asi nekuwedzera kwekushisa, mhedzisiro yeNaOH uye cellulose inowedzera zvishoma nezvishoma. . Inova yakasimba, zvichiita kuti cellulose ideredze uye iwire pasi, zvichiita kuti kuderera kwema molecular weight ye cellulose uye kuberekwa kwemashuga maduku. Kuita kwemamorekuru madiki akadaro ane etherifying agents ari nyore, uye mamwe etherifying agents anozopedzwa, zvichikanganisa dhigirii yekutsiviwa kwechigadzirwa. Naizvozvo, thesis iyi inofunga kuti yakanyanya kufanira kuita tembiricha ye etherification reaction yeBS uye cellulose i80 ℃.

3.3.3 Mhedzisiro yenguva yekuita pane chigadzirwa chekudzikisa mvura

Iyo nguva yekuita yakakamurwa kuita tembiricha yekamuri activation yezvinhu zvakabikwa uye inogara tembiricha synthesis nguva yezvigadzirwa.

(1) Room tembiricha activation nguva yezvinhu mbishi

Pasi pemamiriro epamusoro epamusoro maitiro (MCC degree ye polymerization i45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, suspending agent is isopropanol, synthesis reaction tembiricha i80°C, chigadzirwa. Constant tembiricha synthesis nguva 5h), ongorora pesvedzero yekamuri tembiricha activation nguva padanho rekutsiva chigadzirwa butanesulfonic acid boka.

Zvinogona kuonekwa kuti dhigirii yekutsiviwa kweboka rebutanesulfonic acid yechigadzirwa SBC inowedzera kutanga uye inoderera nekuwedzera kwenguva yekushanda. Chikonzero chekuongorora chingave chokuti nekuwedzera kweNaOH nguva yekuita, kuora kwe cellulose kwakakomba. Deredza huremu hwemamorekuru ecellulose kuti ugadzire mashuga madiki. Kuita kwemamorekuru madiki akadaro ane etherifying agents ari nyore, uye mamwe etherifying agents anozopedzwa, zvichikanganisa dhigirii yekutsiviwa kwechigadzirwa. Naizvozvo, pepa iri rinoona kuti tembiricha yekamuri activation nguva yezvinhu zvakabikwa ndeye 2h.

(2) Chigadzirwa synthesis nguva

Pasi pemamiriro epamusoro pemaitiro ari pamusoro, mhedzisiro ye activation nguva pakudziya kwekamuri pachiyero chekutsiviwa kwechigadzirwa butanesulfonic acid boka yakaongororwa. Zvinogona kuonekwa kuti nekuwedzera kwenguva yekuita, dhigirii yekutsiva inotanga kuwedzera, asi kana nguva yekuita inosvika 5h, DS inoratidza kuderera. Izvi zvine chekuita neyemahara base iripo mune etherification reaction ye cellulose. Pakupisa kwepamusoro, kurebesa kwenguva yekuita kunounza kuwedzera kwechiyero che alkali hydrolysis ye cellulose, kupfupikiswa kwe cellulose molecular chain, kuderera kwehuremu hwechigadzirwa, uye kuwedzera kwemaitiro epadivi, zvichikonzera kutsiva. dhigirii inodzikira. Muchiyedzo ichi, yakanakira synthesis nguva ndeye 5h.

3.3.4 Mhedzisiro yerudzi rweanomisa basa pakudzikisa mvura kwechigadzirwa.

Pasi pemamiriro ekuita zvakanaka (MCC polymerization degree ndeye 45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, nguva ye activation yezvigadzirwa patembiricha yekamuri ndeye 2h, inogara tembiricha synthesis nguva. yezvigadzirwa ndeye 5h, uye tembiricha yekuita 80 ℃), zvichiteerana sarudza isopropanol, ethanol, n-butanol, ethyl acetate uye petroleum ether seanomisa maajenti, uye kurukura nezvesimba ravo pakudzikisa mvura kwechigadzirwa.

Zviripachena, isopropanol, n-butanol uye ethyl acetate zvese zvinogona kushandiswa seanomisa mumiriri mune iyi etherification reaction. Basa remumiriri wekumisa, kunze kwekuparadzira mareactants, anogona kudzora tembiricha yekuita. Iyo yekubikira ye isopropanol i82.3 ° C, saka isopropanol inoshandiswa sechinhu chinomira, tembiricha yehurongwa inogona kudzorwa padyo neyakakwana yekudziya tembiricha, uye dhigirii rekutsinhanisa mapoka ebutanesulfonic acid muchigadzirwa uye fluidity ye. dhaka rakareba; nepo iyo yekubikira ye ethanol yakanyanya Kudzika, iyo inodziya tembiricha haina kusangana nezvinodiwa, dhigirii rekutsinhanisa mapoka ebutanesulfonic acid mune chigadzirwa uye fluidity yedhaka yakaderera; petroleum ether inogona kutora chikamu mukuita, saka hapana chigadzirwa chakaparadzirwa chinogona kuwanikwa.

4 Mhedziso

(1) Kushandisa donje pulp seyekutanga mbishi,microcrystalline cellulose (MCC)ine dhigirii yakakodzera yepolymerization yakagadzirwa, yakashandiswa neNaOH, uye yakaitwa ne 1,4-butane sultone kugadzira mvura-inonyungudika butylsulfonic acid Cellulose ether, kureva, cellulose-based water reducer. Kurongeka kwechigadzirwa chacho kwakaratidzwa, uye zvakaonekwa kuti mushure mekuita kwe etherification ye cellulose, pakanga pane mapoka e-sulfonic acid pacheni yaro ye molecular, iyo yakanga yashandura kuita amorphous structure, uye mvura inoderedza chigadzirwa yakanga ine mvura yakanaka yekunyungudika;

(2) Kuburikidza nemiedzo, inowanikwa kuti kana dhigirii yepolymerization ye microcrystalline cellulose iri 45, mvura inoderedza kushanda kwechigadzirwa chakawanikwa ndiyo yakanakisisa; pasi pemamiriro ekuti dhigirii repolymerization yezvigadzirwa zvakatarwa, chiyero chezvinoita n(MCC):n(NaOH):n(BS)=1:2.1:2.2, iyo activation nguva yezvinhu zvakasvibirira patembiricha yekamuri ndeye. 2h, tembiricha yekugadzirwa kwechigadzirwa i80 ° C, uye nguva yekubatanidza i5h. Kuita kwemvura ndiko kwakaringana.