Synthesis thiab Characterization ntawm Butane Sulfonate Cellulose Ether Water Reducer

Microcrystalline cellulose (MCC) nrog rau qhov tseeb degree ntawm polymerization tau los ntawm acid hydrolysis ntawm cellulose paj rwb pulp yog siv los ua raw khoom. Raws li kev ua haujlwm ntawm sodium hydroxide, nws tau hnov ​​​​mob nrog 1,4-butane sultone (BS) kom tau txais A cellulose butyl sulfonate (SBC) dej reducer nrog dej solubility zoo. Cov qauv khoom yog tus cwj pwm los ntawm infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD) thiab lwm yam kev tshuaj ntsuam xyuas, thiab polymerization degree, raw khoom piv, thiab cov tshuaj tiv thaiv ntawm MCC raug tshawb xyuas. Cov teebmeem ntawm cov txheej txheem hluavtaws xws li qhov kub thiab txias, lub sijhawm tshuaj tiv thaiv, thiab hom kev tshem tawm tus neeg sawv cev ntawm cov dej-txo kev ua haujlwm ntawm cov khoom. Cov txiaj ntsig tau pom tias: thaum lub degree ntawm polymerization ntawm raw khoom MCC yog 45, qhov loj piv ntawm cov reactants yog: AGU (cellulose glucoside unit): n (NaOH): n (BS) = 1.0: 2.1: 2.2, suspending tus neeg sawv cev yog isopropanol, lub sij hawm ua kom cov khoom siv raw ntawm chav tsev kub yog 2 h, thiab lub sij hawm synthesis ntawm cov khoom yog 5 h. Thaum qhov kub thiab txias yog 80 ° C, cov khoom tau txais muaj qhov siab tshaj plaws ntawm kev hloov ntawm butanesulfonic acid pawg, thiab cov khoom muaj qhov zoo tshaj plaws dej-txo kev ua tau zoo.

Cov lus tseem ceeb:cellulose; cellulose butylsulfonate; dej txo tus neeg sawv cev; dej txo kev ua haujlwm

1,Taw qhia

Pob zeb superplasticizer yog ib qho ntawm cov khoom tseem ceeb ntawm cov pob zeb niaj hnub no. Nws yog precisely vim hais tias ntawm cov tsos ntawm cov dej txo tus neeg sawv cev uas lub siab workability, zoo durability thiab txawm siab zog ntawm pob zeb yuav guaranteed. Tam sim no dav siv cov dej ua kom muaj txiaj ntsig zoo tshaj plaws suav nrog cov hauv qab no: naphthalene-raws li dej reducer (SNF), sulfonated melamine resin-raws li dej-reducer (SMF), sulfamate-raws li dej-reducer (ASP), hloov Lignosulfonate superplasticizer ( ML), thiab polycarboxylate superplasticizer (PC), uas tam sim no tshawb fawb ntau dua. Txheeb xyuas cov txheej txheem synthesis ntawm cov dej reducers, feem ntau ntawm yav dhau los cov tsoos condensate dej reducers siv formaldehyde nrog ib tug muaj zog pungent tsw raws li raw khoom rau polycondensation cov tshuaj tiv thaiv, thiab cov txheej txheem sulfonation feem ntau yog nqa tawm nrog heev corrosive fuming sulfuric acid los yog concentrated sulfuric acid. Qhov no yuav ua rau muaj kev cuam tshuam tsis zoo rau cov neeg ua haujlwm thiab ib puag ncig ib puag ncig, thiab tseem yuav tsim kom muaj ntau cov khoom pov tseg thiab cov kua dej pov tseg, uas tsis tsim nyog rau kev txhim kho kom ruaj khov; Txawm li cas los xij, txawm hais tias dej polycarboxylate cov txiaj ntsig me me ntawm cov qhob lub sijhawm zoo, tab sis nws nyuaj rau nws nyob hauv Suav teb vim lub siab nqe. Los ntawm kev txheeb xyuas ntawm qhov chaw ntawm cov khoom siv raw, nws tsis yooj yim los nrhiav pom tias feem ntau ntawm cov dej txo qis saum toj no tau tsim los ntawm cov khoom siv petrochemical / los ntawm cov khoom lag luam, thaum cov roj av, raws li cov peev txheej tsis txuas ntxiv, muaj tsawg zuj zus thiab nws tus nqi yog pheej nce. Yog li ntawd, yuav ua li cas siv pheej yig thiab ntau cov khoom siv txuas ntxiv dua tshiab los ua cov khoom siv los tsim cov kev ua haujlwm siab tshiab ua pob zeb superplasticizers tau dhau los ua ib qho kev tshawb fawb tseem ceeb rau cov pob zeb superplasticizers.

Cellulose yog linear macromolecule tsim los ntawm kev sib txuas ntau D-glucopyranose nrog β-(1-4) glycosidic bonds. Muaj peb pawg hydroxyl ntawm txhua lub nplhaib glucopyranosyl. Kev kho kom zoo tuaj yeem tau txais qee yam kev ua haujlwm. Hauv daim ntawv no, cellulose paj rwb pulp tau siv los ua cov khoom siv thawj zaug, thiab tom qab cov kua qaub hydrolysis kom tau microcrystalline cellulose nrog rau qib tsim nyog ntawm polymerization, nws tau qhib los ntawm sodium hydroxide thiab reacted nrog 1,4-butane sultone los npaj butyl sulfonate Acid. cellulose ether superplasticizer, thiab cov kev cuam tshuam ntawm txhua qhov tshuaj tiv thaiv tau tham.

2. Kev sim

2.1 Cov khoom siv raw

Cellulose paj rwb pulp, polymerization degree 576, Xinjiang Aoyang Technology Co., Ltd.; 1,4-butane sultone (BS), qib kev lag luam, tsim los ntawm Shanghai Jiachen Chemical Co., Ltd.; 52.5R zoo tib yam Portland cement, Urumqi Muab los ntawm lub Hoobkas cement; Tuam Tshoj ISO txheem xuab zeb, tsim los ntawm Xiamen Ace Ou Standard Sand Co., Ltd.; sodium hydroxide, hydrochloric acid, isopropanol, anhydrous methanol, ethyl acetate, n-butanol, roj av ether, thiab lwm yam, yog tag nrho cov tshuaj analytically ntshiab, muag muag.

2.2 Kev sim txoj kev

Ntsuas ib qho ntawm cov paj rwb pulp thiab zom nws kom zoo, muab tso rau hauv ib lub raj mis peb-caj dab, ntxiv ib qho concentration ntawm dilute hydrochloric acid, do kom sov thiab hydrolyze rau ib lub sij hawm ntawm lub sij hawm, txias rau chav tsev kub, lim, Ntxuav nrog dej kom txog thaum nruab nrab, thiab lub tshuab nqus tsev qhuav ntawm 50 ° C kom tau txais Tom qab muaj cov khoom siv microcrystalline cellulose nrog ntau qib ntawm polymerization, ntsuas lawv qib ntawm polymerization raws li cov ntaub ntawv, muab tso rau hauv lub raj mis peb caj dab, tshem tawm nrog Tus neeg sawv cev ncua 10 npaug ntawm nws qhov loj, ntxiv ib qho nyiaj ntawm sodium hydroxide aqueous tov nyob rau hauv nplawm, do thiab qhib rau ntawm chav tsev kub rau ib lub sij hawm ntawm lub sij hawm, ntxiv tus nqi ntawm 1,4-butane sultone (BS), cua sov. mus rau cov tshuaj tiv thaiv kub, react ntawm qhov kub thiab txias rau ib lub sij hawm ntawm lub sij hawm, txias cov khoom rau hauv chav tsev kub, thiab tau txais cov khoom crude los ntawm suction pom. Yaug nrog dej thiab methanol rau 3 zaug, thiab lim nrog nqus kom tau cov khoom kawg, uas yog cellulose butylsulfonate water reducer (SBC).

2.3 Kev txheeb xyuas cov khoom thiab cov yam ntxwv

2.3.1 Kev txiav txim siab ntawm cov khoom sulfur cov ntsiab lus thiab suav cov degree ntawm kev hloov pauv

FLASHEA-PE2400 elemental analyzer tau siv los ua cov tshuaj ntsuam xyuas ntawm cov cellulose qhuav butyl sulfonate dej reducer khoom los txiav txim siab cov ntsiab lus ntawm leej faj.

2.3.2 Kev txiav txim siab ntawm fluidity ntawm mortar

Ntsuas raws li 6.5 hauv GB8076-2008. Ntawd yog, ua ntej ntsuas dej / cement / tus qauv xuab zeb sib xyaw ntawm NLD-3 cement mortar fluidity tester thaum qhov nthuav dav yog (180 ± 2) hli. cement, ntsuas ntsuas dej siv yog 230g), thiab tom qab ntawd ntxiv cov dej txo tus neeg sawv cev uas nws loj yog 1% ntawm cov cement loj rau dej, raws li cov cement / dej txo tus neeg sawv cev / tus qauv dej / qauv xuab zeb = 450g / 4.5g / 230 g / Qhov piv ntawm 1350 g yog muab tso rau hauv JJ-5 cement mortar tov khoom thiab nplawm tusyees, thiab qhov nthuav dav ntawm mortar ntawm lub mortar fluidity tester yog ntsuas, uas yog ntsuas mortar fluidity.

2.3.3 Product Characterization

Cov qauv yog tus cwj pwm los ntawm FT-IR siv EQUINOX 55 hom Fourier hloov infrared spectrometer ntawm Bruker Company; H NMR spectrum ntawm tus qauv yog tus yam ntxwv los ntawm INOVA ZAB-HS plow superconducting nuclear magnetic resonance ntsuas ntawm Varian Company; Lub morphology ntawm cov khoom raug soj ntsuam nyob rau hauv ib tug microscope; XRD tsom xam tau ua tiav ntawm cov qauv los ntawm kev siv X-ray diffractometer ntawm MAC Company M18XHF22-SRA.

3. Cov txiaj ntsig thiab kev sib tham

3.1 Cov txiaj ntsig zoo

3.1.1 FT-IR characterization tshwm sim

Kev tshuaj xyuas infrared tau ua tiav ntawm cov khoom siv raw microcrystalline cellulose nrog qib ntawm polymerization Dp = 45 thiab cov khoom SBC synthesized los ntawm cov khoom siv raw. Txij li thaum lub siab nqus ntawm SC thiab SH yog qhov tsis muaj zog, lawv tsis haum rau kev txheeb xyuas, thaum S = O muaj qhov nqus siab siab. Yog li, seb puas muaj sulfonic acid pawg hauv cov qauv molecular tuaj yeem txiav txim siab los ntawm kev lees paub qhov muaj nyob ntawm S = O ncov. Obviously, nyob rau hauv lub cellulose spectrum, muaj ib tug muaj zog absorption ncov ntawm ib tug yoj tus naj npawb ntawm 3344 cm-1, uas yog ntaus nqi mus rau lub hydroxyl stretching vibration ncov nyob rau hauv cellulose; Qhov siab dua qhov nqus dej ntawm lub nthwv dej ntawm 2923 cm-1 yog qhov ncab vibration ncov ntawm methylene (-CH2). Kev vibration ncov; series ntawm bands muaj xws li 1031, 1051, 1114, thiab 1165cm-1 muaj kev cuam tshuam lub ncov nqus ntawm hydroxyl stretching vibration thiab lub ncov nqus ntawm ether bond (COC) dabtsi yog khoov kev co; yoj tus naj npawb 1646cm-1 qhia txog cov hydrogen tsim los ntawm hydroxyl thiab dej dawb Cov nyiaj nqus nqus ncov; band ntawm 1432 ~ 1318cm-1 qhia txog lub neej ntawm cellulose siv lead ua qauv. Hauv IR spectrum ntawm SBC, qhov kev siv ntawm cov qhab 1432 ~ 1318cm-1 tsis muaj zog; thaum qhov kev siv ntawm lub ncov siab ntawm 1653 cm-1 nce, qhia tias muaj peev xwm tsim hydrogen bonds ntxiv dag zog; 1040, 605cm-1 zoo nkaus li muaj zog Absorption peaks, thiab ob qho no tsis pom nyob rau hauv infrared spectrum ntawm cellulose, lub qub yog tus yam ntxwv absorption ncov ntawm S = O daim ntawv cog lus, thiab tom kawg yog tus yam ntxwv absorption ncov ntawm SO daim ntawv cog lus. Raws li kev soj ntsuam saum toj no, nws tuaj yeem pom tias tom qab cov tshuaj tiv thaiv etherification ntawm cellulose, muaj sulfonic acid pawg hauv nws cov saw hlau molecular.

3.1.2 H NMR characterization tshwm sim

H NMR spectrum ntawm cellulose butyl sulfonate tuaj yeem pom: nyob rau hauv γ = 1.74 ~ 2.92 yog hydrogen proton tshuaj hloov ntawm cyclobutyl, thiab nyob rau hauv γ = 3.33 ~ 4.52 yog cellulose anhydroglucose unit Cov tshuaj hloov pauv ntawm cov pa proton hauv γ = 4.52 ~ 6 yog cov tshuaj hloov pauv ntawm methylene proton nyob rau hauv butylsulfonic acid pawg txuas nrog oxygen, thiab tsis muaj lub ncov ntawm γ = 6 ~ 7, qhia tias cov khoom tsis yog lwm cov protons.

3.1.3 SEM characterization tshwm sim

SEM soj ntsuam ntawm cellulose paj rwb pulp, microcrystalline cellulose thiab khoom cellulose butylsulfonate. Los ntawm kev txheeb xyuas SEM cov txiaj ntsig ntawm cellulose paj rwb pulp, microcrystalline cellulose thiab cov khoom cellulose butanesulfonate (SBC), nws pom tau tias microcrystalline cellulose tau tom qab hydrolysis nrog HCL tuaj yeem hloov pauv cov qauv ntawm cellulose fibers. Cov qauv fibrous raug rhuav tshem, thiab cov khoom zoo agglomerated cellulose tau txais. SBC tau txais los ntawm kev rov ua dua ntxiv nrog BS tsis muaj cov qauv fibrous thiab pib hloov mus rau hauv cov qauv amorphous, uas yog qhov zoo rau nws qhov kev sib cais hauv dej.

3.1.4 XRD characterization tshwm sim

Lub crystallinity ntawm cellulose thiab nws cov derivatives yog hais txog qhov feem pua ​​​​ntawm cov crystalline cheeb tsam tsim los ntawm cellulose unit qauv nyob rau hauv tag nrho. Thaum cellulose thiab nws cov derivatives tau txais cov tshuaj tiv thaiv, cov hydrogen bonds hauv cov molecule thiab ntawm cov molecules raug rhuav tshem, thiab thaj tsam crystalline yuav dhau los ua thaj tsam amorphous, yog li txo cov crystallinity. Yog li ntawd, kev hloov pauv hauv crystallinity ua ntej thiab tom qab cov tshuaj tiv thaiv yog ib qho kev ntsuas ntawm cellulose Ib qho ntawm cov txheej txheem los koom rau hauv cov lus teb los yog tsis. XRD tsom xam tau ua tiav ntawm microcrystalline cellulose thiab cov khoom cellulose butanesulfonate. Nws tuaj yeem pom los ntawm kev sib piv tias tom qab etherification, crystallinity hloov pauv hauv paus, thiab cov khoom tau hloov pauv mus rau hauv cov qauv amorphous, kom nws tuaj yeem yaj hauv dej.

3.2 Cov nyhuv ntawm cov degree ntawm polymerization ntawm raw cov ntaub ntawv ntawm cov dej-txo kev ua tau zoo ntawm cov khoom

Lub fluidity ntawm mortar ncaj qha qhia txog cov dej-txo kev ua tau zoo ntawm cov khoom, thiab cov ntsiab lus sulfur ntawm cov khoom yog ib qho tseem ceeb tshaj plaws cuam tshuam rau lub fluidity ntawm mortar. Lub fluidity ntawm mortar ntsuas cov dej-txo kev ua haujlwm ntawm cov khoom.

Tom qab hloov cov tshuaj tiv thaiv hydrolysis los npaj MCC nrog rau qib sib txawv ntawm polymerization, raws li cov txheej txheem saum toj no, xaiv cov txheej txheem synthesis los npaj SBC cov khoom, ntsuas cov ntsiab lus sulfur los xam cov khoom hloov pauv, thiab ntxiv cov khoom SBC rau hauv dej. / cement / standard sand mixing system Ntsuas qhov fluidity ntawm mortar.

Nws tuaj yeem pom los ntawm cov txiaj ntsig kev sim uas nyob rau hauv kev tshawb fawb ntau yam, thaum lub polymerization degree ntawm microcrystalline cellulose raw khoom yog siab, cov ntsiab lus sulfur (hloov degree) ntawm cov khoom thiab cov fluidity ntawm mortar yog tsawg. Qhov no yog vim: qhov hnyav molecular ntawm cov khoom siv raw yog me me, uas yog qhov tsim nyog rau kev sib xyaw ntawm cov khoom siv raw thiab kev nkag mus ntawm tus neeg sawv cev etherification, yog li txhim kho qib ntawm etherification ntawm cov khoom. Txawm li cas los xij, cov khoom lag luam dej txo tus nqi tsis nce hauv txoj kab ncaj nraim nrog qhov txo qis ntawm cov degree ntawm polymerization ntawm raw cov ntaub ntawv. Cov txiaj ntsig kev sim qhia tau hais tias cov tshuaj khib nyiab ntawm cov cement mortar sib tov nrog SBC npaj los ntawm kev siv microcrystalline cellulose nrog rau qib ntawm polymerization Dp <96 (molecular hnyav <15552) yog ntau dua 180 mm (uas yog ntau dua qhov uas tsis muaj dej reducer) . benchmark fluidity), qhia tias SBC tuaj yeem npaj tau los ntawm kev siv cellulose nrog qhov hnyav ntawm molecular tsawg dua 15552, thiab qee qhov dej txo tus nqi tuaj yeem tau txais; SBC yog npaj los ntawm kev siv microcrystalline cellulose nrog ib tug degree ntawm polymerization ntawm 45 (molecular hnyav: 7290), thiab ntxiv rau cov pob zeb sib tov, qhov ntsuas fluidity ntawm cov mortar yog qhov loj tshaj plaws, yog li nws yog xam tias cov cellulose nrog ib tug degree ntawm polymerization. ntawm txog 45 yog qhov zoo tshaj plaws rau kev npaj ntawm SBC; Thaum lub degree ntawm polymerization ntawm raw cov ntaub ntawv ntau dua 45, lub fluidity ntawm mortar maj mam txo, uas txhais tau hais tias cov dej txo tus nqi txo. Qhov no yog vim hais tias thaum lub luj molecular loj, nyob rau hauv ib tes, lub viscosity ntawm lub sib tov system yuav nce, lub dispersion uniformity ntawm cov cement yuav deteriorated, thiab cov dispersion nyob rau hauv pob zeb yuav qeeb, uas yuav cuam tshuam cov nyhuv dispersion; Ntawm qhov tod tes, thaum qhov hnyav molecular loj, macromolecules ntawm superplasticizer yog nyob rau hauv ib qho kev sib txawv coil conformation, uas yog ib qho nyuaj rau adsorb rau saum npoo ntawm cov cement hais. Tab sis thaum lub degree ntawm polymerization ntawm raw cov ntaub ntawv yog tsawg tshaj li 45, txawm hais tias cov sulfur ntsiab lus (hloov degree) ntawm cov khoom yog loj, fluidity ntawm mortar sib tov kuj pib txo, tab sis qhov txo yog heev me me. Yog vim li cas yog vim li cas thaum lub molecular hnyav ntawm cov dej txo tus neeg saib xyuas me me, txawm hais tias lub molecular diffusion yog ib qho yooj yim thiab muaj wettability zoo, lub adsorption ceev ntawm lub molecule yog loj dua li ntawm cov molecule, thiab cov dej thauj saw yog luv heev, thiab kev sib txhuam ntawm cov khoom yog loj, uas yog teeb meem rau pob zeb. Cov nyhuv dispersion tsis zoo li cov dej reducer nrog qhov hnyav dua molecular. Yog li ntawd, nws yog ib qho tseem ceeb heev kom tswj tau qhov hnyav molecular ntawm npua lub ntsej muag (cellulose ntu) txhawm rau txhim kho kev ua haujlwm ntawm cov dej reducer.

3.3 Cov nyhuv ntawm cov tshuaj tiv thaiv ntawm cov dej-txo kev ua haujlwm ntawm cov khoom

Nws tau pom los ntawm kev sim uas ntxiv rau qib ntawm polymerization ntawm MCC, qhov sib piv ntawm cov tshuaj reactants, cov tshuaj tiv thaiv kub, ua kom cov ntaub ntawv raw, cov khoom sib txuas lub sij hawm, thiab hom suspending tus neeg sawv cev tag nrho cuam tshuam cov dej-txo kev ua tau zoo ntawm cov khoom.

3.3.1 Reactant ratio

(1) Qhov ntau npaum ntawm BS

Raws li cov xwm txheej tau txiav txim los ntawm lwm cov txheej txheem tsis ua haujlwm (lub degree ntawm polymerization ntawm MCC yog 45, n(MCC): n(NaOH) = 1: 2.1, tus neeg sawv cev ncua kev kawm ntawv yog isopropanol, lub sij hawm ua kom cellulose ntawm chav tsev kub yog 2h, synthesis kub yog 80 ° C, thiab lub sij hawm synthesis 5h), los soj ntsuam cov nyhuv ntawm tus nqi ntawm etherification tus neeg sawv cev 1,4-butane sultone (BS) nyob rau theem ntawm kev hloov ntawm butanesulfonic acid pawg ntawm cov khoom thiab cov fluidity ntawm cov khoom. mortar.

Nws tuaj yeem pom tau tias raws li tus nqi ntawm BS nce, qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg thiab fluidity ntawm mortar nce ntau. Thaum qhov sib piv ntawm BS rau MCC nce mus txog 2.2: 1, qhov fluidity ntawm DS thiab mortar ncav cuag qhov siab tshaj plaws. tus nqi, nws tau txiav txim siab tias qhov kev ua haujlwm ntawm cov dej txo qis yog qhov zoo tshaj plaws nyob rau lub sijhawm no. Tus nqi BS txuas ntxiv mus ntxiv, thiab ob qho tib si qib ntawm kev hloov pauv thiab cov kua dej ntawm cov tshuaj khib pib txo qis. Qhov no yog vim tias thaum BS ntau dhau lawm, BS yuav hnov ​​​​mob nrog NaOH los tsim HO-(CH2)4SO3Na. Yog li, daim ntawv no xaiv cov khoom siv zoo tshaj plaws ntawm BS rau MCC li 2.2: 1.

(2) Qhov ntau npaum ntawm NaOH

Raws li cov xwm txheej tau txiav txim los ntawm lwm cov txheej txheem tsis ua haujlwm (qhov degree ntawm polymerization ntawm MCC yog 45, n(BS): n(MCC) = 2.2: 1. Tus neeg sawv cev ncua kev kawm yog isopropanol, lub sijhawm ua kom cellulose ntawm chav tsev kub yog 2h, synthesis kub yog 80 ° C, thiab lub sij hawm synthesis 5h), los soj ntsuam cov nyhuv ntawm sodium hydroxide nyob rau hauv lub degree ntawm kev hloov ntawm butanesulfonic acid pawg nyob rau hauv cov khoom thiab lub fluidity ntawm mortar.

Nws tuaj yeem pom tau tias, nrog qhov nce ntawm qhov txo qis, qhov kev hloov pauv ntawm SBC nce sai, thiab pib txo qis tom qab ncav cuag tus nqi siab tshaj. Qhov no yog vim hais tias, thaum NaOH cov ntsiab lus siab, muaj ntau ntau lub hauv paus dawb hauv lub cev, thiab qhov tshwm sim ntawm cov kev cuam tshuam sab nraud nce, ua rau muaj ntau tus neeg sawv cev etherification (BS) koom nrog cov kev tawm tsam sab nraud, yog li txo qhov kev hloov pauv ntawm sulfonic. acid pawg hauv cov khoom. Nyob rau ntawm qhov kub thiab txias, qhov muaj NaOH ntau dhau yuav ua rau cov cellulose degrade, thiab cov dej txo qhov kev ua tau zoo ntawm cov khoom yuav raug cuam tshuam ntawm qis dua ntawm polymerization. Raws li cov txiaj ntsig kev sim, thaum molar piv ntawm NaOH rau MCC yog li 2.1, qhov kev hloov pauv yog qhov loj tshaj, yog li daim ntawv no txiav txim siab tias molar ratio ntawm NaOH rau MCC yog 2.1: 1.0.

3.3.2 Cov nyhuv ntawm cov tshuaj tiv thaiv kub ntawm cov khoom siv dej-txo kev ua haujlwm

Raws li cov xwm txheej tau txiav txim los ntawm lwm cov txheej txheem tsis ua haujlwm (lub degree ntawm polymerization ntawm MCC yog 45, n(MCC): n(NaOH): n(BS) = 1: 2.1: 2.2, tus neeg sawv cev ncua kev kawm ntawv yog isopropanol, thiab lub sijhawm ua haujlwm ntawm cellulose nyob rau hauv chav tsev kub yog 2h Lub Sij Hawm 5h), qhov cuam tshuam ntawm kev sib txuas ntawm cov tshuaj tiv thaiv kub ntawm qhov kev hloov ntawm butanesulfonic acid pawg hauv cov khoom tau tshawb xyuas.

Nws tuaj yeem pom tau tias thaum cov tshuaj tiv thaiv kub nce ntxiv, sulfonic acid hloov pauv qib DS ntawm SBC maj mam nce, tab sis thaum cov tshuaj tiv thaiv kub siab tshaj 80 ° C, DS qhia txog kev poob qis. Cov tshuaj tiv thaiv etherification ntawm 1,4-butane sultone thiab cellulose yog cov tshuaj tiv thaiv endothermic, thiab ua kom cov tshuaj tiv thaiv kub yog qhov zoo rau cov tshuaj tiv thaiv ntawm etherifying agent thiab cellulose hydroxyl pawg, tab sis nrog qhov kub thiab txias, cov nyhuv ntawm NaOH thiab cellulose maj mam nce. . Nws ua kom muaj zog, ua rau cov cellulose degrade thiab poob tawm, ua rau txo qis hauv qhov hnyav molecular ntawm cellulose thiab tsim cov suab thaj me me. Cov tshuaj tiv thaiv ntawm cov me me molecules nrog etherifying agents yog ib qho yooj yim, thiab ntau etherifying agents yuav tau noj, cuam tshuam cov degree ntawm kev hloov ntawm cov khoom. Yog li, qhov kev tshawb fawb no txiav txim siab tias qhov ntsuas kub zoo tshaj plaws rau cov tshuaj tiv thaiv etherification ntawm BS thiab cellulose yog 80 ℃.

3.3.3 Cov nyhuv ntawm cov tshuaj tiv thaiv lub sijhawm ntawm cov khoom siv dej-txo kev ua haujlwm

Lub sij hawm cov tshuaj tiv thaiv yog muab faib rau hauv chav tsev kub ua kom cov ntaub ntawv raw thiab qhov kub thiab txias synthesis lub sij hawm ntawm cov khoom.

(1) Chav kub ua kom lub sijhawm ntawm cov khoom siv raw

Raws li cov txheej txheem zoo saum toj no (MCC degree ntawm polymerization yog 45, n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, tshem tawm tus neeg sawv cev yog isopropanol, cov tshuaj tiv thaiv kub yog 80 ° C, cov khoom Lub sijhawm ua kom kub tsis tu ncua 5h), tshawb xyuas qhov cuam tshuam ntawm chav tsev kub ua kom lub sijhawm ntawm qhov kev hloov pauv ntawm cov khoom butanesulfonic acid pawg.

Nws tuaj yeem pom tau tias qhov kev hloov pauv ntawm pawg butanesulfonic acid ntawm cov khoom SBC nce ua ntej thiab tom qab ntawd txo qis nrog lub sijhawm ua kom lub sijhawm ntev. Qhov laj thawj kev soj ntsuam tej zaum yuav yog tias nrog kev nce ntawm NaOH lub sijhawm ua haujlwm, kev degradation ntawm cellulose yog qhov hnyav. Txo qhov hnyav molecular ntawm cellulose los tsim cov suab thaj me me. Cov tshuaj tiv thaiv ntawm cov me me molecules nrog etherifying agents yog ib qho yooj yim, thiab ntau etherifying agents yuav tau noj, cuam tshuam cov degree ntawm kev hloov ntawm cov khoom. Yog li, daim ntawv no txiav txim siab tias chav tsev kub ua kom lub sijhawm ntawm cov khoom siv raw yog 2h.

(2) Lub sijhawm khoom sib txuas

Raws li cov txheej txheem zoo tshaj plaws saum toj no, cov txiaj ntsig ntawm kev ua kom lub sijhawm ntawm chav tsev kub ntawm qhov kev hloov pauv ntawm cov khoom butanesulfonic acid pawg tau tshawb xyuas. Nws tuaj yeem pom tau tias nrog lub sijhawm ntev ntawm cov tshuaj tiv thaiv, qib ntawm kev hloov pauv thawj zaug nce, tab sis thaum lub sijhawm tshuaj tiv thaiv mus txog 5h, DS qhia txog kev poob qis. Qhov no muaj feem xyuam rau lub hauv paus dawb tam sim no nyob rau hauv cov tshuaj tiv thaiv etherification ntawm cellulose. Nyob rau ntawm qhov kub thiab txias, qhov ntev ntawm cov tshuaj tiv thaiv lub sij hawm ua rau muaj kev nce qib ntawm alkali hydrolysis ntawm cellulose, shortening ntawm cellulose molecular saw, ib tug txo nyob rau hauv lub molecular yuag ntawm cov khoom, thiab ib tug nce nyob rau hauv cov kev tshwm sim, ua rau muaj kev cuam tshuam ntawm cov cellulose. hloov. degree txo. Hauv qhov kev sim no, lub sijhawm sib xyaw zoo tagnrho yog 5h.

3.3.4 Cov txiaj ntsig ntawm hom kev tshem tawm tus neeg sawv cev ntawm cov dej-txo kev ua haujlwm ntawm cov khoom

Raws li cov txheej txheem zoo tshaj plaws (MCC polymerization degree yog 45, n(MCC): n(NaOH): n(BS) = 1: 2.1: 2.2, lub sijhawm ua kom cov khoom siv raw ntawm chav tsev kub yog 2h, lub sijhawm ua kom kub tsis tu ncua ntawm cov khoom yog 5h, thiab cov synthesis cov tshuaj tiv thaiv kub 80 ℃), feem ntau xaiv isopropanol, ethanol, n-butanol, ethyl acetate thiab roj av ether li suspending agents, thiab sib tham txog lawv lub zog ntawm cov dej-txo kev ua tau zoo ntawm cov khoom.

Obviously, isopropanol, n-butanol thiab ethyl acetate tuaj yeem siv los ua tus neeg sawv cev ncua hauv cov tshuaj tiv thaiv etherification. Lub luag haujlwm ntawm tus neeg sawv cev tshem tawm, ntxiv rau qhov dispersing cov reactants, tuaj yeem tswj qhov kub thiab txias. Cov ntsiab lus kub ntawm isopropanol yog 82.3 ° C, yog li isopropanol yog siv los ua tus neeg sawv cev ncua, qhov ntsuas kub ntawm lub cev tuaj yeem tswj tau nyob ze qhov ntsuas kub zoo tshaj plaws, thiab qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg hauv cov khoom thiab fluidity ntawm cov tshuaj tiv thaiv. mortar yog qhov siab; Thaum lub rhaub dej kub ntawm ethanol siab dhau Tsawg, qhov ntsuas kub tsis ua raws li qhov yuav tsum tau ua, qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg hauv cov khoom thiab fluidity ntawm mortar tsawg; roj av ether tuaj yeem koom nrog hauv cov tshuaj tiv thaiv, yog li tsis muaj cov khoom tawg tuaj yeem tau txais.

4 Kev xaus

(1) Siv paj rwb pulp ua cov khoom siv thawj zaug,microcrystalline cellulose (MCC)Nrog rau qib tsim nyog ntawm polymerization tau npaj, qhib los ntawm NaOH, thiab reacted nrog 1,4-butane sultone los npaj cov dej-soluble butylsulfonic acid Cellulose ether, uas yog, cellulose-raws li dej reducer. Cov qauv ntawm cov khoom yog tus yam ntxwv, thiab nws tau pom tias tom qab cov tshuaj tiv thaiv etherification ntawm cellulose, muaj sulfonic acid pawg ntawm nws cov saw molecular, uas tau hloov mus rau hauv cov qauv amorphous, thiab cov khoom siv dej reducer muaj cov dej zoo solubility;

(2) Los ntawm kev sim, nws pom tias thaum lub degree ntawm polymerization ntawm microcrystalline cellulose yog 45, cov dej-txo kev ua tau zoo ntawm cov khoom tau txais yog qhov zoo tshaj plaws; Nyob rau hauv cov xwm txheej uas lub degree ntawm polymerization ntawm raw cov ntaub ntawv yog txiav txim, qhov ratio ntawm reactants yog n(MCC): n(NaOH): n(BS) = 1:2.1:2.2, lub sij hawm ua kom cov ntaub ntawv raw ntawm chav tsev kub yog 2h, cov khoom sib txuas kub yog 80 ° C, thiab lub sij hawm synthesis yog 5h. Kev ua haujlwm dej yog qhov zoo tshaj plaws.