Kev Tsim Khoom thiab Kev Txheeb Xyuas ntawm Butane Sulfonate Cellulose Ether Dej Txo

Siv cov microcrystalline cellulose (MCC) uas muaj qib polymerization tau los ntawm acid hydrolysis ntawm cellulose paj rwb pulp ua raw khoom. Nyob rau hauv kev ua haujlwm ntawm sodium hydroxide, nws tau reacted nrog 1,4-butane sultone (BS) kom tau txais cellulose butyl sulfonate (SBC) dej reducer nrog zoo solubility tau tsim. Cov qauv khoom tau piav qhia los ntawm infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD) thiab lwm yam kev tshuaj xyuas, thiab kawm txog qib polymerization, raw khoom piv, thiab kev tshuaj ntsuam ntawm MCC. Cov teebmeem ntawm cov txheej txheem synthetic xws li kub, lub sijhawm tshuaj ntsuam, thiab hom suspensioning agent rau kev ua haujlwm txo dej ntawm cov khoom. Cov txiaj ntsig qhia tau tias: thaum qib polymerization ntawm cov khoom siv raw MCC yog 45, qhov sib piv ntawm cov tshuaj reactants yog: AGU (cellulose glucoside unit): n (NaOH): n (BS) = 1.0: 2.1: 2.2, Tus neeg sawv cev ncua yog isopropanol, lub sijhawm ua haujlwm ntawm cov khoom siv raw ntawm chav tsev kub yog 2 teev, thiab lub sijhawm tsim cov khoom yog 5 teev. Thaum qhov kub yog 80 ° C, cov khoom tau txais muaj qib siab tshaj plaws ntawm kev hloov pauv ntawm butanesulfonic acid pawg, thiab cov khoom muaj kev ua tau zoo tshaj plaws ntawm kev txo dej.

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

1,Kev Taw Qhia

Cov tshuaj ua kom cov pob zeb ua kom zoo nkauj yog ib qho tseem ceeb ntawm cov pob zeb niaj hnub no. Vim yog cov tshuaj ua kom cov dej tsis sib xyaw ua ke, nws ua rau cov pob zeb ua haujlwm tau zoo, ruaj khov thiab muaj zog. Cov tshuaj ua kom cov dej tsis sib xyaw ua ke uas siv dav dav feem ntau muaj cov hauv qab no: naphthalene-based water reducer (SNF), sulfonated melamine resin-based water-reducer (SMF), sulfamate-based water-reducer (ASP), modified Lignosulfonate superplasticizer (ML), thiab polycarboxylate superplasticizer (PC), uas tam sim no tau tshawb fawb ntau dua. Thaum tshuaj xyuas cov txheej txheem tsim cov tshuaj ua kom cov dej tsis sib xyaw ua ke, feem ntau ntawm cov tshuaj ua kom cov dej tsis sib xyaw ua ke siv formaldehyde nrog cov ntxhiab tsw qab heev ua cov khoom siv raw rau polycondensation reaction, thiab cov txheej txheem sulfonation feem ntau yog ua nrog fuming sulfuric acid lossis concentrated sulfuric acid. Qhov no yuav ua rau muaj kev cuam tshuam tsis zoo rau cov neeg ua haujlwm thiab ib puag ncig, thiab tseem yuav tsim cov khib nyiab thiab cov kua khib nyiab ntau, uas tsis zoo rau kev txhim kho kom ruaj khov; txawm li cas los xij, txawm hais tias polycarboxylate dej reducers muaj qhov zoo ntawm kev poob me me ntawm cov pob zeb dhau sijhawm, cov tshuaj tsawg, ntws zoo Nws muaj qhov zoo ntawm qhov ceev siab thiab tsis muaj cov tshuaj lom xws li formaldehyde, tab sis nws nyuaj rau txhawb nws hauv Suav teb vim yog tus nqi siab. Los ntawm kev tshuaj xyuas ntawm qhov chaw ntawm cov khoom siv raw, nws tsis nyuaj rau pom tias feem ntau ntawm cov dej reducers saum toj no yog synthesized raws li cov khoom lag luam petrochemical / by-products, thaum roj av, ua cov khoom siv tsis rov ua dua tshiab, yog qhov tsawg zuj zus thiab nws tus nqi pheej yig nce ntxiv. Yog li ntawd, yuav ua li cas siv cov khoom siv rov ua dua tshiab pheej yig thiab muaj ntau yam ua cov khoom siv raw los tsim cov khoom siv superplasticizers ua haujlwm siab tshiab tau dhau los ua qhov kev tshawb fawb tseem ceeb rau cov khoom siv superplasticizers.

Cellulose yog ib qho macromolecule linear uas tsim los ntawm kev 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 qhov reactivity. Hauv daim ntawv no, cellulose paj rwb pulp tau siv ua cov khoom siv raw thawj zaug, thiab tom qab acid hydrolysis kom tau txais microcrystalline cellulose nrog qib polymerization tsim nyog, nws tau qhib los ntawm sodium hydroxide thiab reacted nrog 1,4-butane sultone los npaj butyl sulfonate Acid cellulose ether superplasticizer, thiab cov yam ntxwv cuam tshuam ntawm txhua qhov kev cuam tshuam tau tham txog.

2. Kev sim

2.1 Cov khoom siv raw

Cov paj rwb cellulose, qib polymerization 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 cov cement Portland ib txwm muaj, Urumqi Muab los ntawm lub Hoobkas cement; Tuam Tshoj ISO tus qauv 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 txhua yam ntshiab analytically, muaj nyob rau hauv kev lag luam.

2.2 Txoj kev sim

Hnyav ib qho ntawm cov paj rwb pulp thiab zom nws kom zoo, muab tso rau hauv lub raj mis peb-caj dab, ntxiv qee qhov concentration ntawm dilute hydrochloric acid, do kom sov thiab hydrolyze rau ib lub sijhawm, txias rau chav sov, lim, ntxuav nrog dej kom txog thaum tsis muaj teeb meem, thiab nqus tsev kom qhuav ntawm 50 ° C kom tau txais Tom qab muaj cov khoom siv microcrystalline cellulose raw 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, dai nws nrog tus neeg sawv cev dai 10 npaug nws qhov hnyav, ntxiv qee qhov sodium hydroxide aqueous kua hauv qab do. Do thiab ua kom sov ntawm chav sov rau ib lub sijhawm, ntxiv qhov suav ntawm 1,4-butane sultone (BS), cua sov mus txog qhov kub ntawm cov tshuaj tiv thaiv, tshuaj tiv thaiv ntawm qhov kub tas li rau ib lub sijhawm, txias cov khoom mus rau chav sov, thiab tau txais cov khoom nyoos los ntawm kev nqus lim. Yaug nrog dej thiab methanol rau 3 zaug, thiab lim nrog nqus kom tau txais cov khoom kawg, uas yog cellulose butylsulfonate dej txo (SBC).

2.3 Kev tshuaj xyuas khoom thiab kev piav qhia

2.3.1 Kev txiav txim siab ntawm cov ntsiab lus sulfur ntawm cov khoom thiab kev xam qib ntawm kev hloov pauv

Lub FLASHEA-PE2400 elemental analyzer tau siv los ua qhov kev tshuaj xyuas elemental ntawm cov khoom qhuav cellulose butyl sulfonate dej txo kom paub txog cov ntsiab lus sulfur.

2.3.2 Kev txiav txim siab ntawm qhov fluidity ntawm mortar

Ntsuas raws li 6.5 hauv GB8076-2008. Uas yog, ua ntej ntsuas cov dej/cement/txheej txheem xuab zeb sib xyaw ntawm NLD-3 cement mortar fluidity tester thaum lub cheeb nthuav dav yog (180 ± 2) hli. cement, qhov ntsuas dej siv yog 230g), thiab tom qab ntawd ntxiv cov tshuaj txo dej uas nws qhov hnyav yog 1% ntawm cov cement pawg rau dej, raws li cement/dej txo tus neeg sawv cev/dej txheem/xuab zeb txheem = 450g/4.5g/230 g/ Qhov piv ntawm 1350 g yog muab tso rau hauv JJ-5 cement mortar mixer thiab do kom sib npaug, thiab qhov dav nthuav dav ntawm cov mortar fluidity tester raug ntsuas, uas yog qhov ntsuas mortar fluidity.

2.3.3 Kev piav qhia txog khoom

Cov qauv tau piav qhia los ntawm FT-IR siv EQUINOX 55 hom Fourier transform infrared spectrometer ntawm Bruker Company; H NMR spectrum ntawm cov qauv tau piav qhia los ntawm INOVA ZAB-HS plow superconducting nuclear magnetic resonance instrument ntawm Varian Company; Cov morphology ntawm cov khoom tau pom nyob rau hauv lub tshuab microscope; XRD kev tshuaj xyuas tau ua tiav rau 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 ntawm kev piav qhia tus cwj pwm

3.1.1 Cov txiaj ntsig ntawm kev piav qhia txog FT-IR

Kev tshuaj xyuas infrared tau ua tiav rau ntawm cov khoom siv raw microcrystalline cellulose nrog qib polymerization Dp = 45 thiab cov khoom SBC synthesized los ntawm cov khoom siv raw no. Txij li thaum lub ncov nqus ntawm SC thiab SH tsis muaj zog heev, lawv tsis haum rau kev txheeb xyuas, thaum S = O muaj lub ncov nqus muaj zog. Yog li ntawd, seb puas muaj pawg sulfonic acid hauv cov qauv molecular tuaj yeem txiav txim siab los ntawm kev lees paub qhov muaj nyob ntawm S = O ncov. Nws yog qhov tseeb, hauv cellulose spectrum, muaj lub ncov nqus muaj zog ntawm tus lej nthwv dej ntawm 3344 cm-1, uas yog vim qhov hydroxyl ncab vibration ncov hauv cellulose; lub ncov nqus muaj zog ntawm tus lej nthwv dej ntawm 2923 cm-1 yog lub ncov ncab vibration ntawm methylene (-CH2). Lub ncov vibration; cov koob ntawm cov bands tsim los ntawm 1031, 1051, 1114, thiab 1165cm-1 qhia txog lub ncov nqus ntawm hydroxyl ncab vibration thiab lub ncov nqus ntawm ether bond (COC) bending vibration; tus lej nthwv dej 1646cm-1 qhia txog cov hydrogen uas tsim los ntawm hydroxyl thiab dej dawb Lub ncov nqus ntawm daim ntawv cog lus; cov kab ntawm 1432 ~ 1318cm-1 qhia txog qhov muaj nyob ntawm cov qauv siv lead ua cellulose. Hauv IR spectrum ntawm SBC, qhov muaj zog ntawm cov kab 1432 ~ 1318cm-1 tsis muaj zog; thaum lub zog ntawm qhov nqus ntawm 1653 cm-1 nce, qhia tias lub peev xwm los tsim cov ntawv cog lus hydrogen tau muaj zog; 1040, 605cm-1 zoo li muaj zog dua Cov ncov nqus, thiab ob qho no tsis tau cuam tshuam rau hauv cov spectrum infrared ntawm cellulose, tus qub yog qhov nqus ntawm S = O daim ntawv cog lus, thiab qhov kawg yog qhov nqus ntawm SO daim ntawv cog lus. Raws li kev tshuaj xyuas saum toj no, nws tuaj yeem pom tias tom qab cov tshuaj tiv thaiv etherification ntawm cellulose, muaj cov pab pawg sulfonic acid hauv nws cov saw hlau molecular.

3.1.2 Cov txiaj ntsig ntawm kev piav qhia txog H NMR

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

3.1.3 Cov txiaj ntsig ntawm kev piav qhia txog SEM

Kev soj ntsuam SEM ntawm cellulose paj rwb pulp, microcrystalline cellulose thiab cov khoom cellulose butylsulfonate. Los ntawm kev tshuaj xyuas cov txiaj ntsig SEM ntawm cellulose paj rwb pulp, microcrystalline cellulose thiab cov khoom cellulose butanesulfonate (SBC), nws pom tias microcrystalline cellulose tau txais tom qab hydrolysis nrog HCL tuaj yeem hloov pauv cov qauv ntawm cellulose fibers. Cov qauv fibrous raug rhuav tshem, thiab cov cellulose agglomerated zoo tau txais. SBC tau txais los ntawm kev cuam tshuam ntxiv nrog BS tsis muaj cov qauv fibrous thiab feem ntau hloov mus rau hauv cov qauv amorphous, uas tau txais txiaj ntsig zoo rau nws cov yaj hauv dej.

3.1.4 Cov txiaj ntsig ntawm kev piav qhia XRD

Qhov crystallinity ntawm cellulose thiab nws cov derivatives yog hais txog feem pua ​​ntawm thaj chaw crystalline uas tsim los ntawm cov qauv cellulose hauv tag nrho. Thaum cellulose thiab nws cov derivatives dhau los ntawm kev tshuaj lom neeg, cov hydrogen bonds hauv molecule thiab ntawm cov molecules raug rhuav tshem, thiab thaj chaw crystalline yuav dhau los ua thaj chaw amorphous, yog li txo qhov crystallinity. Yog li ntawd, qhov kev hloov pauv hauv crystallinity ua ntej thiab tom qab kev tshuaj ntsuam yog qhov ntsuas ntawm cellulose Ib qho ntawm cov qauv los koom nrog hauv kev teb lossis tsis. XRD kev tshuaj xyuas tau ua rau microcrystalline cellulose thiab cov khoom cellulose butanesulfonate. Nws tuaj yeem pom los ntawm kev sib piv tias tom qab etherification, crystallinity hloov pauv tseem ceeb, thiab cov khoom tau hloov pauv tag nrho mus rau hauv cov qauv amorphous, yog li nws tuaj yeem yaj hauv dej.

3.2 Qhov cuam tshuam ntawm qib polymerization ntawm cov khoom siv raw rau kev ua haujlwm txo dej ntawm cov khoom

Qhov fluidity ntawm cov mortar ncaj qha qhia txog kev ua haujlwm txo dej ntawm cov khoom, thiab cov sulfur cov ntsiab lus ntawm cov khoom yog ib qho ntawm cov yam tseem ceeb tshaj plaws uas cuam tshuam rau qhov fluidity ntawm cov mortar. Qhov fluidity ntawm cov mortar ntsuas qhov kev ua haujlwm txo dej ntawm cov khoom.

Tom qab hloov cov xwm txheej hydrolysis reaction los npaj MCC nrog ntau qib polymerization, raws li txoj kev saum toj no, xaiv qee cov txheej txheem synthesis los npaj cov khoom SBC, ntsuas cov ntsiab lus sulfur los xam cov khoom hloov pauv degree, thiab ntxiv cov khoom SBC rau hauv dej / cement / txheem xuab zeb sib tov system Ntsuas qhov fluidity ntawm mortar.

Los ntawm cov txiaj ntsig sim, nws tuaj yeem pom tias nyob rau hauv qhov kev tshawb fawb, thaum qib polymerization ntawm cov khoom siv microcrystalline cellulose raw khoom siab, cov ntsiab lus sulfur (hloov chaw degree) ntawm cov khoom thiab cov fluidity ntawm cov mortar qis. Qhov no yog vim: qhov hnyav molecular ntawm cov khoom siv raw yog me me, uas yog qhov zoo rau kev sib xyaw ua ke 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 dej txo qis ntawm cov khoom tsis nce siab hauv kab ncaj nraim nrog qhov txo qis ntawm qib polymerization ntawm cov khoom siv raw. Cov txiaj ntsig sim qhia tau hais tias cov kua dej ntawm cov cement mortar sib xyaw nrog SBC npaj los ntawm kev siv microcrystalline cellulose nrog qib polymerization Dp <96 (molecular weight <15552) yog ntau dua 180 hli (uas yog ntau dua li qhov tsis muaj dej reducer). benchmark fluidity), qhia tias SBC tuaj yeem npaj los ntawm kev siv cellulose nrog qhov hnyav molecular tsawg dua 15552, thiab qee qhov dej txo qis tuaj yeem tau txais; SBC yog npaj los ntawm kev siv microcrystalline cellulose nrog qib polymerization ntawm 45 (molecular hnyav: 7290), thiab ntxiv rau cov pob zeb sib xyaw, qhov ntsuas fluidity ntawm cov mortar yog qhov loj tshaj plaws, yog li nws tau txiav txim siab tias cellulose nrog qib polymerization ntawm txog 45 yog qhov tsim nyog tshaj plaws rau kev npaj SBC; thaum qib polymerization ntawm cov khoom siv raw yog ntau dua 45, qhov fluidity ntawm cov mortar maj mam txo qis, uas txhais tau tias tus nqi txo dej txo qis. Qhov no yog vim tias thaum qhov hnyav molecular loj, ntawm ib sab tes, qhov viscosity ntawm qhov sib xyaw system yuav nce ntxiv, qhov sib txawv ntawm cov cement yuav raug puas tsuaj, thiab qhov sib txawv hauv cov pob zeb yuav qeeb, uas yuav cuam tshuam rau qhov cuam tshuam dispersion; ntawm qhov tod tes, thaum qhov hnyav molecular loj, Cov macromolecules ntawm superplasticizer yog nyob rau hauv ib qho random coil conformation, uas yog qhov nyuaj rau adsorb ntawm qhov chaw ntawm cov cement particles. Tab sis thaum qib polymerization ntawm cov khoom siv raw tsawg dua 45, txawm hais tias cov ntsiab lus sulfur (hloov chaw degree) ntawm cov khoom loj heev, qhov fluidity ntawm cov mortar sib tov kuj pib txo qis, tab sis qhov txo qis yog me heev. Qhov laj thawj yog tias thaum qhov hnyav molecular ntawm tus neeg sawv cev txo dej me me, txawm hais tias qhov sib txawv molecular yooj yim thiab muaj qhov zoo wettability, qhov adsorption ceev ntawm lub molecule yog loj dua li ntawm lub molecule, thiab cov saw hlau thauj dej luv heev, thiab kev sib txhuam ntawm cov khoom me me yog loj, uas yog teeb meem rau cov pob zeb. Cov nyhuv dispersion tsis zoo li ntawm cov dej reducer nrog qhov hnyav molecular loj dua. Yog li ntawd, nws yog ib qho tseem ceeb heev kom tswj tau qhov hnyav molecular ntawm lub ntsej muag npua (cellulose ntu) kom zoo kom txhim kho kev ua tau zoo ntawm cov dej reducer.

3.3 Cov nyhuv ntawm cov xwm txheej tshuaj tiv thaiv rau kev ua haujlwm txo dej ntawm cov khoom

Los ntawm kev sim, nws pom tau tias ntxiv rau qib polymerization ntawm MCC, qhov sib piv ntawm cov tshuaj reactants, qhov kub ntawm cov tshuaj tiv thaiv, kev ua haujlwm ntawm cov khoom siv raw, lub sijhawm tsim cov khoom, thiab hom tshuaj ncua tag nrho cuam tshuam rau kev ua haujlwm txo dej ntawm cov khoom.

3.3.1 Qhov sib piv ntawm cov tshuaj reactant

(1) Cov tshuaj ntawm BS

Nyob rau hauv cov xwm txheej txiav txim siab los ntawm lwm cov txheej txheem txheej txheem (qib ntawm polymerization ntawm MCC yog 45, n (MCC): n (NaOH) = 1: 2.1, tus neeg sawv cev ncua yog isopropanol, lub sijhawm ua haujlwm ntawm cellulose ntawm chav tsev kub yog 2 teev, qhov kub ntawm kev tsim khoom yog 80 ° C, thiab lub sijhawm tsim khoom 5 teev), los tshawb xyuas qhov cuam tshuam ntawm qhov ntau ntawm tus neeg sawv cev etherification 1,4-butane sultone (BS) ntawm qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg ntawm cov khoom thiab qhov fluidity ntawm cov mortar.

Pom tau tias thaum BS ntau ntxiv, qib kev hloov pauv ntawm cov pab pawg butanesulfonic acid thiab qhov fluidity ntawm cov mortar nce ntxiv ntau heev. Thaum qhov piv ntawm BS rau MCC ncav cuag 2.2: 1, qhov fluidity ntawm DS thiab cov mortar ncav cuag qhov siab tshaj plaws. tus nqi, nws raug suav hais tias qhov kev ua haujlwm txo dej yog qhov zoo tshaj plaws rau lub sijhawm no. Tus nqi BS txuas ntxiv nce ntxiv, thiab ob qho tib si qib kev hloov pauv thiab qhov fluidity ntawm cov mortar pib txo qis. Qhov no yog vim tias thaum BS ntau dhau, BS yuav cuam tshuam nrog NaOH los tsim HO-(CH2)4SO3Na. Yog li ntawd, daim ntawv no xaiv qhov piv ntawm cov khoom siv zoo tshaj plaws ntawm BS rau MCC raws li 2.2: 1.

(2) Cov tshuaj NaOH

Nyob rau hauv cov xwm txheej txiav txim siab los ntawm lwm cov txheej txheem txheej txheem (qib ntawm polymerization ntawm MCC yog 45, n (BS): n (MCC) = 2.2: 1. Tus neeg sawv cev ncua yog isopropanol, lub sijhawm ua haujlwm ntawm cellulose ntawm chav tsev kub yog 2 teev, qhov kub ntawm kev tsim khoom yog 80 ° C, thiab lub sijhawm tsim khoom 5 teev), los tshawb xyuas qhov cuam tshuam ntawm qhov ntau ntawm sodium hydroxide rau qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg hauv cov khoom thiab qhov fluidity ntawm cov mortar.

Nws tuaj yeem pom tias, nrog rau kev nce ntawm qhov txo qis, qib ntawm kev hloov pauv ntawm SBC nce sai, thiab pib txo qis tom qab mus txog qhov siab tshaj plaws. Qhov no yog vim tias, thaum cov ntsiab lus NaOH siab, muaj ntau lub hauv paus dawb hauv lub cev, thiab qhov tshwm sim ntawm cov tshuaj tiv thaiv sab nraud nce ntxiv, ua rau muaj ntau tus neeg sawv cev etherification (BS) koom nrog cov tshuaj tiv thaiv sab nraud, yog li txo qhov qib ntawm kev hloov pauv ntawm cov pab pawg sulfonic acid hauv cov khoom. Ntawm qhov kub siab dua, qhov muaj ntau dhau NaOH kuj tseem yuav ua rau cov cellulose puas tsuaj, thiab kev ua haujlwm txo dej ntawm cov khoom yuav raug cuam tshuam ntawm qib qis dua ntawm polymerization. Raws li cov txiaj ntsig sim, thaum qhov piv ntawm NaOH rau MCC yog li 2.1, qib ntawm kev hloov pauv yog qhov loj tshaj plaws, yog li daim ntawv no txiav txim siab tias qhov piv ntawm NaOH rau MCC yog 2.1: 1.0.

3.3.2 Cov nyhuv ntawm qhov kub thiab txias ntawm cov tshuaj tiv thaiv rau kev ua haujlwm ntawm cov khoom txo dej

Nyob rau hauv cov xwm txheej txiav txim siab los ntawm lwm cov txheej txheem txheej txheem (qib ntawm polymerization ntawm MCC yog 45, n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, tus neeg sawv cev ncua yog isopropanol, thiab lub sijhawm ua haujlwm ntawm cellulose ntawm chav tsev kub yog 2 teev. Lub sijhawm 5 teev), qhov cuam tshuam ntawm qhov kub ntawm kev sib xyaw ua ke rau qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg hauv cov khoom tau tshawb xyuas.

Nws tuaj yeem pom tias thaum qhov kub ntawm cov tshuaj tiv thaiv nce ntxiv, qib sulfonic acid hloov DS ntawm SBC maj mam nce ntxiv, tab sis thaum qhov kub ntawm cov tshuaj tiv thaiv tshaj 80 ° C, DS qhia txog qhov sib txawv qis. Qhov kev sib xyaw ua ke ntawm 1,4-butane sultone thiab cellulose yog qhov kev sib xyaw ua ke endothermic, thiab kev nce qhov kub ntawm cov tshuaj tiv thaiv yog qhov zoo rau qhov kev sib xyaw ua ke ntawm tus neeg sawv cev etherifying thiab cellulose hydroxyl pawg, tab sis nrog rau qhov kub nce ntxiv, qhov cuam tshuam ntawm NaOH thiab cellulose maj mam nce ntxiv. Nws ua rau muaj zog, ua rau cellulose puas tsuaj thiab poob tawm, ua rau qhov hnyav molecular ntawm cellulose txo qis thiab tsim cov suab thaj molecular me me. Qhov kev sib xyaw ua ke ntawm cov molecules me me nrog cov neeg sawv cev etherifying yog qhov yooj yim, thiab ntau tus neeg sawv cev etherifying yuav raug noj, cuam tshuam rau qib ntawm kev hloov pauv ntawm cov khoom. Yog li ntawd, daim ntawv no xav tias qhov kub ntawm cov tshuaj tiv thaiv zoo tshaj plaws rau qhov kev sib xyaw ua ke ntawm BS thiab cellulose yog 80 ℃.

3.3.3 Cov nyhuv ntawm lub sijhawm teb rau kev ua haujlwm txo dej ntawm cov khoom

Lub sijhawm ua haujlwm yog muab faib ua chav sov ua kom cov khoom siv raw ua haujlwm thiab lub sijhawm ua kom cov khoom sib xyaw ua ke tas li.

(1) Lub sijhawm ua kom sov ntawm chav tsev ntawm cov khoom siv raw

Nyob rau hauv cov txheej txheem zoo tshaj plaws saum toj no (MCC degree ntawm polymerization yog 45, n(MCC):n(NaOH):n(BS)=1:2.1:2.2, tus neeg sawv cev ncua yog isopropanol, qhov kub ntawm cov tshuaj synthesis yog 80°C, cov khoom kub tas li synthesis lub sijhawm 5 teev), tshawb xyuas qhov cuam tshuam ntawm lub sijhawm ua haujlwm kub hauv chav rau qib ntawm kev hloov pauv ntawm cov khoom butanesulfonic acid pawg.

Nws tuaj yeem pom tias qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg ntawm cov khoom SBC nce ua ntej thiab tom qab ntawd txo qis nrog lub sijhawm ntev ntawm lub sijhawm ua haujlwm. Qhov laj thawj ntawm kev tshuaj xyuas yuav yog tias nrog kev nce ntawm NaOH lub sijhawm ua haujlwm, qhov kev puas tsuaj ntawm cellulose yog qhov loj heev. Txo qhov hnyav molecular ntawm cellulose los tsim cov suab thaj molecular me me. Cov tshuaj tiv thaiv ntawm cov molecules me me nrog cov neeg sawv cev etherifying yog qhov yooj yim, thiab ntau tus neeg sawv cev etherifying yuav raug noj, cuam tshuam rau qib ntawm kev hloov pauv ntawm cov khoom. Yog li ntawd, daim ntawv no xav tias lub sijhawm ua haujlwm hauv chav sov ntawm cov khoom siv raw yog 2 teev.

(2) Lub sijhawm tsim khoom

Nyob rau hauv cov txheej txheem zoo tshaj plaws saum toj no, qhov cuam tshuam ntawm lub sijhawm ua haujlwm ntawm chav tsev kub rau qib ntawm kev hloov pauv ntawm cov khoom butanesulfonic acid pawg tau tshawb xyuas. Nws tuaj yeem pom tias nrog lub sijhawm ntev ntawm lub sijhawm teb, qib ntawm kev hloov pauv thawj zaug nce, tab sis thaum lub sijhawm teb mus txog 5 teev, DS qhia txog kev poob qis. Qhov no yog cuam tshuam nrog lub hauv paus dawb uas muaj nyob rau hauv cov tshuaj tiv thaiv etherification ntawm cellulose. Thaum kub dua, lub sijhawm ntev ntawm lub sijhawm teb ua rau muaj kev nce qib ntawm alkali hydrolysis ntawm cellulose, luv luv ntawm cov saw hlau molecular cellulose, txo qis hauv qhov hnyav molecular ntawm cov khoom, thiab nce ntxiv ntawm cov tshuaj tiv thaiv sab, ua rau muaj kev hloov pauv. degree txo qis. Hauv qhov kev sim no, lub sijhawm tsim khoom zoo tagnrho yog 5 teev.

3.3.4 Qhov cuam tshuam ntawm hom tshuaj uas ua rau cov khoom tsis lo rau dej

Nyob rau hauv 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 haujlwm ntawm cov khoom siv raw ntawm chav tsev kub yog 2 teev, lub sijhawm ua kom sov tas li ntawm cov khoom yog 5 teev, thiab qhov kub ntawm kev ua kom sov 80 ℃), xaiv isopropanol, ethanol, n-butanol, ethyl acetate thiab roj av ether ua cov neeg sawv cev, thiab tham txog lawv cov kev cuam tshuam rau kev ua haujlwm txo dej ntawm cov khoom.

Nws yog qhov tseeb tias isopropanol, n-butanol thiab ethyl acetate siv tau ua tus neeg sawv cev rau kev ncua hauv qhov kev sib xyaw ua ke no. Lub luag haujlwm ntawm tus neeg sawv cev rau kev ncua, ntxiv rau kev faib cov tshuaj reactants, tuaj yeem tswj qhov kub ntawm cov tshuaj tiv thaiv. Lub ntsiab lus kub ntawm isopropanol yog 82.3 ° C, yog li isopropanol siv ua tus neeg sawv cev rau kev ncua, qhov kub ntawm lub kaw lus tuaj yeem tswj tau ze rau qhov kub ntawm cov tshuaj tiv thaiv zoo tshaj plaws, thiab qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg hauv cov khoom thiab qhov fluidity ntawm cov mortar yog qhov siab heev; thaum lub ntsiab lus kub ntawm ethanol siab dhau qis, qhov kub ntawm cov tshuaj tiv thaiv tsis ua tau raws li qhov yuav tsum tau ua, qib ntawm kev hloov pauv ntawm butanesulfonic acid pawg hauv cov khoom thiab qhov fluidity ntawm cov mortar yog qis; roj av ether tuaj yeem koom nrog hauv qhov kev sib xyaw, yog li tsis muaj cov khoom tawg tuaj yeem tau txais.

4 Xaus Lus

(1) Siv cov paj rwb pulp ua cov khoom siv raw thawj zaug,microcrystalline cellulose (MCC)nrog rau qib polymerization tsim nyog tau npaj, ua haujlwm los ntawm NaOH, thiab reacted nrog 1,4-butane sultone los npaj cov dej-soluble butylsulfonic acid Cellulose ether, uas yog, cellulose-based dej reducer. Cov qauv ntawm cov khoom tau piav qhia, thiab nws tau pom tias tom qab etherification reaction ntawm cellulose, muaj sulfonic acid pawg ntawm nws cov saw molecular, uas tau hloov mus ua ib qho qauv amorphous, thiab cov dej reducer khoom muaj dej zoo solubility;

(2) Los ntawm kev sim, nws pom tias thaum qib polymerization ntawm microcrystalline cellulose yog 45, qhov kev ua tau zoo ntawm cov khoom tau txais yog qhov zoo tshaj plaws; nyob rau hauv qhov xwm txheej uas qib polymerization ntawm cov ntaub ntawv raw tau txiav txim siab, qhov piv ntawm reactants yog n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, lub sijhawm ua haujlwm ntawm cov ntaub ntawv raw ntawm chav tsev kub yog 2 teev, qhov kub ntawm cov khoom synthesis yog 80 ° C, thiab lub sijhawm synthesis yog 5 teev. Kev ua tau zoo ntawm dej yog qhov zoo tshaj plaws.