Qalabaynta iyo Sifada Butane Sulfonate Cellulose Ether Biyo Yareeyaha

Microcrystalline cellulose (MCC) oo leh shahaado qeexan oo polymerization ah oo laga helay hydrolysis acid ee saxarka suufka cellulose ayaa loo isticmaalay walxo ceeriin ah. Marka loo eego firfircoonida sodium hydroxide, waxaa lagu falceliyay 1,4-butane sultone (BS) si loo helo biyo yareeya A cellulose butyl sulfonate (SBC) oo leh milmi biyo wanaagsan ayaa la sameeyay. Qaab dhismeedka wax soo saarka ayaa lagu gartaa infrared spectroscopy (FT-IR), nukliyeerka magnetic resonance spectroscopy (NMR), iskaanka mikroskoobyada elektarooniga ah (SEM), raajada diffraction (XRD) iyo hababka kale ee falanqaynta, iyo shahaadada polymerization, saamiga alaabta ceeriin, iyo falcelinta MCC ayaa la baaray. Saamaynta xaaladaha habka dardargelinta sida heerkulka, wakhtiga falcelinta, iyo nooca wakiilka hakinta ee waxqabadka-yaraynta biyaha ee alaabta. Natiijooyinku waxay muujinayaan in: marka heerka polymerization ee alaabta ceeriin ee MCC ay tahay 45, saamiga baaxadda ee fal-celiyeyaasha waa: AGU (unug glucoside cellulose): n (NaOH): n (BS) = 1.0: 2.1: 2.2, Wakiilka joojinta waa isopropanol, wakhtiga firfircoonida walxaha ceeriin ee heerkulka qolka waa 2 h, iyo wakhtiga isku-darka alaabtu waa 5 saacadood. Marka heerkulku yahay 80 ° C, badeecada la helay ayaa leh heerka ugu sarreeya ee beddelka kooxaha butanesulfonic acid, badeecaduna waxay leedahay waxqabadka ugu wanaagsan ee yaraynta biyaha.

Erayada muhiimka ah:cellulose; butylsulfonate cellulose; wakiilka biyaha dhimaya; waxqabadka yaraynta biyaha

1,Hordhac

Superplasticizer-ka la taaban karo waa mid ka mid ah qaybaha lagama maarmaanka ah ee shubka casriga ah. Waa si sax ah sababtoo ah muuqaalka wakiilka yaraynta biyaha in la dammaanad qaadi karo kartida sare ee shaqada, adkeysiga wanaagsan iyo xitaa xoogga sare ee shubka. Biyo yareeyaha waxtarka sare leh ee hadda aadka loo isticmaalo waxaa ka mid ah qaybahan soo socda: Biyo yareeyaha ku salaysan naphthalene (SNF), biyo yareeya resin-kusalaysan melamine (SMF), biyo yareeyaha sulfmate-ku salaysan (ASP), Lignosulfonate superplasticizer oo la beddelay ML), iyo polycarboxylate superplasticizer (PC), kaas oo hadda si firfircoon loo baaray. Falanqaynta habka isku dhafan ee biyo-dhimiyeyaasha, badi dhaqameedyadii hore ee yareeyayaasha biyaha kondensate waxay isticmaalaan formaldehyde oo leh ur udgoon xooggan sida walxo ceeriin ah oo loogu talagalay falcelinta polycondensation, iyo habka sulfonation-ka waxaa guud ahaan lagu fuliyaa qiiqa qiiqa ah ee sulfuric acid ama sulfuric acid. Tani waxay si lama huraan ah u keeni doontaa saameyn xun shaqaalaha iyo deegaanka ku xeeran, waxayna sidoo kale dhalin doontaa xaddi badan oo haraaga qashinka ah iyo dareeraha wasakhda ah, taas oo aan ku habboonayn horumar waara; si kastaba ha ahaatee, inkastoo polycarboxylate biyaha yareeyayaasha ay leeyihiin faa'iidooyinka khasaaraha yar ee la taaban karo waqti ka dib, qiyaasta hooseeya, socodka wanaagsan Waxay leedahay faa'iidooyinka cufnaanta sare iyo ma jiraan walxo sun ah sida formaldehyde, laakiin way adagtahay in lagu dhiirrigeliyo Shiinaha sababtoo ah sare u kaca. qiimaha. Marka la eego falanqaynta ilaha alaabta ceeriin, ma adka in la ogaado in badi biyaha yareeya ee kor ku xusan ay yihiin kuwo isku dhafan oo ku salaysan wax soo saarka petrochemical / alaabta, halka batroolka, oo ah kheyraad aan la cusboonaysiin karin, uu sii kordhayo yaraanta iyo qiimihiisu si joogto ah ayuu kor ugu kacayaa. Sidaa darteed, sida loo isticmaalo kheyraadka dabiiciga ah ee raqiis ah oo badan oo la cusboonaysiin karo sida alaabta ceeriin si loo horumariyo wax-qabadka sare ee superplasticizers-ka cusub ayaa noqday jihada cilmi-baarista muhiimka ah ee superplasticizers la taaban karo.

Cellulose waa macromolecule toosan oo la sameeyay iyadoo lagu xirayo D-glucopyranose badan oo leh β- (1-4) bonds glycosidic. Giraan kasta oo glucopyranosyl ah waxaa ku jira saddex kooxood oo hydroxyl ah. Daawaynta saxda ah waxay heli kartaa falcelis gaar ah. Warqadan, saxarka suufka cellulose ayaa loo isticmaalay sidii alaabta ceeriin ee bilowga ah, ka dib hydrolysis acid si loo helo microcrystalline cellulose oo leh heer ku habboon polymerization, waxaa lagu hawlgeliyay sodium hydroxide waxayna ka falcelisay 1,4-butane sultone si loogu diyaariyo butyl sulfonate Acid. cellulose ether superplasticizer, iyo arrimaha saamaynta leh ee falcelin kasta ayaa laga hadlay.

2. Tijaabi

2.1 Qalabka ceeriin

Saxarka suufka Cellulose, shahaadada polymerization 576, Xinjiang Aoyang Technology Co., Ltd.; 1,4-butane sultone (BS), heerka warshadaha, oo ay soo saartay Shanghai Jiachen Chemical Co., Ltd .; 52.5R sibidhka Portland ee caadiga ah, Urumqi Waxaa bixisa warshadda sibidhka; Ciidda Shiinaha ISO caadiga ah, oo ay soo saartay Xiamen Ace Ou Standard Sand Co., Ltd .; sodium hydroxide, hydrochloric acid, isopropanol, methanol anhydrous, ethyl acetate, n-butanol, petroleum ether, iwm, dhamaantood waa lafagur ahaan saafi ah, ganacsi ahaan la heli karo.

2.2 Habka tijaabada ah

Miisaami xaddi go'an oo saxarka suufka ah oo si fiican u shiid, ku rid dhalada saddex qoorta leh, ku dar fiirsi gaar ah oo ah hydrochloric acid, walaaq si aad u kululeyso oo biyo ku shubto muddo cayiman, qabooji heerkulka qolka, filter, ku dhaq biyo ilaa dhexdhexaad ah, oo faakiyuumku qallaji 50 ° C si aad u hesho Ka dib markaad haysato alaabta ceeriin ee microcrystalline cellulose leh darajo kala duwan oo polymerization ah, cabbir heerkooda polymerization sida ku cad suugaanta, ku rid dhalada falcelinta saddex-lugood leh, laal Wakiilka ganaaxa 10 jeer cufkiisa, ku dar qadar go'an oo ah sodium hydroxide xal aqueous hoos walaaqaya, Walaaq oo dhaqaaji heerkulka qolka muddo cayiman, ku dar qadarka la xisaabiyay ee 1,4-butane sultone (BS), kululaynta heerkulka falcelinta, ka falcelisa heerkul joogto ah muddo cayiman, ku qabooji badeecada heerkulka qolka, oo hel badeecada cayriin iyadoo la sifeynayo nuugista. Ku luqluq biyo iyo methanol 3 jeer, oo ku sifee nuugista si aad u hesho badeecada u dambaysa, kuwaas oo ah cellulose butylsulfonate water reducer (SBC).

2.3 Falanqaynta badeecada iyo sifada

2.3.1 Go'aaminta waxa ku jira baaruudka alaabta iyo xisaabinta heerka beddelka

Falanqeeyaha aasaasiga ah ee FLASHEA-PE2400 ayaa loo adeegsaday in lagu sameeyo falanqaynta aasaasiga ah ee engegan sheyga biyo-yareeya cellulose butyl sulfonate si loo go'aamiyo waxa ku jira baaruudka.

2.3.2 Go'aaminta dareeraha hoobiye

Lagu qiyaasay 6.5 gudaha GB8076-2008. Taasi waa, marka hore qiyaas isku dhafka biyaha/sibidhka/cidada caadiga ah ee tijaabiyaha dareeraha hoobiye NLD-3 marka dhexroorka ballaadhinta uu yahay (180±2)mm. sibidhka, isticmaalka biyaha ee la qiyaasay waa 230g), ka dibna ku dar wakiilka biyaha dhimaya oo miisaankiisu yahay 1% cufka sibidhka biyaha, marka loo eego sibidhka/biyaha yareeya wakiilka/biyaha caadiga ah/carada caadiga ah=450g/4.5g/ 230 g / Saamiga 1350 g waxaa lagu dhejiyaa isku-dhafka hoobiye sibidhka JJ-5 oo si siman loo walaaqay, iyo dhexroorka ballaadhiyey ee hoobiye ee tijaabiyaha dareeraha hoobiye ayaa la cabbiraa, taas oo ah dareeraha hoobiye ee la qiyaasay.

2.3.3 Tilmaamaha Alaabta

Muunadda waxaa lagu gartaa FT-IR iyadoo la adeegsanayo EQUINOX 55 nooca Fourier transform spectrometer infrared ee Shirkadda Bruker; spectrum H NMR ee muunad waxaa lagu gartaa INOVA ZAB-HS xaaqida superconducting ee nukliyeerka resonance ee Shirkadda Varian; Qaab-dhismeedka badeecada waxaa lagu arkay mikroskoob; Falanqaynta XRD waxaa lagu sameeyay muunada iyadoo la adeegsanayo raajada diffractometer ee Shirkadda MAC M18XHF22-SRA.

3. Natiijooyinka iyo doodaha

3.1 Natiijooyinka sifada

3.1.1 FT-IR natiijooyinka sifada

Falanqaynta infrared waxaa lagu sameeyay alaabta ceeriin ee microcrystalline cellulose oo leh shahaado polymerization Dp=45 iyo badeecada SBC ee laga sameeyay alaabtan ceeriin. Mar haddii meelaha ugu sarreeya ee nuugista SC iyo SH ay aad u daciif yihiin, kuma habboona in lagu aqoonsado, halka S=O ay leedahay nuugista ugu sarreysa. Sidaa darteed, haddii ay jiraan koox sulfonic acid ee qaab-dhismeedka molecular waxaa lagu go'aamin karaa xaqiijinta jiritaanka S=O ugu sarreysa. Sida cad, spectrum cellulose, waxaa jira nuugista ugu sarreysa ee tirada mowjadaha 3344 cm-1, taas oo loo aaneynayo gariirka fidsan ee hydroxyl ee cellulose; nuugista xoogga badan ee tirada mowjadaha 2923 cm-1 waa heerka ugu sarreeya ee gariirka ee methylene (-CH2). Gariirka ugu sarreeya; silsiladaha taxanaha ah ee ka kooban 1031, 1051, 1114, iyo 1165cm-1 waxay ka tarjumaysaa heerka ugu sarreeya ee nuugista gariirka fiditaanka hydroxyl iyo nuugista ugu sarreysa ee curaarta ether (COC) qaloocinta gariir; nambarka mowjadda 1646cm-1 wuxuu ka tarjumayaa hydrogen-ka ay sameeyeen hydroxyl iyo biyaha bilaashka ah ee nuugista curaarta; band of 1432 ~ 1318cm-1 muujinaysaa jiritaanka qaab-dhismeedka crystal cellulose. In spectrum IR ee SBC, xoojinta band 1432 ~ 1318cm-1 daciifin; halka xoojinta ugu sarreysa nuugista ee 1653 cm-1 ay kordho, taas oo muujinaysa in awoodda samaynta curaarta hydrogen la xoojiyay; 1040, 605cm-1 waxay u muuqataa mid ka xoog badan nuugista ugu sarreysa, labadan kuma jiraan spectrum infrared of cellulose, kan hore waa nuugista ugu sarreysa ee S=O bond, kan dambena waa midka ugu sarreeya nuugista dabeecadda SO bond. Iyada oo ku saleysan falanqaynta sare, waxaa la arki karaa in ka dib falcelinta etherification ee cellulose, waxaa jira kooxo sulfonic acid ee silsiladda kelli.

3.1.2 H NMR natiijooyinka sifada

H NMR spectrum ee cellulose butyl sulfonate waa la arki karaa: gudahood γ=1.74 ~ 2.92 waa hydrogen proton kiimikaad wareejinta cyclobutyl, iyo gudaha γ=3.33 ~ 4.52 waa unugga anhydroglucose cellulose Isbedelka kiimikaad ee proton oxygen ee γ=4.52 ~ 6 waa isbeddelka kiimikaad ee methylene proton ee kooxda butylsulfonic acid ee ku xiran oksijiinta, mana jirto meel sare oo ah γ=6 ~ 7, taasoo muujineysa in alaabtu aysan ahayn borotoonno kale ayaa jira.

3.1.3 Natiijooyinka sifada SEM

U fiirsashada SEM ee saxarka suufka cellulose, cellulose microcrystalline iyo cellulose butylsulfonate. Iyadoo la falanqeynayo natiijooyinka falanqaynta SEM ee saxarka suufka cellulose, microcrystalline cellulose iyo sheyga cellulose butanesulfonate (SBC), waxaa la ogaaday in microcrystalline cellulose ee la helay ka dib hydrolysis leh HCL ay si weyn u bedeli karto qaabdhismeedka fiilooyinka cellulose. Qaab dhismeedka fibroeska ah ayaa la burburiyay, waxaana la helay qayb ka mid ah unugyada cellulose-ka agglomerated. SBC-da lagu helay falcelinta dheeraadka ah ee BS ma lahayn qaab-dhismeed fibro ah oo asal ahaan isku beddelay qaab-dhismeedka amorphous, kaas oo faa'iido u leh ku milma biyaha.

3.1.4 XRD sifada natiijooyinka

Karistalinnimada cellulose iyo ka-soo-saarkeeda waxaa loola jeedaa boqolleyda gobolka crystalline ee uu sameeyay qaab-dhismeedka unugga cellulose ee guud ahaan. Marka cellulose iyo kuwa ka soo jeeda ay maraan falcelin kiimikaad, curaarta hydrogen ee ku jirta molecule iyo inta u dhaxaysa molecules waa la burburiyaa, gobolka crystalline wuxuu noqon doonaa gobol aan caadi ahayn, taas oo yareyneysa crystallinity. Sidaa darteed, isbeddelka crystallinity ka hor iyo ka dib falcelinta waa cabbirka cellulose Mid ka mid ah shuruudaha si ay uga qayb qaataan jawaabta ama in aan. Falanqaynta XRD waxaa lagu sameeyay microcrystalline cellulose iyo cellulose butanesulfonate. Waxaa lagu arki karaa marka la barbardhigo in etherification ka dib, crystallinity isbeddelo aasaasi ah, iyo alaabtu waxay si buuxda u beddeshay qaab-dhismeedka amorphous, si ay u milmi karto biyaha.

3.2 Saamaynta heerka polymerization ee alaabta ceeriin ee waxqabadka yaraynta biyaha ee alaabta

Dheecaannada hoobiye ayaa si toos ah uga tarjumaya waxqabadka biyaha-yaraynta ee alaabta, iyo maadada baaruudda ee alaabtu waa mid ka mid ah arrimaha ugu muhiimsan ee saameeya dareeraha hoobiye. Dheecaannada hoobiyeyaashu waxay cabbiraan waxqabadka yaraynta biyaha ee alaabta.

Ka dib marka la beddelo xaaladaha falcelinta hydrolysis si loogu diyaariyo MCC oo leh darajooyin kala duwan oo polymerization ah, marka loo eego habka kor ku xusan, dooro habraac gaar ah si aad u diyaariso alaabta SBC, cabbiro maadada baaruudda si aad u xisaabiso shahaadada beddelka alaabta, oo ku dar alaabta SBC biyaha. /sibidhka/nidaamka isku dhafka ciidda ee caadiga ah Cabbir dareeraha hoobiye.

Waxaa laga arki karaa natiijooyinka tijaabada ah oo ku dhex jira qiyaasta cilmi-baarista, marka heerka polymerization ee alaabta ceeriin ee microcrystalline cellulose uu sarreeyo, maadada baaruudda (darajada beddelka) ee alaabta iyo dareeraha hoobiye ayaa hooseeya. Tani waa sababta oo ah: miisaanka kelli ee alaabta ceeriin waa yar yahay, taas oo ku habboon isku dhafka isku midka ah ee alaabta ceeriin iyo dhexgalka wakiilka etherification, taas oo hagaajinaysa heerka etherification ee alaabta. Si kastaba ha noqotee, heerka dhimista biyaha alaabtu kuma kiciso xariiq toosan oo leh hoos u dhaca heerka polymerization ee alaabta ceeriin. Natiijooyinka tijaabada ah waxay muujinayaan in dareeraha hoobiye ee isku dhafka sibidhka ee isku dhafan ee SBC lagu diyaariyey iyadoo la adeegsanayo microcrystalline cellulose oo leh darajo polymerization Dp<96 (miisaanka kelli <15552) uu ka weyn yahay 180 mm (taas oo ka weyn taas iyada oo aan biyo-dhimis lahayn) . dareeraha benchmark), oo tilmaamaya in SBC lagu diyaarin karo iyadoo la isticmaalayo cellulose miisaankeedu ka yar yahay 15552, waxaana la heli karaa qiyaas yar oo biyo ah; SBC waxaa lagu diyaariyaa iyadoo la isticmaalayo microcrystalline cellulose oo leh darajo polymerization 45 (miisaanka kelli: 7290), oo lagu daray isku dhafka la taaban karo , Dheecaannada cabbirka ee hoobiye ayaa ah kan ugu weyn, sidaas darteed waxaa loo tixgeliyaa in cellulose leh darajo polymerization ah. ilaa 45 ayaa ugu haboon diyaarinta SBC; marka heerka polymerization ee alaabta ceeriin ay ka weyn tahay 45, dareeraha hoobiye ayaa si tartiib tartiib ah hoos u dhacaya, taas oo macnaheedu yahay in heerka yaraynta biyaha hoos u dhaco. Tani waa sababta oo ah marka miisaanka kelli uu weyn yahay, dhinaca kale, viscosity ee nidaamka isku dhafka ah ayaa kordhi doona, kala firidhsanaanta kala firdhisan ee sibidhka ayaa xumaan doona, iyo kala firidhsan ee la taaban karo waxay noqon doontaa mid gaabis ah, taas oo saamayn doonta saamaynta kala firdhiso; Dhanka kale, marka miisaanka unugyadu uu weyn yahay, makromolecules-ka superplasticizer-ku waxay ku jiraan conformation gariiradda random, taas oo ay adag tahay in lagu dhajiyo dusha sare ee qaybaha sibidhka. Laakiin marka heerka polymerization ee alaabta ceeriin ay ka yar tahay 45, inkastoo maadada baaruudda (degree bedelka) ee alaabtu ay aad u weyn tahay, dareeraha isku dhafka hoobiye ayaa sidoo kale bilaaba inuu hoos u dhaco, laakiin hoos u dhacu waa mid aad u yar. Sababtu waxay tahay marka miisaanka molecular ee wakiilka biyo-yaraynta uu yaraado, inkasta oo faafinta unugyadu ay fududahay oo ay leedahay qoyaan wanaagsan, xajinta adsorption molecule-ka ayaa ka weyn kan molecule-ka, silsiladda gaadiidka biyuhu aad ayey u gaaban tahay. iyo khilaafka u dhexeeya qaybuhu waa weyn yahay, taas oo waxyeello u leh shubka. Saamaynta kala firdhiso uma fiicna sida kan biyo-yareeya ee leh miisaanka kelli ka weyn. Sidaa darteed, aad bay muhiim u tahay in si habboon loo xakameeyo miisaanka molecular ee wejiga doofaarka (qaybta cellulose) si loo hagaajiyo waxqabadka biyo-yareeyaha.

3.3 Saamaynta xaaladaha falcelinta ee waxqabadka yaraynta biyaha ee alaabta

Waxaa lagu ogaadaa tijaabooyinka in marka lagu daro heerka polymerization ee MCC, saamiga falcelinta, heerkulka falcelinta, firfircoonida alaabta ceeriin, waqtiga wax soo saarka badeecada, iyo nooca wakiilka joojinta oo dhan waxay saameeyaan waxqabadka yaraynta biyaha ee alaabta.

3.3.1 saamiga falcelinta

(1) Qiyaasta BS

Marka la eego shuruudaha lagu go'aamiyay hababka kale ee habka (heerka polymerization ee MCC waa 45, n (MCC): n (NaOH) = 1: 2.1, wakiilka hakinta waa isopropanol, wakhtiga firfircoonida ee cellulose heerkulka qolka waa 2h, Heerkulka synthesis waa 80 ° C, iyo waqtiga isku-darka 5h), si loo baaro saameynta qadarka wakiilka etherification 1,4-butane sultone (BS) ee heerka beddelka kooxaha butanesulfonic acid ee badeecada iyo dareeraha hoobiye.

Waxaa la arki karaa in marka xaddiga BS uu kordho, heerka beddelka kooxaha butanesulfonic acid iyo dareeraha hoobiyeyaasha ay si weyn u kordheen. Marka saamiga BS iyo MCC uu gaaro 2.2:1, dareeraha DS iyo hoobiye ayaa gaaraya ugu badnaan. qiimaha, waxaa loo arkaa in waxqabadka biyo-yaraynta uu yahay kan ugu fiican waqtigan. Qiimaha BS ayaa sii waday inuu kordho, iyo labadaba heerka beddelka iyo dareeraha hoobiyeyaashu waxay bilaabeen inay hoos u dhacaan. Tani waa sababta oo ah marka BS ay xad dhaaf tahay, BS waxay la falgali doontaa NaOH si ay u dhaliso HO-(CH2)4SO3Na. Sidaa darteed, warqadani waxay dooranaysaa saamiga ugu fiican ee BS ilaa MCC sida 2.2: 1.

(2) Qiyaasta NaOH

Marka la eego shuruudaha lagu go'aamiyo hababka kale ee habka (heerka polymerization ee MCC waa 45, n (BS): n (MCC) = 2.2: 1. Wakiilka joojinta waa isopropanol, wakhtiga firfircoonida ee cellulose heerkulka qolka waa 2h, Heerkulka isku-dhafka ah waa 80 ° C, iyo wakhtiga isku-darka 5h), si loo baaro saameynta qaddarka sodium hydroxide ee heerka beddelka kooxaha butanesulfonic acid ee badeecada iyo dareeraha hoobiye.

Waxaa la arki karaa, marka ay korodho qaddarka dhimista, heerka beddelka SBC uu si degdeg ah u kordho, oo uu bilaabo inuu hoos u dhaco ka dib markii uu gaaro qiimaha ugu sarreeya. Tani waa sababta oo ah, marka nuxurka NaOH uu sarreeyo, waxaa jira saldhigyo badan oo bilaash ah oo ku jira nidaamka, iyo suurtogalnimada falcelinta dhinacyadu way korodhaa, taasoo keentay in wakiilada etherification badan (BS) ay ka qayb qaataan falcelinta dhinaca, taas oo yaraynaysa heerka beddelka sulfonic. kooxaha acid ee alaabta. Heerkulka sare, joogitaanka NaOH aad u badan ayaa sidoo kale hoos u dhigi doonta cellulose, iyo wax-qabadka yaraynta biyaha ee alaabta ayaa saameyn doonta heerka hoose ee polymerization. Marka loo eego natiijooyinka tijaabada, marka saamiga molarka ee NaOH ilaa MCC uu ku saabsan yahay 2.1, heerka beddelka ayaa ah kan ugu weyn, markaa warqaddani waxay go'aaminaysaa in saamiga molar ee NaOH ilaa MCC uu yahay 2.1: 1.0.

3.3.2 Saamaynta heerkulka falcelinta ee waxqabadka yaraynta biyaha

Marka la eego shuruudaha lagu go'aamiyay hababka kale ee habka (heerka polymerization ee MCC waa 45, n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, wakiilka hakinta waa isopropanol, iyo wakhtiga hawlgelinta cellulose heerkulka qolka waa 2h Time 5h), saamaynta heerkulka falcelinta synthesis ee heerka beddelka kooxaha butanesulfonic ee alaabta ayaa la baaray.

Waxaa la arki karaa marka heerkulka falcelinta uu kordho, heerka beddelka sulfonic acid DS ee SBC si tartiib tartiib ah u kordho, laakiin marka heerkulka falcelinta uu ka sarreeyo 80 °C, DS waxay muujineysaa isbeddel hoos u dhac ah. Dareen-celinta etherification ee u dhaxaysa 1,4-butane sultone iyo cellulose waa fal-celin endothermic ah, iyo kordhinta heerkulka falcelinta waxay faa'iido u leedahay falcelinta u dhaxaysa wakiilka etherifying iyo cellulose hydroxyl group, laakiin kororka heerkulka, saamaynta NaOH iyo cellulose si tartiib tartiib ah u kordhiyaa. . Waxay noqotaa mid xoog badan, taasoo keenta in cellulose uu hoos u dhaco oo uu dhaco, taasoo keentay hoos u dhac ku yimaada miisaanka kelli ee cellulose iyo jiilka sonkorta unugyada yaryar. Dareen-celinta molecules-yar oo kale oo leh wakiilada etherifying waa mid sahlan, iyo wakiillo badan oo etherifying ah ayaa la wada baabbi'in doonaa, saameynaya heerka beddelka alaabta. Sidaa darteed, qoraalkani wuxuu tixgelinayaa in heerkulka falcelinta ugu habboon ee falcelinta etherification ee BS iyo cellulose ay tahay 80 ℃.

3.3.3 Saamaynta wakhtiga falcelinta ee wax qabadka yaraynta biyaha

Waqtiga falcelinta waxaa loo qaybiyaa firfircoonida heerkulka qolka ee alaabta ceeriin iyo heerkulka joogtada ah ee wakhtiga alaabta.

(1) Waqtiga firfircoonida heerkulka qolka alaabta ceeriin

Marka la eego shuruudaha habka ugu wanaagsan ee kor ku xusan (shahaadada MCC ee polymerization waa 45, n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, wakiilka joojinta waa isopropanol, heerkulka falcelinta synthesis waa 80 ° C, badeecada Waqtiga isku-dhafka heerkulka joogtada ah 5h), baar saameynta waqtiga firfircoonida heerkulka qolka heerka beddelka badeecada butanesulfonic acid.

Waxaa la arki karaa in heerka beddelka kooxda butanesulfonic acid ee badeecada SBC ay kor u kacdo marka hore ka dibna hoos u dhigto kordhinta wakhtiga firfircoonida. Sababta falanqayntu waxay noqon kartaa iyadoo korodhka wakhtiga waxqabadka NaOH, hoos u dhaca cellulose uu yahay mid halis ah. Iska yaree miisaanka molecular ee cellulose si aad u dhaliso sonkor yar yar. Dareen-celinta molecules-yar oo kale oo leh wakiilada etherifying waa mid sahlan, iyo wakiillo badan oo etherifying ah ayaa la wada baabbi'in doonaa, saameynaya heerka beddelka alaabta. Sidaa darteed, warqadani waxay tixgelinaysaa in wakhtiga firfircoonida heerkulka qolka ee alaabta ceeriin ay tahay 2h.

(2) Waqtiga wax soo saarka alaabta

Marka la eego shuruudaha habka ugu wanaagsan ee kor ku xusan, saameynta waqtiga firfircoonida heerkulka qolka ee heerka beddelka kooxda butanesulfonic acid ee alaabta ayaa la baaray. Waxaa la arki karaa in kordhinta waqtiga falcelinta, heerka beddelka marka hore uu kordho, laakiin marka waqtiga falcelinta uu gaaro 5h, DS waxay muujineysaa hoos u dhac. Tani waxay la xiriirtaa saldhigga xorta ah ee ku jira falcelinta etherification ee cellulose. Heerkulka sare, kordhinta wakhtiga falcelinta waxay keenaysaa korodhka heerka alkali hydrolysis ee cellulose, gaabin silsiladda unugyada unugyada, hoos u dhaca miisaanka kelli ee alaabta, iyo korodhka falcelinta dhinaca, taasoo keentay badalid. shahaadadu hoos u dhacdo. Tijaabadaan, wakhtiga isku xidhka ugu habboon waa 5h.

3.3.4 Saamaynta nooca wakiilka ka joojinta ee waxqabadka yaraynta biyaha ee alaabta

Marka la eego shuruudaha habka ugu wanaagsan (shahaadada polymerization MCC waa 45, n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, wakhtiga firfircoonida alaabta ceeriin ee heerkulka qolka waa 2h, heerkulka joogtada ah ee wakhtiga isku-dhafka ee alaabta waa 5h, iyo heerkulka falcelinta synthesis 80 ℃), siday u kala horreeyaan dooro isopropanol, ethanol, n-butanol, ethyl acetate iyo petroleum ether sida wakiilada hakinta, iyo ka wada hadlaan saamayntooda ku saabsan waxqabadka biyaha-yaraynta alaabta.

Sida iska cad, isopropanol, n-butanol iyo ethyl acetate ayaa dhamaantood loo isticmaali karaa sidii wakiilka joojinta falcelintan etherification. Doorka wakiilka hakinta, marka lagu daro kala firdhinta fal-celinta, waxay xakameyn kartaa heerkulka falcelinta. Barta karkarinta ee isopropanol waa 82.3 ° C, sidaa darteed isopropanol waxaa loo isticmaalaa sidii wakiilka joojinta, heerkulka nidaamka waxaa lagu xakameyn karaa meel u dhow heerkulka falcelinta ugu wanaagsan, iyo heerka beddelka kooxaha butanesulfonic acid ee badeecada iyo dareeraha hoobiye ayaa aad u sarreeya; halka barta karkaraya ee ethanol ay aad u sarreeyso Hoos u dhac, heerkulka falcelinta ma buuxinayo shuruudaha, heerka beddelka kooxaha butanesulfonic acid ee alaabta iyo dareeraha hoobiye ayaa hooseeya; Eter batroolka ayaa laga yaabaa inuu ka qaybqaato falcelinta, markaa lama heli karo badeeco kala firidhsan.

4 Gabagabo

(1) Isticmaalka saxarka suufka sida alaabta ceeriin ee bilowga ah,Microcrystalline cellulose (MCC)oo leh heer ku habboon polymerization ayaa la diyaariyey, oo ay kicisay NaOH, oo ay ku falcelisay 1,4-butane sultone si loogu diyaariyo biyo-milmi kara butylsulfonic acid Cellulose ether, taas oo ah, biyo-yareeyaha ku salaysan cellulose. Qaab dhismeedka sheyga ayaa lagu gartaa, waxaana la ogaaday in ka dib falcelinta etherification ee cellulose, waxaa jiray kooxo sulfonic acid silsiladdeeda kelli, kuwaas oo isu beddelay qaab-dhismeedka amorphous, iyo wax soo saarka biyaha yareeya ayaa lahaa milanka biyaha wanaagsan;

(2) Tijaabooyin, waxaa la ogaaday in marka heerka polymerization ee cellulose microcrystalline uu yahay 45, waxqabadka yaraynta biyaha ee alaabta la helay ayaa ah kan ugu fiican; Iyadoo la raacayo shuruudaha in heerka polymerization ee alaabta ceeriin la go'aamiyo, saamiga fal-celinta waa n (MCC): n (NaOH): n ( BS) = 1: 2.1: 2.2, waqtiga firfircoonida alaabta ceeriin heerkulka qolka waa 2h, heerkulka wax soo saarka alaabtu waa 80 ° C, wakhtiga wax-soo-saarka waa 5h. Waxqabadka biyuhu waa mid aad u wanaagsan.