ʻO ka Synthesis a me ke ʻano o ka Butane Sulfonate Cellulose Ether Water Reducer

Ua hoʻohana ʻia ka microcrystalline cellulose (MCC) me kahi definite definite o polymerization i loaʻa e ka acid hydrolysis o ka pulupulu pulupulu cellulose e like me ka mea maka. Ma lalo o ka ho'ā 'ana o ka sodium hydroxide, ua reacted me 1,4-butane sultone (BS) e loaa A cellulose butyl sulfonate (SBC) wai reducer me ka wai maikai solubility ua hoʻomohala. Hōʻike ʻia ka ʻōnaehana huahana e ka infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD) a me nā ʻano analytical ʻē aʻe, a me ke degere polymerization, raw material ratio, a ua noiʻi ʻia ka hopena o MCC. Nā hopena o nā kūlana kaʻina hana synthetic e like me ka mahana, ka manawa pane, a me ke ʻano o ka mea hoʻomaha i ka hana hoʻemi wai o ka huahana. Hōʻike nā hualoaʻa: i ka wa o ka polymerization o ka maka mea MCC he 45, ka nuipa o ka reactants mea: AGU (cellulose glucoside wae): n (NaOH): n (BS) = 1.0: 2.1: 2.2, Ka ʻO ka mea hoʻokuʻu i ka isopropanol, ʻo ka manawa hoʻāla o ka mea maka ma ka lumi wela he 2 h, a ʻo ka manawa synthesis o ka huahana he 5 h. Ke 80 ° C ka mahana, ʻo ka huahana i loaʻa ke kiʻekiʻe kiʻekiʻe o ka hoʻololi ʻana i nā pūʻulu waikawa butanesulfonic, a ʻoi aku ka maikaʻi o ka huahana hoʻemi wai.

Hua'ōlelo nui:cellulose; cellulose butylsulfonate; mea hoemi wai; hana hoemi wai

1、Hoʻolauna

ʻO ka superplasticizer concrete kekahi o nā mea pono ʻole o ka ʻenehana hou. Ma muli o ke ʻano o ka mea hoʻohaʻahaʻa wai e hiki ai ke hōʻoia i ka hana kiʻekiʻe, ka lōʻihi maikaʻi a me ka ikaika kiʻekiʻe o ke konima. ʻO nā mea hoʻohaʻahaʻa wai kiʻekiʻe i hoʻohana nui ʻia i kēia manawa e pili ana i kēia mau ʻāpana: naphthalene-based water reducer (SNF), sulfonated melamine resin-based water-reducer (SMF), sulfamate-based water-reducer (ASP), modified Lignosulfonate superplasticizer ( ML), a me ka polycarboxylate superplasticizer (PC), ka mea i noiʻi ʻia i kēia manawa. Ke nānā nei i ke kaʻina hana synthesis o nā mea hoʻemi wai, ʻo ka hapa nui o nā mea hoʻohaʻahaʻa wai condensate kahiko e hoʻohana i ka formaldehyde me kahi ʻala ʻala ikaika e like me ka mea maka no ka hopena polycondensation, a ʻo ke kaʻina hana sulfonation e hoʻokō ʻia me ka sulfuric acid nui corrosive a i ʻole sulfuric acid concentrated. ʻO kēia ka mea e hiki ai ke hoʻopilikia i nā limahana a me nā kaiapuni a puni, a e hoʻopuka pū i ka nui o nā koena ʻōpala a me nā wai ʻōpala, ʻaʻole kūpono i ka hoʻomohala hoʻomau; akā naʻe, ʻoiai nā mea hoʻemi wai polycarboxylate i loaʻa nā pōmaikaʻi o ka nalowale liʻiliʻi o ke koneki i ka manawa, haʻahaʻa haʻahaʻa, kahe maikaʻi Loaʻa iā ia nā mea maikaʻi o ke kiʻekiʻe kiʻekiʻe a ʻaʻohe mea ʻona e like me formaldehyde, akā paʻakikī ke hoʻolaha ʻia ma Kina ma muli o ke kiʻekiʻe. kumukūʻai. Mai ka nānā ʻana i ke kumu o nā mea maka, ʻaʻole paʻakikī ka ʻike ʻana ʻo ka hapa nui o nā mea hoʻemi wai i ʻōlelo ʻia ma luna nei ua synthesized ma muli o nā huahana petrochemical / by-products, ʻoiai ʻo ka ʻaila, ma ke ʻano he kumu waiwai ʻole hiki ke hoʻololi ʻia. ke pii mau nei kona kumukuai. No laila, pehea ka hoʻohana ʻana i nā kumuwaiwai kūlohelohe kūlohelohe a nui e like me nā mea maka no ka hoʻomohala ʻana i nā superplasticizers kiʻekiʻe kiʻekiʻe i lilo i alakaʻi noiʻi koʻikoʻi no nā superplasticizers.

ʻO ka Cellulose kahi macromolecule laina i hana ʻia ma ka hoʻopili ʻana i nā D-glucopyranose he nui me nā paʻa β-(1-4) glycosidic. Aia ʻekolu pūʻulu hydroxyl ma kēlā me kēia apo glucopyranosyl. Hiki i ka lapa'au kūpono ke loa'a i kekahi reactivity. I loko o kēia pepa, ua hoʻohana ʻia ka pulupulu pulupulu cellulose e like me ka mea maka mua, a ma hope o ka hydrolysis waika e loaʻa ai ka microcrystalline cellulose me kahi degere kūpono o ka polymerization, ua hoʻāla ʻia e ka sodium hydroxide a hana ʻia me ka 1,4-butane sultone e hoʻomākaukau ai i ka butyl sulfonate Acid. Ua kūkākūkā ʻia ka cellulose ether superplasticizer, a me nā mea hoʻoikaika o kēlā me kēia pane.

2. Hoao

2.1 Mea maka

Cellulose pulupulu pulp, polymerization degere 576, Xinjiang Aoyang Technology Co., Ltd.; 1,4-butane sultone (BS), papa hana, hana ʻia e Shanghai Jiachen Chemical Co., Ltd.; 52.5R maʻamau Portland sima, Urumqi Hāʻawi ʻia e ka hale hana sima; ʻO ke one maʻamau ISO Kina, i hana ʻia e Xiamen Ace Ou Standard Sand Co., Ltd.; ʻO ka sodium hydroxide, hydrochloric acid, isopropanol, anhydrous methanol, ethyl acetate, n-butanol, petroleum ether, a me nā mea ʻē aʻe, he maʻemaʻe analytically maʻemaʻe, loaʻa ma ke kālepa.

2.2 Hana hoʻokolohua

E kaupaona i ka nui o ka pulupulu pulupulu a wili pono ia, e hookomo i loko o ka omole ekolu-'ā'ī, e hoʻohui i kekahi manaʻo o ka waika hydrochloric dilute, e hoʻoulu i ka wela a me ka hydrolyze no kekahi manawa, maʻalili i ka lumi wela, kānana, holoi me ka wai a hiki i ke kūʻokoʻa, a maloʻo maloʻo ma 50 ° C e loaʻa ai Ma hope o ka loaʻa ʻana o ka microcrystalline cellulose maka mea me nā degere like ʻole o ka polymerization, e ana i ko lākou degere o ka polymerization e like me ka palapala, e hoʻokomo i loko o ka ʻōmole hopena ʻekolu ʻāʻī, e hoʻokuʻu me ka wai. he mea hoʻokuʻu ʻia he 10 mau manawa i kona nui, e hoʻohui i kahi nui o ka sodium hydroxide aqueous solution ma lalo o ka hoʻoulu ʻana, E hoʻoulu a hoʻāla i ka lumi wela no kekahi manawa, e hoʻohui i ka helu helu o 1,4-butane sultone (BS), wela i ka wela o ka hopena, e hana i ka wela mau no kekahi manawa, e hooluolu i ka huahana a hiki i ka lumi wela, a e loaa ka hua palau ma ka kānana kānana. Holoi me ka wai a me ka methanol no 3 mau manawa, a kānana me ka momi no ka loaʻa ʻana o ka huahana hope loa, ʻo ia hoʻi ka cellulose butylsulfonate water reducer (SBC).

2.3 Ka nānā 'ana a me ka hō'ike 'ana i ka huahana

2.3.1 Ka ho'oholo 'ana i ka ma'i sulfur huahana a me ka helu 'ana i ke degere o ka ho'ololi 'ana

Ua hoʻohana ʻia ka FLASHEA-PE2400 elemental analyzer e hana i ka ʻikepili elemental ma ka cellulose butyl sulfonate water reducer huahana e hoʻoholo ai i ka ʻike sulfur.

2.3.2 Ka hoʻoholo ʻana i ka wai o ka mortar

Ana e like me 6.5 ma GB8076-2008. ʻO ia hoʻi, e ana mua i ka hui ʻana o ka wai/cement/one maʻamau ma ka NLD-3 sima mortar fluidity tester i ka wā o ka hoʻonui ʻana he (180±2)mm. ʻO ka sima, ʻo ka hoʻohana ʻana i ka wai benchmark he 230g), a laila hoʻohui i kahi mea hoʻohaʻahaʻa wai nona ka nuipa he 1% o ka nui sima i ka wai, e like me ka sima/wai hoʻemi mea hoʻohaʻahaʻa / wai maʻamau / one maʻamau = 450g/4.5g/ 230 g/ Ka lākiō o 1350 g i loko o ka JJ-5 sima mortar mixer a hoʻoulu like, a me ka hoʻonui ana o ke anawaena o ka mortar ma luna o ka mortar fluidity mea ho'āʻo ua ana, ka mea i ana i ka mortar fluidity.

2.3.3 Hōʻikeʻike Huahana

Ua hōʻike ʻia ka laʻana e FT-IR e hoʻohana ana i ka EQUINOX 55 type Fourier transform infrared spectrometer o Bruker Company; ʻO ka H NMR spectrum o ka hāpana i hōʻike ʻia e ka INOVA ZAB-HS plow superconducting nuclear magnetic resonance instrument o Varian Company; Ua nānā ʻia ka morphology o ka huahana ma lalo o kahi microscope; Ua hoʻokō ʻia ka loiloi XRD ma ka hāpana me ka hoʻohana ʻana i kahi diffractometer X-ray o MAC Company M18XHF22-SRA.

3. Nā hopena a me ke kūkākūkā

3.1 Nā hopena hōʻike

3.1.1 Nā hualoaʻa hiʻona FT-IR

Ua lawe ʻia ka loiloi infrared ma ka microcrystalline cellulose maka me kahi degere o ka polymerization Dp=45 a me ka huahana SBC synthesized mai kēia mea maka. No ka nawaliwali loa o na peaks absorption o SC a me SH, aole kupono ia lakou no ka ike ana, oiai o S=O he peak absorption ikaika. No laila, hiki ke hoʻoholo ʻia inā he pūʻulu ʻakika sulfonic i loko o ka molekala ma ka hōʻoia ʻana i ke ola o ka piko S=O. ʻIke loa, i loko o ka cellulose spectrum, aia kahi kiʻekiʻe absorption ikaika ma ka helu hawewe o 3344 cm-1, i pili i ka hydroxyl stretching vibration peak i cellulose; ʻO ka piko hoʻoemi ikaika ma ka helu nalu o 2923 cm-1 ka piko haʻalulu o ka methylene (-CH2). Kiʻekiʻe haʻalulu; ʻO ka pūʻulu o nā pūʻali i haku ʻia me 1031, 1051, 1114, a me 1165cm-1 e hōʻike ana i ka piko absorption o ka haʻalulu hoʻolōʻihi hydroxyl a me ka puʻu absorption o ka ether bond (COC) bending vibration; ʻO ka helu hawewe 1646cm-1 e hōʻike ana i ka hydrogen i hana ʻia e ka hydroxyl a me ka wai manuahi ʻO ka piko absorption peak; ʻO ka hui o 1432 ~ 1318cm-1 e hōʻike ana i ka noho ʻana o ka hale aniani cellulose. Ma ka IR spectrum o SBC, nāwaliwali ka ikaika o ka hui 1432 ~ 1318cm-1; ʻoiai ke piʻi nei ka ikaika o ka absorption peak ma 1653 cm-1, e hōʻike ana ua hoʻoikaika ʻia ka hiki ke hana i nā paʻa hydrogen; 1040, 605cm-1 ike ikaika Absorption peaks, a me keia mau mea elua, aole i ikeia i loko o ka infrared spectrum o cellulose, ka mua ka hiʻona o ka absorption piko o ka S=O, a me ka hope o ka 'ano o ka absorption peak o ka pili SO. Ma muli o ka loiloi i luna, hiki ke ʻike ʻia ma hope o ka hopena etherification o cellulose, aia nā pūʻulu waikawa sulfonic i kāna kaulahao mole.

3.1.2 H NMR mau hopena

Hiki ke ʻike ʻia ka H NMR spectrum o cellulose butyl sulfonate: i loko o γ=1.74~2.92 ka hoʻololi kemika hydrogen proton o cyclobutyl, a i loko o γ=3.33~4.52 ka pūʻulu cellulose anhydroglucose ʻO ka hoʻololi kemika o ka proton oxygen ma γ=4.52 ʻO ~ 6 ka hoʻololi kemika o ka methylene proton i loko o ka hui butylsulfonic acid i pili i ka oxygen, a ʻaʻohe piko ma γ=6~7, e hōʻike ana ʻaʻole ka huahana ʻē aʻe nā protons.

3.1.3 Nā hopena hōʻikeʻike SEM

Nānā SEM o ka pulupulu pulupulu cellulose, cellulose microcrystalline a me ka butylsulfonate huahana cellulose. Ma ke kālailai ʻana i nā hualoaʻa SEM o ka pulupulu pulupulu pulupulu, microcrystalline cellulose a me ka huahana cellulose butanesulfonate (SBC), ua ʻike ʻia ʻo ka microcrystalline cellulose i loaʻa ma hope o ka hydrolysis me HCL hiki ke hoʻololi nui i ke ʻano o nā fibers cellulose. Ua luku ʻia ka hale fibrous, a ua loaʻa nā ʻāpana cellulose agglomerated maikaʻi. ʻO ka SBC i loaʻa ma ka hana hou ʻana me BS ʻaʻohe ʻano fibrous a ua hoʻololi maoli ʻia i kahi ʻano amorphous, i mea e pono ai ka hemo ʻana i ka wai.

3.1.4 Nā hualoaʻa hōʻailona XRD

ʻO ka crystallinity o cellulose a me kāna mau derivatives e pili ana i ka pākēneka o ka ʻāpana crystalline i hana ʻia e ka ʻāpana cellulose i loko o ka holoʻokoʻa. Ke hoʻopau ʻia ka cellulose a me nā mea i loaʻa i ka hopena kemika, ua luku ʻia nā paʻa hydrogen i loko o ka mole a ma waena o nā molekala, a lilo ka ʻāina crystalline i ʻāina amorphous, a laila e hōʻemi i ka crystallinity. No laila,ʻo ka hoʻololiʻana i ka crystallinity ma mua a ma hope o ka hopena he ana o ka cellulose ʻO kekahi o nā pae hoʻohālike e komo i ka pane aʻaʻole paha. Ua hana ʻia ka loiloi XRD ma ka microcrystalline cellulose a me ka huahana cellulose butanesulfonate. Hiki ke ʻike ʻia ma ka hoʻohālikelike ʻana ma hope o ka etherification, hoʻololi maoli ka crystallinity, a ua hoʻololi loa ka huahana i kahi ʻano amorphous, i hiki ke hoʻoheheʻe ʻia i ka wai.

3.2 Ka hopena o ka degere o ka polymerization o nā mea maka i ka hana hoʻemi wai o ka huahana

Hōʻike pololei ka wai o ka mortar i ka hana hoʻohaʻahaʻa wai o ka huahana, a ʻo ka sulfur content o ka huahana kekahi o nā mea nui e pili ana i ka wai o ka mortar. ʻO ka wai o ka mortar e ana i ka hana hoʻemi wai o ka huahana.

Ma hope o ka hoʻololi ʻana i nā kūlana hydrolysis e hoʻomākaukau ai i ka MCC me nā degere like ʻole o ka polymerization, e like me ke ʻano o luna, e koho i kahi kaʻina hana synthesis e hoʻomākaukau ai i nā huahana SBC, e ana i ka ʻike sulfur e helu ai i ka degere pani huahana, a hoʻohui i nā huahana SBC i ka wai. /cement/pūnaewele hui one maʻamau E ana i ka wai o ka pahū.

Hiki ke ʻike ʻia mai nā hopena hoʻokolohua i loko o ka pae noiʻi, i ka wā i kiʻekiʻe ai ka degere polymerization o ka microcrystalline cellulose maka waiwai, ʻoi aku ka haʻahaʻa o ka sulfur content (substitution degree) o ka huahana a me ka wai o ka mortar. ʻO kēia no ka mea: he liʻiliʻi ka paona molekala o ka mea maka, kahi e kūpono ai i ka hui pū ʻana o ka mea maka A me ke komo ʻana o ka mea etherification, a laila e hoʻomaikaʻi ai i ke ʻano o ka etherification o ka huahana. Eia nō naʻe, ʻaʻole piʻi ka nui o ka wai o ka huahana i kahi laina pololei me ka emi ʻana o ke degere o ka polymerization o nā mea maka. Hōʻike nā hopena hoʻokolohua ʻoi aku ka nui o ka mortar fluidity o ka hui mortar sima i hui pū ʻia me SBC i hoʻomākaukau ʻia ma ka hoʻohana ʻana i ka microcrystalline cellulose me kahi degere o ka polymerization Dp<96 (molecular weight<15552) ʻoi aku ka nui ma mua o 180 mm (ʻoi aku ka nui ma mua o kēlā me ka ʻole o ka mea hoʻemi wai). . benchmark fluidity), e hōʻike ana e hiki ke hoʻomākaukau ʻia ka SBC ma o ka hoʻohana ʻana i ka cellulose me ke kaumaha molekala ʻoi aʻe ma mua o 15552, a hiki ke loaʻa i kahi helu hoʻemi wai; Hoʻomākaukau ʻia ʻo SBC ma ka hoʻohana ʻana i ka microcrystalline cellulose me kahi degere o ka polymerization o 45 (molecular weight: 7290), a hoʻohui ʻia i ka hui ʻana o ka pahu, ʻo ke ana ʻana o ka wai o ka mortar ka nui loa, no laila ua manaʻo ʻia ʻo ka cellulose me kahi degere o ka polymerization. ma kahi o 45 ka mea kūpono loa no ka hoʻomākaukau ʻana o SBC; ke ʻoi aku ka nui o ka polymerization o nā mea maka ma mua o 45, e emi mālie ka wai o ka mortar, ʻo ia hoʻi ka emi ʻana o ka wai. ʻO kēia no ka mea i ka wā e nui ai ke kaumaha o ka molekala, ma ka ʻaoʻao hoʻokahi, e hoʻonui ka viscosity o ka ʻōnaehana hui ʻana, e hōʻemi ʻia ka dispersion uniformity o ka sima, a e lohi ka dispersion i ke kaʻa, e hoʻopilikia i ka hopena dispersion; ma ka lima 'ē aʻe, i ka wā o ka molecular kaumaha nui, Ka macromolecules o ka superplasticizer i loko o ka random coil conformation, i mea paʻakikī e adsorb ma luna o ka ili o ka ciment particles. Akā, ke emi ka degere o ka polymerization o ka mea maka ma mua o 45, ʻoiai ʻoi aku ka nui o ka sulfur content (substitution degree) o ka huahana, e hoʻomaka ana ka wai o ka hui mortar e emi iho, akā liʻiliʻi loa ka emi ʻana. ʻO ke kumu ʻo ia ka wā liʻiliʻi o ke kaumaha o ka wai hoʻohaʻahaʻa wai, ʻoiai he maʻalahi ka molecular diffusion a maikaʻi ka wettability, ʻoi aku ka nui o ka adsorption fastness o ka mole ma mua o ka mole, a pōkole loa ke kaulahao lawe wai. a he nui ka paio ma waena o nā ʻāpana, he mea ʻino ia i ke kaʻa. ʻAʻole maikaʻi ka hopena dispersion e like me ka mea hoʻemi wai me ke kaumaha molekala nui. No laila, he mea nui e hoʻomalu pono i ke kaumaha molekala o ka maka puaʻa (cellulose segment) e hoʻomaikaʻi i ka hana o ka mea hoʻemi wai.

3.3 Ka hopena o nā kūlana hopena i ka hana hoʻemi wai o ka huahana

Ua ʻike ʻia ma o nā hoʻokolohua ma ka hoʻohui ʻana i ke degere o ka polymerization o MCC, ʻo ka ratio o nā reactants, ka wela o ka hopena, ka hoʻōla ʻana o nā mea maka, ka manawa synthesis o ka huahana, a me ke ʻano o ka mea hoʻopaneʻe e pili ana i ka hana hoʻemi wai o ka huahana.

3.3.1 Lakiō reactant

(1) Ka helu o BS

Ma lalo o nā kūlana i hoʻoholo ʻia e nā ʻāpana kaʻina hana ʻē aʻe (ʻo ka degere o ka polymerization o MCC he 45, n (MCC): n (NaOH) = 1: 2.1, ʻo ka mea hoʻokuʻu ʻia he isopropanol, ʻo ka manawa hoʻāla o cellulose ma ka lumi wela he 2h, ka ʻO ka mahana synthesis he 80 ° C, a me ka manawa synthesis 5h), e noiʻi i ka hopena o ka nui o ka etherification agent 1,4-butane sultone (BS) ma ke degere o ka hoʻololi ʻana i nā pūʻulu waikawa butanesulfonic o ka huahana a me ka wai o ka mea. moka.

Hiki ke ʻike ʻia e like me ka piʻi ʻana o ka nui o ka BS, piʻi nui ka degere o ka hoʻololi ʻana o nā pūʻulu waikawa butanesulfonic a me ka wai o ka mortar. Ke piʻi ka lakio o BS a MCC i ka 2.2: 1, hiki i ka wai o DS a me ka mortar ke kiʻekiʻe. waiwai, ua manaʻo ʻia ʻo ka hana hoʻohaʻahaʻa wai ka mea maikaʻi loa i kēia manawa. Ua hoʻomau ka hoʻonui ʻana o ka waiwai BS, a ua hoʻomaka ka emi ʻana o ke degere o ka hoʻololi ʻana a me ka wai o ka mortar. No ka mea, ke oi aku ka BS, e hana ka BS me NaOH e hoopuka i ka HO-(CH2)4SO3Na. No laila, koho kēia pepa i ka lākiō mea maikaʻi loa o BS i MCC e like me 2.2:1.

(2) Ka nui o ka NaOH

Ma lalo o nā kūlana i hoʻoholo ʻia e nā ʻāpana kaʻina hana ʻē aʻe (ʻo ka degere o ka polymerization o MCC he 45, n (BS): n (MCC) = 2.2: 1. ʻO ka mea hoʻokuʻu ʻia he isopropanol, ʻo ka manawa hoʻāla o cellulose ma ka lumi wela he 2h, ka ʻO ka mahana o ka synthesis he 80 ° C, a me ka manawa synthesis 5h), e noiʻi i ka hopena o ka nui o ka sodium hydroxide ma ke kiʻekiʻe o ka hoʻololi ʻana o nā pūʻulu waikawa butanesulfonic i ka huahana a me ka wai o ka mortar.

Hiki keʻikeʻia, me ka hoʻonuiʻana i ka nui o ka ho'ēmiʻana, ke piʻi wikiwiki nei ke kiʻekiʻe o ka paniʻana o SBC, a hoʻomaka e emi ma hope o ka hikiʻana i ka waiwai kiʻekiʻe. ʻO kēia no ka mea, ke kiʻekiʻe ka maʻiʻo NaOH, nui loa nā kumu manuahi i loko o ka ʻōnaehana, a piʻi aʻe ka nui o ka hopena o ka ʻaoʻao, e hoʻonui ana i nā mea etherification (BS) i komo i nā ʻaoʻao ʻaoʻao, a laila e hōʻemi ana i ke ʻano o ka hoʻololi ʻana o ka sulfonic. nā hui waikawa i loko o ka huahana. Ma kahi kiʻekiʻe o ka wela, e hoʻohaʻahaʻa ka nui o ka NaOH i ka cellulose, a e hoʻopili ʻia ka hana hoʻohaʻahaʻa wai o ka huahana ma kahi haʻahaʻa o ka polymerization. E like me nā hopena hoʻokolohua, inā ʻo ka lākiō molar o NaOH i MCC ma kahi o 2.1, ʻo ke degere o ka hoʻololi ʻana ʻo ia ka nui loa, no laila e hoʻoholo kēia pepa i ka ratio molar o NaOH a MCC he 2.1:1.0.

3.3.2 Ka hopena o ka wela o ka hopena i ka hana ho'ēmi wai

Ma lalo o nā kūlana i hoʻoholo ʻia e nā kaʻina hana ʻē aʻe (ʻo ka degere o ka polymerization o MCC he 45, n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, ʻo ka mea hoʻomaha ka isopropanol, a ʻo ka manawa hoʻāla o cellulose ma lumi lumi he 2h Time 5h), ka mana o ka synthesis reaction temperature ma ke degere o ka hoololi ana i na hui waika butanesulfonic i ka huahana.

Hiki ke ʻike ʻia i ka piʻi ʻana o ka wela o ka hopena, e piʻi mālie ka degere hoʻololi o ka sulfonic acid DS o SBC, akā inā ʻoi aku ka mahana o ka hopena ma mua o 80 °C, hōʻike ʻo DS i kahi ʻano iho. ʻO ka hopena etherification ma waena o 1,4-butane sultone a me cellulose he hopena endothermic, a ʻo ka hoʻonui ʻana i ka mahana o ka hopena he mea maikaʻi ia i ka hopena ma waena o ka etherifying agent a me cellulose hydroxyl group, akā me ka piʻi ʻana o ka mahana, piʻi mālie ka hopena o NaOH a me cellulose. . E lilo ana ia i mea ikaika, e hoʻohaʻahaʻa a hāʻule i ka cellulose, ka hopena i ka emi ʻana o ke kaumaha molekala o cellulose a me ka hoʻokumu ʻana o nā kōkō liʻiliʻi. He mea maʻalahi ka pane ʻana o ia mau molekele liʻiliʻi me nā mea etherifying, a ʻoi aku ka nui o nā mea etherifying e hoʻopau ʻia, e pili ana i ke kiʻekiʻe o ka hoʻololi ʻana o ka huahana. No laila, ke manaʻo nei kēia ʻatikala ʻo ka mahana hopena kūpono loa no ka hopena etherification o BS a me cellulose ʻo 80 ℃.

3.3.3 Ka hopena o ka manawa pane i ka hana hōʻemi wai o ka huahana

Hoʻokaʻawale ʻia ka manawa pane i loko o ka lumi wela o ka hoʻoulu ʻana o nā mea maka a me ka manawa synthesis mau o nā huahana.

(1) lumi wela manawa ho'ā o ka maka

Ma lalo o nā kūlana kaʻina hana maikaʻi loa (MCC degere o ka polymerization ʻo 45, n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, ʻo ka mea hoʻokuʻu ʻia he isopropanol, ʻo ka mahana hopena synthesis he 80 ° C, ka huahana. Manawa manawa synthesis mau 5h), e noiʻi i ka mana o ka lumi wela manawa ho'ā 'ana ma ke degere o ka pani o ka huahana butanesulfonic acid hui.

Hiki ke ʻike ʻia ka piʻi mua ʻana o ke kiʻekiʻe o ka hoʻololi ʻana o ka hui waikawa butanesulfonic o ka huahana SBC a laila hoʻemi me ka hoʻolōʻihi ʻia o ka manawa hoʻāla. ʻO ke kumu o ka nānā ʻana ʻo ia paha me ka piʻi ʻana o ka manawa hana NaOH, he koʻikoʻi ka degradation o cellulose. E ho'ēmi i ka paona molekala o ka cellulose e hoʻohua i nā kōpaʻa liʻiliʻi. He mea maʻalahi ka pane ʻana o ia mau molekele liʻiliʻi me nā mea etherifying, a ʻoi aku ka nui o nā mea etherifying e hoʻopau ʻia, e pili ana i ke kiʻekiʻe o ka hoʻololi ʻana o ka huahana. No laila, ke manaʻo nei kēia pepa he 2h ka manawa hoʻonā wela o ka lumi.

(2) Ka manawa hoʻohui huahana

Ma lalo o nā kūlana kaʻina hana maikaʻi loa ma luna, ua noiʻi ʻia ka hopena o ka manawa hoʻāla ma ka lumi wela ma ke degere o ka hoʻololi ʻana o ka hui waikawa butanesulfonic o ka huahana. Hiki ke ʻike ʻia me ka hoʻolōʻihi ʻia o ka manawa pane, piʻi mua ke degere o ka hoʻololi ʻana, akā ke hiki i ka manawa pane i 5h, hōʻike ka DS i kahi ʻano iho. Pili kēia i ka waihona manuahi i loaʻa i ka hopena etherification o cellulose. I nā mahana kiʻekiʻe, ʻo ka hoʻolōʻihi ʻana o ka manawa pane e alakaʻi i ka piʻi ʻana o ke kiʻekiʻe o ka hydrolysis alkali o cellulose, ka pōkole o ke kaulahao mole cellulose, ka emi ʻana o ke kaumaha molekala o ka huahana, a me ka piʻi ʻana o nā hopena ʻaoʻao, ka hopena. pani. emi ke degere. Ma kēia hoʻokolohua, ʻo 5h ka manawa synthesis kūpono.

3.3.4 ʻO ka hopena o ke ʻano o ka mea hoʻokuʻu i ka hana hoʻemi wai o ka huahana

Ma lalo o nā kūlana kaʻina hana maikaʻi loa (MCC polymerization degere he 45, n (MCC): n (NaOH): n (BS) = 1: 2.1: 2.2, ka manawa hoʻonā o nā mea maka ma ka lumi wela he 2h, ka manawa synthesis mau. ʻO nā huahana he 5h, a ʻo ka mahana hopena synthesis he 80 ℃), koho i ka isopropanol, ethanol, n-butanol, ethyl acetate a me ka petroleum ether ma ke ʻano he mea hoʻomaha, a kūkākūkā i kā lākou hopena i ka hana hoʻemi wai o ka huahana.

ʻIke loa, hiki ke hoʻohana ʻia ka isopropanol, n-butanol a me ka ethyl acetate ma ke ʻano he mea hoʻokuʻu i kēia hopena etherification. ʻO ke kuleana o ka mea hoʻopaneʻe, ma waho aʻe o ka hoʻopuehu ʻana i nā reactants, hiki ke hoʻomalu i ka mahana hopena. ʻO 82.3 ° C ka paila paila o ka isopropanol, no laila ua hoʻohana ʻia ka isopropanol ma ke ʻano he mea hoʻomaha, hiki ke hoʻomalu ʻia ka mahana o ka ʻōnaehana kokoke i ka mahana hopena maikaʻi loa, a me ke degere o ka hoʻololi ʻana o nā pūʻulu waikawa butanesulfonic i ka huahana a me ka wai o ka wai. kiʻekiʻe ka pahū; ʻoiai ke kiʻekiʻe loa o ka paila paila o ka ethanol Haʻahaʻa, ʻaʻole i hoʻokō ka mahana hopena i nā koi, ʻo ke degere o ka hoʻololi ʻana o nā pūʻulu waikawa butanesulfonic i ka huahana a me ka wai o ka mortar he haʻahaʻa; Hiki i ka petroleum ether ke komo i ka hopena, no laila ʻaʻole hiki ke loaʻa ka huahana i hoʻopuehu ʻia.

4 Ka hopena

(1) Ke hoʻohana nei i ka pulupulu pulupulu ma ke ʻano he kumu mua,microcrystalline cellulose (MCC)me ka degere kūpono o ka polymerization ua hoomakaukauia, ho'ā e NaOH, a reacted me 1,4-butane sultone e hoomakaukau i ka wai-soluble butylsulfonic acid Cellulose ether, 'o ia hoʻi, cellulose-ma muli o ka wai reducer. ʻO ke ʻano o ka huahana ua ʻike ʻia, a ua ʻike ʻia ma hope o ka hopena etherification o cellulose, aia nā pūʻulu sulfonic acid ma kona kaulahao mole, i hoʻololi ʻia i kahi ʻano amorphous, a ua loaʻa i ka huahana reducer wai i ka wai solubility maikaʻi;

(2) Ma o nā hoʻokolohua, ʻike ʻia i ka wā o ka degere o ka polymerization o microcrystalline cellulose he 45, ʻoi aku ka maikaʻi o ka hana hoʻemi wai o ka huahana i loaʻa; ma lalo o ke kūlana i hoʻoholo ʻia ke degere o ka polymerization o nā mea maka, ʻo ka lakio o nā reactants ʻo n (MCC): n (NaOH): n ( BS) = 1: 2.1: 2.2, ʻo ka manawa hoʻāla o nā mea maka ma ka lumi wela. 2h, ʻo 80 ° C ka mahana o ka synthesis, a ʻo 5h ka manawa synthesis. ʻOi aku ka maikaʻi o ka hana wai.