Etherification pane ma cellulose ether

Ua aʻo ʻia ka hana etherification o cellulose e ka mīkini kāwili a me ka hoʻoulu ʻana i ka reactor, a ua hoʻomākaukau ʻia ka hydroxyethyl cellulose a me ka carboxymethyl cellulose e ka chloroethanol a me ka monochloroacetic acid. Ua hōʻike ʻia nā hopena ua lawe ʻia ka hopena etherification o cellulose e ka hoʻoulu ʻana i ka reactor ma lalo o ke ʻano o ka hoʻonāukiuki kiʻekiʻe. Loaʻa i ka Cellulose ka reactivity etherification maikaʻi, ʻoi aku ka maikaʻi ma mua o ke ʻano kneader i ka hoʻomaikaʻi ʻana i ka maikaʻi o ka etherification a me ka hoʻonui ʻana i ka lawe māmā ʻana o ka huahana i ka wai wai. huahana.

Hua'ōlelo nui:ka hopena etherification; Cellulose;Hydroxyethyl cellulose; Carboxymethyl cellulose

I ka hoʻomohala ʻana i nā huahana cellulose ether i hoʻomaʻemaʻe ʻia, hoʻohana nui ʻia ke ʻano solvent a hoʻohana ʻia ka mīkini kneading e like me nā mea hana. Eia naʻe, ʻo ka pulupulu cellulose ka nui o nā ʻāpana aniani kahi i hoʻonohonoho pono ʻia ai nā molekala. Ke hoʻohana ʻia ka mīkini kneading e like me nā mea hana pane, ua lohi ka lima kneading o ka mīkini kneading i ka wā o ka pane ʻana, a ʻo ke kūʻē o ka etherifying agent e komo i nā papa like ʻole o ka cellulose he nui a lohi ka wikiwiki, e hopena i ka manawa pane lōʻihi, kiʻekiʻe o ka ʻaoʻao. nā hopena a me ka hāʻawi like ʻole ʻana o nā pūʻulu pani ma nā kaulahao molekula cellulose.

ʻO ka maʻamau ka hopena etherification o cellulose he hopena heterogeneous ma waho a ma loko. Inā ʻaʻohe hana hoʻoikaika o waho, paʻakikī ka etherifying agent ke komo i ka crystallization zone o cellulose. A ma o ka pretreatment o ka pulupulu i hoʻomaʻemaʻeʻia (e like me ka hoʻohana 'ana i ke kino e hoʻonui i ka ili o ka pulupulu i hoʻomaʻemaʻeʻia), i ka manawa hoʻokahi me ka hoʻouluʻana i ka reactor no nā mea hana pane, me ka hoʻohana wikiwikiʻana i ka etherification reaction, e like me ka noʻonoʻo, hiki i ka cellulose ke pehu ikaika, ka pehu. o ka cellulose amorphous wahi a me ka crystallization wahi e like me ka hoʻoikaika 'ana i ka hana. Hiki ke ho'okō 'ia ka pu'unaue like 'ana o ka cellulose ether substituents ma ka ho'onui 'ana i ka mana o waho. No laila, ʻo ia ke alakaʻi hoʻomohala e hiki mai ana o ko mākou ʻāina e hoʻomohala i nā huahana cellulose etherification kiʻekiʻe me ke ʻano hoʻoulu ʻana i ka ipu hao e like me nā mea hana.

1. Māhele hoʻokolohua

1.1 Ka pulupulu pulupulu cellulose maka mea no ka hoao ana

E like me nā mea hana ʻokoʻa i hoʻohana ʻia i ka hoʻokolohua, ʻokoʻa nā ʻano pretreatment o ka pulupulu cellulose. Ke hoʻohana ʻia ka kneader ma ke ʻano he mea hoʻonā, ʻokoʻa nā ʻano hana mua. Ke hoʻohana ʻia ka kneader e like me nā mea hana pane, ʻo ka crystallinity o ka cellulose pulupulu hoʻomaʻemaʻe i hoʻohana ʻia he 43.9%, a ʻo ka awelika lōʻihi o ka cellulose pulupulu hoʻomaʻemaʻe ʻia he 15 ~ 20mm. ʻO ka crystallinity o ka pulupulu cellulose i hoʻomaʻemaʻe ʻia he 32.3% a ʻo ka awelika ka lōʻihi o ka pulupulu cellulose i hoʻomaʻemaʻe ʻia ma lalo o 1mm ke hoʻohana ʻia ka reactor hoʻoulu ʻia e like me nā mea hana.

1.2 Hoʻomohala ʻana i ka carboxymethyl cellulose a me ka hydroxyethyl cellulose

Hiki ke hoʻomākaukau ʻia ka carboxymethyl cellulose a me ka hydroxyethyl cellulose ma o ka hoʻohana ʻana i ka kneader 2L ma ke ʻano he mea hoʻokō (ʻo ka wikiwiki awelika i ka wā o ka pane ʻana he 50r/min) a me 2L stirring reactor e like me nā mea hana pane (ʻo ka wikiwiki awelika i ka wā o ka pane ʻana he 500r/min).

I ka wā o ka hopena, loaʻa nā mea maka a pau mai ka hopena quantitative koʻikoʻi. Holoi ʻia ka huahana i loaʻa mai ka hopena me w=95% ethanol, a laila hoʻomaloʻo ʻia e ka momi no 24h ma lalo o ke kaomi ʻino o 60 ℃ a me 0.005mpa. ʻO ka maʻamau o ka hāpana i loaʻa he w = 2.7% ± 0.3%, a holoiʻia ka huahana no ka nānāʻana a hiki i ka lehu w <0.2%.

ʻO nā ʻanuʻu hoʻomākaukau o ka mīkini kneading e like me nā mea hana pane penei:

Etherification reaction → holoi huahana → hoʻomaloʻo → grated granulation → lawe ʻia ka ʻeke ma ka kneader.

ʻO nā ʻanuʻu hoʻomākaukau no ka hoʻoulu ʻana i ka reactor e like me kēia:

Etherification reaction → holoi huahana → hoʻomaloʻo a me ka granulation → lawe ʻia ka pahu i loko o kahi reactor hoʻoulu ʻia.

Hiki ke ʻike ʻia ua hoʻohana ʻia ka kneader e like me nā mea hana no ka hoʻomākaukau ʻana i nā hiʻohiʻona o ka hopena haʻahaʻa haʻahaʻa, ka maloʻo a me ka wili ʻana i ka granulation i kēlā me kēia pae, a e hoʻemi nui ʻia ka maikaʻi o ka huahana i ke kaʻina hana.

ʻO nā hiʻohiʻona o ka hoʻomākaukau ʻana me ka reactor hoʻoulu ʻia e like me nā mea hana e like me kēia: ʻoi aku ka maikaʻi o ka hopena kiʻekiʻe, ʻaʻole ʻae ka granulation huahana i ke kaʻina hana granulation kuʻuna o ka maloʻo a me ka wili ʻana, a ke hana ʻia ka hoʻomaloʻo a me ka granulation i ka manawa like me nā huahana i hoʻomaloʻo ʻole ʻia ma hope o ka holoi ʻana, a ʻaʻole i hoʻololi ʻia ka maikaʻi o ka huahana i ke kaʻina hoʻomaloʻo a me ka granulation.

1.3 X-ray diffraction kālailai

X-ray diffraction kālailai ua hana ia e Rigaku D/max-3A X-ray diffractometer, graphite monochromator, Θ Angle ua 8 ° ~ 30°, CuKα kukuna, paipu kaomi a me ka paipu kahe he 30kV a me 30mA.

1.4 Ka nānā 'ana i ka spectrum infrared

Ua hoʻohana ʻia ka Spectrum-2000PE FTIR infrared spectrometer no ka nānā ʻana i ka spectrum infrared. ʻO nā laʻana a pau no ka nānā ʻana i ka spectrum infrared i ke kaumaha o 0.0020g. Ua hui pū ʻia kēia mau laʻana me 0.1600g KBr, a laila kaomi ʻia (me ka mānoanoa o <0.8mm) a nānā ʻia.

1.5 ʻIke ʻana i ka lawe ʻana

Ua ʻike ʻia ka transmittance e 721 spectrophotometer. Hoʻokomo ʻia ka hoʻonā CMC w=w1% i loko o kahi kīʻaha kala 1cm ma 590nm lōʻihi hawewe.

1.6 Degere o ka ʻike pani

Ua ana ʻia ka pae hoʻololi HEC o ka hydroxyethyl cellulose e ke ʻano loiloi kemika maʻamau. ʻO ke kumu o ka HEC hiki ke decomposed e HI hydroiodate ma 123 ℃, a hiki ke ʻike ʻia ke degere o ka hoʻololi ʻana o HEC ma ke ana ʻana i nā mea decomposed ethylene a me ethylene iodide i hana ʻia. Hiki ke hoʻāʻo ʻia ke kiʻekiʻe o ka hoʻololi ʻana o ka hydroxymethyl cellulose e nā ʻano loiloi kemika maʻamau.

2. Nā hopena a me ke kūkākūkā

Hoʻohana ʻia ʻelua ʻano ʻano kīʻaha pane: ʻo kekahi ka mīkini kāwili ʻana e like me nā mea hana pane, ʻo ka mea ʻē aʻe e hoʻouluulu ʻano ʻano kīʻaha e like me nā lako hana, ma ka ʻōnaehana heterogeneous reaction, alkaline condition and alcoholic water solvent system, etherification reaction of refined cotton cellulose is studyed. I waena o lākou, ʻo nā hiʻohiʻona ʻenehana o ka mīkini kneading e like me nā mea hana pane: I ka hopena, ua lohi ka wikiwiki o ka lima kneading, lōʻihi ka manawa pane, kiʻekiʻe ka nui o nā ʻaoʻao ʻaoʻao, haʻahaʻa ka hoʻohana ʻana o ka mea etherifying agent, a me ka ʻAʻole maikaʻi ke kūlike o ka hoʻololi ʻana i ka puʻunaue i ka etherizing. Hiki ke kaupalena ʻia ke kaʻina hana noiʻi i nā kūlana hoʻohālikelike haiki. Eia kekahi, ʻo ka adjustability a me ka controllability o nā kūlana hopena koʻikoʻi (e like me ka ratio bath, alkali concentration, kneading arm's speed of kneading machine) he ʻilihune loa. He paʻakikī ka loaʻa ʻana o ka like like o ka hopena etherification a me ke aʻo ʻana i ka hoʻololi nui a me ke komo ʻana o ke kaʻina hana etherification i ka hohonu. ʻO nā hiʻohiʻona o ka hoʻoulu ʻana i ka reactor e like me nā mea hana: ʻo ka wikiwiki o ka hoʻoulu ʻana i ka hopena, ka wikiwiki o ka hopena, ka nui o ka hoʻohana ʻana o ka etherizing agent, ka hāʻawi like ʻana o ka etherizing substituents, hiki ke hoʻololi a mālama ʻia nā kūlana pane nui.

Ua hoʻomākaukau ʻia ʻo Carboxymethyl cellulose CMC e nā mea hana kneader reaction a me ka hoʻoulu ʻana i nā mea hana reactor reaction. I ka wā i hoʻohana ʻia ai ka kneader e like me nā mea hana pane, ua haʻahaʻa ka ikaika o ka hoʻoulu ʻana a ʻo ka wikiwiki o ka hoʻololi ʻana he 50r/min. I ka hoʻohana ʻia ʻana o ka reactor hoʻoulu ʻia e like me nā mea hana pane, ua kiʻekiʻe ka ikaika o ka hoʻoulu ʻana a ʻo ka wikiwiki o ka huli ʻana he 500r/min. Inā he 1:5:1 ka ratio molar o ka waikawa monochloroacetic i ka cellulose monosaccharide, ʻo ka manawa pane he 1.5h ma 68 ℃. ʻO ka māmā māmā o CMC i loaʻa i ka mīkini kneading he 98.02% a ʻo ka etherification efficiency ʻo 72% ma muli o ka permeability maikaʻi o CM i ka chloroacetic acid etherifying agent. I ka wā i hoʻohana ʻia ai ka reactor hoʻoulu ʻia e like me nā mea hana pane, ʻoi aku ka maikaʻi o ka permeability o ka etherifying agent, ʻo ka transmittance o CMC ʻo 99.56%, a ua hoʻonui ʻia ka hopena etherizing i 81%.

Ua hoʻomākaukau ʻia ʻo Hydroxyethyl cellulose HEC me ka kneader a me ka hoʻoulu ʻana i ka reactor e like me nā mea hana. I ka wā i hoʻohana ʻia ai ka kneader ma ke ʻano he mea hana pane, ʻo 47% ka maikaʻi o ka pane ʻana o ka etherizing agent a ua maikaʻi ʻole ka hoʻoheheʻe wai i ka wā ʻilihune ka permeability o ka chloroethyl alcohol etherizing agent a ʻo ka ratio molar o chloroethanol i cellulose monosaccharide he 3:1 ma 60 ℃ no 4h. . Aia wale nō ke 6:1 ka ratio molar o ka chloroethanol a me ka cellulose monosaccharides, hiki ke hoʻokumu ʻia nā huahana me ka hoʻoheheʻe wai maikaʻi. I ka hoʻohana ʻia ʻana o ka reactor hoʻoulu ʻia e like me nā mea hana pane, ʻoi aku ka maikaʻi o ka chloroethyl alcohol etherification agent ma 68 ℃ no 4h. Ke 3:1 ka ratio molar o ka chloroethanol a me cellulose monosaccharide, ʻoi aku ka maikaʻi o ka hoʻoheheʻe wai o ka HEC, a ua hoʻonui ʻia ka hopena etherification i 66%.

ʻOi aku ka kiʻekiʻe o ka hopena o ka hopena a me ka wikiwiki o ka etherizing agent chloroacetic acid ma mua o ka chloroethanol, a ʻo ka reactor hoʻoulu ʻana e like me ka etherizing reaction machine he mau mea maikaʻi loa ma mua o ka kneader, kahi e hoʻomaikaʻi nui ai i ka etherizing reaction efficiency. ʻO ka transmittivity kiʻekiʻe o CMC e hōʻike ana i ka mea hoʻouluulu e like me ka etherizing reaction machine hiki ke hoʻomaikaʻi i ka homogeneity o ka etherizing reaction. ʻO kēia no ka mea he ʻekolu mau pūʻulu hydroxyl i ke kaulahao cellulose ma kēlā me kēia apo pūʻulu glucose, a ma kahi ʻano pehu nui a i ʻole ka hoʻoheheʻe ʻia ʻana e hiki ke loaʻa i nā pālua cellulose hydroxyl āpau o nā molekole etherifying agent. ʻO ka hopena etherification o ka cellulose ka mea maʻamau he hopena heterogeneous mai waho a i loko, ʻoi aku hoʻi ma ka ʻāpana crystalline o cellulose. Ke hoʻomau nei ka ʻano aniani o ka cellulose me ka ʻole o ka hopena o ka ikaika o waho, paʻakikī ka etherifying agent e komo i ke ʻano crystalline, e pili ana i ka homogeneity o ka hopena heterogeneous. No laila, ma ka hana mua ʻana i ka pulupulu hoʻomaʻemaʻe ʻia (e like me ka hoʻonui ʻana i ka ʻili kiko o ka pulupulu hoʻomaʻemaʻe ʻia), hiki ke hoʻomaikaʻi ʻia ka hana ʻana o ka pulupulu hoʻomaʻemaʻe. I ka nui o ka wai auau (ethanol / cellulose a isopropyl waiʻona / cellulose a kiʻekiʻe-wikiwiki hoʻoulu ʻana i ka hopena, e like me ke kumu, e hoʻemi ʻia ke kauoha o ka cellulose crystallization zone, i kēia manawa hiki i ka cellulose ke pehu ikaika, no laila ka pehu. o ka amorphous a me ka crystalline cellulose wahi e like me ka like, no laila, ua like ka reactivity o ka amorphous aina a me ka crystalline.

Ma ke ʻano o ka nānā ʻana i ka spectrum infrared a me ka nānā ʻana i ka diffraction X-ray, hiki ke hoʻomaopopo ʻia ke kaʻina hana etherification o cellulose i ka wā e hoʻohana ʻia ai ka reactor hoʻouluulu e like me nā mea hana etherification.

Ma ʻaneʻi, ua kālailai ʻia ke ʻano kikoʻī infrared a me nā kikoʻī hoʻokaʻawale X-ray. Ua hoʻokō ʻia ka hopena etherification o CMC a me HEC i loko o kahi reactor i hoʻoulu ʻia ma lalo o nā kūlana hopena i hōʻike ʻia ma luna.

Hōʻike ka loiloi infrared spectrum e hoʻololi mau ana ka hopena etheration o CMC a me HEC me ka hoʻonui ʻia o ka manawa pane, ʻokoʻa ke kiʻekiʻe o ka hoʻololi.

Ma o ka nānā ʻana o ka X-ray diffraction pattern, ʻo ka crystallinity o CMC a me HEC i ka zero me ka hoʻonui ʻana o ka manawa pane, e hōʻike ana ua ʻike maoli ʻia ke kaʻina hana decrystallization i ka pae alkalization a me ka pae wela ma mua o ka hopena etherification o ka pulupulu hoʻomaʻemaʻe. . No laila, ʻaʻole i kaupalena ʻia ka carboxymethyl a me ka hydroxyethyl etherification reactivity o ka pulupulu hoʻomaʻemaʻe ʻia e ka crystallinity o ka pulupulu hoʻomaʻemaʻe. Ua pili i ka permeability o ka etherifying agent. Hiki ke hōʻike ʻia ke hoʻokō ʻia ka hopena etherification o CMC a me HEC me ka stirring reactor ma ke ʻano he mea hana. Ma lalo o ka wikiwiki o ka hoʻoulu ʻana, pono ia i ke kaʻina hana decrystallization o ka pulupulu i hoʻomaʻemaʻe ʻia i ka pae alkalization a me ka pae hoʻomehana ma mua o ka hopena etherification, a kōkua i ka etherification agent e komo i loko o ka cellulose, i mea e hoʻomaikaʻi ai i ka maikaʻi o ka etherification reaction a me ka hoʻololi like ʻana. .

I ka hopena, ua hoʻoikaika kēia haʻawina i ka mana o ka mana hoʻoulu a me nā mea ʻē aʻe i ka hopena hopena i ka wā o ke kaʻina hana. No laila, ʻo ka manaʻo o kēia haʻawina e pili ana i kēia mau kumu: I loko o ka ʻōnaehana heterogeneous etheration reaction, ka hoʻohana ʻana i ka lākiō ʻauʻau nui a me ka ikaika hoʻoulu ʻana kiʻekiʻe, a me nā mea ʻē aʻe, ʻo ia ke kumu kumu no ka hoʻomākaukau ʻana o ka homogeneous cellulose ether me ka hui substituent. mahele; I loko o kahi ʻōnaehana hoʻohālikelike heterogeneous etheration, hiki ke hoʻomākaukau ʻia ka cellulose ether hana kiʻekiʻe me ka hāʻawi like ʻana o nā substituent ma o ka hoʻohana ʻana i ka reactor hoʻoulu ʻia e like me nā mea hoʻonaninani, e hōʻike ana i ka cellulose ether aqueous solution he transmittance kiʻekiʻe, he mea nui ia e hoʻonui i nā waiwai. a me nā hana o ka cellulose ether. Hoʻohana ʻia ka mīkini kneading e like me nā mea hana e aʻo ai i ka hopena etherification o ka pulupulu hoʻomaʻemaʻe. Ma muli o ka haʻahaʻa haʻahaʻa o ka hoʻoulu ʻana, ʻaʻole maikaʻi ia no ke komo ʻana o ka etherification agent, a loaʻa kekahi mau hemahema e like me ke kiʻekiʻe o ka ʻaoʻao o ka ʻaoʻao a me ka hāʻawi maikaʻi ʻole i ka like ʻole o ka etherification substituents.