Cellulose Etera ma ka Epoxy Resin

Hoʻohana ʻia ka pulupulu ʻōpala a me ka sawdust e like me nā mea maka, a hydrolyzed i alkalicellulose eterama lalo o ka hana o 18% alkali a me kahi ʻano o nā mea hoʻohui. A laila e hoʻohana i ka epoxy resin no ka grafting, ʻo ka molar ratio o ka epoxy resin a me ka fiber alkali he 0.5:1.0, ʻo ka mahana hopena he 100.°C, ʻo ka manawa pane he 5.0h, ʻo ka helu catalyst he 1%, a ʻo ka etherification grafting rate he 32%. Hoʻohui ʻia ka epoxy cellulose ether i loaʻa me 0.6mol Cel-Ep a me 0.4mol CAB e synthesize i kahi huahana uhi hou me ka hana maikaʻi. Ua hōʻoia ʻia ke ʻano huahana me IR.

Hua'ōlelo nui:cellulose ether; hoʻohuihui; CAB; nā waiwai hoʻouhi

Cellulose etera he polymer maoli, i hanaia e ka condensation oβ-ke koko. Loaʻa i ka Cellulose kahi kiʻekiʻe o ka polymerization, kahi kūlana maikaʻi o ka orientation, a me ke kūpaʻa kemika maikaʻi. Hiki ke loaʻa iā ia ma ka mālama ʻana i ka cellulose (esterification a i ʻole etherification). ʻO kahi pūʻulu o ka cellulose derivatives, ua hoʻohana nui ʻia kēia mau huahana i nā plastics, nā pahu ʻaina awakea biodegradable, nā uhi kaʻa kaʻa kiʻekiʻe, nā ʻāpana kaʻa, nā ʻīnika paʻi, nā adhesives, a me nā mea ʻē aʻe. e hoʻonui mau ana, e hana mālie i kahi ʻōnaehana ʻoihana fiber. ʻO kēia kumuhana ka hoʻohana ʻana i ka sawdust a i ʻole ka pulupulu ʻōpala e hoʻoheheʻe ʻia i loko o nā fiber pōkole e ka lye, a laila grafted kemika a hoʻololi ʻia e hana i kahi ʻano uhi hou ʻaʻole i hōʻike ʻia ma ka palapala.

1. Hoao

1.1 Reagents a me na mea hana

ʻO ka pulupulu ʻōpala (holoi a maloʻo), NaOH, 1,4-butanediol, methanol, thiourea, urea, epoxy resin, acetic anhydride, butyric acid, trichloroethane, formic acid, glyoxal, toluene, CAB, etc. (Purity is CP grade) . ʻO ka Magna-IR 550 infrared spectrometer i hana ʻia e Nicolet Company o ʻAmelika Hui Pū ʻIa i hoʻohana ʻia e hoʻomākaukau i nā laʻana e ka solvent tetrahydrofuran coating. Tu-4 viscometer, FVXD3-1 'ano wela mau e ho'omalu 'ia e ka uila ho'oulu 'ana i ka ipu hao, hana 'ia e Weihai Xiangwei Chemical Machinery Factory; rotational viscometer NDJ-7, Z-10MP5 ʻano, hana ʻia e Shanghai Tianping Instrument Factory; ana ke kaumaha mole e Ubbelohde viscosity; E hoʻokō ʻia ka hoʻomākaukau a me ka hoʻāʻo ʻana o ka kiʻi pena e like me ke kūlana aupuni GB-79.

1.2 Manaʻo pane

1.3 Hoʻohui

Synthesis o ka epoxy cellulose: E hoʻohui i ka 100g o ka pulupulu ʻokiʻoki i kahi wela mau i ka hoʻoulu ʻana i ka uila, hoʻohui i kahi oxidant a hana no 10 mau minuke, a laila hoʻohui i ka waiʻona a me ka alkali e hana i ka lye me ka 18%. E hoʻohui i nā mea holo wikiwiki A, B, a pēlā aku no ka impregnation. Hoʻopili i kahi mahana ma lalo o ka vacuum no 12 mau hola, kānana, maloʻo a kaupaona 50g o ka cellulose alkalized, e hoʻohui i ka solvent hui ʻia e hana i kahi slurry, hoʻohui i ka catalyst a me ka epoxy resin me ke kaumaha molekala, wela a hiki i 90 ~ 110℃no ka etherification pane 4.0~ 6.0h a hiki i na reactants e miscible. E hoʻohui i ka waika formic e hoʻopau a wehe i ka alkali nui, e hoʻokaʻawale i ka wai a me ka solvent, holoi me 80℃wai wela e wehe i ka paʻakai sodium, a maloʻo no ka hoʻohana hope. Ua ana 'ia ka viscosity intrinsic me ka Ubbelohde viscometer a ua helu 'ia ka viscosity-average molecular weight e like me ka palapala.

Hoʻomākaukau ʻia ka acetate butyl cellulose e like me ke ʻano palapala, kaupaona 57.2g o ka pulupulu i hoʻomaʻemaʻe ʻia, hoʻohui i 55g o ka anhydride acetic, 79g o ka waikawa butyric, 9.5g o ka magnesium acetate, 5.1g o ka waikawa sulfuric, hoʻohana i ka butyl acetate ma ke ʻano he mea hoʻoheheʻe, a hana i ka. kahi mahana a hiki i ke kūpono , neutralized ma ka hoʻohui ʻana i ka sodium acetate, precipitated, kānana, holoi ʻia, kānana, a maloʻo no ka hoʻohana ma hope. E lawe iā Cel-Ep, e hoʻohui i ka nui kūpono o CAB a me ka mea hoʻoheheʻe i hui ʻia, e wela a hoʻoulu no 0.5h e hana i kahi wai mānoanoa like ʻole, a ʻo ka hoʻomākaukau ʻana o ke kiʻiʻoniʻoni a me ka hoʻāʻo hana e hahai i ke ʻano GB-79.

Ka hoʻoholo ʻana i ke ʻano o ka esterification o ka cellulose acetate: e hoʻoheheʻe mua i ka cellulose acetate i ka dimethyl sulfoxide, e hoʻohui i ka nui o ka hopena alkali i ka wela a me ka hydrolyze, a titrate i ka hopena hydrolyzed me ka hopena maʻamau NaOH e helu i ka pau ʻana o ka alkali. Ka hoʻoholo ʻana o ka ʻike wai: E kau i ka hāpana i loko o ka umu ma 100~105°C e maloʻo no 0.2h, kaupaona a helu i ka wai absorption ma hope o ka hooluolu. Ka ho'oholo 'ana i ka ho'omoe 'ana i ka alkali: e kaupaona i kahi la'ana nui, e ho'ohehe'e ia i ka wai wela, e ho'ohui i ka methyl violet indicator, a laila e ho'oemi me 0.05mol/L H2SO4. Ka ho'oholo 'ana i ke degere ho'onui: E kaupaona i ka la'ana he 50g, e uha'i a ho'okomo i loko o ka paipu puka puka, e heluhelu i ka leo ma hope o ka ha'alulu uila, a e hoohalike me ka nui o ka pauda cellulose unalkalined e helu i ke degere ho'onui.

2. Nā hopena a me ke kūkākūkā

2.1 ʻO ka pilina ma waena o ka neʻe ʻana o ka alkali a me ka degere pehu cellulose

ʻO ka hopena o ka cellulose me kahi ʻano o ka hopena NaOH hiki ke hoʻopau i ka crystallization maʻamau a hoʻonohonoho pono ʻia o cellulose a hoʻoulu i ka cellulose. A hiki i nā ʻano hoʻohaʻahaʻa like ʻole i ka lye, e hōʻemi ana i ke ʻano o ka polymerization. Hōʻike nā hoʻokolohua i ka nui o ka pehu o ka cellulose a me ka nui o ka hoʻopaʻa ʻana o ka alkali a i ʻole adsorption e hoʻonui me ka neʻe o ka alkali. Hoʻonui ka degere o ka hydrolysis me ka piʻi ʻana o ka mahana. Ke piʻi ka alkaline i ka 20%, ʻo ke degere o ka hydrolysis he 6.8% ma t=100.°C; he 14% ka degere o ka hydrolysis ma t=135°C. I ka manawa like, hōʻike ka hoʻokolohua i ka wā i ʻoi aku ka alkali ma mua o 30%, ua hoʻemi nui ʻia ka degere o ka hydrolysis o ka cellulose chain scission. Ke piʻi ka alkaline i ka 18%, ʻoi aku ka nui o ka adsorption a me ka pehu ʻana o ka wai, hoʻomau ka piʻi ʻana o ka neʻe ʻana, hāʻule koke i kahi pāpū, a laila loli mau. I ka manawa like, ua maʻalahi kēia hoʻololi i ka mana o ka mahana. Ma lalo o ka hoʻohālikelike alkali like, ke haʻahaʻa ka mahana (<20°C), he nui ka pehu o ka cellulose, a he nui ka adsorption o ka wai; i ka wela kiʻekiʻe, he mea nui ka pehu a me ka nui o ka adsorption wai. hoemi.

Ua hoʻoholo ʻia nā fibers alkali me nā ʻano wai like ʻole a me nā ʻano alkali e ka X-ray diffraction analysis method e like me ka palapala. I ka hana maoli, hoʻohana ʻia ka 18% ~ 20% lye e hoʻomalu i kahi wela o ka hopena e hoʻonui ai i ka pehu o ka cellulose. Hōʻike nā hoʻokolohua e hiki ke hoʻoheheʻe ʻia ka cellulose e ka hoʻomehana ʻana no 6 ~ 12h i nā solvents polar. Ma muli o kēia ʻoiaʻiʻo, manaʻo ka mea kākau i ka solubility o ka cellulose i ka decisive hana i ke degere o ka luku ʻia ʻana o ka hydrogen bond ma waena o nā molekole cellulose i ka mahele crystalline, a ukali ʻia e ka degere o ka luku ʻana i ka hydrogen bond o intramolecular glucose pūʻulu C3-C2. ʻOi aku ka nui o ka luku ʻana i ka hydrogen bond, ʻoi aku ka nui o ka pehu ʻana o ka fiber alkali, a ua luku loa ʻia ka paʻa hydrogen, a ʻo ka hydrolyzate hope he mea hiki ke hoʻoheheʻe ʻia i ka wai.

2.2 Ka hopena o ka Accelerator

ʻO ka hoʻohui ʻana i ka waiʻona kiʻekiʻe-boiling-point i ka wā o ka cellulose alkalization hiki ke hoʻonui i ka wela o ka hopena, a me ka hoʻohui ʻana i kahi mea hoʻolalelale liʻiliʻi e like me ka waiʻona haʻahaʻa a me ka thiourea (a i ʻole ka urea) hiki ke hoʻoikaika nui i ke komo ʻana a me ka pehu ʻana o ka cellulose. Ke piʻi nei ka nui o ka waiʻona, piʻi ka alkali absorption o cellulose, a aia kahi wahi hoʻololi koke i ka 20% o ka neʻe ʻana, ʻo ia paha ke komo ʻana o ka waiʻona monofunctional i loko o nā molekole cellulose e hana i nā paʻa hydrogen me ka cellulose, e pale ana i ka cellulose. nā molekala ʻO nā paʻa hydrogen ma waena o nā kaulahao a me nā kaulahao molecular e hoʻonui i ka degere o ka maʻi, hoʻonui i ka ʻili, a hoʻonui i ka nui o ka adsorption alkali. Eia nō naʻe, ma lalo o nā kūlana like, haʻahaʻa ka lawe ʻana o ka alkali o nā ʻāpana lāʻau, a hoʻololi ke ʻano i kahi kūlana fluctuating. Hiki paha ke pili i ka haʻahaʻa haʻahaʻa o ka cellulose i loko o nā ʻāpana lāʻau, aia ka nui o ka lignin, kahi e pale ai i ke komo ʻana o ka waiʻona, a maikaʻi ke kūpaʻa wai a me ke kūpaʻa alkali.

2.3 Etherification

Hoʻohui i ka 1% B catalyst, hoʻomalu i nā ʻano wela o ka hopena, a hoʻokō i ka hoʻololi etherification me ka epoxy resin a me ka fiber alkali. He haʻahaʻa ka hana etherification reaction ma 80°C. He 28% wale nō ka grafting rate o Cel, a ua aneane pālua ʻia ka hana etherification ma 110.°C. E noʻonoʻo ana i nā kūlana hoʻonā e like me ka solvent, ʻo 100 ka wela o ka hopena°C, a ʻo ka manawa pane he 2.5h, a hiki i ka grafting rate o Cel ke hiki i 41%. Eia kekahi, i ka manawa mua o ka hopena etherification (<1.0h), ma muli o ka hopena heterogeneous ma waena o ka cellulose alkali a me ka resin epoxy, ua haʻahaʻa ka grafting rate. Me ka piʻi ʻana o ke kēkelē etherification Cel, huli mālie ia i ka hopena homogeneous, no laila ua hoʻonui nui ʻia ka hana, a piʻi ka grafting rate.

2.4 Ka pilina ma waena o ka grafting rate a me ka solubility

Ua hōʻike ʻia nā hoʻokolohua ma hope o ke kālai ʻana i ka resin epoxy me ka cellulose alkali, hiki ke hoʻomaikaʻi maikaʻi ʻia nā waiwai kino e like me ka viscosity huahana, adhesion, ka wai a me ke kūpaʻa wela. Ka ho'āʻo hoʻoheheʻe Hiki ke hoʻoheheʻe ʻia ka huahana me ka helu grafting Cel <40% i ka haʻahaʻa alcohol-ester, alkyd resin, polyacrylic acid resin, acrylic pimaric acid a me nā resins ʻē aʻe. Loaʻa i ka resin Cel-Ep ka hopena solubilizing.

Hoʻohui pū ʻia me ka hoʻāʻo ʻana i ke kiʻi ʻoniʻoni, ʻoi aku ka maikaʻi o ka hui ʻana me ka grafting rate o 32% ~ 42% maʻamau, a ʻo nā hui pū me ka helu grafting o <30% he maikaʻi ʻole a me ka haʻahaʻa haʻahaʻa o ke kiʻi uhi; ʻOi aku ka kiʻekiʻe o ka grafting rate ma mua o 42%, ua hoʻemi ʻia ke kūʻē ʻana o ka wai paila, ka pale ʻana i ka waiʻona, a me ka polar organic solvent resistance o ke kiʻi uhi. I mea e hoʻomaikaʻi ai i ka hoʻohālikelike waiwai a me ka hana uhi, ua hoʻohui ka mea kākau i ka CAB e like me ke ʻano ma ka Papa 1 e hoʻoheheʻe hou a hoʻololi e hāpai i ka noho pū ʻana o Cel-Ep a me CAB. Hoʻokumu ka hui ʻana i kahi ʻōnaehana homogeneous kokoke. ʻO ka mānoanoa o ka hui ʻana o ka hui ʻana he lahilahi loa a hoʻāʻo e noho i loko o ke kūlana o nā nano-cell.

2.5 Pili ma waena o Cel—Ep/CAB hui pū ʻana a me nā waiwai kino

Ke hoʻohana nei iā Cel-Ep e hui pū me CAB, hōʻike nā hopena hoʻāʻo uhi e hiki i ka cellulose acetate ke hoʻomaikaʻi nui i nā waiwai o ka uhi ʻana o ka mea, ʻoi aku ka wikiwiki o ka maloʻo. ʻO ka mea maʻemaʻe o Cel-Ep paʻakikī e maloʻo i ka lumi wela. Ma hope o ka hoʻohui ʻana i ka CAB, ʻike ʻia nā mea ʻelua i ka hoʻokō pono.

2.6 ʻike kikoʻī FTIR

3. Ka hopena

(1) Hiki ke pehu ka pulupulu cellulose i 80°C me ka> 18% alkaline concentrated a me ka moʻo o nā mea hoʻohui, hoʻonui i ka mahana hopena, hoʻolōʻihi i ka manawa pane, hoʻonui i ka degere o ka pehu a me ka degradation a hiki i ka hydrolyzed loa.

(2) Etherification reaction, ʻo ka Cel-Ep molar feed ratio he 2, ʻo ka mahana hopena he 100°C, ʻo 5h ka manawa, ʻo ka helu catalyst he 1%, a hiki i ka etherification grafting rate ke hiki i 32% ~ 42%.

(3) ʻO ka hoʻololi ʻana i ka hui ʻana, i ka wā o ka molar ratio o Cel-Ep: CAB = 3: 2, maikaʻi ka hana o ka huahana synthesized, akā ʻaʻole hiki ke hoʻohana ʻia ʻo Cel-Ep maʻemaʻe ma ke ʻano he uhi, e like me ka mea hoʻopili.