I-Cellulose Ether kwi-Epoxy Resin

Umqhaphu ongcolileyo kunye ne-sawdust zisetyenziswa njengemathiriyeli ekrwada, kwaye i-hydrolyzed ibe yialkalii-cellulose etherphantsi kwesenzo se-18% ye-alkali kunye nochungechunge lwezongezo. Emva koko sebenzisa i-epoxy resin xa uxhunyelelwa, i-molar ratio ye-epoxy resin kunye ne-alkali fiber yi-0.5: 1.0, iqondo lokushisa li-100.°C, ixesha lokuphendula liyi-5.0h, idosi ye-catalyst yi-1%, kunye ne-etherification grafting rate yi-32%. I-epoxy cellulose ether efunyenweyo ixutywe kunye ne-0.6mol Cel-Ep kunye ne-0.4mol CAB ukudibanisa imveliso entsha yokugqoka kunye nokusebenza kakuhle. Ulwakhiwo lwemveliso luqinisekisiwe nge-IR.

Amagama angundoqo:i-cellulose ether; ukudibanisa IKHEBHU; iimpawu zokugquma

Iselulosi ether yipolymer yendalo, eyenziwa yi-condensation yeβ-iglucose. I-Cellulose inezinga eliphezulu le-polymerization, iqondo elihle lokuqhelaniswa, kunye nokuzinza okulungileyo kweekhemikhali. Inokufumaneka ngokuphatha i-cellulose ngamachiza (i-esterification okanye i-etherification). Uluhlu lwee-cellulose derivatives, ezi mveliso zisetyenziswa ngokubanzi kwiiplastiki, iibhokisi zesidlo sasemini ezibolayo, i-automotive coatings, i-auto parts, i-inki yokuprinta, i-adhesives, njl. Okwangoku, iintlobo ezintsha ze-cellulose ezitshintshiweyo zihlala zivela, kwaye imimandla yesicelo ukwandisa rhoqo, ngokuthe ngcembe ukwenza inkqubo yoshishino lwefayibha. Esi sihloko kukusebenzisa i-sawdust okanye i-cotton enkunkuma ukuba ifakwe i-hydrolyzed ibe yimicu emifutshane nge-lye, kwaye emva koko ixutywe ngekhemikhali kwaye iguqulwe ukuze yenze uhlobo olutsha lokugquma olungakhange luchazwe kuxwebhu.

1. Linge

1.1 Ii-reagents kunye nezixhobo

Umqhaphu wenkunkuma (ihlanjwe kwaye yomiswe), i-NaOH, i-1,4-butanediol, i-methanol, i-thiourea, i-urea, i-epoxy resin, i-acetic anhydride, i-butyric acid, i-trichloroethane, i-formic acid, i-glyoxal, i-toluene, i-CAB, njl. (Ubunyulu yi-CP grade) . I-Magna-IR 550 ye-infrared spectrometer eveliswe yiNicolet Inkampani yase-United States yayisetyenziselwa ukulungiselela iisampuli nge-solvent tetrahydrofuran coating. Tu-4 viscometer, FVXD3-1 uhlobo iqondo lobushushu rhoqo self-controlled ombane evuselela reaction ketile, eveliswe Weihai Xiangwei Chemical Machinery Factory; I-viscometer ejikelezayo i-NDJ-7, uhlobo lwe-Z-10MP5, oluveliswe yi-Shanghai Tianping Instrument Factory; ubunzima bemolekyuli bulinganiswa ne-Ubbelohde viscosity; Ukulungiswa kunye nokuvavanywa kwefilimu yepeyinti kuya kwenziwa ngokwemigangatho yesizwe ye-GB-79.

1.2 Umgaqo wokuphendula

1.3 Ukudibanisa

Ukwenziwa kwe-epoxy cellulose: Yongeza i-100g yefayibha yomqhaphu enqunqiweyo kwiqondo lobushushu elingaguqukiyo elizilawulayo lombane elishukumisayo, yongeza i-oxidant kwaye usabele imizuzu eyi-10, emva koko wongeze utywala kunye nealkali ukwenza i-lye kunye noxinzelelo lwe-18%. Yongeza i-accelerators A, B, njalo njalo ukwenzela ukukhulelwa. Ukuphendula kubushushu obuthile phantsi kwe-vacuum iiyure ezili-12, hluza, yome kwaye ulinganise i-50g ye-alkalized cellulose, yongeza isinyibilikisi esixubeneyo ukwenza i-slurry, yongeza i-catalyst kunye ne-epoxy resin enobunzima obuthile be-molecular, ukushisa ukuya kuma-90 ~ 110.℃ukwenzela ukusabela kwe-etherification 4.0 ~ 6.0h de i-reactants iyaxubana. Yongeza i-asidi ye-formic ukuze unciphise kwaye ususe i-alkali engaphezulu, yahlula isisombululo se-aqueous kunye ne-solvent, hlamba nge-80.℃amanzi ashushu ukususa ityuwa yesodium, kwaye yome ukuze isetyenziswe kamva. I-intrinsic viscosity yalinganiswa nge-viscometer ye-Ubbelohde kunye ne-viscosity-avareji ye-molecular weight ibalwa ngokweencwadi.

I-acetate butyl cellulose ilungiswe ngokwendlela yoncwadi, ilinganisa i-57.2g yekotoni ecocekileyo, yongeza i-55g ye-acetic anhydride, i-79g ye-butyric acid, i-9.5g ye-magnesium acetate, i-5.1g ye-sulfuric acid, sebenzisa i-butyl acetate njenge-solvent, kwaye uphendule kuyo. iqondo lobushushu elithile de ube ufanelekile, ungathathi hlangothi ngokongeza i-acetate ye-sodium, i-precipitated, ihluziwe, ihlanjwe, ihluzwe, kwaye yomiswe ukuze isetyenziswe kamva. Thatha i-Cel-Ep, yongeza inani elifanelekileyo le-CAB kunye ne-solvent ethile edibeneyo, fudumeza kwaye uvuselele i-0.5h ukuze wenze ulwelo olungqingqwa olufanayo, kunye nokulungiswa kwefilimu yokugqoka kunye novavanyo lokusebenza lulandela indlela ye-GB-79.

Ukuzimisela kweqondo le-esterification ye-cellulose acetate: okokuqala ukunyibilikisa i-cellulose acetate kwi-dimethyl sulfoxide, yongeza inani elilinganisiweyo lesisombululo se-alkali ukutshisa kunye ne-hydrolyze, kunye ne-titrate isisombululo se-hydrolyzed kunye nesisombululo esiqhelekileyo se-NaOH sokubala ukusetyenziswa okupheleleyo kwe-alkali. Ukumiselwa komxholo wamanzi: Beka isampuli kwi-oven kwi-100 ~ 105°C ukomisa i-0.2h, ulinganise kwaye ubale ukufunxa kwamanzi emva kokupholisa. Ukumiselwa kwe-alkali yokufunxa: linganisa isampuli yobungakanani, yinyibilikise emanzini ashushu, yongeza isalathisi se-methyl violet, kwaye emva koko i-titrate nge-0.05mol / L H2SO4. Ukuzimisela kweqondo lokwandisa: Ukulinganisa isampuli ye-50g, uyiqhekeze kwaye uyibeke kwi-tube ethweswe isidanga, funda umthamo emva kokunyakaza kombane, kwaye uthelekise kunye nomthamo we-cellulose powder unalkalined ukubala idigri yokwandisa.

2. Iziphumo kunye nengxoxo

2.1 Ubudlelwane phakathi koxinzelelo lwe-alkali kunye nesidanga sokudumba seselulosi

Ukusabela kwe-cellulose kunye noxinzelelo oluthile lwesisombululo se-NaOH kunokutshabalalisa i-crystallization eqhelekileyo kunye neyocwangco ye-cellulose kwaye yenza i-cellulose ivuvuke. Kwaye ukuthotywa okuhlukeneyo kwenzeka kwi-lye, ukunciphisa iqondo le-polymerization. Iimvavanyo zibonisa ukuba iqondo lokudumba kwe-cellulose kunye nomthamo wokubopha i-alkali okanye i-adsorption yonyuka ngokuxinwa kwe-alkali. Iqondo le-hydrolysis liyanda ngokunyuka kweqondo lokushisa. Xa i-alkali concentration ifikelela kwi-20%, iqondo le-hydrolysis yi-6.8% kwi-t=100.°C; iqondo le-hydrolysis yi-14% kwi-t = 135°C. Ngelo xesha, uvavanyo lubonisa ukuba xa i-alkali ingaphezulu kwe-30%, iqondo le-hydrolysis ye-cellulose chain scission liyancipha kakhulu. Xa ugxininiso lwe-alkali lufikelela kwi-18%, umthamo we-adsorption kunye neqondo lokuvuvukala lamanzi liphezulu, ugxininiso luqhubeka lukhula, luhla ngokukhawuleza kwi-plateau, kwaye lutshintshe ngokuthe ngcembe. Kwangaxeshanye, olu tshintsho lunobuntununtunu kwimpembelelo yobushushu. Ngaphantsi koxinzelelo olufanayo lwealkali, xa ubushushu buphantsi (<20°C), iqondo lokudumba kwe-cellulose likhulu, kwaye inani le-adsorption yamanzi likhulu; kwiqondo lokushisa eliphezulu, iqondo lokudumba kunye nexabiso le-adsorption yamanzi libalulekile. nciphisa.

Iifiber ze-alkali ezinomxholo ohlukeneyo wamanzi kunye nomxholo we-alkali zinqunywe yindlela yohlalutyo lwe-X-ray ye-diffraction ngokweencwadi. Kumsebenzi wokwenyani, i-18% ~ 20% yelye isetyenziselwa ukulawula ubushushu bokusabela ukunyusa iqondo lokudumba kweselulosi. Iimvavanyo zibonisa ukuba i-cellulose iphendule ngokufudumeza i-6 ~ 12h inokuchithwa kwii-solvents ze-polar. Ngokusekelwe kule nyaniso, umbhali ucinga ukuba i-solubility ye-cellulose idlala indima ecacileyo kwiqondo lokutshabalalisa i-hydrogen bond phakathi kwee-molecule ze-cellulose kwi-crystalline segment, ilandelwa yi-degree of hydrogen bond yokutshatyalaliswa kwamaqela e-intramolecular glucose C3-C2. Iqondo elikhulu lokutshabalalisa i-hydrogen bond, iqondo elikhulu lokudumba kwefiber yealkali, kunye ne-hydrogen bond itshatyalaliswe ngokupheleleyo, kwaye i-hydrolyzate yokugqibela yinto enyibilikayo emanzini.

2.2 Isiphumo se-Accelerator

Ukongeza iqondo eliphezulu lokubilisa utywala ngexesha le-cellulose alkalization inokunyusa ubushushu bokusabela, kwaye ukongeza inani elincinci le-propellant efana ne-alcohol ephantsi kunye ne-thiourea (okanye i-urea) inokukhuthaza kakhulu ukungena kunye nokudumba kweselulosi. Njengoko uxinaniso lotywala lusanda, ukufunxwa kwe-alkali kweselulosi kuyanda, kwaye kukho inqaku lotshintsho ngequbuliso xa ugxininiso luyi-20%, enokuthi i-alcohol engasebenziyo ingene kwiimolekyuli zeselulosi ukuze zenze i-hydrogen bond kunye neselulosi, ikhusela i-cellulose. Iimolekyuli Iibhondi zehydrogen phakathi kwamatyathanga kunye namatyathanga emolekyuli zonyusa izinga lokuphazamiseka, zandise indawo engaphezulu, kwaye zandise ubungakanani be-alkali adsorption. Nangona kunjalo, phantsi kweemeko ezifanayo, ukufunxwa kwee-alkali zeetshiphu zomthi kuphantsi, kwaye ijika liyatshintsha kwimeko eguquguqukayo. Inokuthi ihambelane nomxholo ophantsi we-cellulose kwiitshiphu zokhuni, eziqulethe inani elikhulu le-lignin, elithintela ukungena kotywala, kwaye inokumelana nokuchasana kwamanzi kunye nokuchasana kwe-alkali.

2.3 I-Etherification

Yongeza i-1% B catalyst, lawula amaqondo obushushu ahlukeneyo, kwaye wenze ukuguqulwa kwe-etherification nge-epoxy resin kunye ne-alkali fiber. Umsebenzi we-etherification reaction uphantsi kwi-80°C. Izinga lokuxhunyelelwa kweCel yi-28% kuphela, kwaye umsebenzi we-etherification uphantse uphindwe kabini kwi-110.°C. Ukuqwalasela iimeko zokusabela ezifana ne-solvent, iqondo lokushisa lokuphendula liyi-100°C, kwaye ixesha lokuphendula liyi-2.5h, kwaye izinga lokuxhunyelelwa kweCel linokufikelela kwi-41%. Ukongezelela, kwinqanaba lokuqala le-etherification reaction (<1.0h), ngenxa ye-heterogeneous reaction phakathi kwe-alkali cellulose kunye ne-epoxy resin, izinga lokuxhunyelelwa liphantsi. Ngokunyuka kweqondo le-Cel etherification, ngokuthe ngcembe ijika ibe yi-homogeneous reaction, ngoko ukusabela Umsebenzi wanda ngokukhawuleza, kwaye izinga lokuxhunyelelwa liye landa.

2.4 Ubudlelwane phakathi kweqondo lokuxhunyelelwa kweCel kunye nokunyibilika

Iimvavanyo zibonise ukuba emva kokufaka i-epoxy resin kunye ne-alkali cellulose, iimpawu ezibonakalayo ezifana ne-viscosity yemveliso, ukunamathela, ukuxhathisa kwamanzi, kunye nokuzinza kwe-thermal kunokuphuculwa kakhulu. Uvavanyo lwe-Solubility Imveliso enezinga lokuxhunyelelwa kwe-Cel <40% inokunyibilika kwi-alcohol-ester ephantsi, i-alkyd resin, i-polyacrylic acid resin, i-acrylic pimaric acid kunye nezinye ii-resin. I-resin ye-Cel-Ep inesiphumo esicacileyo sokunyibilikisa.

Ukudibanisa kunye novavanyo lwefilimu yokugqoka, ukudibanisa kunye nesantya sokuxutywa kwe-32% ~ 42% ngokubanzi kunokuhambelana okungcono, kwaye ukudibanisa kunye nesantya se-grafting <30% sinokuhambelana okungahambi kakuhle kunye ne-gloss ephantsi yefilimu yokugqoka; izinga lokuxhunyelelwa liphezulu kune-42%, ukuxhathisa kwamanzi abilayo, ukunganyangeki kotywala, kunye ne-polar organic solvent resistance yefilimu yokugquma iyancitshiswa. Ukuze kuphuculwe ukuhambelana kwezinto eziphathekayo kunye nokusebenza kweengubo, umbhali wongezelela i-CAB ngokwefomula kwiThebhile 1 ukuqhubela phambili u-solubilize kunye nokuguqula ukukhuthaza ukubambisana kwe-Cel-Ep kunye ne-CAB. Umxube wenza inkqubo ye-homogeneous esondeleyo. Ubungakanani be-interface yokwakheka komxube buthande ukuba mncinci kakhulu kwaye uzame ukuba kwimeko yeeseli ze-nano.

2.5 Ubudlelwane phakathi kukaCel-I-Ep / CAB yokudibanisa umlinganiselo kunye neempawu ezibonakalayo

Ukusebenzisa i-Cel-Ep ukudibanisa ne-CAB, iziphumo zovavanyo lokugquma zibonisa ukuba i-cellulose acetate inokuphucula kakhulu iipropati zokugubungela izinto, ngakumbi isantya sokumisa. Icandelo elicocekileyo leCel-Ep linzima ukomisa kwiqondo lokushisa. Emva kokongeza i-CAB, ezi zixhobo zimbini zinokuhambelana okucacileyo kokusebenza.

2.6 Ukubona i-FTIR spectrum

3. Isiphelo

(1) I-cotton cellulose inokudumba kwi-80°C kunye > 18% yealkali egxininisiweyo kunye nothotho lwezongezo, ukwandisa ubushushu bokusabela, ukwandisa ixesha lokuphendula, ukwandisa iqondo lokudumba kunye nokuthotywa de kube yi-hydrolyzed ngokupheleleyo.

(2) Ukusabela kwe-Etherification, i-Cel-Ep ye-molar feed ratio yi-2, iqondo lokushisa liyi-100°C, ixesha yi-5h, i-dosage ye-catalyst yi-1%, kwaye izinga lokuxhunyelelwa kwe-etherification linokufikelela kwi-32% ~ 42%.

(3) Ukuguqulwa kokudibanisa, xa umlinganiselo we-molar we-Cel-Ep: CAB = 3: 2, ukusebenza kwemveliso edibeneyo kulungile, kodwa i-Cel-Ep ecocekileyo ayinakusetyenziswa njengengubo, kuphela njengento yokubambelela.