Cellulose Ether paEpoxy Resin

Donje remarara nesawdust zvinoshandiswa semidziyo, uye zvinoiswa hydrolyzed kuita alkalicellulose etherpasi pechiito che18% alkali uye nhevedzano yezvinowedzera. Wobva washandisa epoxy resin yekubatanidza, iyo molar ratio ye epoxy resin uye alkali fiber i 0.5: 1.0, the reaction tembiricha i100.°C, nguva yekuita ndeye 5.0h, iyo catalyst dosage i1%, uye etherification grafting rate i32%. Iyo yakawanikwa epoxy cellulose ether inosanganiswa ne 0.6mol Cel-Ep uye 0.4mol CAB kugadzira chigadzirwa chitsva chekunamira nekushanda kwakanaka. Chimiro chechigadzirwa chakasimbiswa neIR.

Mazwi akakosha:cellulose ether; synthesis; CAB; kupfeka zvinhu

Cellulose ether is a natural polymer, iyo inoumbwa ne condensation yeβ-glucose. Cellulose ine yakakwira dhigirii yekupolymerization, yakanaka dhigirii yekumisikidza, uye yakanaka kugadzikana kwemakemikari. Inogona kuwanikwa nemakemikari kurapa cellulose (esterification kana etherification). Mutsara wezvinobva muselulosi, zvigadzirwa izvi zvinonyanya kushandiswa mumapurasitiki, biodegradable lunch boxes, high-end emota coatings, auto parts, printing inki, adhesives, etc. Parizvino, mhando itsva dzakagadziridzwa cellulose dziri kuramba dzichibuda, uye minda yekushandisa iri ichiramba ichiwedzera, zvishoma nezvishoma ichigadzira fiber industry system. Musoro uyu ndewekushandisa sawdust kana donje remarara kuti riitwe hydrolyzed kuita shinda pfupi nelye, yozobatanidzwa nekemikari nekugadziridzwa kuita rudzi rutsva rwejasi risina kutaurwa mugwaro.

1. Kuedza

1.1 Reagents uye zviridzwa

Donje tsvina (yakashambidzwa uye yakaomeswa), NaOH, 1,4-butanediol, methanol, thiourea, urea, epoxy resin, acetic anhydride, butyric acid, trichloroethane, formic acid, glyoxal, toluene, CAB, nezvimwewo (Kuchena iCP grade) . Magna-IR 550 infrared spectrometer inogadzirwa neNicolet Company yekuUnited States yakashandiswa kugadzira sampuli ne solvent tetrahydrofuran coating. Tu-4 viscometer, FVXD3-1 mhando inoramba tembiricha inozvidzora yemagetsi inobvongodza mhinduro kettle, inogadzirwa neWeihai Xiangwei Chemical Machinery Factory; rotational viscometer NDJ-7, Z-10MP5 mhando, yakagadzirwa neShanghai Tianping Instrument Factory; molecular weight inoyerwa neUbbelohde viscosity; Kugadzirira uye kuyedzwa kwefirimu repende kuchaitwa zvinoenderana nenyika standard GB-79.

1.2 Maitiro ekuita

1.3 Synthesis

Synthesis ye epoxy cellulose: Wedzera 100g yedonje faibha yakachekwa kune tembiricha inozvidzora inozvidzora yemagetsi inobvongodza, wedzera oxidant uye ita kwemaminetsi gumi, wobva wawedzera doro nealkali kugadzira lye ine 18%. Wedzera accelerators A, B, nezvimwewo zvekuisa pamuviri. React pane imwe tembiricha pasi pevacuum kwemaawa gumi nemaviri, sefa, yakaoma uye uremu 50g yealkalized cellulose, wedzera yakasanganiswa solvent kugadzira slurry, wedzera catalyst uye epoxy resin ine chaiwo mamorekuru uremu, kupisa kusvika 90 ~ 110.℃ye etherification reaction 4.0 ~ 6.0h kusvika ma reactants akanganisa. Wedzera formic acid kuti iite neutralize uye bvisa yakawandisa alkali, patsanura iyo aqueous solution uye solvent, geza ne80.℃mvura inopisa kubvisa sodium munyu, uye wooma kuti ushandise gare gare. Iyo intrinsic viscosity yakayerwa neUbbelohde viscometer uye viscosity-avhareji yemamorekuru uremu yakaverengerwa maererano nezvinyorwa.

Acetate butyl cellulose inogadzirirwa maererano nemaitiro ezvinyorwa, kuyera 57.2g yekotoni yakanatswa, kuwedzera 55g yeacetic anhydride, 79g yebutyric acid, 9.5g ye magnesium acetate, 5.1g ye sulfuric acid, shandisa butyl acetate se solvent, uye ita pa imwe tembiricha kusvika yakwana, yakaderedzwa nekuwedzera sodium acetate, yakanyoroveswa, yakasefa, yakagezwa, yakapepetwa, uye yakaomeswa kuti ishandiswe gare gare. Tora Cel-Ep, wedzera huwandu hwakakodzera hweCAB uye chaiyo yakasanganiswa solvent, kupisa uye kurunga kwe 0.5h kuti uite yunifomu gobvu mvura, uye kugadzirira firimu rekuputira uye bvunzo yekuita inotevedzera iyo GB-79 nzira.

Kutsunga kwedhigirii ye esterification ye cellulose acetate: tanga nyungudutsa cellulose acetate mu dimethyl sulfoxide, wedzera metered yealkali mhinduro yekupisa uye hydrolyze, uye titrate iyo hydrolyzed mhinduro neNaOH yakajairwa mhinduro kuverenga iyo yakazara kushandiswa kwealkali. Kutsunga kwehuwandu hwemvura: Isa sampuli muovheni pa100 ~ 105°C kuoma kwe 0.2h, kuyera uye kuverenga kutorwa kwemvura mushure mekutonhora. Kutsunga kwekunyura kwealkali: kuyera chiyero chekuenzanisa, kuinyungudutsa mumvura inopisa, wedzera methyl violet chiratidzo, uyezve titrate ne 0.05mol/L H2SO4. Kutsunga kwedhigirii rekuwedzera: Weresa 50g sampuli, woipwanya woiisa muchubhu yapedza kudzidza, verenga vhoriyamu mushure mekudengenyeka kwemagetsi, uye enzanisa nehuwandu hweunalkalined cellulose poda kuverenga dhigirii rekuwedzera.

2. Migumisiro uye nhaurirano

2.1 Hukama huri pakati pealkali concentration uye cellulose kuzvimba degree

Kuita kwe cellulose ine imwe denderedzwa yeNaOH mhinduro inogona kuparadza yakajairika uye yakarongeka crystallization ye cellulose uye kuita kuti cellulose izimbe. Uye kukanganisa kwakasiyana-siyana kunoitika mulye, kuderedza dhigirii repolymerization. Ongororo dzinoratidza kuti dhigirii rekuzvimba kweselulosi uye huwandu hwealkali kusunga kana adsorption inowedzera nekuwanda kwealkali. Dhigirii ye hydrolysis inowedzera nekuwedzera kwekushisa. Kana iyo alkali concentration yasvika 20%, dhigirii re hydrolysis i 6.8% pa t = 100.°C; dhigirii rehydrolysis i14% pa t = 135°C. Panguva imwecheteyo, kuedza kunoratidza kuti kana alkali inopfuura 30%, dhigirii ye hydrolysis ye cellulose chain scission yakaderera zvikuru. Kana iyo alkali concentration inosvika 18%, iyo adsorption kugona uye kuzvimba dhigirii remvura ndiyo yakanyanya, iyo yekuisa inoenderera ichiwedzera, inodonha zvakanyanya kune bani, uyezve inoshanduka zvishoma nezvishoma. Panguva imwecheteyo, shanduko iyi inonyatsonzwa kune simba rekushisa. Pasi peiyo yakafanana alkali concentration, kana tembiricha yakadzikira (<20°C), iyo yekuzvimba degree ye cellulose yakakura, uye adsorption huwandu hwemvura hwakakura; pakupisa kwakanyanya, dhigirii yekuzvimba uye huwandu hwemvura adsorption hwakakosha. kuderedza.

Alkali fibers ine mvura yakasiyana-siyana uye alkali yemukati yakatemwa neX-ray diffraction yekuongorora nzira maererano nezvinyorwa. Mukushanda chaiko, 18% ~ 20% lye inoshandiswa kudzora imwe reaction tembiricha kuwedzera dhigirii yekuzvimba yeselulosi. Ongororo dzinoratidza kuti cellulose yakaitwa nekudziya kwe6 ~ 12h inogona kunyungudika mu polar solvents. Zvichienderana nechinhu ichi, munyori anofunga kuti kunyungudika kweselulosi kunoita basa rakasimba padanho rekuparadza kwehydrogen bond pakati pemamorekuru e cellulose muchikamu checrystalline, chinoteverwa nedhigirii rehydrogen bond kuparadzwa kwemapoka e-intramolecular glucose C3-C2. Iyo yakakura dhigirii yehydrogen bond kuparadzwa, iyo yakakura dhigirii yekuzvimba yealkali fiber, uye hydrogen bond inoparadzwa zvachose, uye yekupedzisira hydrolyzate chinhu chinonyungudika nemvura.

2.2 Mhedzisiro yeAccelerator

Kuwedzera yakakwira-inofashaira-doro panguva ye cellulose alkalization inogona kuwedzera tembiricha yekuita, uye kuwedzera diki diki yepropellant senge yakaderera doro uye thiourea (kana urea) inogona kukurudzira zvakanyanya kupinda uye kuzvimba kweselulosi. Sezvo kuwanda kwedoro kunowedzera, kunyura kwealkali kwe cellulose kunowedzera, uye pane kamwe-kamwe shanduko yekuchinja kana fungidziro iri 20%, inogona kunge iri iyo monofunctional doro inopinda mumamorekuru ecellulose kuumba hydrogen bonds ne cellulose, kudzivirira cellulose. mamorekuru Iyo haidrojeni zvisungo pakati pecheni nemacheni mamorekuru inowedzera dhigirii yekusagadzikana, inowedzera nzvimbo yepamusoro, uye inowedzera huwandu hwealkali adsorption. Nekudaro, pasi pemamiriro akafanana, kutorwa kwealkali kwehuni machipisi kwakadzikira, uye curve inoshanduka mumamiriro ekuchinja. Inogona kunge yakabatana nechepasi ye cellulose muhuni chips, iyo ine yakawanda ye lignin, iyo inodzivisa kupinda kwedoro, uye ine mvura yakanaka yekudzivirira uye alkali resistance.

2.3 Etherification

Wedzera 1% B catalyst, dzora tembiricha dzakasiyana, uye ita etherification gadziriso ine epoxy resin uye alkali fiber. Iyo etherification reaction chiitiko yakaderera pa80°C. The grafting rate yeCel inongova 28%, uye etherification chiitiko chakapetwa kaviri pa110.°C. Tichifunga nezvemaitiro ekuita senge solvent, the reaction tembiricha i100°C, uye nguva yekuita ndeye 2.5h, uye chiyero chekubatanidza cheCel chinogona kusvika 41%. Mukuwedzera, padanho rekutanga re etherification reaction (<1.0h), nekuda kwekuita kwakasiyana-siyana pakati pealkali cellulose uye epoxy resin, chiyero chekubatanidza chakaderera. Nekuwedzera kweCel etherification degree, zvishoma nezvishoma inoshanduka kuita homogeneous reaction, saka maitiro Chiitiko chacho chakawedzera zvakanyanya, uye chiyero chekubatanidza chakawedzera.

2.4 Hukama pakati peCel grafting rate uye solubility

Ongororo dzakaratidza kuti mushure mekubatanidza epoxy resin nealkali cellulose, zvimiro zvemuviri senge chigadzirwa viscosity, adhesion, kuramba mvura, uye kugadzikana kwekupisa kunogona kuvandudzwa zvakanyanya. Solubility bvunzo Chigadzirwa neCel grafting rate <40% inogona kunyungudika mune yakaderera doro-ester, alkyd resin, polyacrylic acid resin, acrylic pimaric acid uye mamwe marekeni. Cel-Ep resin ine pachena solubilizing mhedzisiro.

Yakasanganiswa neyekuputira firimu bvunzo, iyo yakasanganiswa neiyo grafting rate ye 32% ~ 42% kazhinji ine zvirinani kuenderana, uye iyo yakasanganiswa neiyo grafting rate ye <30% ine urombo kuenderana uye yakaderera gloss yefirimu yekupfeka; chiyero chekubatanidza chakakwira kupfuura 42%, kuvira kwemvura inofashaira, kusagadzikana kwedoro, uye polar organic solvent resistance yefirimu yekuputira yakaderedzwa. Kuti uvandudze kuwirirana kwezvinhu uye kuita kwekuputira, munyori akawedzera CAB zvinoenderana neformula iri muTable 1 kuti iwedzere kunyungudika nekugadzirisa kusimudzira kugarisana kweCel-Ep neCAB. Musanganiswa unoumba inenge iine homogeneous system. Iyo yekuumbwa interface ukobvu hwemusanganiswa hunoita kunge hutete zvakanyanya uye edza kuve muchimiro che nano-masero.

2.5 Hukama pakati paCel-Ep/CAB kusanganisa chiyero uye zvimiro zvemuviri

Uchishandisa Cel-Ep kusanganisa neCAB, mhedzisiro yekuyedza yekuputira inoratidza kuti cellulose acetate inogona kuvandudza zvakanyanya mabatiro emidziyo, kunyanya kumhanya kwekuomesa. Iyo yakachena chikamu cheCel-Ep inonetsa kuomesa patembiricha yekamuri. Mushure mekuwedzera CAB, zvinhu zviviri izvi zvine kuenderana kuri pachena kwekuita.

2.6 FTIR spectrum kuonekwa

3. Mhedziso

(1) Cotton cellulose inogona kuzvimba kusvika makumi masere°C ine > 18% yakanyungudutswa alkali uye nhevedzano yezvinowedzera, wedzera maitiro ekushisa, kurebesa nguva yekuita, kuwedzera dhigirii yekuzvimba uye kuderera kusvika yanyatso hydrolyzed.

(2) Etherification reaction, iyo Cel-Ep molar feed ratio ndeye 2, iyo yekudziya tembiricha i100°C, nguva i5h, iyo catalyst dosage i1%, uye etherification grafting rate inogona kusvika 32% ~ 42%.

(3) Kusanganiswa kwekugadzirisa, apo chiyero chemolar cheCel-Ep: CAB = 3: 2, kushanda kwechigadzirwa chakagadzirwa zvakanaka, asi Cel-Ep yakachena haigoni kushandiswa sechifukidzo, sechinhu chinonamatira.