Cellulose Ether pa Epoxy Resin

Thonje lotayidwa ndi utuchi amagwiritsidwa ntchito ngati zopangira, ndipo amapangidwa ndi hydrolyzed kukhala alkalicellulose etherpansi pa zochita za 18% alkali ndi mndandanda wa zowonjezera. Kenako gwiritsani ntchito epoxy resin polumikiza, chiŵerengero cha molar cha epoxy resin ndi utomoni wa alkali ndi 0.5: 1.0, kutentha komweko ndi 100°C, nthawi yochitira ndi 5.0h, chothandizira mlingo ndi 1%, ndi etherification Ankalumikiza mlingo ndi 32%. Epoxy cellulose ether yomwe yapezedwa imaphatikizidwa ndi 0.6mol Cel-Ep ndi 0.4mol CAB kuti apange chinthu chatsopano chopaka ndi ntchito yabwino. Mapangidwe azinthu adatsimikiziridwa ndi IR.

Mawu ofunikira:cellulose ether; kaphatikizidwe; ZASHUGA; ❖ kuyanika katundu

Ma cellulose ether ndi polima zachilengedwe, amene amapangidwa ndi condensation waβ- glucose. Ma cellulose ali ndi ma polymerization apamwamba kwambiri, ali ndi mawonekedwe abwino, komanso kukhazikika kwamankhwala. Itha kupezeka pochiza cellulose (esterification kapena etherification). Mndandanda wazinthu zochokera ku cellulose, zinthuzi zimagwiritsidwa ntchito kwambiri m'mapulasitiki, mabokosi a nkhomaliro a biodegradable, zokutira zamagalimoto apamwamba, zida zamagalimoto, inki zosindikizira, zomatira, ndi zina zambiri. kukula mosalekeza, pang'onopang'ono kupanga makina opanga fiber. Mutuwu ndi kugwiritsa ntchito utuchi kapena zinyalala thonje kuti hydrolyzed kukhala ulusi waufupi ndi sopo, ndiyeno kumezanitsidwa ndi mankhwala ndi kusinthidwa kupanga mtundu watsopano wa zokutira zomwe sizinafotokozedwe mu chikalata.

1. Yesani

1.1 Reagents ndi zida

Zinyalala thonje (zotsukidwa ndi zouma), NaOH, 1,4-butanediol, methanol, thiourea, urea, epoxy resin, acetic anhydride, butyric acid, trichloroethane, formic acid, glyoxal, toluene, CAB, etc. (Purity is CP grade) . Magna-IR 550 infrared spectrometer yopangidwa ndi Nicolet Company ya ku United States inagwiritsidwa ntchito pokonzekera zitsanzo ndi zokutira zosungunulira za tetrahydrofuran. Tu-4 viscometer, FVXD3-1 mtundu nthawi zonse kutentha kudziletsa magetsi yogwira mtima anachita ketulo, opangidwa ndi Weihai Xiangwei Chemical Machinery Factory; rotational viscometer NDJ-7, Z-10MP5 mtundu, opangidwa ndi Shanghai Tianping Instrument Factory; kulemera kwa maselo kumayesedwa ndi kukhuthala kwa Ubbelohde; Kukonzekera ndi kuyesa filimu ya utoto kudzachitika molingana ndi muyezo wadziko lonse wa GB-79.

1.2 Mfundo yochitira

1.3 Zophatikiza

Kaphatikizidwe ka cellulose epoxy: Onjezani 100g ya ulusi wa thonje wodulidwa ku kutentha kosalekeza kwamagetsi oyendetsa magetsi, onjezerani oxidant ndikuchitapo kanthu kwa mphindi 10, kenaka yikani mowa ndi zamchere kuti mupange sopo ndi ndende ya 18%. Onjezani ma accelerator A, B, ndi ena. Chitani pa kutentha kwina pansi vakuyumu kwa maola 12, fyuluta, youma ndi kulemera kwa 50g ya cellulose ya alkali, onjezerani zosungunulira zosakaniza kuti mupange slurry, onjezerani chothandizira ndi epoxy resin ndi kulemera kwake kwa maselo, kutentha mpaka 90 ~ 110.℃chifukwa etherification anachita 4.0 ~ 6.0h mpaka reactants ndi miscible. Onjezani formic acid kuti muchepetse ndikuchotsa alkali wowonjezera, patulani yankho lamadzi ndi zosungunulira, sambani ndi 80.℃madzi otentha kuchotsa mchere wa sodium, ndi kuumitsa ntchito pambuyo pake. The intrinsic viscosity anayesedwa ndi Ubbelohde viscometer ndi viscosity-average molekyulu kulemera anawerengedwa malinga ndi mabuku.

Acetate butyl cellulose imakonzedwa molingana ndi njira ya mabuku, kulemera kwa 57.2g wa thonje woyengedwa, kuwonjezera 55g ya acetic anhydride, 79g ya butyric acid, 9.5g ya magnesium acetate, 5.1g ya sulfuric acid, gwiritsani ntchito butyl acetate monga zosungunulira, ndikuchitapo kanthu. kutentha kwina mpaka kuyeneretsedwa, kuchepetsedwa powonjezera sodium acetate, kutenthedwa, kusefedwa, kutsukidwa, kusefedwa, ndi zouma kuti zigwiritsidwe ntchito mtsogolo. Tengani Cel-Ep, onjezani kuchuluka koyenera kwa CAB ndi zosungunulira zosakanikirana, tenthetsani ndi kusonkhezera kwa 0.5h kuti mupange yunifolomu yamadzimadzi yamadzimadzi, ndikukonzekera filimu yokutira ndi kuyesa ntchito kumatsatira njira ya GB-79.

Kutsimikiza kwa mlingo wa esterification wa cellulose acetate: choyamba sungunulani cellulose acetate mu dimethyl sulfoxide, onjezerani madzi okwanira a alkali yothetsera kutentha ndi hydrolyze, ndi titrate yankho la hydrolyzed ndi NaOH njira yothetsera kuwerengera kuchuluka kwa alkali. Kutsimikiza kwa madzi: Ikani chitsanzo mu uvuni pa 100 ~ 105°C kuti ziume kwa 0,2h, kuyeza ndi kuwerengera mayamwidwe amadzi mutatha kuzirala. Kutsimikiza kwa mayamwidwe a alkali: yezani chitsanzo chochulukira, sungunulani m'madzi otentha, onjezani chizindikiro cha methyl violet, kenako titrate ndi 0.05mol/L H2SO4. Kutsimikiza kwa digiri yowonjezera: Kulemera 50g chitsanzo, kuphwanya ndi kuika mu chubu anamaliza maphunziro, kuwerenga voliyumu pambuyo kugwedera magetsi, ndi yerekezerani ndi voliyumu wa unalkalined mapadi ufa kuwerengera kukula digiri.

2. Zotsatira ndi zokambirana

2.1 Ubale pakati pa ndende ya alkali ndi digiri ya kutupa kwa cellulose

Zomwe cellulose imakhala ndi njira ina ya NaOH imatha kuwononga kukhazikika komanso mwadongosolo kwa cellulose ndikupangitsa kuti cellulose kutupa. Ndipo kuwonongeka kosiyanasiyana kumachitika mu lye, kuchepetsa kuchuluka kwa polymerization. Mayesero akuwonetsa kuti kuchuluka kwa kutupa kwa cellulose ndi kuchuluka kwa alkali kumanga kapena kutsatsa kumawonjezeka ndi kuchuluka kwa zamchere. Mlingo wa hydrolysis ukuwonjezeka ndi kuwonjezeka kutentha. Pamene ndende yamchere ifika 20%, digiri ya hydrolysis ndi 6.8% pa t = 100.°C; digiri ya hydrolysis ndi 14% pa t = 135°C. Panthawi imodzimodziyo, kuyesa kumasonyeza kuti pamene alkali ndi yoposa 30%, digiri ya hydrolysis ya cellulose chain scission imachepetsedwa kwambiri. Pamene ndende ya alkali ifika 18%, mphamvu ya adsorption ndi kuchuluka kwa madzi otupa ndipamwamba kwambiri, ndendeyo ikupitiriza kuwonjezeka, imatsika kwambiri kumapiri, ndiyeno imasintha pang'onopang'ono. Panthawi imodzimodziyo, kusintha kumeneku kumakhudzidwa kwambiri ndi kutentha. Pansi pa ndende ya alkali yomweyo, kutentha kumakhala kotsika (<20°C), mlingo wotupa wa cellulose ndi wawukulu, ndipo kuchuluka kwa madzi kumachuluka; pa kutentha kwakukulu, digiri yotupa ndi kuchuluka kwa madzi adsorption ndizofunikira. kuchepetsa.

Ulusi wa alkali wokhala ndi madzi osiyanasiyana komanso zamchere zinatsimikiziridwa ndi X-ray diffraction analysis njira malinga ndi mabuku. Mu ntchito yeniyeni, 18% ~ 20% lye ntchito kulamulira zina anachita kutentha kuonjezera kutupa mlingo wa mapadi. Kuyesera kukuwonetsa kuti mapadi omwe amawotchedwa 6 ~ 12h amatha kusungunuka mu zosungunulira za polar. Kutengera mfundo imeneyi, wolemba akuganiza kuti solubility wa mapadi amatenga mbali yaikulu mu mlingo wa haidrojeni chomangira chiwonongeko pakati pa mamolekyu mapadi mu gawo crystalline, kutsatiridwa ndi mlingo wa hydrogen chomangira chiwonongeko cha intramolecular shuga magulu C3-C2. Kuchuluka kwa chiwonongeko cha haidrojeni chomangira chiwonongeko, kuchuluka kwa kutupa kwa mchere wa alkali, ndipo mgwirizano wa haidrojeni umawonongeka, ndipo hydrolyzate yomaliza ndi chinthu chosungunuka m'madzi.

2.2 Mphamvu ya Accelerator

Kuonjezera mowa wowiritsa kwambiri panthawi ya cellulose alkalization kumatha kuonjezera kutentha kwa zomwe zimachitika, ndikuwonjezerapo kachulukidwe kakang'ono monga mowa wocheperako ndi thiourea (kapena urea) kumatha kulimbikitsa kwambiri kulowa ndi kutupa kwa cellulose. Pamene kuchuluka kwa mowa kumawonjezeka, mayamwidwe a alkali a cellulose akuwonjezeka, ndipo pamakhala kusintha kwadzidzidzi pamene ndende ndi 20%, zomwe zingakhale kuti mowa wa monofunctional umalowa mu mamolekyu a cellulose kuti apange hydrogen zomangira ndi mapadi, kuteteza mapadi. mamolekyu Kumangika kwa haidrojeni pakati pa maunyolo ndi unyolo wa maselo kumawonjezera kuchuluka kwa chisokonezo, kukulitsa malo, ndikuwonjezera kuchuluka kwa alkali adsorption. Komabe, mumikhalidwe yomweyi, kuyamwa kwa alkali kwa tchipisi tamatabwa kumakhala kotsika, ndipo mapindikira amasintha pakasinthasintha. Zitha kukhala zokhudzana ndi zomwe zili mu cellulose mumitengo yamatabwa, yomwe imakhala ndi lignin yambiri, yomwe imalepheretsa kulowa kwa mowa, ndipo imakhala ndi madzi abwino komanso kukana kwa alkali.

2.3 Etherification

Onjezani 1% B chothandizira, wongolerani kutentha kosiyanasiyana, ndikusintha etherification ndi epoxy resin ndi fiber alkali. Ntchito ya etherification reaction ndiyotsika pa 80°C. Kuphatikizika kwa Cel ndi 28% yokha, ndipo ntchito ya etherification yatsala pang'ono kuwirikiza pa 110.°C. Poganizira mmene zinthu monga zosungunulira, kutentha anachita ndi 100°C, ndipo nthawi yochitapo ndi 2.5h, ndipo kulumikizidwa kwa Cel kumatha kufika 41%. Kuonjezera apo, pa gawo loyambirira la etherification reaction (<1.0h), chifukwa cha momwe zimakhalira pakati pa alkali cellulose ndi epoxy resin, mlingo wa kumezanitsa ndi wotsika. Ndi kuwonjezeka kwa digiri ya Cel etherification, pang'onopang'ono imasandulika kukhala yofanana, kotero zomwe zimachitika Ntchitoyi inakula kwambiri, ndipo mlingo wa kumezanitsa ukuwonjezeka.

2.4 Ubale pakati pa Cel Ankalumikiza mlingo ndi solubility

Kuyesera kwawonetsa kuti mutatha kulumikiza epoxy resin ndi cellulose yamchere, zinthu zakuthupi monga kukhuthala kwazinthu, kumamatira, kukana madzi, komanso kukhazikika kwamafuta kumatha kusintha kwambiri. Mayeso osungunuka The mankhwala ndi Cel Ankalumikiza mlingo <40% akhoza kusungunuka m'munsi mowa-ester, alkyd utomoni, polyacrylic asidi utomoni, acrylic pimaric acid ndi utomoni ena. Utoto wa Cel-Ep umakhala ndi mphamvu yosungunulira.

Kuphatikizidwa ndi kuyesa kwa filimu yophimba, kusakanikirana ndi chiwerengero cha 32% ~ 42% nthawi zambiri kumakhala kogwirizana bwino, ndipo kuphatikizika ndi chiwerengero cha <30% kumakhala ndi kugwirizana kosauka komanso kutsika kwa filimu yophimba; Mlingo wa kumezanitsa ndi woposa 42%, kukana kwa madzi otentha, kukana mowa, ndi kukana kwa polar organic zosungunulira za filimu yokutira kumachepetsedwa. Pofuna kupititsa patsogolo kuyanjana kwa zinthu ndi ntchito zokutira, wolembayo adawonjezera CAB molingana ndi ndondomeko yomwe ili mu Table 1 kuti apitirize kusungunuka ndikusintha kuti alimbikitse kukhalapo kwa Cel-Ep ndi CAB. The osakaniza amapanga pafupifupi homogeneous dongosolo. Makulidwe a mawonekedwe ophatikizikawo amakhala ochepa kwambiri ndipo amayesa kukhala mumtundu wa nano-maselo.

2.5 Ubale pakati pa Cel-Ep/CAB kuphatikiza chiŵerengero ndi katundu wakuthupi

Pogwiritsa ntchito Cel-Ep kusakanikirana ndi CAB, zotsatira zoyesa zokutira zikuwonetsa kuti cellulose acetate imatha kusintha kwambiri makulidwe azinthu, makamaka kuthamanga kwa kuyanika. Chigawo choyera cha Cel-Ep ndizovuta kuumitsa kutentha. Pambuyo powonjezera CAB, zida ziwirizi zimakhala ndi magwiridwe antchito.

2.6 FTIR kuzindikira sipekitiramu

3. Mapeto

(1) Ma cellulose a thonje amatha kutupa mpaka 80°C ndi> 18% anaikira zamchere ndi mndandanda wa zina, kuwonjezera kutentha anachita, kutalikitsa anachita nthawi, kuonjezera mlingo wa kutupa ndi kuwonongeka mpaka kwathunthu hydrolyzed.

(2) Etherification reaction, ndi Cel-Ep molar chakudya chiŵerengero ndi 2, kutentha anachita ndi 100°C, nthawi ndi 5h, chothandizira mlingo ndi 1%, ndi etherification Ankalumikiza mlingo akhoza kufika 32% ~ 42%.

(3) Kusintha kosakanikirana, pamene chiwerengero cha molar cha Cel-Ep: CAB = 3: 2, ntchito ya mankhwala opangidwa ndi yabwino, koma Cel-Ep yoyera singagwiritsidwe ntchito ngati zokutira, monga zomatira.