Zotsatira za Zosintha ndi Kulemera kwa Mamolekyulu Pazinthu Zapamwamba za Nonionic Cellulose Ether
Malinga ndi chiphunzitso cha Washburn's impregnation (Theory Penetration Theory) ndi chiphunzitso chophatikiza cha van Oss-Good-Chaudhury (Combining Theory) komanso kugwiritsa ntchito ukadaulo wa waya wa columnar (Column Wicking Technique), ma ether angapo omwe si a ionic cellulose, monga methyl cellulose The surface properties of cellulose, hydroxypropyl cellulose ndi hydroxypropyl methylcellulose anayesedwa. Chifukwa cha zosiyana siyana, madigiri olowa m'malo ndi kulemera kwa maselo a cellulose ethers, mphamvu zawo zam'mwamba ndi zigawo zake ndizosiyana kwambiri. Deta imasonyeza kuti maziko a Lewis a non-ionic cellulose ether ndi aakulu kuposa Lewis acid, ndipo chigawo chachikulu cha mphamvu yaulere pamwamba ndi mphamvu ya Lifshitz-van der Waals. Mphamvu zapamwamba za hydroxypropyl ndi kapangidwe kake ndizokulirapo kuposa za hydroxymethyl. Pansi pa malo omwewo m'malo ndi digiri ya m'malo, pamwamba mphamvu yaulere ya hydroxypropyl cellulose ndi yofanana ndi kulemera kwa maselo; pomwe mphamvu yaulere ya hydroxypropyl methylcellulose imayenderana ndi kuchuluka kwa kulowetsa m'malo komanso mosagwirizana ndi kulemera kwa maselo. Kuyeseraku kunapezanso kuti mphamvu yapamtunda ya hydroxypropyl ndi hydroxypropylmethyl mu non-ionic cellulose ether ikuwoneka ngati yayikulu kuposa mphamvu yapa cellulose, ndipo kuyesaku kumatsimikizira kuti mphamvu yapamtunda ya cellulose yoyesedwa ndi kapangidwe kake mogwirizana ndi mabuku.
Mawu ofunikira: nonionic cellulose ethers; zoloŵa m'malo ndi madigirii olowa m'malo; kulemera kwa maselo; pamwamba katundu; teknoloji yamagetsi
Cellulose ether ndi gulu lalikulu la zotumphukira za cellulose, zomwe zimatha kugawidwa kukhala ma anionic, cationic ndi nonionic ethers molingana ndi kapangidwe kake kazinthu zolowa m'malo mwa ether. Ma cellulose ether ndi amodzi mwazinthu zakale kwambiri zomwe zidafufuzidwa ndikupangidwa mu chemistry ya polima. Mpaka pano, ether ya cellulose yakhala ikugwiritsidwa ntchito kwambiri muzamankhwala, ukhondo, zodzoladzola komanso mafakitale azakudya.
Ngakhale ma cellulose ethers, monga hydroxymethylcellulose, hydroxypropylcellulose ndi hydroxypropylmethylcellulose, apangidwa m'mafakitale ndipo zambiri mwazinthu zawo zaphunziridwa, mphamvu zawo zam'mwamba, asidi Alkali-reactive properties sizinafotokozedwe mpaka pano. Popeza ambiri mwa mankhwala ntchito mu chilengedwe madzi, ndi makhalidwe pamwamba, makamaka asidi-m'munsi anachita makhalidwe, mwina zimakhudza ntchito yawo, m'pofunika kwambiri kuphunzira ndi kumvetsa pamwamba mankhwala makhalidwe a malonda mapadi efa.
Poganizira kuti zitsanzo za zotumphukira za cellulose ndizosavuta kusintha ndikusintha kwazinthu zokonzekera, pepalali limagwiritsa ntchito zinthu zamalonda monga zitsanzo kuti ziwonetse mphamvu zawo zapamtunda, ndipo potengera izi, chikoka cha olowa m'malo ndi mamolekyu amafuta azinthu zotere pamtunda. katundu amaphunziridwa.
1. Gawo loyesera
1.1 Zopangira
The non-ionic cellulose ether yomwe imagwiritsidwa ntchito poyesera ndi mankhwala aMalingaliro a kampani KIMA CHEMICAL CO., LTD,. Zitsanzozi sizinapatsidwe chithandizo chilichonse musanayesedwe.
Poganizira kuti zotumphukira za cellulose zimapangidwa ndi cellulose, zida ziwirizi zili pafupi, ndipo mawonekedwe amtundu wa cellulose adanenedwa m'mabuku, kotero pepalali limagwiritsa ntchito mapadi ngati chitsanzo chokhazikika. Chitsanzo cha cellulose chomwe chinagwiritsidwa ntchito chinali chotchedwa C8002 ndipo chinagulidwa kuchokeraKIMA, CN. Chitsanzocho sichinapatsidwe chithandizo chilichonse panthawi ya mayesero.
Zomwe zimagwiritsidwa ntchito poyesera ndi: ethane, diiodomethane, deionized madzi, formamide, toluene, chloroform. Zamadzimadzi zonse zinali zopangidwa mwadongosolo kupatula madzi omwe anali ogulitsidwa.
1.2 Njira yoyesera
Pakuyesa uku, njira yopangira mizati idakhazikitsidwa, ndipo gawo (pafupifupi 10 cm) la pipette yokhazikika yokhala ndi mainchesi amkati a 3 mm idadulidwa ngati chubu. Ikani 200 mg ya ufa mu chubu nthawi zonse, kenaka mugwedezeni kuti ifanane ndikuyiyika pansi pa chidebe cha galasi ndi mkati mwake pafupifupi 3 cm, kuti madzi azitha kugulitsidwa mwachisawawa. Yezerani 1 mL yamadzimadzi kuti ayezedwe ndikuyika mu chidebe chagalasi, ndipo lembani nthawi yomiza t ndi mtunda wa kumizidwa X nthawi yomweyo. Zoyesera zonse zidachitika kutentha kwachipinda (25±1°C). Deta iliyonse ndi avareji ya zoyeserera zitatu zofanana.
1.3 Kuwerengera deta yoyesera
Maziko ongoyerekeza ogwiritsira ntchito njira yopangira mizati kuyesa mphamvu ya pamwamba pa zinthu za ufa ndi Washburn impregnation equation (Washburn penetration equation).
1.3.1 Kutsimikiza kwa radius yogwira mtima ya capillary Reff ya chitsanzo choyezedwa
Mukamagwiritsa ntchito njira yomiza ya Washburn, chikhalidwe choti munyowetse kwathunthu ndi cos=1. Izi zikutanthauza kuti madzi akasankhidwa kuti amizidwe kukhala olimba kuti akwaniritse kunyowa kwathunthu, titha kuwerengera radius yogwira mtima ya capillary Reff ya chitsanzo choyezedwa poyesa mtunda wa kumizidwa ndi nthawi molingana ndi nkhani yapadera ya kumiza kwa Washburn.
1.3.2 Lifshitz-van der Waals kuwerengera mphamvu kwa zitsanzo zoyezedwa
Malinga ndi malamulo ophatikiza a van Oss-Chaudhury-Good, mgwirizano pakati pa zomwe zimachitika pakati pa zakumwa ndi zolimba.
1.3.3 Kuwerengera mphamvu ya Lewis acid-base ya zitsanzo zoyezedwa
Nthawi zambiri, zinthu za acid-base za zolimba zimayesedwa kuchokera ku data yomwe imayikidwa ndi madzi ndi formamide. Koma m'nkhani ino, tapeza kuti palibe vuto pamene ntchito awiriwa madzi polar kuyeza mapadi, koma mu mayeso a mapadi ether, chifukwa kumizidwa kutalika kwa polar njira dongosolo madzi / formamide mu mapadi ether ndi otsika kwambiri. , kupanga nthawi yojambula kukhala yovuta kwambiri. Choncho, njira yothetsera toluene/chloroform yomwe idayambitsidwa ndi Chibowsk idasankhidwa. Malinga ndi Chibowski, toluene/chloroform polar solution system ndiyonso njira. Izi ndichifukwa choti zakumwa ziwirizi zimakhala ndi acidity yapadera komanso alkalinity, mwachitsanzo, toluene ilibe Lewis acidity, ndipo chloroform ilibe Lewis alkalinity. Kuti tipeze deta yomwe idapezedwa ndi njira ya toluene/chloroform kufupi ndi njira yoyezera madzi/formamide, timagwiritsa ntchito njira ziwiri zamadzimadzi za polar kuyesa mapadi pa nthawi imodzi, ndiyeno timapeza makulidwe ofananirako kapena ma contraction coefficients. Musanagwiritse ntchito Zomwe zapezedwa polowetsa cellulose ether ndi toluene/chloroform zili pafupi ndi zomwe zapezedwa pamadzi/formamide system. Popeza ma cellulose ethers amachokera ku cellulose ndipo pali mawonekedwe ofanana kwambiri pakati pa awiriwa, njira yowerengera iyi ikhoza kukhala yolondola.
1.3.4 Kuwerengera mphamvu zonse zaulere padziko lapansi
2. Zotsatira ndi Zokambirana
2.1 Muyezo wa cellulose
Popeza zotsatira za mayeso athu pamiyeso ya cellulose zidapeza kuti izi zikugwirizana bwino ndi zomwe zafotokozedwa m'mabuku, ndizomveka kukhulupirira kuti zotsatira za mayeso pa cellulose ether ziyeneranso kuganiziridwa.
2.2 Zotsatira zoyesa ndikukambirana za cellulose ether
Pakuyesa kwa cellulose ether, zimakhala zovuta kwambiri kulemba mtunda wa kumizidwa ndi nthawi chifukwa cha kutalika kwa madzi otsika kwambiri ndi formamide. Choncho, pepala ili limasankha njira yothetsera toluene / chloroform ngati njira yothetsera vutoli, ndikuyerekeza Lewis acidity ya cellulose ether potengera zotsatira za mayeso a madzi / formamide ndi toluene / chloroform pa cellulose ndi mgwirizano wofanana pakati pa machitidwe awiriwa. ndi mphamvu ya alkaline.
Kutenga cellulose ngati chitsanzo chokhazikika, mndandanda wa ma acid-base a cellulose ethers amaperekedwa. Popeza zotsatira za kuyimitsa cellulose ether ndi toluene/chloroform zimayesedwa mwachindunji, ndizotsimikizika.
Izi zikutanthauza kuti mtundu ndi kulemera kwa maselo a m'malo mwake zimakhudza katundu wa asidi-m'munsi wa cellulose ether, ndi mgwirizano pakati pa olowa m'malo awiri, hydroxypropyl ndi hydroxypropylmethyl, pamtundu wa asidi-m'munsi wa cellulose ether ndi kulemera kwa maselo mosiyana kwambiri. Koma zitha kukhalanso zokhudzana ndi mfundo yoti a MP ndi olowa m'malo osiyanasiyana.
Popeza olowa m'malo a MO43 ndi K8913 ndi osiyana ndipo ali ndi kulemera kwa mamolekyu ofanana, mwachitsanzo, m'malo wakale ndi hydroxymethyl ndipo m'malo mwake ndi hydroxypropyl, koma kulemera kwa mamolekyu onse ndi 100,000, motero zikutanthauza kuti maziko a kulemera kwa maselo omwewo Pazimenezi, S + ndi S- ya gulu la hydroxymethyl ikhoza kukhala yaying'ono kuposa gulu la hydroxypropyl. Koma mlingo woloweza m'malo umathekanso, chifukwa mlingo wolowa m'malo wa K8913 uli pafupi 3.00, pamene MO43 ndi 1.90 yokha.
Popeza kuti mlingo wa kulowetsedwa ndi olowa m'malo a K8913 ndi K9113 ndi ofanana koma kulemera kwa maselo kumakhala kosiyana, kuyerekezera pakati pa awiriwa kumasonyeza kuti S + ya hydroxypropyl cellulose imachepa ndi kuwonjezeka kwa kulemera kwa maselo, koma S- imawonjezeka mosiyana. .
Kuchokera ku chidule cha zotsatira za mayeso a mphamvu ya pamwamba pa ma cellulose ethers ndi zigawo zake, zikhoza kuwoneka kuti kaya ndi cellulose kapena cellulose ether, chigawo chachikulu cha mphamvu yawo yapamwamba ndi mphamvu ya Lifshitz-van der Waals, yowerengera pafupifupi 98% ~ 99%. Kuphatikiza apo, mphamvu za Lifshitz-van der Waals za ma nonionic cellulose ethers (kupatulapo MO43) nawonso amakhala ochulukirapo kuposa a cellulose, zomwe zikuwonetsa kuti etherification process of cellulose ndi njira yowonjezera mphamvu ya Lifshitz-van der Waals. Ndipo kuwonjezeka kumeneku kumapangitsa kuti mphamvu yapamtunda ya cellulose ether ikhale yayikulu kuposa ya cellulose. Chodabwitsa ichi ndi chosangalatsa kwambiri chifukwa ma cellulose ethers amagwiritsidwa ntchito kwambiri popanga ma surfactants. Koma deta ndi yochititsa chidwi, osati chifukwa chakuti deta yokhudzana ndi chitsanzo choyesedwa muyesoyi ikugwirizana kwambiri ndi mtengo womwe wafotokozedwa m'mabuku, zomwe zafotokozedwa muzolembazo zimagwirizana kwambiri ndi mtengo womwe wafotokozedwa m'mabuku, chifukwa Mwachitsanzo: onsewa cellulose SAB ya ethers ndi yaying'ono kwambiri kuposa ya cellulose, ndipo izi ndichifukwa cha maziko awo akuluakulu a Lewis. Pansi pa malo omwewo m'malo ndi digiri ya m'malo, pamwamba mphamvu yaulere ya hydroxypropyl cellulose ndi yofanana ndi kulemera kwa maselo; pomwe mphamvu yaulere ya hydroxypropyl methylcellulose imayenderana ndi kuchuluka kwa kulowetsa m'malo komanso mosagwirizana ndi kulemera kwa maselo.
Kuphatikiza apo, chifukwa ma cellulose ethers ali ndi SLW yayikulu kuposa mapadi, koma tikudziwa kale kuti dispersibility yawo ndiyabwino kuposa mapadi, kotero zitha kuganiziridwa kuti gawo lalikulu la SLW lopanga ma nonionic cellulose ethers liyenera kukhala mphamvu yaku London.
3. Mapeto
Kafukufuku wasonyeza kuti mtundu wa m'malo, digiri ya m'malo ndi maselo kulemera ndi chikoka chachikulu padziko mphamvu ndi zikuchokera sanali ionic mapadi efa. Ndipo izi zikuwoneka kuti zimakhala ndi nthawi zonse:
(1) S+ ya non-ionic cellulose ether ndi yaying'ono kuposa S-.
(2) Mphamvu yapamtunda ya nonionic cellulose ether imayendetsedwa ndi mphamvu ya Lifshitz-van der Waals.
(3) Kulemera kwa mamolekyu ndi zolowa m'malo zimakhala ndi mphamvu pamtunda wa ma ethers omwe si a ionic cellulose, koma makamaka zimadalira mtundu wa zolowa m'malo.
(4) Pansi pa malo omwewo ndi digiri ya kulowetsa m'malo, mphamvu yaulere ya hydroxypropyl cellulose ndi yofanana ndi kulemera kwa maselo; pomwe mphamvu yaulere ya hydroxypropyl methylcellulose imayenderana ndi kuchuluka kwa kulowetsa m'malo komanso mosagwirizana ndi kulemera kwa maselo.
(5) Njira ya etherification ya cellulose ndi njira yomwe mphamvu ya Lifshitz-van der Waals imawonjezeka, komanso ndi njira yomwe Lewis acidity imachepa ndipo Lewis alkalinity amawonjezeka.
Nthawi yotumiza: Mar-13-2023