TAP CHi HOA H O C
DOI: 10.15625/0866-7144.2016-322 54(3)377-381
THANG 6 NAM 2016
NGHIEN Ciru SI/ TRUYEN DAN PROTON TRONG CAC CHAT OIEN Ll DAN PROTON DANG POLYMER GEL TREN CO Sd
P0LY(METYLMETACRYLAT) Ngnyln Vin Th4c", NgnyJn Thj c i m Ha
KhaaHoahgc, Truing Dgi hgc Khoa hgc Tu nhien, Dgi hgc Quic gia Hi Ngi Din Tda soan 24-11-2015; Chip nhan dang 10-6-2016 Abstract
J ^ T : Z ^ r'tS^rnnTde'^^ i^ZHT^' •""^'-=> <''-"' ^
•ti H-NMR specm»copy. „e leponed thil p S o r i c »M Z l S I ' ^ ^ " T . " ' ^ " ' " ' ' ' ' ' * " ' ^ - ° " "•=''=^» ° f « M7MA, which was die model oU?m/^,^7i^.^f^^^"°^ ^'^'^ ^ ^ "«> PMMA and praposed with the solvent and die polymer mattS ^ ™ ' ' "' ^'°° ' ™ " ' " " ""c gel have been
Keywoidi. Mechanism, proton, Grotthuss, gel, polymer.
1. MO DAU
Chit difn li polyme gel dupc coi nhu li v|t lifu dan fliay die eho chat difn li dang rin hifn nay Polymer geUa mpt dang ciu ttuc dupc tao flianh ni
* hpp chat cao phjn di nhu nhirng mang ludi khong gian, ben ttpng mang ludi dd cd chua dung dich axit vdi dung moi phin cue Gel cd dp din difn nfng nim ttong khoang ImS.cm' d nhift dp phong la du kha ning ung dpng vao cac fliiit bj difn hda khac iJiau ttong dd cd pin nhien lifu. MJc du, da cd mpt so luong khi Ion cac chit difn Ii din proton dupc tao ra. Tuy nhien, vifc nghien ciru chi tjo chit dipn h moi cung nhu bien dnh cic chit dien li cd an nhim mpc dich cii fliifn dfc Unh din difn, dp Mn nhipt, do ben CO hpc,... vln la mpt muc deu cin dupc nghien cim cp dii nhieu hon.
Nghiin Clhi dnh chit cua cac chit difn U din proton dang gel tten cp sd cua PoMmetyhnetaciylat) cimg vdi dung dich axit ttong dung mil nghjch proton da dupc nghien cuu kha 1908 Iii [1-3] Tuy nhien, hifn nay vln chua cd mpt CO so IJ thuyet nao cd die chi ra dupc su php fliupc cua dp din dien neng vdi flianh phin ciu tao ciia gel, cOng nhu mo hinh vi co chi ttiiyln din proton ttong gel.
Prottm la mpt ion d}c bift bdi nd khong cd Ido vd electton ngoai cdng, do dd proton tp do chi tin l«i ttong moi ttudng chin khong Trong dung djch
proton ton tai dudi dang ion bj sonvat hda VI vJy qua ttmh ttuyen din proton dudi tac dimg cUa difii truong cd flie xay ra theo CO chi day ttnyln (co chi Grofliuss) hoJc CO chi djch chuyin [4]. Dii vdi co che d|ch chuyen proton, cimg vdi Idp vd sonvat hda dl chuyen giihi hai ban difn cue flidng qua su khuech tan vi chuyin dpng nhift Co chi day chuyen fliong qua lien kit hidro giiia proton vdi cac phannr dung moi hoJc phan ni polyme se lim cho qua ttmh ttuyen dan proton xay ra nhanh hon va dp dan difn tii dd cung cao hon.
, Trong nghien cdu chung tdi tiin hanh tun hiiu ve CO che va dua ra mo htah ciia qui ttinh ttuyin dan proton ttong cac polyme gel, dupc tao flianh tten CO MT cua poly(metyl metacrylat) (PMMA) Di giai quyet dupc vin di phiie tap tten. chiing toi da ket hpp giiia cic ket qui dipc nghifm va kit qui toan lupng tii ttf n co sd mo hinh mpt nhanh cua phan tii PMMA.
2. THl/C NGHIEM 2.1. Hoa chat
P-o^metyl metacrylat) (M. = 350000 Aldrich) metyl tnmetylaxetat (Aldrich). axit photphoric (dung dich 85 % - Khimmed - Nga), axit ph^phonc ran (Aldrich), N,N-dimetylfonnamid (DMF - Panreae), benzoyl peroxid (70 %, Aldrich)
TCHH, 54(3), 2016 2.2. Phinmg phap nghien cuu
DO din di^n ciia gel dir^c xac djnh bSng phirong phap do pho t6ng tra trSn thigt bi do Solartron 1260A vdri khoang tan s6 Ixr 0,1 Hz-1 MHz, U = 10 raV, va sai s6 ciia phep do < 0^ %; BQ nhot dirge do tren thi^t bj BROOKFIELD DV-H, d0 chinh xac
± 1 %. Pho hong ngo^i IR-ATR dugc ghi tren thiet bi VERTEX 80v (Bruker) voi tin so tir 400 cm' tdi 4000 cm"', d0 phan giai 2 cm"'. Ph6 cpng hucmg ti>
h^t nhan dugc ghi tren thigt bj Bruker AVANCE- 500 tgi nhi?t dp phong.
3. KET QUA VA T H A O LUAN
Nhihlg nghien cmi tnroc day ciia chiing toi [5, 6]
da chi ra rang, cac polyme gel trfin ca so ciia PMMA va mOt so hgp chat cao phan tii khac co dp din di?n riSng lan hon nhilu lan so voi dung djch axit ban dau. Dong thai, khao sat nh&ng ylu t6 anh hucmg t6i dp din di^n rieng ciia h? polyme gel cho thay, PMMA d6ng vai tro quan trpng trong qua trinh truyen din proton. Poly(metyI metacrylat) co the d6ng vai tro djnh huong s^ chuyin djch ciia cdc ion du6i tac dgng cua di?n truong ben ngoii, ciing co the la do ban th|n phan tii polyme tham gia vao tao thanh Hen ket hydro voi proton cua phan tir axit dl qu4 trinh truyin din proton dugc di^n ra vai toe dp nhanh han theo ca che Grothuss.
Can phai chu y riing, khi qua trinh truyin din ion thvc hi?n theo co che di chuyin ciia timg ion rieng re thi nang lugng ho^t dpng hoa dugc xac dinh tiir gia trj dp dan di^n rieng va tit gia trj dp nhot la tuang duong nhau. Trong nghien cuu, nang lugng hogt dpng h6a ciia gel dugc xac djnh tir phuong trinh AiThenius thong qua sir phy thupc cua dp din di|n rieng va dp nhot vao nhi?t dp. Nghien cuu cho thay sir phy thupc cua dp din di?n neng va dp nhat ciia gel vao nhi?t dp (trong khoang khao sat) thi hi^n theo phuong trinh Arrhenius.
Bang so 1 thi hi?n kit qua tinh nang lugng hogt dpng h6a thong qua gia trj dp din di?n rieng va gia trj dO nhot cua gel.
Bang 1: Gia trj n^ng lugng hogt hoa theo dp din di^n rieng va dp nhcrt ciia gel
NgiQ^n Van Thuc vac^ngsi/rf, (AE j) nhd hon nhieu so vin nSng lugng hogt d ^ h6a tinh theo dp rdidt (AE*,,). Ket qua tr6n cho t h ^ qua trinh truyin din proton trong h? gel dugc d$c tnm^ boi ca chl truyin din Grotthuss, ti]rc li str truyen din proton theo mpt mgch dki thong qua cic lien kit hydro.
De chung minh sg ton tgi cua lien kit hydro gifla phan tii H3PO4 vdi phan tur DMF va phfin tfr PMMA chung t6i dS su dyng phuang phi^j do phi hong ngogi (IR) \k pho cpng hucmg tii hgt nhSn cho cac h§ polyme gel.
Thanh phan cua gel 5%PMMA-I0,1 H,PO,-DMF|
7%PMMA-[0.1 H,P0,-DMF1 9%PMMA-fO, 1 H,P04-DMF]
(kj/mol) 7,89 7,91 7,02
{kJ/moD 20,25 14,26 23,08
djch dich do.
Hinh 1 thg hi?n ket qua do ph6 hong ngoai dung 1 H,P04-DMF va gel duoc tao thanh tir duno gel duoc tao thanh tir dung
- • D M F
— 9 . 0 H P M M A . OMF
• - 0 . f i M H , P O , - D M F j 9.0W P M M A . 10.fiM H,PO,. DMFl
Theo ket qua bang 1 dl dang nhan thSy ning lirpng hoat dpng h6a tinh theo dp din dijn riSng
Htnh I: Pho h6ng ngoai ciia polyme gel co thSnh phan 9,0 % PMMA - [0,6 M HjPO, - DMF] v4 cic
h? thanh phin
Til hinh 1 dl dang nhJn thiy hinh anh phS hong ngoai cua dun^ djch HjPO, - DMF va polyme gel tuong iin| li rat gi6ng nhau vi giong voi DMF tinh khiet. Dieu nay co thi dupc giai thich li do him lupng DMF hong cic hp khio sil Icm hon nhieu so vol HjPO, vi PMMA. MJt khic. cOng can chu y rang tuong nrong tic giSa axit voi PMMA vi DMF se dirpc the hipn chii yeu qua nhom C=0 cua DMF (voi tan so -1660 cm') va PMMA (1727 cm'') [7- 8]. Vi viy, khio sat cii thi vimg tin so niy c6 the sJ cho ket qui ve sir tuong tac giiia cic thinh phin trong gel.
S\f mo rpng pic tuong ling vii dao djng C=0 ciia PMMA vi DMF ve vimg tan so thip (hinh 2), chirng to sir ton lai nrong tic giOa phan tt DMF vi PMMA vcri H1PO4 thong qua lien kit hydro viM nhom C=0 [8]. Sir djch chuyen khong dang kl {-5 cm") pic dao dpng P-O(H) tai vung tan so -lOOO cm" giua polyme gel va dung djch HjPOrDMF cA the chimg minh ton tai hrong tic {lien ket hydro) giua PMMA vd'i phan tt HjPO,. Tii hinh so 2(b) ciS the thay pic dao dpng cua lien kit C=0 trong phin tt PMMA li rat nhd vi tl 1, ham lupng PMMVHjPO, li nho hon nhilu so voi him lirong DMF/H,PO,, do d6 viec khao sit ttong tic g™
TCHH, 54(3), 2016
<>0 Cila PMMA vdi proton cOa H J « , g}p rit nhieu kho khin. Bi khic phpc khi khan niy, trong nghien cmi chiing toi da tiln hanh khao sat ttong He giiia cac phin tt frong dung djch HjPO. v<ii metyl trimetyaxetat (MTMA), duvc coi nhu mo htah 1 nhinh ciia phan tt PMMA. Hinh 3 tfil hipn ket qua do pho hong ngoai ciia dung djch HiPO,- MTMA voi nhihlg ti l | phan mol khic nhau.
'9% PMMA-OMF
•9% PMMA- ia6HU,PO,-nMF1
Nghien ctiu sir truyen din proton..
Hinh 2: Pho h6ng ngoai cua gel co thanh phan la 9 0
% PMMA - [0,6 MH,PO,-DMF] va 9,0% ' PMMA - DMF trong vimg tin so dao dpng C=0
ciia phan tt DMF (a) va PMMA (b) Chung toi di tiln hinh phan tich cic pic ttong mg vft dao dOng ciia nhirng nhom chiic trong phan tt H,PO. vi MTMA. Tren hinh 3(a) dl ding Shjn My, khi giam nong dp phin mol cua axit xuIng 0 1 mi v, tri pic dap dOng ciia nhom 0-P-O djch chuyin khoang 40 cm" ve vimg tin s6 cao so vol vi tri pic ttong tt tiong pho IR cua H3PO. nguyen chit (446 cm ). Dieu do co the liSn quan toi sir tao thanh lien ket hydro giOa phan tt H3PO. va MTMA, nhu dupe Wnh bay* hinh 4.
vrrl'i'f",™''''^ ^°"^ " 8 ? ' ="^^ dung djch chiia MTMA-HiPO, trong vnng tin s6 ling vol dao dpng Hia nhdm cacboxyl n-ong phan tt MTMA (1734 cm ) cho thay, khi cho thim axit vio MTMA xiy ra su mo rpng^ pic_C=0 va sir tao thanh pic moi nim o viing tin so thap. Sir tao thanh pic moi nay li kit qui cia su ttong tic giSa proton hong phan tt axit
ABS
>H,PO,.MrMA MTMA
Hinh 3: Ket qua phi hing ngoai ciia dung djch HJPO4-MTMA voi ti Ip mol khic nhau: (a) tt 400cm" -1200 cm' va (b) tt 1200 cm"'-2000 cm"'
Htnh 4: Lien kit co thi giira MTMA-H3PO, vol nhom cacboxyl trong phan tt MTMA. Pic moi dupc tao thanh co the dfc trung djnh lupng cho ttong tac hydro, dupc tao thanh giira cac phan tt MTMA va axit. Ket qui ttong tt dii voi pic dao dpng C>0 cua hp HiPO,-DMF [8, 9]. Trong nghien cm, [10] tac gia di su, dpng cac phuong phap tinh toan hoa lupng tt de xac djnh ciu tnic hinh hpc va S f , T ^ '"°"8 '*'' eitta phin tt H3PO. vi MTMA. Ket qui thu dupc cho thiy sir tin 1,1 ttong tac giua hai phan tt tren, tuy nhien tuong tie nay
TCHH, 54(3), 2016
ylu hon so voi tuang tac giua phan tu H3PO4 va DMF (dung moi).
Sg tao thanh lien kit hydro giua phan tii axit va MTMA con dugc khSng dinh trong kit qua phi cpng huong tu hgt nhan 'H-NMR. Hinh 5 cho thay, tin hi?u cpng huong tii ciia proton trong phan tir axit tang len cung vcri su tang nong dp axit trong khoang tu 0 toi 0,3 (nong dp phan mol) trong DMF [8] cung nhu trong MTMA. Dilu nay, co lien quan tai sg tgo thanh kien ket hydro giffa phan tii axit vai MTMA Cling nhu vai DMF.
X, % mol Hinh 5: Sg phy diupc vj tri pic proton ciia phan tii
H3PO4 trong phi H-NMR vao nong dp axit trong dung djch vai DMF va MTMA
^
Nguyin Van Thiic va cQng stf Nhflng proton tgo thanh lien kit hydro c6 c6 Sff giam mgt dp electron vi thi lam giam hi^u iing chin, vi viy, tin hi^u cpng hudng tii sS djch chuyin vl vung CO tan so thip han. Ngoai ra, co thi nhgn thdy tin hi^u cOng huong tii cua proton trong phfin t i H3PO4 trong dung djch vcri DMF cao han trx)ng dung djch MTMA, dilu nay co thi khing djnh tuang tac giua H3PO,, va DMF cao hem tuong tfie giua H3PO4 vk MTMA. Kit qua thu dugc phii hgp vai ket qua tinh todn lugng tur cho h? H3PO4-DMF vaH3PO4-MTMA[10].
TCr cac kit qufi thu dugc ciing co thi dua ra dupc nhgt djnh ring, PMMA c6 tham gia vao qua trinh truyin din proton. Kit hgp cac kit qua thu dugc vdi nhung ket qua thu dugc tu phuang phfip tfnh h6a lugng tii [7, 10], trong nghien ciiu chiing toi dS dgt ra nhOng mo hinh truyen din proton trong h§ gel theo ca chl Grotthuss qua phfin tii DMF ciing nhir theo chuoi cua phan hi polyme thfing qua phan tii axit (sa do I).
Qua trinh truyin din proton tg do theo ca chl Grotthuss qua phdn tii DMF (so do a) gom sg dfnh hucmg phfin tii DMFH+ va truyen proton tdi phfin tii DMF ben cgnh. Tinh toan hoa lugng tii cho thay, str chuyin proton tg do tii DMF sang phfin tii axit kh6ng thugn lgi ve m^t nfing lugng [11], Vi vgy, trong truang hgp nfiy, sg truyen dfin proton chi xfiy ra qua phan tii DMF.
Di?n truong
r^
r\ •
H Me Me +H o ^le
\ Ll Kila
•4-OH—C CH, 9 - ) - .
•0—H OMe
— { - C H ^
(a)
CH; C ^ . •CHJ—C CH, 1:-^
-0 H OMe
" 0 OH ( b )
& * /. M6 hinh SIT truyin din proton co thi xiy ra frong hp gel theo co chl Grotthuss qua phan tir DMF (a) vi qua chuli polyme (b)
TCHH, 54(3), 2016
Tii s o d l b cd t h i diay, khac voi su truyin din qua phan tt DMF, m i y l n din proton dieo chuli polyme xay ra qua phan tt axit. Tinh toin lupng tt cho d u y , xac xuat chuyin proton tt do tt axit sang MTMA v i tt MTMA sang axit la ttong duong
So sanh nang lupng hoat dong hoa theo gia tri dp dan dipn rieng v i dp nhot ciia gel cho t h i y q u i tnnh miyen dan proton ffong he gel dupc dac tnmg boi CO che niiyen dan Grotthuss. Tren c a s o ' k i t qua phan tich pho hong ngoai va p h i cpng huong tt hat nhan cho thay sir ton tai lien k i t hydro giiia phan tt H3PO, vol phan tt PMMA va MTMA. Sir dung k i t qui thirc nghipm v i k i t qua tinh toan luong tt da dua ra dupc mo hinh ve q u i Wnh truyin d i n proton trong gel cung voi sn tham gia ciia phin tt dung mOi DMF va phin tt polyme PMMA.
L*i cam on. Nghien ah, nay dugc tii trg bii
Isntiffi'""' **"'' *'"''" "*'"" """^ *' '*''""
T A I L 1 $ U THAM KHAO
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Nghien ahi sir truyin dan proton...
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Lien hi: Nguyln Van Thirc
Khoa Hoa hpc, Traimg Dai hpc Khoa hoc tt nhien tJai hpc Quoc gia Ha Npi
So 19, Le Thanh Tong, Hoin Kilm, H i Npi
E-mail: [email protected]; Dipn thoai: 0942568599.
