(12) BAN MOTA SANG CHE THUOC BANG BOC QUYEN SANG CHE (19) Cong héa x4 héi chi nghia Viet nam (VN) cuc s6 HOU TRI TUE (517 CO8K 5/00, 5/05, 5/14, 5/16, COBF (13) B 299/04, CO8G 63/91, CO8K 3/00, CO8G 63/698 (21) 1-2013-02952 (22) 21.03.2012 (86) PCT/EP2012/054931 21.03.2012 (87) W02012/126917 27.09.2012 (30) 11159558.3 24.03.2011 EP 61/467,510 25.03.2011 US (45) 25.06.2017 351 (43) 27.01.2014 310 (73) AKZO NOBEL CHEMICALS INTERNATIONAL B.¥. (NL) Velperweg 76, 6824 BM Amhem, the Netherlands. (72) REUNDERS Johannes Martinus Gerardus Maria (NL), KOERS Frederik Willem Karel (NL), TALMA Auke Gerardus (NL) (74) Cong ty TNHH Tu vn sb hitu tri tue Viet (VIET IP CO..LTD.) (54) DUNG DICH CHAT TANG TOC, HON HOP NHUA DA DUOC LAM TANG TOC SO BO VA CHE PHAM HAI THANH PHAN (S57) Sing ché dé cap dén dung dich chat tang t6c thich hgp dé tao ra hé oxy héa- khir véi peroxit, chia (i) hgp chat cia kim loai chuyén tiép thé nhat dge chon ti mangan va déng, (ii) hgp chat ciia kim loai chuyén tigp thtt hai; ty 1¢ trong Iuong gitta kim loai chuyén tiép tht nhat va kim loai chuyén tiép tht hai nim trong khodng tix 3:1 dén 200:1, (ii) bazo chifa nito, va (iv) dung moi c6 nhém chic hydroxy, v6i diéu ki¢n dung dich chat tang tc nay khong chia axit ascorbic. Sang ché cdn dé cap dén hén hgp nhya duge ting t6c so bd va ché phim hai thinh phan tuong ting.16997 Linh vue ky thudt duge 48 cfip én dung dich chit ting téc thich hgp 4é tgo ra hé oxy héa-khir Sang ché dé hon hop nhua da duge lam ting téc so bé chita nhya polyeste chua bio v6i peroxi hoa hodc nhya este vinyl, va ché phdm hai thanh phan bao g6m hén hgp nhya da duge Jam tang téc so bé nay, Tinh trang ky thuat cia sang ché Hé oxy héa-khir c6 thé duge ding dé héa rin nhya, Thong thudng, hé oxy hoa- khir bao gdm chit oxy héa (vi du, peroxit) va ion kim loai chuyén tiép dé hoa tan lam chat tang téc, Chat c6 tac dung lam tang hoat tinh ctia chét oxy héa 6 ving nhiét 46 thap va, do d6, lam ting téc d6 hoa rin. Hé chat tang tdc cé thé dugc bé sung vao nhya cdn héa rin theo céc céch khdc nhau, Mot phuong phap bao gém vigc bé sung cdc thanh phan rigng 1é iia chat ting ft vao nhya, truéc khi bé sung peroxit. Viéc nay c6 thé dug thuc hién ngay truéc khi bé sung peroxit hodc vai ngay hoc vai tuan trude 46. Trong tring hop sau, thu durge hén hop nhya da duge lam tng téc so b6, bao gdm nhwa va cdc thanh phan chat ting tc, va c6 thé duge bao quan cho dén khi sir dung tiép va héa rn v6i peroxit. Mot phuong phap khdc lién quan dén viée diéu ché trudc dung dich chat ting téc chtra thanh phan chat tang téc, dung dich nay cé thé duge béo quan cho dén khi sir dung tiép va bé sung vao nhya. Nhya da duge lm ting téc so bd 6 thé duge diéu ché bing cach bd sung cae thanh phan riéng lé ctia hé ting téc vao nhya hogc bd sung cac thanh phan nay duéi dang hén hop dé lam dung dich chat ting téc. He chat ting téc thudng chtta mudi hode phite chat cia kim logi chuyén tiép. Kim loai chuyén tiép duge sir dung thudng xuyén nhét cho myc dich nay 1a coban. Tuy nhién, can phai giam lugng coban do ddc tinh cla nd,16997 Do d6, nguéi ta da tim cach tao ra chat tang téc khong chita coban. Tuy nhién, cac hé chat ing téc khong chita coban 4 duoc phat trién dén nay van chua c6 durge tinh nang tét nhu hé chira coban truyén théng. Vi dy vé cdc tai ligu dé cap dén hé chat ting tdc khong chita coban 1a WO 2008/003492, WO 2008/003793, va WO 2008/003500. Theo cdc tai ligu nay, kim logi duge sir dung trong hé chat tng téc 1A Mn, Cu, Fe va Ti thay vi Co. Céc hé chat ting tdc d6 duge ding trong polyeste cha bao ha hogc nhya este vinyl ¢ dang nhya da duge lam ting te so b6. Nhya da duge lam tang t6c so bg nay duge cho la chira it hon 0,01mmol Co trong méi kg nha. Da phat hién ra rang, kha nang phan img cia cdc hé chat tng td trén co sé kim loai chuyén tiép khéc Co ~ vi dy, Mn va Cu ~cé thé duge tang cudng bing cach bé sung chit lam tang kha nang phan ting. Chat lam ting kha ning phin tmg nay la mudi hoge phite hop cia kim logi chuyén tiép c6 mat trong hé tang téc voi Iuong nhé kim Joai chuyén tiép co ban (vi du, Mn hode Cu). Ban chit kj thuat cia sing ché Vi vay, sang ché dé xudt dung dich chat tang téc thich hop dé tao hé oxy hoa- khit véi peroxit, chita: (i) hgp chat ctia kim loai chuyén tiép thir nhdt duge chon tir mangan va déng, (ii) hop chat eda kim loai chuyén tigp thir hai; t¥ 18 trong lugng gitra kim logi chuyén tiép thir nhdt va kim logi chuyén tip thir hai nm trong khoang ti 3:1 dén 200:1, (iii) bazo chia nito, va (iv) dung méi ¢6 nhém chitc hydroxy, v6i diéu kign dung dich chat ting téc nay khong chira axit ascorbic. Sang ché cing d8 xuat hén hop nhua da duge lam ting t6c so b6 chira: (i) nhya déng rin duge, (ii) hgp chat ciia kim loai chuyén tiép thtr nhét duge chon tir mangan va déng, (iv) hp chét cua kim loai chuyén tiép thir hai; ty 1¢ trong lugng gitta kim logi chuyén tiép thir nhat va kim loai chuyén tigp thir hai nim trong khong tir 3:1 dén 200:1, ae16997 (v) baza chita nito, va (vi) dung mdi cé nhém chite hydroxy, ‘v6i diéu kign nhya da duge lam tang téc so b6 nay khéng chita axit ascorbic. Séng ché cing dé xudt ché phim hai thanh phan bao gdm thanh phan thé nhat va thanh phan thir hai, trong dé thanh phan thir nhdt bao gdm hén hgp nhya da duge lam tang t6c sob ahu duge xdc dinh trén day, thanh phan thir hai la peroxit. M6 tac! sang ché Kim loat chuyén tiép thé nhat durge chon tir déng va mangan. ‘Tét hon néu, kim loai chuyén tiép ther nhdt co mat trong dung dich chat ting ., due xdc dinh 1a kim logi, véi lung it nhat 1a SOmmol/|, tét hon nita néu it nhat la 100mmoV/I. Tét hon 1a né c6 mat trong dung dich chat tang téc voi higng nhd hon 5000mmol/|, tit hon nifa 1a nhé hon 2500mmol/|, va tét nhat [a nhé hon 1000mmol/1. Tét hon néu, kim loai chuyén tiép thir nhdt c6 mat trong nhya da duge lam wing tée so b6, duge xde dinh 1a kim Jogi, voi lugng it nhdt 1 Immol/kg nhya, 16t hon nia néu it nhat la 2mmol/kg nhya. Tét hon 1a n6 cé mat véi lugng khdng 16n hon 75mmol/kg nhya, t6t hon nia la khong 1én hon 50mmoV/kg nhua, con tt hon ntfa la khéng lon hon 25mmol/kg nhya, va tt nhit la khong lén hon 10mmol/kg nhya. Vi dy vé kim loai chuyén tigp thir hai, tire 1a cht lam ting kha nang phan img, 1a kim logi chuyén tigp cé thé t8n tai & hai trang thai oxy héa nh coban, titan, vanadi, sit, mangan, déng, thiéc, crom, niken, molipden, germani, stronti, paladi, platin, niobi, antimon, reni, osmi, iridi, platin, vang, thy ngdn, telu, rubidi va bismut. Kim loai chuyén tiép thir hai durgc wu tién Lam chat Lim ting kha ning phan img. theo sang ché la déng, coban, titan, sat, vi mangan. Dugc wu tién hon nita ld coban, titan, sit, va mangan. Duge wu tién nhat la coban va titan. Cac hop chit coban c6 thé duge sir dung lam kim loai chuyén tiép thir hai (chat lam ting kha nang phan tng) ma Khdng gay ra cae van dé lién quan dén luat phép va déc tinh vi ching c6 thé duge sir dung véi hrgng nhé. Tét hon néu, kim loai chuyén tiép thir hai co mat trong dung dich chat ting téc, duge xac dinh 1a kim Jogi, voi lugng it nhat 1a 10mmol/I, tét hon nia néu it nhat 116997 25mmol/l. Tét hon la cé mat trong dung dich chat tang téc voi Iugng nhé hon 1000mmol/|, t6t hon nifa JA nhé hon 500mmol/, va t6t nhét la nhé hon 250mmol/. ‘Tét hon néu, kim loai chuyén tiép thir hai cé mat trong nhya 4a duge lam ting téc so bé, durge xdc dinh 1a kim loai, vi lugng it nhdt 1 0,02mmol/kg nhya, tét hon nia néu it nhat 14 0,10mmol/kg nhya, con tét hon nia néu it nhat 14 0,25mmol/kg nhya, va tét nhat 14 0,50mmol/kg nhya. Tét hon la né ¢6 mat voi luong khéng l6n hon 10mmol/kg nhya, tét hon nita la khong lon hon Smmol/kg nhya, va tét nhat 1a khong, én hon 2mmol/kg nhya. RO rang 1a, kim logi chuyén tigp thir nhat va thir hai trong dung dich hose nhya cu thé phai 1a khae nhau. N6i cach khdc, dung dich hog nhya phai chira it nhat hai kim loai khée nhau. Cc hop chat thich hop cia kim loai chuyén tiép ther nhat va thir hai 1a mudi va cae phite hop cia ching nhw halogenua, nitrat, sulphat, sulphonat, phosphat, phosphonat, oxit ho%e carboxylat ctia ching. Vi dy vé carboxylat thich hgp 1a lactat, 2-etyl hexanoat, axetat, proprionat, butyrat, oxalat, laurat, oleat, linoleat, palmitat, stearat, axetyl axetonat, octanoat, nonanoat, heptanoat, neodecanoat, hodc naphtenat, Céc hgp chat mangan duge wu tién 14 mangan clorua, nitrat, sulphat, lactat, 2-etyl hexanoat, octanoat, nonanoat, heptanoat, neodecanoat, naphtenat, va axetat va phic hop Mn cia pyridin, bipyridin va din xudt cia ching, va ciia phdi tir cho nite tridentat, tetradentat, pentadentat, hodc hexadentat duge dé cap trong WO 2011/8309, Phi tir cho nito duge wa tién theo WO 2011/83309 1 phdi tir bispidon va phéi tir TACN-Nx. Phdi tir bispidon durgc wu tién 1a dimetyl-2,4-di-(2-pyridyl)-3-metyl-7- (pyridyl-2-ylmetyl)-3,7-diaza-bixyclo[3,3, 1 ]nonan-9-on-1,5-dicarboxylat (N2py30-Cl). Ph (Mes-TACN). i tir TACN-Nx duge uu tién ta 1,4,7-trimetyl-1 ,4,7-triazaxyclononan Hop chat bat ky trong s6 cde hop chdt Mn(11), Mn(IID), Mn([V) va Mn(VID) co thé duge six dung. Cac hop chét déng duge wu tién 1a ding clorua, nitrat, sulphat, lactat, 2-etyl hexanoat, octanoat, nonanoat, heptanoat, neodecanoat, naphtenat, va axetat. Ca hop chat Cu(1) va Cu(II) 06 thé duge str dung.16997 Cie bazo chita nito thich hgp cé mat trong dung dich chat tang tée va nhya da duge lim tang téc so bé 1a amin bac ba nhu trictyl amin, dimetylanilin, dietylanilin, hoac N,N-dimetyl-p-toludin (OMPT), polyamin nhwr 1,2-(dimetylamin)etan, amin bac hai nhy dietyl amin, amin duge etoxylat héa nhu trietanol amin, dimetylamino etanol, dictanol amin, hodc monoetanol amin, va amin thom nhu bipyridin. Tét hon 1a, bazo chua nito cé mat trong dung dich chat ting téc vai lugng nim trong khoang tir 5 dén 50% trong hrong. Tét hon la, né ¢6 mat trong nhya da duge lam ting tdc so bd vai hrgng nam trong khoang ti 0,5 dén 10g/kg nhya. ‘Thudt ngir “dung mdi cd nhém chite hydroxy” bao gdm céc hgp chat co céng thire HO-(-CH)-C(R")p-(CHp)q-O-),-R”, trong d6 mai R! dée lap duge chon ty nhom bao gm hydro, nhém alkyl cé tir 1 dén 10 nguyén tir cacbon, va nhém hydroxyalkyl c6 tir 1 dén 10 nguyén tir cacbon, n 14 sé nguyén tir 1 dén 10, m a 0 hode 1, va R? la hydro hode nhém alkyl 6 th 1 dén 10 nguyén tir cacbon. Tét nhét i, mdi R’ doc lap duge chon tir H, CH3, va CH,OH. Vi du vé dung méi c6 nhém chite hydroxy thich hop 14 glycol nhur dietylen monobutyl ete, etylen glycol, dietylen glycol, dipropylen glycol, va polyetylen glycol, glyxerol, va pentaerythritol. ‘Tt hon la q 06 nhém chite hydroxy c6 mat trong dung dich chat ting te voi luong nam trong khoang tir 1 dén 50% trong luong, tét hon 14 nam trong khoang tir 5 dén 30% trong hong, Tét hon 1a, né co mat trong nha da duge lam tang téc so b6 véi hugng nam trong khoang tir 0,1 dén 100 g/kg nhya, t6t hon la nam trong khoang tir 0,5 dén 60 g/kg nhua. Dung dich chat ting téc va nhya da lam ting téc so b6 theo sing ché khéng chita axit ascorbic, béi vi axit ascorbic c6 xu huéng lim mit tie dung eda chat lam tang kha nang phan dng. V6i su c6 mat cita axit ascorbic, kim loai thir hai c6 thé e6 tac dung nhu chat ic ché thay vi lam tang kha nang phan img. ‘Trong pham vi bin mé ta nay, thuat ngit axit ascorbic bao gdm axit L-ascorbic va axit D-isoascorbic. Dung dich chat tang tée va nhya da duge lim ting téc so b6 theo sing ché c6 thé tay y chita m6t hodc nhiéu chat trg xtc tée, nude, chat phu gia, va/ hoge chat d6n.16997 C6 ba nhém chit trg xtc téc quan trong 1a: cdc mudi cia kim loai carboxylat, 1,3-diketon, va hgp chat chita phospho. Vi dy vé 1,3-diketon la axetyl axeton, benzoyl axeton, va dibenzoyl metan, va axetoaxetat nhu dietyl axetoaxetamit, dimetyl axetoaxetamit, dipropylaxetoaxetamit, dibutylaxetoaxetamit, metyl axetoaxetat, ety] axetoaxetat, propyl axetoaxetat, va butylaxctoaxetat. Vi dy vé cae mnéi cia kim loai carboxylat thich hop 1a 2-etyl hexanoat, ‘octanoat, nonanoat, heptanoat, neodecanoat, va naphtenat cia amoni, kim loai kiém, va kim Jogi kiém thé. Kim loai kiém duge uu tign la K. Mu6i c6 thé duge bé sung vao dung dich chat ting téc hoc nhya pr dang nhu vay, hoge ching ¢é thé duge tao thanh hai chd. Vi dy, 2-etyl hexanoat kim loai kiém cé thé duge diéu ché tai ché trong dung dich chat tang téc, sau khi bé sung hydroxit kim loai kiém va axit 2-etyl hexanoic vio dung dich. Vi du vé hop chat chita phospho la hgp chat co céc céng thite P(R)s va P(R)3= O, trong dé mdi R AGc lip duge chon tir hydro, alkyl cé tir 1 dén 10 nguyén tir cdc bon. T6t hon 1a, it nhat hai nhém R duge chon tirnhém alkyl cia nhém alkoxy. Vi dy dae bigt v8 cdc hop chét chtra phospho thich hyp 1a dietyl phosphat, dibutyl phosphat, tributyl phosphat, triety! phosphat (TEP), dibutyl phosphit, va trietyl phosphat. Axetoaxetat [a chit tra xiie téc duge dic biét uu tién. Duge dc biét uu tién la dietyl axctoaxetamit. Duge wu tién hon nita la hén hgp cia dietyl axetoaxetamit va kali 2-ctyl hexanoat. Cling duge uu tién 1a hdn hgp ciia dietyl axctoaxetamit va kali 2-etyl hexanoat. Ciing duge wu tién 1a hon hop cia dietyl axetoaxetamit va dibutyl phosphat. Néu m6t hode nhién chat try xite téc cd mat trong dung dich chit ting téc, tét hon néu ching 06 mat véi long it nhét 14 0,01% trong Iugng, t6t hon nita néu it nhdt la 0.1% trong lugng, con tét hon nita néu it nhdt 1% trong lwong, tét hon nita néu it nhat la 10% trong Iuong, va tét nhat néu it nhat 14 20% trong Iwong; tt hon 1a khong lén hon 90% trong Iuong, tét hon nifa 1a khdng lén hon 80% trong lugng, va tét nhit la khong én hon 70% trong luong, tat ca déu tinh theo téng trong Irong dung dich tang tdc,16997 Dung dich ting tdc theo sing ché cin c6 thé chira cic hgp chat hitu co bd sung nhu dung méi hydrocacbon béo, dung méi hydrocacbon thom, va cae dung méi chira nh6m aldehyt, keton, ete, este, rugu, phosphat, ho8c axit carboxylic. Vi du vé céc dung mdi thich hop 1a dung moi hydrocacbon béo nhu spirit tring va xng khoing khng mii (OMS), dung mdi hydrocacbon thom nhu naphaten va hén hop cia naphaten va parafin, isobutanol; pentanol; 1,2-dioxim, N-metyl pyrolidinon, N-ety! pyrolidinon; dimetyl formamit (DMF); dimetylsulfoxit (DMSO); 2,2. diisobutyrat (TxIB); c4c este nhu dibutyl maleat, dibutyl sucxinat, ctyl axetat, Arimetylpentandiol mono- va dieste cila axit ketoglutaric, pyruvat, va cdc este cla axit ascorbic nhu ascobic palmitat; aldchyt; mono- va dieste, dic biét hon la dietyl malonat va sucxinat; 1.2-diketon, dic biét Ia diaxetyl va glyoxal; rugu benzylic, va rugu béo. Dung dich chat tang tc c6 thé ty ¥ chira nuéc. Néu cé mat, tét hon néu ham luong nude cia dung dich it nhat 1a 0,01% trong Iuong va tét hon nia néu it nhat 1a 0.1% trong lrgng. Tét hon 1a, ham lugng nude khong Ién hon 50% trong lugng, tit hon nifa 14 kh6ng 1én hon 40% trong lung, t6t hon nia 14 khong lén hon 20% trong lung, con t6t hon nifa 1a khong lén hon 10% trong Ingng, va tét nhét 1a khéng lén hon 5% trong Iugng, tat c4 déu tinh theo tong trong long dung dich chat tang téc. Dung dich chat ving téc c6 thé dugc diéu ché bing cach tron don gian cdc thanh phan, tay ¥ voi buée lam néng va/hodc tr6n trung gian. Nhua da duge lam tang téc so b6 cé thé duge diéu ché theo nhiéu céch khac nhau: bing cdch tron céc thanh phan riéng lé voi nhya, hoc bing cach trn nhya, bao g6m monome tay ¥, véi dung dich chat tang téc theo sang ché. Phuong phap sau dugc wu tin, Nhya thich hep can duge héa rin bing céch sir dung dung dich chat ting téc theo sang ché va cé mat trong hn hop nhya da duge tam ting téc so b6 bao gdm nhira alkyt, nhya polyeste chua bdo hda (UP), nhya este vinyl, nhya (metjacrylat, polyuretan, nhya epoxy, vi hdn hop cia chang. Nhya dugc wu tién 1a nhya (met)acrylat, nhya UP va nhua este vinyl. Trong pham vi don sang ché nay, cde thuat ngir “nhya polyeste chura bao hoa” va “nhya UP” ding 4é chi sy két hp cia nhya polyeste chua bao héa va hyp chat monome cé lién két chua bao hda kiéu etylen. Thugt ngit “nhya (met)acrylat” ding dé chi sy két hop cia nhya acrylat hodc -8-16997 metacrylat va hop chét monome cé lién két chua bao hoa kiéu etylen, Nhua UP va nhya acrylat nhu duge x4e dinh trén day duge 4p dyng thyc té phd bién va dang co irén thj treéng. Quy trinh héa rin thudng bat du bing cach bd sung dung dich chat tang téc theo sang ché va chat khoi mao (peroxit) vio nhya, hoc bé sung peroxit vao nhya da duoc lam tang téc so bd. Nhua UP thich hop cdn dugc héa rin bang quy trinh theo sang ché la nhya ortho, nhya iso, nhya iso-npg, va nhya dixyclopentadien (DCPD). Vi dy vé céc nhya nhw vay li maleic, fumaric, alylic, vinylic, va nhya dang epoxy, nhya bisphenol A, nhua terephtalic, va hén hop nhya. Nhya este vinyl bao gém nhya acrylat trén co sé, vi du, metacrylat, diacrylat, va oligome ciia ching. Nhva acrylat bao gém acrylat, metacrylat, diacrylat, va dimetacrylat, va oligome cia ching. Vi du vé cac hop chét monome cé lién két chwra bao hda kidu etylen bao gim styren va dan xuat styren nhu a-metyl styren, vinyl toluen, inden, divinyl benzen, viny! pyrolidon, vinyl siloxan, vinyl caprolactam, stilben, va ca dialy! phtalat, dibenzyliden axeton, aly! benzen, metyl metacrylat, metylacrylat, axit (met)acrylic, diacrylat, dimetacrylat, acrylamit; vinyl axetat, trialyl xyanurat, trialyl isoxyanurat, cdc hop chat alyl duge str dung cho img dung quang hoe (nhu (di)etylen glycol dialyl cacbonat), clostyren, tert-butyl styren, tert-butylacrylat, butandiol dimetacrylat va hon hop cia 5200 ching. Vi du thich hop vé chat pha loang phan img (met)acrylat 1 PE di(met)acrylat, 1,4-butandiol di(met)acrylat, 1,3-butandiol di(met)acrylat, 2,3-butandioldi(met)acrylat, 1,6-hexandiol di(met)acrylat va cdc chat déng phan cua n6, dietylenglycol di(met)acrylat, trietylenglycol di(met)acrylat, glyxerol di(metjacrylat, trimetylolpropan di(met)acrylat, neopentyl glycol di(met)acrylat, dipropylenglycol di (met)acrylat, tripropyllenglycol di(met)acrylat, PPG250 di(metjacrylat, trixyclodetan dimetylol di(met)acrylat, 1,10-decandiol di(met)acrylat, tetractylen glycol di(met)acrylat, trimetylolpropantri(met)acrylat, glyxidy! (met)acrylat, (bis)maleimit, (bis)xitraconimit, (bis)itaconimit, va hdn hgp cia ching, Tot hon 1a, lugng monome cé lién két chua bao hoa kiéu etylen trong nhya da duge lam tang tc so bd it nhat 1a 0,1% trong hong, tinh theo trong hrong nhya, tét 9.16997 hon nia néu it nhat 1a 1% trong rong, va tdt nhat la it nhat 5% trong lugng. Tét hon 14, lugng monome cé lién két chua bdo héa kiéu etylen khong lén hon 50% trong long, tét hon nita 1a khong 1én hon 40% trong luong, va tét nhét 1a khéng 1én hon 35% trong hong. Néu dung dich chat ting téc duge sir dung dé héa rin nhua hoe dé diéu ché nhya di duge lim ting téc so bé, dung dich chat tang téc thudng duge sir dung véi St hon nita néu it nhdt 14 0,1% trong lugng, va tét lugng it nhat 14 0,01% trong lyons hon [a khéng I6n hon 5% trong wong, t6t hon ntta f& khong 1én hon 3% trong rong dung dich chat ting téc, tinh theo trong Iugng nhya. Peroxit thich hgp dé héa rin nhyra va thich hop dé c6 mat trong thanh phan thir hai cia ché phdm hai thanh phin bao gém peroxit v6 co va peroxit him co nhu keton peroxit, peroxyeste, diaryl peroxit, dialkyl peroxit, va peroxydicacbonat duge sir dung thong thudng, va ca peroxycacbonat, peroxyketal, hydroperoxit, diaxyl peroxit, va hydro peroxit. Peroxit duge wu tién la hydroperoxit hitu co, keton peroxit, peroxyeste, va peroxycacbonat, Duge wu tién hon nita la hydroperoxit va keton peroxit. Duge wu tién hydroperoxit bao gdm cumyl hydroperoxit, 1,1,3,3-tetrametylbuty] hydroperoxit, tert-butyl hydroperoxit, isopropylcumyl hydroperoxit, tert-amyl _hydroperoxit, 2, terpen-hydroperoxit va pinen hydroperoxit. Keton peroxit duge wu tién bao gdm metyl imetylhexy!-2,5-dihydroperoxit, pinan hydroperoxit, para-mentan-hydroperoxit, etyl keton peroxit, metyl isopropyl keton peroxit, metyl isobutyl keton peroxit, xyclohexanon peroxit, va axetylaxeton peroxit. ‘Tat nhién, c hdn hop cia hai hode nhiéu peroxit c6 thé duge sit dung, vi du, hn hop cia hydroperoxit hoe keton peroxit véi peroxyeste. Peroxit duge dic biét uu tién 1a metyl etyl keton peroxit. Chuyén gia trong linh vuc sé hidu rling cdc peroxit nay cé thé duge két hop véi chat phu gia thong thudng, vi du. chat don, chat mau, va chdt ham né. Vi du vé chat ham né 18 cdc este ua nude va ic dung méi hydrocacbon. Tét hon nifa, néu lugng peroxit duge sir dung dé héa rin nhya it nhdt la 0, 1 phan trim nhya (phr), t6t hon nia néu it nat 14 0,5 phr, va tét hat la it nhat 1 phr. Tét hon 1a lung peroxit khong lon hon 8 phr, tét hon nifa la khéng lon hon 5 phr, tét nhat la khéng 16n hon 2 phr. -10-16997 Khi peroxit duge tron véi nhya da duge lam ting téc so bo duge bé sung vao hén hop so 66 cua nhya va dung dich chat ting téc, hodc duge tron so b6 voi nhya sau do, dung dich chit tang téc dugc bé sung. hn hop thu duge duge trén va duge phan tén. Quy trinh héa ran c6 thé duge thyc hién & nhiét 46 bat ky nim trong khoang tir - 15°C lén dén 250°C, tay thuge vao hé chat khoi mao, hé tang téc, cae hop chat phi hop véi téc d6 héa ran, va hén hop nhya duge héa ran. Tét hon 1a, né durge thyre hign & ohiét dé méi trutmg therng duge str dung trong cac tng dung nhu ép rap bing tay, phun gia cong, cuén day t6c dic chuyén nhya, tao lop phi (vi du, cae lop phir gel va J6p pha chudn), san xuat khuy, dic ly tim, cdc tam dap séng hoe cdc tim panen rot, v.v.. Tuy nhién, né cling c6 phing, hé thay 16, chu rita nha bép no cée hop ch thé duge str dung tong SMC, BMC, ky thuat din edn, va nhiét d6 len dén 180°C, tt hon nia la lén dén 150°C, tét nhat la 1én dén 100°C, duge ic ky thugt wong ty, & sir dung, Cie chat phu gia tiy y khac c6 thé duge ding trong quy trinh héa rin theo sing ché nhu chat dn, soi thy tinh, chét mau, chat ire ché, va chat trg xiic tic. Nhua dong rin duge str dung trong nhiéu img dung khéc nhau, bao gdm cdc img dung trén bién, c6 dinh héa chat, lop mai, x4y dung, thay lép 1ét, éng va thiing, lit san, canh cia c6i xay gid, v.v.. Vidu thue sang ché Vidy lL Hai dung dich chat ting téc chira Cu duoc diéu ché, khac nhau vé Iugng Co. Co duge bé sung va bang cach bé sung 0,045% trong lugng (tinh theo trong lugng dung dich chat tang téc) chat tang téc dang ban trén thi trudmg NL-53 (ex-AkzoNobel), chira coban (If) 2-etylhexanoat v6i luong 1 10% trong liugng Co (duéi dang kim loai), Cac thanh phan ctta dung dich duge thé hign trong Bang 1. Cic dung dich chat tang t6c nay ~ 0,5 phe ( phan tram nhya) ~ duge sir dung dé héa rin nhya polyeste chua bao hda trén co si axit ortho phtalic (Palatal® P6 ex DSM nhya) & 20°C véi 1,5 phr metyl etyl keton peroxit (Butanox® M50, ex-AkzoNobel). Tinh nang héa rin duge phan tich bing phuong phap cla Hiép hi nhya (Society of Plastic Institute) (phuong phép SPI F/77,1; mua cia Akzo Nobel Polymer -lL16997 Chemicals). Phuong phap nay bao gém do mic téa nhiét dinh, thai gian dén dinh, va théi gian tao thanh gel. Theo phuong ph4p nay, 25g hn hgp bao gdm 100 phan nhya, 1.5 phan peroxit, va 0,5 phan dung dich chat ting tc duoc rét vao éng thir nghiém va cap nhigt dign duge dat xuyén qua vach 6 gitta éng. Tiép theo, éng thiy tinh duge dat vio phdng duge kiém soat khi hiu duge duy tri ¢ 20°C va do dumg cong théi gian- nhiét dé. Tt dudng cong nay, cdc thong sé sau duge tinh toan: Thoi gian tao thanh gel (Gt) = thdi gian tinh theo phut tr6i qua gita thai diém bit dau thir nghiém va 5,6°C trén nhiét 46 bén. ‘Thdi gian dén dinh (TTP) = thoi gian tri qua gitta thoi diém bat diu thir nghiém va thai diém dat dén nhiét 49 dinh. Mite t6a nhiét (PE) ~ nhiét d6 dat dén 16i da Cac két qua duge thé hign trong Bang 1, cing bao gdm thir nghiém tham chiéu bang cach chi str dung chat ting toc NL-53 (0,045phr). Bang 1 Thi nghiém | Thir nghiém : Thir nghiém 3 so sinh | so sinh 2 Dietylen glycol (% trong hrgng) : 20 1995 | — SSeS fz 4 Dietanol amin (% trong hrgng) - 25 25 axetoaxetamin (% trong - 40 40 Dibuty! phosphat (% trong long) - 10 10 Cu(L) clorua (% trong lugng) - 5 5 Chat tang téc NL-53 (% trong 100 : 0,045 luong) 18 2 3 -12-16997 TTP (phat) 32 2 8 |PE(°C) 152,3 153,4 151,9 Vidu2 Vi du 1 duge thu hién lap lai v6i hai dung dich chat tang téc chita Cu khic. Cac két qui durgc thé hign trong bang 2. Bang 2 Thit nghiém ahem te nghiém 3 so sanh 1 so sanh 2 Dietylen glycol (% trong lugng) - 5 5 Dictanol amin (% trong lugng) - 25 Dietyl axetoaxetamit, (% tron} : teenie - 45 45 | twang) i LK octanoat (% trong lugng) q 20 20 Cu(U) axetat (% trong lugng) - 5 5 \Chat tang tée NL-53- (% tron, : tence 100 - 0,045 lugng) Gt (pha) 18 26 4 TTP (phat) 32 38 7 PE (°C) 152,3 163,7 1754 “1B.16997 YEU CAU BAO HO 1. Dung dich chat tang t6c thich hgp dé tao ra hé oxy héa-Khtr véi peroxit, chira: (i) hop chat cia kim logi chuyén tigp thir nhét, trong dé kim logi chuyén tiép thir nhat la Cu(), (ii) hgp chat cua kim loai chuyén tiép thé hai, trong 46 kim loai chuyén tiép thir hai duge chon tir nhém bao gém Co, Ti, Fe, va Mn; ty 1¢ trong long gita kim loai chuyén tiép thir nhdt va kim loai chuyén tiép thir hai nim trong khodng tir 20:1 dén 200:1, (ii) bazo chia nito, va (iv) dung mdi c6 nhém chite hydroxyl, voi digu kign dung dich chat tang téc nay khOng chia axit ascorbic. 2. Dung dich chat tang téc theo diém 1, trong dé kim loai chuyén tiép thir nhat cé mat trong dung dich véi lang nam trong khoang tir 50 dén 5000mmoll/1 3. Dung dich chat ting téc theo diém 1, trong dé kim loai chuyén tiép thir hai co mat trong dung dich véi lugng nam trong khoang tir 10 dén 1000mmol/l. 4, Dung dich chat tang tc theo diém 1, trong dé dung dich chat ting téc nay cn chira hop chét kim logi kiém ho%e kim loai kiém thé, hop chdt chira phospho, va/hodc 1.3-diketon. 5. Hén hop nhya da duge lam tang téc so bd chira: (3) nhya déng rin duge, (ii) hop chat eta kim loai chuyén tiép thir nhat, trong d6 kim loai chuyén tiép thir nhat la Cu(I), Gil) hyp chat cua kim loai chuyén tiép thir hai, trong 6 kim logi chuyén tigp thir hai duge chon tir nhom bao gém Co, Ti, Fe, va Mn; ty 1é trong lugng giita kim loai chuyén tiép thir nhat va kim loai chuyén tiép th hai n’im trong khoang tir 20:1 dén 200:1 (iv) bazo chita nito, va () dung méi cé nhém chite hydroxy, -14-16997 véi diéu kign nhya da dugc Kim tang téc so b6 nay kh6ng chita axit ascorbic. 6. Hén hop nhya da duge lim tng téc so bO theo diém 5, trong 46 kim logi chuyén tiép thar nhdt c mat trong dung dich v6i luong nim trong khoang ti 1 dén 7Smmol/kg nhya. 7, Hén hop nhya da duge lam ting t6c so b6 theo diém 5, trong 46 kim loai chuyén liép thir hai co mat trong dung dich véi hrgng n&m trong khodng tir 0,10 dén 10mmol/kg nhya. 8. Hén hop nhya da duge lam tang téc so b6 theo diém 5, trong 46 hon hop nhya nay con chira hop chat kim loai kiém hoc kim loai kiém thé, hop chat chita phospho, vahode 1,3-diketon. 9. Hén hop nhua di duge lam ting téc so bd theo diém 5, trong 46 nhya déng rin duge la nhya polyeste chira bao hoa, nhya este vinyl, hoge nhya (met)acrylat. 10. Ché phdm hai thanh phan, bao gdm thanh phan thir nhat va thanh phan thir hai, trong dé thanh phan thir nhat bao gdm hén hgp nhya da duge lam tang téc so bé theo diém 7, thanh phan thi hai la peroxit. 11. Ché pham hai thanh phan theo diém 10, trong dé peroxit dugc chon tir nhém bao yom hydroperoxit hitu co, keton peroxit, peroxycacbonat, va peroxyeste. 12. Dung dich cht tang t6c theo diém 1, trong 46 kim loai chuyén tiép tht hai la Co. 13. Hin hop nhua da dug Jam ting téc so bd theo diém 5, trong dé kim loai chuyén tiép thir hai la Co. 14, Dung dich chat tang téc thich hop dé tao ra hé oxy héa khit v6i peroxit, chira: (i) hop chat ctia kim loai chuyén tiép thir nhét, trong 46 kim loai chuyén tiép thir nat 1a Cu(1), Gi) hop chat ciia kim Jogi chuyén tiép thir hai, trong dé kim loai chuyén tigp thir hai duge chon tir nhém bao gdm Co, Ti, Fe, va Mn; ty Ie trong lugng gitra kim logi chuyén tiép thir nhat va kim loai chuyén tiép thir hai nim trong khodng tir 20:1 dén 200:1, ii) bazar chita nito, va (iv) dung méi cé nhém chie hydroxyl, -15-16997 voi digu kign dung dich chat tang tc nay khéng chira axit ascorbic. thir nat cd 15. Dung dich chat tang téc theo diém 14, trong dé kim loai chuyén mat trong dung dich véi lugng nam trong khoang tir 50 dén 5000mmol/I. 16. Dung dich chat tang tc theo diém 14, trong dé kim loai chuyén tiép thir hai c6 mat trong dung dich véi long nam trong khoang tir 10 dén 1000mmol/. 17. Dung dich chat ting téc theo diém 14, trong 46 dung dich chat tang téc nay con chia hop cht kim logi kiém hoge kim loai kiém thd, hgp chat chita phospho, va/ho%e 1,3-diketon 18. Hén hop nhua da duge lam tang t6c so b6 chita: (i) nhya déng rin duge, Gi) hop chat cha kim Joai chuyén tiép thir nat, trong dé kim logi chuyén tiép thir nhat 1a Cu), (iii) hop chat cia kim logi chuyén tiép thir hai, trong d6 kim loai chuyén tiép thir hai duge chon tir nhém bao gém Co, Ti, Fe, va Mn; ty 1é trong long gitta kim loai chuyén tiép thir nhdt va kim loai chuyén tiép thir hai trong khoang tir 20:1 dén 200:1 (iv) bazo chia nito, va (¥) dung dich cé nhom chite hydroxy, ‘v6i diéu kign nhua da dugc lam tang téc so b6 nay khong chita axit ascorbic. 19. Hn hop nhya da duge lam tang téc so bé theo diém 18, trong dé kim loai chuyén tigp thir nhat cé mat trong dung dich voi luong nm trong khoang tir 1 dén 7Smmol/kg nhya. 20. Hén hop nhya di duge lam ting téc so b6 theo diém 18, trong dé kim logi chuyén tiép thir hai cé mit trong dung dich voi lugng nam trong khodng tir 0,10 dén 10mmol/kg nhya. 21, Hin hop nhya da duge lam ting téc so b6 theo diém 18, trong d6 hén hop nhya nay con bao gom hop chat kim loai kiém hodc kim loai kiém thé, hop chat chira phospho, va/hoae 1,3-diketon. -16-16997 22. Hin hop nhya da duoc lam ting téc so bé theo diém 18, trong dé nhya dng rin duge 1a nhya polyeste chwra bao hda, nhura este vinyl, howe nhya (met)acrylat 23. Ché phim hai thanh phan, bao gdm thanh phan thi nhdt va thanh phan thir hai, thir nhét bao gdm hdn hop nhya da duge lim ting t6c so b6 theo trong dé thanh pha © diém 18, thinh phan thir hai a peroxit. 24. Ché phim hai thanh phan theo diém 23, trong 46 peroxit drge chon tir nhém bao gém hydroperoxit hitu co, Keton peroxit, peroxycacbonat, va peroxyeste. -17-