Faeba ea polyester (PET) ke mofuta o moholo ka ho fetisisa oa faeba ea maiketsetso. Liaparo tse entsoeng ka faeba ea polyester li phutholohile, lia hlaka, li bonolo ho hlatsuoa, 'me li oma kapele. Polyester e boetse e sebelisoa haholo e le thepa e tala bakeng sa ho paka, likhoele tsa indasteri le polasetiki ea boenjiniere. Ka lebaka leo, polyester e ntlafetse ka potlako lefatšeng ka bophara, e eketseha ka karolelano ea selemo le selemo ea 7% 'me e na le tlhahiso e kholo.
Tlhahiso ea polyester e ka aroloa ka tsela ea dimethyl terephthalate (DMT) le tsela ea terephthalic acid (PTA) ho latela tsela ea ts'ebetso 'me e ka aroloa ka mokhoa o sa khaotseng le mokhoa o tsoelang pele ho latela ts'ebetso. Ho sa tsotelehe tsela ea ts'ebetso ea tlhahiso e sebelisitsoeng, karabelo ea polycondensation e hloka tšebeliso ea metsoako ea tšepe e le li-catalyst. Karabelo ea polycondensation ke mohato oa bohlokoa ts'ebetsong ea tlhahiso ea polyester, 'me nako ea polycondensation ke bothata ba ho ntlafatsa chai. Ntlafatso ea sistimi ea catalyst ke ntlha ea bohlokoa ho ntlafatseng boleng ba polyester le ho khutsufatsa nako ea polycondensation.
UrbanMines Tech. Limited ke khamphani e etellang pele ea Chaena e ikhethang ka ho etsa lipatlisiso le nts'etsopele, tlhahiso le phepelo ea antimony trioxide ea sehlopha sa catalyst sa polyester, antimony acetate, le antimony glycol. Re entse lipatlisiso tse tebileng ka lihlahisoa tsena—lefapha la lipatlisiso le nts'etsopele la UrbanMines joale le akaretsa lipatlisiso le ts'ebeliso ea li-catalyst tsa antimony sehloohong sena ho thusa bareki ba rona ho sebelisa ka mokhoa o feto-fetohang, ho ntlafatsa lits'ebetso tsa tlhahiso, le ho fana ka tlholisano e felletseng ea lihlahisoa tsa polyester fiber.
Litsebi tsa lehae le tsa kantle ho naha ka kakaretso li lumela hore polyester polycondensation ke karabelo ea katoloso ea ketane, 'me mokhoa oa catalytic ke oa coordination ea chelation, e hlokang hore athomo ea tšepe ea catalyst e fane ka li-orbital tse se nang letho ho hokahanya le para ea arc ea lielektrone tsa carbonyl oxygen ho fihlela sepheo sa catalysis. Bakeng sa polycondensation, kaha bongata ba leru la lielektrone tsa carbonyl oxygen sehlopheng sa hydroxyethyl ester bo tlase haholo, electronegativity ea li-ion tsa tšepe e phahame haholo nakong ea coordination, ho nolofatsa coordination le ketane katoloso.
Tse latelang li ka sebelisoa e le li-catalyst tsa polyester: Li, Na, K, Be, Mg, Ca, Sr, B, Al, Ga, Ge, Sn, Pb, Sb, Bi, Ti, Nb, Cr, Mo, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Hg le li-oxide tse ling tsa tšepe, li-alcoholate, li-carboxylate, li-borate, li-halide le li-amine, li-ureas, li-guanidine, metsoako ea lintho tse phelang e nang le sebabole. Leha ho le joalo, li-catalyst tse sebelisoang le ho ithutoa hona joale tlhahisong ea indasteri ke metsoako ea letoto la Sb, Ge, le Ti. Palo e kholo ea lithuto e bontšitse hore: Li-catalyst tse thehiloeng ho Ge li na le likarabo tse fokolang tse mpe 'me li hlahisa PET ea boleng bo holimo, empa ts'ebetso ea tsona ha e holimo, 'me li na le mehloli e fokolang 'me li bitsa chelete e ngata; Li-catalyst tse thehiloeng ho Ti li na le ts'ebetso e phahameng le lebelo le potlakileng la karabelo, empa liketso tsa tsona tse ka thoko tsa catalytic li totobetse haholoanyane, e leng se fellang ka botsitso bo fokolang ba mocheso le 'mala o mosehla oa sehlahisoa, 'me ka kakaretso li ka sebelisoa feela bakeng sa tlhahiso ea PBT, PTT, PCT, jj.; Li-catalyst tse thehiloeng ho Sb ha li sebetse feela haholoanyane. Boleng ba sehlahisoa bo holimo hobane li-catalyst tse thehiloeng ho Sb li sebetsa haholoanyane, li na le liketso tse fokolang tse ka thoko, 'me li theko e tlase. Ka hona, li 'nile tsa sebelisoa haholo. Har'a tsona, li-catalyst tse thehiloeng ho Sb tse sebelisoang haholo ke antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), jj.
Ha re sheba nalane ea nts'etsopele ea indasteri ea polyester, re ka fumana hore limela tse fetang 90% tsa polyester lefatšeng li sebelisa metsoako ea antimony e le li-catalyst. Ka selemo sa 2000, Chaena e ne e se e hlahisitse limela tse 'maloa tsa polyester, tseo kaofela li neng li sebelisa metsoako ea antimony e le li-catalyst, haholo-holo Sb2O3 le Sb(CH3COO)3. Ka boiteko bo kopanetsoeng ba lipatlisiso tsa saense tsa Chaena, liunivesithi le mafapha a tlhahiso, li-catalyst tsena tse peli joale li se li hlahisitsoe ka botlalo ka hare ho naha.
Ho tloha ka 1999, k'hamphani ea lik'hemik'hale ea Fora Elf e qalile catalyst ea antimony glycol [Sb2 (OCH2CH2CO) 3] e le sehlahisoa se ntlafalitsoeng sa catalyst ea setso. Li-chip tsa polyester tse hlahisoang li na le bosoeu bo phahameng le ho potoloha hantle, e leng se hohetseng tlhokomelo e kholo ho tsoa litsi tsa lipatlisiso tsa catalyst tsa malapeng, likhoebong le bahlahisi ba polyester Chaena.
I. Patlisiso le ts'ebeliso ea antimoni trioxide
United States ke e 'ngoe ea linaha tsa pele ho hlahisa le ho sebelisa Sb2O3. Ka 1961, tšebeliso ea Sb2O3 United States e fihlile ho lithane tse 4,943. Lilemong tsa bo-1970, lik'hamphani tse hlano Japane li hlahisitse Sb2O3 ka kakaretso ea bokhoni ba tlhahiso ea lithane tse 6,360 ka selemo.
Diyuniti tse ka sehloohong tsa lipatlisiso le nts'etsopele tsa Sb2O3 tsa Chaena li shebane haholo le likhoebo tsa mehleng tsa mmuso Profinseng ea Hunan le Shanghai. UrbanMines Tech. Limited e boetse e thehile mohala oa tlhahiso oa profeshenale Profinseng ea Hunan.
(I). Mokhoa oa ho hlahisa antimoni trioxide
Tlhahiso ea Sb2O3 hangata e sebelisa manya a antimony sulfide e le thepa e tala. Antimony ea tšepe e lokisoa pele, ebe Sb2O3 e hlahisoa ho sebelisoa antimony ea tšepe e le thepa e tala.
Ho na le mekhoa e 'meli e meholo ea ho hlahisa Sb2O3 ho tsoa ho antimony ea tšepe: oxidation e tobileng le ho bola ha naetrojene.
1. Mokhoa oa ho oxidation ka kotloloho
Antimony ea tšepe e arabela le oksijene e futhumatsoang ho etsa Sb2O3. Ts'ebetso ea karabelo ke e latelang:
4Sb＋3O2＝＝2Sb2O3
2. Ammolysis
Tšepe ea antimony e arabela le chlorine ho hlahisa antimony trichloride, e ntan'o hloekisoa, e haelloa ke hydrolyzed, e tšeloa ka ammonolyzed, e hlatsuoa le ho omisoa ho fumana sehlahisoa se felileng sa Sb2O3. Tekanyo ea motheo ea karabelo ke:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Tšebeliso ea antimony trioxide
Tšebeliso e ka sehloohong ea antimony trioxide ke e le catalyst bakeng sa polymerase le e thibelang malakabe bakeng sa thepa ea maiketsetso.
Indastering ea polyester, Sb2O3 e ile ea sebelisoa pele e le catalyst. Sb2O3 e sebelisoa haholo-holo e le catalyst ea polycondensation bakeng sa tsela ea DMT le tsela ea pele ea PTA 'me hangata e sebelisoa hammoho le H3PO4 kapa li-enzyme tsa eona.
(III). Mathata ka antimoni trioxide
Sb2O3 e na le ho qhibiliha ho fokolang ho ethylene glycol, ka ho qhibiliha ha 4.04% feela ho 150°C. Ka hona, ha ethylene glycol e sebelisoa ho lokisa catalyst, Sb2O3 e na le ho qhalana ho fokolang, e leng se ka bakang catalyst e feteletseng tsamaisong ea polymerization, sa hlahisa li-trimer tsa cyclic tse nang le ntlha e phahameng ea ho qhibiliha, 'me sa tlisa mathata ho potoloha. Ho ntlafatsa ho qhibiliha le ho qhalana ha Sb2O3 ho ethylene glycol, hangata ho amoheloa ho sebelisa ethylene glycol e ngata kapa ho eketsa mocheso oa ho qhibiliha ho feta 150°C. Leha ho le joalo, ka holimo ho 120°C, Sb2O3 le ethylene glycol li ka hlahisa pula ea antimony ea ethylene glycol ha li sebetsa hammoho nako e telele, 'me Sb2O3 e ka fokotsoa ho ba antimony ea tšepe karabelong ea polycondensation, e ka bakang "moholi" ho li-chips tsa polyester le ho ama boleng ba sehlahisoa.
II. Patlisiso le ts'ebeliso ea acetate ea antimony
Mokhoa oa ho lokisa antimony acetate
Qalong, acetate ea antimony e ne e lokisoa ka ho kopanya antimony trioxide le asiti ea acetic, 'me acetic anhydride e ne e sebelisoa e le moemeli oa ho monya metsi a hlahisoang ke karabelo. Boleng ba sehlahisoa se felileng se fumanoeng ka mokhoa ona bo ne bo se holimo, 'me ho nkile lihora tse fetang 30 hore antimony trioxide e qhibilihe ka har'a asiti ea acetic. Hamorao, acetate ea antimony e ile ea lokisoa ka ho kopanya tšepe ea antimony, antimony trichloride, kapa antimony trioxide le acetic anhydride, ntle le tlhoko ea moemeli oa ho monya metsi.
1. Mokhoa oa antimoni trichloride
Ka 1947, H. Schmidt le ba bang Jeremane Bophirima ba ile ba lokisa Sb(CH3COO)3 ka ho kopanya SbCl3 le acetic anhydride. Foromo ea karabelo ke e latelang:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Mokhoa oa tšepe ea antimoni
Ka 1954, TPaybea ea Soviet Union ea mehleng e ile ea lokisa Sb(CH3COO)3 ka ho kopanya antimony ea tšepe le peroxyacetyl ka tharollong ea benzene. Foromo ea karabelo ke:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Mokhoa oa antimoni trioxide
Ka 1957, F. Nerdel oa Jeremane Bophirima o ile a sebelisa Sb2O3 ho arabela le acetic anhydride ho hlahisa Sb(CH3COO)3.
Sb2O3＋3(CH3CO)2O(2Sb)(CH3COO)3
Bothata ba mokhoa ona ke hore likristale li atisa ho kopana likotoana tse kholo ebe li khomarela leboteng le ka hare la reactor, e leng se fellang ka boleng bo bobe ba sehlahisoa le 'mala.
4. Mokhoa oa ho rarolla li-antimony trioxide
Ho hlola mefokolo ea mokhoa o boletsoeng ka holimo, hangata ho eketsoa solvent e sa nke lehlakore nakong ea karabelo ea Sb2O3 le acetic anhydride. Mokhoa o ikhethileng oa ho lokisa ke o latelang:
(1) Ka 1968, R. Thoms oa American Mosun Chemical Company o ile a phatlalatsa patente ea ho lokisa acetate ea antimony. Patente ena e sebelisitse xylene (o-, m-, p-xylene, kapa motsoako oa eona) e le tharollo e sa nke lehlakore ho hlahisa likristale tse ntle tsa acetate ea antimony.
(2) Ka 1973, Rephaboliki ea Czech e ile ea qapa mokhoa oa ho hlahisa acetate e ntle ea antimony e sebelisang toluene e le solvent.
III. Papiso ea li-catalyst tse tharo tse thehiloeng ho antimoni
| Antimony Trioxide | Antimony ea acetate | Antimony Glycolate | |
| Matlotlo a Motheo | E tsebahala haholo e le antimony e tšoeu, formula ea limolek'hule Sb 2O3, boima ba limolek'hule 291.51, phofo e tšoeu, ntlha ea ho qhibiliha 656℃. Bongata ba antimony ba khopolo-taba bo ka ba 83.53%. Boima bo amanang le 5.20g/ml. E qhibiliha ka har'a hydrochloric acid e kopaneng, sulfuric acid e kopaneng, nitric acid e kopaneng, tartaric acid le tharollo ea alkali, e sa qhibiliheng metsing, joala, sulfuric acid e hlapollotsoeng. | Foromo ea limolek'hule Sb(AC) 3, boima ba limolek'hule 298.89, tekanyo ea antimoni ea khopolo-taba e ka bang 40.74%, ntlha ea ho qhibiliha 126-131℃, bongata ba 1.22g/ml (25℃), phofo e tšoeu kapa e sa soeufalang, e qhibilihang habonolo ka har'a ethylene glycol, toluene le xylene. | Foromo ea limolek'hule Sb 2 (EG) 3, Boima ba limolek'hule bo ka ba 423.68, ntlha ea ho qhibiliha ke ＞ 100℃ (dec.), tekanyo ea antimony ea khopolo-taba e ka ba 57.47%, ponahalo ke kristale e tšoeu e tiileng, ha e na chefo ebile ha e na tatso, e bonolo ho monya mongobo. E qhibiliha habonolo ka har'a ethylene glycol. |
| Mokhoa oa ho Kopanya le Theknoloji | E entsoe haholo-holo ka mokhoa oa stibnite: 2Sb 2 S 3 +9O 2 →2Sb 2 O 3 +6SO 2 ↑Sb 2 O 3 +3C→2Sb+3CO↑ 4Sb+O 2 →2Sb 2 O 3Hlokomela: Stibnite / Tšepe ea Ore / Lejoe la mokoetla → Ho futhumatsa le ho Futhumatsa → Pokello | Indasteri e sebelisa haholo-holo mokhoa oa Sb 2 O 3 -solvent bakeng sa tlhahiso: Sb2O3 ＋ 3 (CH3CO) 2O→ 2Sb(AC) 3Ts'ebetso: ho futhumatsa reflux → hot filtration → crystallization → vacuum omisa → sehlahisoaHlokomela: Sb(AC) 3 e haelloa habonolo ke hydrolyzed, kahoo toluene e sa nke lehlakore kapa xylene e sebelisoang e tlameha ho ba anhydrous, Sb 2 O 3 e ke ke ea ba boemong ba metsi, 'me lisebelisoa tsa tlhahiso le tsona li tlameha ho oma. | Indasteri e sebedisa haholo-holo mokgwa wa Sb 2 O 3 ho kopanya: Sb 2 O 3 +3EG→ Sb 2 (EG) 3 +3H 2 OP Tshebediso: Ho fepa (Sb 2 O 3, di-additives le EG) → karabelo ya ho futhumatsa le ho hatella → ho tlosa slag, ditshila le metsi → ho tlosa mmala → ho sefa ho chesang → ho phodisa le ho etsa kristale → karohano le ho omisa → sehlahiswaHlokomela: Tshebetso ya tlhahiso e hloka ho arolwa ho metsi ho thibela hydrolysis. Karabelo ena ke karabelo e ka fetolwang, mme ka kakaretso karabelo e kgothalletswa ka ho sebedisa ethylene glycol e ngata le ho tlosa metsi a sehlahiswa. |
| Molemo | Theko e theko e tlase haholo, e bonolo ho e sebelisa, e na le ts'ebetso e itekanetseng ea ho kenya lintho ka har'a khetla le nako e khuts'oane ea ho kolobisa. | Antimony acetate e na le ho qhibiliha ho hotle ho ethylene glycol mme e hasantsoe ka ho lekana ho ethylene glycol, e leng se ka ntlafatsang ts'ebeliso e ntle ea antimony; Antimony acetate e na le litšobotsi tsa ts'ebetso e phahameng ea catalytic, karabelo e fokolang ea ho senyeha, khanyetso e ntle ea mocheso le botsitso ba ts'ebetso; Ka nako e ts'oanang, ho sebelisa acetate ea antimony e le catalyst ha ho hloke ho eketsoa ha co-catalyst le stabilizer. Karabelo ea sistimi ea antimony acetate catalytic e batla e le bonolo, 'me boleng ba sehlahisoa bo holimo, haholo-holo' mala, o leng betere ho feta oa sistimi ea antimony trioxide (Sb2O3). | Sesebediswa sa catalyst se na le ho qhibiliha ho hoholo ho ethylene glycol; antimony ea zero-valent ea tlosoa, 'me litšila tse kang limolek'hule tsa tšepe, li-chloride le li-sulfate tse amang polycondensation li fokotseha ho ea boemong bo tlaase ka ho fetisisa, e leng ho felisang bothata ba ho bola ha ion ea acetate lisebelisoa; Sb 3+ ho Sb 2 (EG) 3 e phahame haholo, e leng se ka bang hobane ho qhibiliha ha eona ho ethylene glycol mochesong oa karabelo ho feta oa Sb 2 O 3 Ha ho bapisoa le Sb(AC) 3, palo ea Sb 3+ e bapalang karolo ea catalytic e kholo. 'Mala oa sehlahisoa sa polyester se hlahisoang ke Sb 2 (EG) 3 o betere ho feta oa Sb 2 O 3 E phahame hanyane ho feta ea pele, e etsang hore sehlahisoa se shebahale se khanya ebile se le sesoeu; |
| Bothata | Ho qhibiliha ha ethylene glycol ho fokola, ke 4.04% feela ho 150°C. Ha e le hantle, ethylene glycol e phahame haholo kapa mocheso oa ho qhibiliha o eketsoa ho ea holimo ho 150°C. Leha ho le joalo, ha Sb 2O3 e arabela le ethylene glycol ka nako e telele ho feta 120°C, pula ea antimony ea ethylene glycol e ka etsahala, 'me Sb 2O3 e ka fokotsoa ho ba lere la tšepe karabelong ea polycondensation, e ka bakang "moholi o moputsoa" ka har'a li-chips tsa polyester le ho ama boleng ba sehlahisoa. Ketsahalo ea li-oxide tsa antimony tse nang le polyvalent e etsahala nakong ea ho lokisoa ha Sb 2O3, 'me bohloeki bo sebetsang ba antimony boa ameha. | Dikahare tsa antimony tsa catalyst di tlase haholo; ditshila tsa acetic acid tse kentseng disebediswa tsa ho bola, di silafatsa tikoloho, mme ha di lokele kalafo ya metsi a ditshila; tshebetso ya tlhahiso e rarahane, maemo a tikoloho ya tshebetso a mabe, ho na le tshilafalo, mme sehlahiswa se bonolo ho fetola mmala. Ho bonolo ho bola ha se futhumatswa, mme dihlahiswa tsa hydrolysis ke Sb2O3 le CH3COOH. Nako ya ho dula ha thepa e telele, haholoholo mohatong wa ho qetela wa polycondensation, o phahameng haholo ho feta sistimi ya Sb2O3. | Tšebeliso ea Sb 2 (EG) 3 e eketsa litšenyehelo tsa catalyst tsa sesebelisoa (keketseho ea litšenyehelo e ka fokotsoa feela haeba 25% ea PET e sebelisoa bakeng sa ho iphetolela ha likhoele). Ho phaella moo, boleng ba b ba 'mala oa sehlahisoa bo eketseha hanyane. |