Cov xov polyester (PET) yog cov xov hluavtaws loj tshaj plaws. Cov khaub ncaws ua los ntawm cov xov polyester yog xis nyob, mos, yooj yim ntxuav, thiab qhuav sai. Polyester kuj tseem siv dav ua cov khoom siv raw rau kev ntim khoom, cov xov paj kev lag luam, thiab cov yas engineering. Yog li ntawd, polyester tau tsim kho sai thoob ntiaj teb, nce ntxiv ntawm qhov nruab nrab txhua xyoo ntawm 7% thiab nrog cov zis loj.
Kev tsim cov polyester tuaj yeem muab faib ua dimethyl terephthalate (DMT) txoj kev thiab terephthalic acid (PTA) txoj kev hais txog txoj kev ua haujlwm thiab tuaj yeem muab faib ua cov txheej txheem tsis tu ncua thiab cov txheej txheem txuas ntxiv mus rau hauv kev ua haujlwm. Txawm hais tias txoj kev tsim khoom siv li cas los xij, cov tshuaj polycondensation xav tau kev siv cov hlau sib xyaw ua cov tshuaj catalysts. Cov tshuaj polycondensation yog ib kauj ruam tseem ceeb hauv cov txheej txheem tsim polyester, thiab lub sijhawm polycondensation yog qhov tsis zoo rau kev txhim kho cov txiaj ntsig. Kev txhim kho ntawm lub kaw lus catalyst yog ib qho tseem ceeb hauv kev txhim kho qhov zoo ntawm polyester thiab luv lub sijhawm polycondensation.
UrbanMines Tech. Limited yog ib lub tuam txhab ua lag luam hauv Suav teb uas tshwj xeeb hauv kev tshawb fawb thiab kev txhim kho, kev tsim khoom, thiab kev muab cov tshuaj polyester catalyst-grade antimony trioxide, antimony acetate, thiab antimony glycol. Peb tau ua kev tshawb fawb tob txog cov khoom no - lub chaw haujlwm R&D ntawm UrbanMines tam sim no sau cov kev tshawb fawb thiab kev siv cov tshuaj antimony catalysts hauv tsab xov xwm no los pab peb cov neeg siv khoom siv tau yooj yim, ua kom zoo dua cov txheej txheem tsim khoom, thiab muab kev sib tw ntawm cov khoom polyester fiber.
Cov kws tshawb fawb hauv tsev thiab txawv teb chaws feem ntau ntseeg tias polyester polycondensation yog ib qho kev sib txuas ntawm cov saw hlau, thiab lub tshuab catalytic koom nrog chelation coordination, uas xav tau cov hlau catalyst atom los muab cov orbitals khoob los sib koom tes nrog cov khub arc ntawm cov electrons ntawm carbonyl oxygen kom ua tiav lub hom phiaj ntawm catalysis. Rau polycondensation, txij li thaum lub electron huab ceev ntawm carbonyl oxygen hauv hydroxyethyl ester pawg yog qhov tsawg, qhov electronegativity ntawm cov hlau ions yog qhov siab thaum lub sijhawm sib koom tes, los pab txhawb kev sib koom tes thiab kev txuas ntxiv ntawm cov saw hlau.
Cov hauv qab no tuaj yeem siv ua cov tshuaj catalysts 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 thiab lwm yam hlau oxides, alcoholates, carboxylates, borates, halides thiab amines, ureas, guanidines, sulfur-muaj cov organic compounds. Txawm li cas los xij, cov catalysts uas tam sim no siv thiab kawm hauv kev tsim khoom lag luam feem ntau yog Sb, Ge, thiab Ti series compounds. Ntau qhov kev tshawb fawb tau qhia tias: Ge-based catalysts muaj tsawg dua cov tshuaj tiv thaiv sab thiab tsim cov PET zoo, tab sis lawv cov haujlwm tsis siab, thiab lawv muaj tsawg cov peev txheej thiab kim; Cov catalysts uas ua raws li Ti muaj kev ua haujlwm siab thiab kev teb sai, tab sis lawv cov tshuaj tiv thaiv sab catalytic pom tseeb dua, ua rau tsis muaj kev ruaj khov thermal thiab xim daj ntawm cov khoom, thiab feem ntau lawv tsuas yog siv rau kev tsim cov PBT, PTT, PCT, thiab lwm yam; Cov catalysts uas ua raws li Sb tsis yog tsuas yog ua haujlwm ntau dua xwb. Cov khoom zoo yog siab vim tias cov catalysts uas ua raws li Sb muaj kev ua haujlwm ntau dua, muaj tsawg dua cov tshuaj tiv thaiv sab, thiab pheej yig dua. Yog li ntawd, lawv tau siv dav. Ntawm lawv, cov catalysts uas ua raws li Sb feem ntau yog antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), thiab lwm yam.
Saib ntawm keeb kwm kev loj hlob ntawm kev lag luam polyester, peb tuaj yeem pom tias ntau dua 90% ntawm cov nroj tsuag polyester hauv ntiaj teb siv cov tshuaj antimony ua cov tshuaj catalysts. Los ntawm xyoo 2000, Tuam Tshoj tau qhia txog ntau lub Hoobkas polyester, txhua tus siv cov tshuaj antimony ua cov tshuaj catalysts, feem ntau yog Sb2O3 thiab Sb (CH3COO) 3. Los ntawm kev sib koom tes ntawm kev tshawb fawb Suav teb, cov tsev kawm qib siab, thiab cov chaw tsim khoom, ob qho tshuaj catalysts no tau tsim tawm hauv tsev.
Txij li xyoo 1999, lub tuam txhab tshuaj lom neeg Fabkis Elf tau tsim cov tshuaj antimony glycol [Sb2 (OCH2CH2CO) 3] ua cov khoom hloov kho dua tshiab ntawm cov tshuaj catalysts ib txwm muaj. Cov polyester chips tsim tawm muaj qhov dawb siab thiab spinnability zoo, uas tau nyiam kev saib xyuas zoo los ntawm cov koom haum tshawb fawb catalyst hauv tsev, cov tuam txhab lag luam, thiab cov chaw tsim khoom polyester hauv Suav teb.
I. Kev tshawb fawb thiab kev siv antimony trioxide
Tebchaws Meskas yog ib lub tebchaws uas tau tsim thiab siv Sb2O3 thaum ub. Xyoo 1961, kev siv Sb2O3 hauv Tebchaws Meskas tau txog 4,943 tons. Xyoo 1970, tsib lub tuam txhab hauv Nyiv Pooj tau tsim Sb2O3 nrog tag nrho cov peev xwm tsim khoom ntawm 6,360 tons hauv ib xyoos.
Tuam Tshoj cov chaw tshawb fawb thiab kev txhim kho Sb2O3 tseem ceeb feem ntau yog tsom mus rau cov tuam txhab lag luam qub hauv xeev Hunan thiab Shanghai. UrbanMines Tech. Limited kuj tau tsim cov kab tsim khoom tshaj lij hauv xeev Hunan.
(I). Txoj kev tsim cov antimony trioxide
Kev tsim cov Sb2O3 feem ntau siv cov tshuaj antimony sulfide ua cov khoom siv raw. Cov hlau antimony raug npaj ua ntej, thiab tom qab ntawd Sb2O3 yog tsim los ntawm kev siv cov hlau antimony ua cov khoom siv raw.
Muaj ob txoj hauv kev tseem ceeb rau kev tsim Sb2O3 los ntawm cov hlau antimony: kev oxidation ncaj qha thiab kev rhuav tshem nitrogen.
1. Txoj kev oxidation ncaj qha
Cov hlau antimony reacts nrog oxygen nyob rau hauv cua sov los ua Sb2O3. Cov txheej txheem tshuaj tiv thaiv yog raws li nram no:
4Sb + 3O2 = = 2Sb2O3
2. Kev rhuav tshem cov tshuaj ammonia
Cov hlau antimony reacts nrog chlorine los ua cov antimony trichloride, uas tom qab ntawd distilled, hydrolyzed, ammonolyzed, ntxuav, thiab ziab kom tau txais cov khoom tiav Sb2O3. Cov qauv tshuaj tiv thaiv yooj yim yog:
2Sb + 3Cl2 = 2SbCl3
SbCl3 + H2O = = SbOCl + 2HCl
4SbOCl + H2O = = Sb2O3 · 2SbOCl + 2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Kev siv cov antimony trioxide
Kev siv tseem ceeb ntawm antimony trioxide yog ua tus catalyst rau polymerase thiab nplaim taws retardant rau cov ntaub ntawv hluavtaws.
Hauv kev lag luam polyester, Sb2O3 tau siv thawj zaug ua tus catalyst. Sb2O3 feem ntau yog siv ua tus catalyst polycondensation rau txoj kev DMT thiab txoj kev PTA thaum ntxov thiab feem ntau yog siv ua ke nrog H3PO4 lossis nws cov enzymes.
(III). Teeb meem nrog antimony trioxide
Sb2O3 muaj qhov tsis zoo hauv ethylene glycol, nrog rau qhov solubility ntawm tsuas yog 4.04% ntawm 150 ° C. Yog li ntawd, thaum ethylene glycol siv los npaj cov catalyst, Sb2O3 muaj qhov tsis zoo dispersibility, uas tuaj yeem ua rau catalyst ntau dhau hauv lub kaw lus polymerization, tsim cov cyclic trimers siab-melting-point, thiab coj teeb meem rau spinning. Txhawm rau txhim kho qhov solubility thiab dispersibility ntawm Sb2O3 hauv ethylene glycol, nws feem ntau yog saws los siv ntau dhau ethylene glycol lossis nce qhov kub yaj mus rau saum 150 ° C. Txawm li cas los xij, saum toj no 120 ° C, Sb2O3 thiab ethylene glycol tuaj yeem tsim cov ethylene glycol antimony nag thaum lawv ua haujlwm ua ke ntev, thiab Sb2O3 yuav raug txo kom ua rau cov hlau antimony hauv cov tshuaj tiv thaiv polycondensation, uas tuaj yeem ua rau "pos huab" hauv polyester chips thiab cuam tshuam rau cov khoom zoo.
II. Kev tshawb fawb thiab kev siv antimony acetate
Txoj kev npaj ntawm antimony acetate
Thaum xub thawj, antimony acetate tau npaj los ntawm kev sib xyaw antimony trioxide nrog acetic acid, thiab acetic anhydride tau siv los ua tus neeg sawv cev dehydrating kom nqus cov dej uas tsim los ntawm kev sib xyaw. Qhov zoo ntawm cov khoom tiav tau los ntawm txoj kev no tsis siab, thiab nws siv sijhawm ntau dua 30 teev rau antimony trioxide kom yaj hauv acetic acid. Tom qab ntawd, antimony acetate tau npaj los ntawm kev sib xyaw hlau antimony, antimony trichloride, lossis antimony trioxide nrog acetic anhydride, tsis tas yuav siv tus neeg sawv cev dehydrating.
1. Txoj kev siv Antimony trichloride
Xyoo 1947, H. Schmidt et al. nyob rau sab hnub poob lub teb chaws Yelemees tau npaj Sb (CH3COO) 3 los ntawm kev sib xyaw SbCl3 nrog acetic anhydride. Cov mis tshuaj tiv thaiv yog raws li nram no:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Txoj kev siv hlau antimony
Xyoo 1954, TAPaybea ntawm lub tebchaws Soviet yav dhau los tau npaj Sb (CH3COO) 3 los ntawm kev sib xyaw cov hlau antimony thiab peroxyacetyl hauv cov kua benzene. Cov mis tshuaj yog:
Sb + (CH3COO) 2 = = Sb (CH3COO) 3
3. Txoj kev siv Antimony trioxide
Xyoo 1957, F. Nerdel ntawm West Germany siv Sb2O3 los tshuaj nrog acetic anhydride los tsim Sb (CH3COO) 3.
Sb2O3＋3(CH3CO)2O＝＝2Sb(CH3COO)3
Qhov tsis zoo ntawm txoj kev no yog tias cov siv lead ua feem ntau yuav sib sau ua ke ua tej daim loj thiab lo rau ntawm phab ntsa sab hauv ntawm lub reactor, ua rau cov khoom tsis zoo thiab xim tsis zoo.
4. Txoj kev siv tshuaj yaj Antimony trioxide
Yuav kom kov yeej qhov tsis zoo ntawm txoj kev saum toj no, feem ntau cov kuab tshuaj nruab nrab raug ntxiv thaum lub sijhawm ua haujlwm ntawm Sb2O3 thiab acetic anhydride. Txoj kev npaj tshwj xeeb yog raws li nram no:
(1) Xyoo 1968, R. Thoms ntawm American Mosun Chemical Company tau tshaj tawm daim ntawv pov thawj txog kev npaj cov tshuaj antimony acetate. Daim ntawv pov thawj siv xylene (o-, m-, p-xylene, lossis cov khoom sib xyaw ua ke) ua cov tshuaj yaj tsis muaj zog los tsim cov siv lead ua zoo ntawm antimony acetate.
(2) Xyoo 1973, Czech Republic tau tsim ib txoj kev los tsim cov tshuaj antimony acetate zoo siv toluene ua cov kuab tshuaj.
III. Kev sib piv ntawm peb cov tshuaj catalysts uas siv antimony
| Antimony Trioxide | Antimony Acetate | Antimony Glycolate | |
| Cov Khoom Siv Tseem Ceeb | Feem ntau hu ua antimony dawb, cov mis molecular Sb 2 O 3, molecular hnyav 291.51, hmoov dawb, melting point 656 ℃. Cov ntsiab lus theoretical antimony yog li 83.53%. Qhov ceev sib piv 5.20g / ml. Yaj hauv concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, tartaric acid thiab alkali kua, insoluble hauv dej, cawv, dilute sulfuric acid. | Cov mis mos molecular Sb (AC) 3, qhov hnyav molecular 298.89, cov ntsiab lus theoretical antimony txog 40.74%, melting point 126-131 ℃, qhov ceev 1.22g / ml (25 ℃), hmoov dawb lossis dawb, yooj yim soluble hauv ethylene glycol, toluene thiab xylene. | Cov mis molecular Sb 2 (EG) 3, Qhov hnyav molecular yog li 423.68, qhov melting point yog > 100 ℃ (dec.), cov ntsiab lus antimony theoretical yog li 57.47%, qhov tsos yog dawb crystalline khoom, tsis muaj tshuaj lom thiab tsis muaj saj, yooj yim nqus dej noo. Nws yog yooj yim soluble hauv ethylene glycol. |
| Txoj Kev Sib Xyaws thiab Tshuab | Feem ntau yog tsim los ntawm txoj kev 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 3Note: Stibnite / Hlau Ore / Limestone → Cua Sov thiab Fuming → Sau | Kev lag luam feem ntau siv Sb 2 O 3 -solvent txoj kev rau kev tsim cov tshuaj: Sb 2 O 3 + 3 (CH 3 CO ) 2 O → 2 Sb (AC) 3 Txheej Txheem: cua sov reflux → lim dej kub → crystallization → qhuav nqus tsev → khoom Ceeb Toom: Sb (AC) 3 yooj yim hydrolyzed, yog li cov kuab tshuaj nruab nrab toluene lossis xylene siv yuav tsum tsis muaj dej, Sb 2 O 3 tsis tuaj yeem nyob hauv lub xeev ntub, thiab cov khoom siv tsim khoom kuj yuav tsum qhuav. | Kev lag luam feem ntau siv txoj kev Sb 2 O 3 los ua ke: Sb 2 O 3 + 3EG → Sb 2 (EG) 3 + 3H 2 O Txheej Txheem: Kev pub mis (Sb 2 O 3, cov khoom ntxiv thiab EG) → cua sov thiab kev ua kom siab → tshem tawm cov slag, cov khoom tsis huv thiab dej → decolorization → lim dej kub → txias thiab crystallization → sib cais thiab ziab → khoom Ceeb Toom: Cov txheej txheem ntau lawm yuav tsum tau cais tawm ntawm dej kom tiv thaiv hydrolysis. Cov tshuaj tiv thaiv no yog cov tshuaj tiv thaiv rov qab tau, thiab feem ntau cov tshuaj tiv thaiv tau txhawb nqa los ntawm kev siv cov ethylene glycol ntau dhau thiab tshem tawm cov dej khoom. |
| Qhov zoo | Tus nqi pheej yig heev, nws yooj yim siv, muaj kev ua haujlwm catalytic nruab nrab thiab lub sijhawm luv luv polycondensation. | Antimony acetate muaj cov solubility zoo hauv ethylene glycol thiab sib npaug zos hauv ethylene glycol, uas tuaj yeem txhim kho kev siv cov tshuaj antimony; Antimony acetate muaj cov yam ntxwv ntawm kev ua haujlwm catalytic siab, tsawg dua qhov kev puas tsuaj, tiv taus cua sov zoo thiab kev ua haujlwm ruaj khov; Tib lub sijhawm, siv antimony acetate ua tus catalyst tsis tas yuav ntxiv cov co-catalyst thiab stabilizer. Qhov tshuaj tiv thaiv ntawm antimony acetate catalytic system yog qhov tsis tshua muaj zog, thiab cov khoom zoo yog siab, tshwj xeeb tshaj yog cov xim, uas zoo dua li ntawm antimony trioxide (Sb 2 O 3) system. | Cov catalyst muaj qhov solubility siab hauv ethylene glycol; xoom-valent antimony raug tshem tawm, thiab cov khoom tsis huv xws li cov hlau molecules, chlorides thiab sulfates uas cuam tshuam rau polycondensation raug txo kom qis tshaj plaws, tshem tawm qhov teeb meem ntawm acetate ion corrosion ntawm cov khoom siv; Sb 3+ hauv Sb 2 (EG) 3 yog qhov siab heev, uas tej zaum yuav yog vim nws qhov solubility hauv ethylene glycol ntawm qhov kub ntawm cov tshuaj tiv thaiv yog ntau dua li ntawm Sb 2 O 3 Piv nrog Sb (AC) 3, qhov ntau ntawm Sb 3+ uas ua lub luag haujlwm catalytic yog ntau dua. Cov xim ntawm cov khoom polyester tsim los ntawm Sb 2 (EG) 3 zoo dua li ntawm Sb 2 O 3 Me ntsis siab dua li qhov qub, ua rau cov khoom zoo li ci dua thiab dawb dua; |
| Qhov tsis zoo | Qhov solubility hauv ethylene glycol tsis zoo, tsuas yog 4.04% ntawm 150 ° C. Hauv kev xyaum, ethylene glycol ntau dhau lossis qhov kub yaj nce mus txog 150 ° C. Txawm li cas los xij, thaum Sb 2 O 3 reacts nrog ethylene glycol ntev ntawm 120 ° C, ethylene glycol antimony precipitation yuav tshwm sim, thiab Sb 2 O 3 yuav raug txo kom ua rau hlau ntaiv hauv polycondensation reaction, uas tuaj yeem ua rau "grey pos huab" hauv polyester chips thiab cuam tshuam rau cov khoom zoo. Qhov tshwm sim ntawm polyvalent antimony oxides tshwm sim thaum lub sijhawm npaj ntawm Sb 2 O 3, thiab qhov purity ntawm antimony raug cuam tshuam. | Cov ntsiab lus antimony ntawm cov catalyst yog qhov tsawg heev; cov acetic acid impurities tau nkag mus rau cov khoom siv corrode, ua rau ib puag ncig tsis zoo, thiab tsis zoo rau kev kho dej khib nyiab; cov txheej txheem ntau lawm yog qhov nyuaj, qhov chaw ua haujlwm tsis zoo, muaj kuab paug, thiab cov khoom yooj yim hloov xim. Nws yooj yim rau decompose thaum cua sov, thiab cov khoom hydrolysis yog Sb2O3 thiab CH3COOH. Lub sijhawm nyob ntawm cov khoom siv yog ntev, tshwj xeeb tshaj yog nyob rau theem kawg polycondensation, uas yog siab dua li Sb2O3 system. | Kev siv Sb 2 (EG) 3 ua rau tus nqi catalyst ntawm lub cuab yeej nce ntxiv (qhov nce nqi tsuas yog tuaj yeem them rov qab yog tias 25% ntawm PET siv rau kev tig tus kheej ntawm cov filaments). Tsis tas li ntawd, tus nqi b ntawm cov khoom hue nce me ntsis. |