Ulusi wa polyester (PET) ndiye mtundu waukulu kwambiri wa ulusi wopangira. Zovala zopangidwa ndi ulusi wa poliyesitala ndi zabwino, zonyezimira, zosavuta kuchapa komanso zowuma mwachangu. Polyester imagwiritsidwanso ntchito kwambiri ngati zopangira zopangira, ulusi wamafakitale, ndi mapulasitiki aumisiri. Chotsatira chake, poliyesitala yakula mofulumira padziko lonse lapansi, ikuwonjezeka pa chiwerengero cha pachaka cha 7% ndi kutulutsa kwakukulu.
Kupanga poliyesitala kungagawidwe mu njira ya dimethyl terephthalate (DMT) ndi njira ya terephthalic acid (PTA) potengera njira yopangira njira ndipo imatha kugawidwa m'njira zapakatikati komanso mosalekeza potengera ntchito. Mosasamala kanthu za njira yopangira njira yomwe idakhazikitsidwa, njira ya polycondensation imafuna kugwiritsa ntchito zinthu zachitsulo monga chothandizira. Zomwe zimachitika pa polycondensation ndi gawo lofunikira kwambiri popanga poliyesitala, ndipo nthawi ya polycondensation ndizomwe zimalepheretsa zokolola. Kusintha kwa makina othandizira ndi chinthu chofunikira kwambiri pakuwongolera mtundu wa polyester ndikufupikitsa nthawi ya polycondensation.
Malingaliro a kampani UrbanMines Tech. Limited ndi kampani yotsogola yaku China yomwe imagwira ntchito bwino pa R&D, kupanga, ndikupereka ma polyester chothandizira-grade antimony trioxide, antimony acetate, ndi antimony glycol. Tachita kafukufuku wozama pazamankhwalawa—dipatimenti ya R&D ya UrbanMines tsopano ikufotokoza mwachidule kafukufuku ndi kugwiritsa ntchito zida za antimoni m'nkhaniyi kuthandiza makasitomala athu kugwiritsa ntchito mosinthika, kukhathamiritsa njira zopangira, komanso kupereka mpikisano wokwanira wa zinthu za polyester fiber.
Akatswiri apakhomo ndi akunja amakhulupirira kuti polyester polycondensation ndi njira yowonjezera maunyolo, ndipo njira yothandizira ndi ya chelation coordination, yomwe imafuna kuti atomu yachitsulo chothandizira kuti apereke orbitals opanda kanthu kuti agwirizane ndi ma arc awiri a ma electron a carbonyl oxygen kuti akwaniritse cholinga cha catalysis. Pakuti polycondensation, popeza ma elekitironi mtambo kachulukidwe carbonyl mpweya mu hydroxyethyl ester gulu ndi otsika, electronegativity zitsulo ayoni ndi mkulu pa kugwirizana, kuti atsogolere kugwirizana ndi unyolo kutambasuka.
Zotsatirazi zitha kugwiritsidwa ntchito ngati zopangira poliyesitala: 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 ndi zitsulo zina oxides, alcoholates, carboxylates, borates, halides ndi amines, ureas, guanidines, sulfure munali organic mankhwala. Komabe, zoyambitsa zomwe zimagwiritsidwa ntchito ndikuphunziridwa pakupanga mafakitale makamaka Sb, Ge, ndi Ti mndandanda wamagulu. Kafukufuku wambiri wasonyeza kuti: Zothandizira za Ge-based zimakhala ndi zotsatira zochepa ndipo zimapanga PET yapamwamba kwambiri, koma ntchito yawo sipamwamba, ndipo imakhala ndi zinthu zochepa ndipo ndi yokwera mtengo; Ma catalysts okhala ndi Ti amakhala ndi zochitika zambiri komanso kuthamanga kwachangu, koma machitidwe awo am'mbali amawonekera bwino, zomwe zimapangitsa kusakhazikika kwamafuta ndi mtundu wachikasu wa chinthucho, ndipo zitha kugwiritsidwa ntchito popanga PBT, PTT, PCT, ndi zina; Sb-based catalysts samangogwira ntchito. Ubwino wa mankhwalawa ndi wapamwamba chifukwa zopangira Sb zochokera ku Sb zimagwira ntchito kwambiri, zimakhala ndi zotsatira zochepa, ndipo ndizotsika mtengo. Choncho, akhala akugwiritsidwa ntchito kwambiri. Zina mwa izo, zomwe zimagwiritsidwa ntchito kwambiri ndi Sb-based catalysts ndi antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), etc.
Kuyang'ana mbiri ya chitukuko cha mafakitale a polyester, tikhoza kupeza kuti zoposa 90% za zomera za polyester padziko lapansi zimagwiritsa ntchito mankhwala a antimoni monga chothandizira. Pofika m'chaka cha 2000, dziko la China linali litayambitsa zomera zingapo za poliyesitala, zonse zomwe zinkagwiritsa ntchito mankhwala a antimony monga chothandizira, makamaka Sb2O3 ndi Sb(CH3COO)3. Kupyolera mu kuyesetsa kophatikizana kwa kafukufuku wa sayansi waku China, mayunivesite, ndi madipatimenti opanga zinthu, zothandizira ziwirizi zapangidwa kwathunthu mdziko muno.
Kuyambira 1999, kampani yamankhwala yaku France ya Elf yakhazikitsa antimony glycol [Sb2 (OCH2CH2CO) 3] chothandizira ngati chinthu chokwezeka chazothandizira zachikhalidwe. Tchipisi ta poliyesitala zomwe zimapangidwa zimakhala ndi zoyera kwambiri komanso kupota kwabwino, zomwe zakopa chidwi chachikulu kuchokera ku mabungwe ofufuza othandizira kunyumba, mabizinesi, ndi opanga ma polyester ku China.
I. Kafukufuku ndi kugwiritsa ntchito antimony trioxide
United States ndi amodzi mwa mayiko oyamba kupanga ndikugwiritsa ntchito Sb2O3. Mu 1961, kumwa kwa Sb2O3 ku United States kunafika matani 4,943. M'zaka za m'ma 1970, makampani asanu ku Japan anapanga Sb2O3 ndi mphamvu yokwanira yopangira matani 6,360 pachaka.
Magawo akuluakulu aku China ofufuza ndi chitukuko a Sb2O3 amayang'ana kwambiri mabizinesi akale a boma m'chigawo cha Hunan ndi Shanghai. Malingaliro a kampani UrbanMines Tech. Limited komanso wakhazikitsa akatswiri kupanga mzere m'chigawo Hunan.
(ine). Njira yopangira antimony trioxide
Kupanga kwa Sb2O3 nthawi zambiri kumagwiritsa ntchito ore antimony sulfide ngati zopangira. Antimoni yachitsulo imakonzedwa koyamba, kenako Sb2O3 imapangidwa pogwiritsa ntchito antimoni yachitsulo ngati zopangira.
Pali njira ziwiri zazikulu zopangira Sb2O3 kuchokera ku antimoni yachitsulo: makutidwe ndi okosijeni mwachindunji ndi kuwonongeka kwa nayitrogeni.
1. Direct makutidwe ndi okosijeni njira
Antimoni yachitsulo imakhudzidwa ndi okosijeni ikatenthedwa kupanga Sb2O3. The reaction process ndi motere:
4Sb＋3O2＝＝2Sb2O3
2. Ammonolysis
Chitsulo cha Antimony chimakhudzidwa ndi klorini kupanga antimony trichloride, yomwe imasungunuka, hydrolyzed, ammonolyzed, kutsukidwa, ndi zouma kuti apeze mankhwala a Sb2O3. The Basic reaction equation ndi:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl(H2O)(Sb2O3·2SbOCl)2HCl
Sb2O3·2SbOCl＋OH＝(2Sb2O3＋2NH4Cl＋H2O)
(II). Kugwiritsa ntchito antimony trioxide
Ntchito yaikulu ya antimony trioxide ndi monga chothandizira polymerase ndi retardant lawi la zipangizo kupanga.
M'makampani a polyester, Sb2O3 idagwiritsidwa ntchito koyamba ngati chothandizira. Sb2O3 imagwiritsidwa ntchito makamaka ngati chothandizira polycondensation panjira ya DMT ndi njira yoyambirira ya PTA ndipo imagwiritsidwa ntchito limodzi ndi H3PO4 kapena ma enzymes ake.
(III). Mavuto ndi antimony trioxide
Sb2O3 ili ndi kusungunuka kosauka mu ethylene glycol, ndi kusungunuka kwa 4.04% kokha pa 150 ° C. Chifukwa chake, ethylene glycol ikagwiritsidwa ntchito pokonzekera chothandizira, Sb2O3 imakhala ndi dispersibility yosauka, yomwe imatha kuyambitsa chothandizira kwambiri mu dongosolo la polymerization, kupanga ma trimers osungunuka kwambiri, ndikubweretsa zovuta pakupota. Kupititsa patsogolo kusungunuka ndi kusungunuka kwa Sb2O3 mu ethylene glycol, nthawi zambiri amaloledwa kugwiritsa ntchito ethylene glycol kwambiri kapena kuonjezera kutentha kwa kutentha kufika pamwamba pa 150 ° C. Komabe, pamwamba pa 120 ° C, Sb2O3 ndi ethylene glycol zimatha kutulutsa mpweya wa ethylene glycol antimoni pamene achita pamodzi kwa nthawi yaitali, ndipo Sb2O3 ikhoza kuchepetsedwa kukhala antimony yachitsulo mu polycondensation reaction, yomwe ingayambitse "chifunga" mu tchipisi ta polyester ndikukhudza. khalidwe la mankhwala.
II. Kafukufuku ndi kugwiritsa ntchito antimony acetate
Kukonzekera njira ya antimoni acetate
Poyamba, antimony acetate inakonzedwa mwa kuchitapo kanthu antimony trioxide ndi acetic acid, ndipo acetic anhydride ankagwiritsidwa ntchito ngati dehydrating agent kuti atenge madzi opangidwa ndi zomwe zimachitika. Ubwino wa chinthu chomalizidwa chomwe chidapezedwa ndi njirayi sichinali chokwera, ndipo zidatenga maola opitilira 30 kuti antimony trioxide isungunuke mu acetic acid. Pambuyo pake, antimony acetate inakonzedwa mwakuchitapo kanthu antimony zitsulo, antimony trichloride, kapena antimoni trioxide ndi acetic anhydride, popanda kufunikira kwa wothandizira kuchotsa madzi m'thupi.
1. Njira ya Antimony trichloride
Mu 1947, H. Schmidt et al. ku West Germany adakonza Sb(CH3COO)3 pochita SbCl3 ndi acetic anhydride. The reaction formula ndi motere:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Njira yachitsulo ya Antimony
Mu 1954, TAPaybea ya dziko lomwe kale linali Soviet Union inakonza Sb(CH3COO)3 pochita chitsulo cha antimony ndi peroxyacetyl mu njira ya benzene. Reaction formula ndi:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Njira ya Antimony trioxide
Mu 1957, F. Nerdel waku West Germany adagwiritsa ntchito Sb2O3 kuti achite ndi acetic anhydride kupanga Sb(CH3COO)3.
Sb2O3(CH3CO)(CH3CO)2O(2Sb)(CH3COO)3
Choyipa cha njirayi ndikuti makhiristo amatha kuphatikizira mu zidutswa zazikulu ndikumamatira mwamphamvu khoma lamkati la riyakitala, zomwe zimapangitsa kuti zinthu zikhale bwino komanso mtundu.
4. Njira yosungunulira ya Antimony trioxide
Pofuna kuthana ndi zofooka za njira yomwe ili pamwambayi, zosungunulira za ndale nthawi zambiri zimawonjezeredwa panthawi ya Sb2O3 ndi acetic anhydride. Njira yeniyeni yokonzekera ndi iyi:
(1) Mu 1968, R. Thoms wa American Mosun Chemical Company adafalitsa chivomerezo chokonzekera antimony acetate. Patent idagwiritsa ntchito xylene (o-, m-, p-xylene, kapena chosakaniza chake) ngati chosungunulira chosalowerera ndale kuti apange makhiristo abwino a antimony acetate.
(2) Mu 1973, dziko la Czech Republic linatulukira njira yopangira acetate yabwino kwambiri ya antimony pogwiritsa ntchito toluene monga zosungunulira.
III. Kuyerekeza kwa zida zitatu za antimony
| Antimony Trioxide | Antimony Acetate | Antimony Glycolate | |
| Basic Properties | Zomwe zimadziwika kuti antimony white, molecular formula Sb 2 O 3, molecular weight 291.51, ufa woyera, malo osungunuka 656 ℃. Theoretical antimony zili pafupi 83.53 %. Kachulukidwe wachibale 5.20g/ml. Kusungunuka mu anaikira hydrochloric asidi, anaikira sulfuric acid, anaikira nitric asidi, asidi tartaric ndi alkali njira, insoluble m'madzi, mowa, kuchepetsa sulfuric acid. | Molecular formula Sb(AC) 3, molecular weight 298.89, theoretical antimony content about 40.74%, melting point 126-131℃, kachulukidwe 1.22g/ml (25 ℃), ufa woyera kapena wopanda-woyera, sungunuka mosavuta mu ethyleneglycol. ndi xylene. | Molecular formula Sb 2 (EG) 3, Kulemera kwa maselo ndi pafupifupi 423.68, malo osungunuka ndi ＞ 100 ℃ (dec.) zosavuta kuyamwa chinyezi. Amasungunuka mosavuta mu ethylene glycol. |
| Njira Yophatikizira ndi Tekinoloje | Zopangidwa makamaka ndi njira ya 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 3Zindikirani: Stibnite / Lime Iron Ore Kutentha ndi Kutentha → Kusonkhanitsa | Makampaniwa amagwiritsa ntchito njira ya Sb 2 O 3 -solvent pophatikizira:Sb2O3 ＋ 3 ( CH3CO ) 2O→ 2Sb(AC) 3Njira: kutentha reflux → kusefa kotentha → crystallization → vacuum kuyanika → productZindikirani: Sb(AC) 3 ndi mosavuta hydrolyzed, kotero ndale zosungunulira toluene kapena xylene ntchito ayenera kukhala anhydrous, Sb 2 O 3 sangakhale mu chikhalidwe chonyowa, ndi zipangizo kupanga ayeneranso youma. | Makampaniwa amagwiritsa ntchito njira ya Sb 2 O 3 popanga:Sb 2 O 3 +3EG→Sb 2 (EG) 3 +3H 2 OProcess: Kudyetsa (Sb 2 O 3, zowonjezera ndi EG) → Kutentha ndi kupanikizika → kuchotsa slag , zonyansa ndi madzi → decolorization → kusefa kotentha → kuziziritsa ndi crystallization → kulekanitsa ndi kuyanika → mankhwalaZindikirani: Ntchito yopangira iyenera kukhala yosiyana ndi madzi kuti isawonongeke. Izi ndizochitika zosinthika, ndipo nthawi zambiri zomwe zimachitika zimalimbikitsidwa pogwiritsa ntchito owonjezera ethylene glycol ndikuchotsa madzi opangira. |
| Ubwino | Mtengo wake ndi wotsika mtengo, ndi wosavuta kugwiritsa ntchito, uli ndi zochitika zolimbitsa thupi komanso nthawi yayifupi ya polycondensation. | Antimony acetate imakhala ndi kusungunuka kwabwino mu ethylene glycol ndipo imamwazika mofanana mu ethylene glycol, yomwe imatha kupititsa patsogolo kugwiritsa ntchito bwino kwa antimony; Antimony acetate ili ndi mawonekedwe achitetezo chapamwamba, kutsika kwapang'onopang'ono, kukana kutentha komanso kukhazikika kwadongosolo; Pa nthawi yomweyi, kugwiritsa ntchito antimony acetate monga chothandizira sikufuna kuwonjezeredwa kwa co-catalyst ndi stabilizer. Zochita za antimony acetate catalytic system ndizochepa, ndipo khalidwe la mankhwala ndilopamwamba, makamaka mtundu, womwe ndi wabwino kuposa wa antimony trioxide (Sb 2 O 3) dongosolo. | Chothandizira chimakhala ndi kusungunuka kwakukulu mu ethylene glycol; antimoni ya zero-valent imachotsedwa, ndipo zonyansa monga mamolekyu achitsulo, ma chlorides ndi sulfates omwe amakhudza polycondensation amachepetsedwa mpaka pansi kwambiri, kuthetsa vuto la acetate ion corrosion pa zipangizo;Sb 3+ mu Sb 2 (EG) 3 ndi yokwera kwambiri. , zomwe zingakhale chifukwa chakuti kusungunuka kwake mu ethylene glycol pa kutentha kwa kutentha kumakhala kwakukulu kuposa kwa Sb 2 O 3 Poyerekeza ndi Sb (AC) 3, kuchuluka kwa Sb 3+ komwe kumagwira ntchito yothandiza kwambiri. Mtundu wa mankhwala a polyester opangidwa ndi Sb 2 (EG) 3 ndi abwino kuposa a Sb 2 O 3 Pang'ono pang'ono kuposa choyambirira, kupangitsa kuti mankhwalawa awonekere owala ndi oyera; |
| Kuipa | Kusungunuka mu ethylene glycol ndi kosauka, kokha 4.04% pa 150 ° C. Pochita, ethylene glycol ndi yochuluka kapena kutentha kwa kutentha kumawonjezeka kufika pa 150 ° C. Komabe, pamene Sb 2 O 3 imachita ndi ethylene glycol kwa nthawi yaitali pamwamba pa 120 ° C, mpweya wa ethylene glycol antimony ukhoza kuchitika, ndipo Sb 2 O 3 ikhoza kuchepetsedwa kukhala makwerero achitsulo mu polycondensation reaction, yomwe ingayambitse "imvi chifunga. " mu tchipisi ta poliyesitala komanso zimakhudza mtundu wazinthu. Chodabwitsa cha polyvalent antimony oxides chimachitika pokonzekera Sb 2 O 3, ndipo chiyero chogwira ntchito cha antimony chimakhudzidwa. | Antimony zili mu chothandizira ndi otsika; zonyansa za acetic acid zomwe zidayambitsa zida zowonongeka, zimawononga chilengedwe, ndipo siziyenera kuyeretsa madzi oyipa; njira yopanga ndi yovuta, malo ogwirira ntchito ndi osauka, pali kuipitsa, ndipo mankhwala ndi osavuta kusintha mtundu. Ndizosavuta kuwola zikatenthedwa, ndipo mankhwala a hydrolysis ndi Sb2O3 ndi CH3COOH. Zomwe zimakhala nthawi yayitali, makamaka pomaliza polycondensation siteji, yomwe ili yochuluka kwambiri kuposa dongosolo la Sb2O3 . | Kugwiritsiridwa ntchito kwa Sb 2 (EG) 3 kumawonjezera mtengo wothandizira wa chipangizocho (kuwonjezeka kwa mtengo kungathetsedwe ngati 25% ya PET imagwiritsidwa ntchito podzipangira okha filaments). Kuonjezera apo, mtengo wa b wa mtundu wa mankhwala ukuwonjezeka pang'ono. |