Ulusi wa polyester (PET) ndi mtundu waukulu kwambiri wa ulusi wopangidwa. Zovala zopangidwa ndi ulusi wa polyester ndi zomasuka, zouma, zosavuta kutsuka, komanso zouma msanga. Polyester imagwiritsidwanso ntchito kwambiri ngati zinthu zopangira ma CD, ulusi wa mafakitale, ndi mapulasitiki aukadaulo. Zotsatira zake, polyester yakula mofulumira padziko lonse lapansi, ikuwonjezeka pa avareji ya 7% pachaka ndipo imatulutsa zinthu zambiri.
Kupanga kwa polyester kungagawidwe m'njira ya dimethyl terephthalate (DMT) ndi njira ya terephthalic acid (PTA) malinga ndi njira yogwirira ntchito ndipo kungagawidwe m'njira yosinthasintha komanso yopitilira malinga ndi ntchito. Mosasamala kanthu za njira yopangira yomwe yagwiritsidwa ntchito, polycondensation reaction imafuna kugwiritsa ntchito mankhwala achitsulo ngati ma catalyst. Polycondensation reaction ndi gawo lofunika kwambiri pakupanga polyester, ndipo nthawi ya polycondensation ndiyo vuto lokulitsa zokolola. Kukonza kwa catalyst system ndi chinthu chofunikira kwambiri pakukweza ubwino wa polyester ndikufupikitsa nthawi ya polycondensation.
UrbanMines Tech. Limited ndi kampani yotsogola yaku China yomwe imadziwika bwino pa kafukufuku ndi chitukuko, kupanga, ndi kupereka antimony trioxide ya polyester catalyst-grade, antimony acetate, ndi antimony glycol. Tachita kafukufuku wozama pa zinthuzi—dipatimenti ya kafukufuku ndi chitukuko ya UrbanMines tsopano ikufotokoza mwachidule kafukufuku ndi kugwiritsa ntchito antimony catalysts m'nkhaniyi kuti tithandize makasitomala athu kugwiritsa ntchito mosavuta, kukonza njira zopangira, komanso kupereka mpikisano wathunthu wa zinthu za polyester fiber.
Akatswiri akumayiko ndi akunja nthawi zambiri amakhulupirira kuti polyester polycondensation ndi njira yowonjezera unyolo, ndipo njira yothandizira ndi ya chelation coordination, yomwe imafuna kuti atomu yachitsulo chothandizira ipereke ma orbitals opanda kanthu kuti agwirizane ndi arc pair of electrons of carbonyl oxygen kuti akwaniritse cholinga cha catalysis. Pa polycondensation, popeza kuchuluka kwa ma electron cloud kwa carbonyl oxygen mu gulu la hydroxyethyl ester ndi kochepa, electronegativity ya ma ions achitsulo imakhala yayikulu panthawi yogwirizanitsa, kuti ithandize kulumikizana ndi kukulitsa unyolo.
Zotsatirazi zingagwiritsidwe ntchito ngati zoyambitsa 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 ndi ma metal oxides ena, alcoholates, carboxylates, borates, halides ndi amines, ureas, guanidines, organic containing sulfure. Komabe, zoyambitsa zomwe zimagwiritsidwa ntchito ndi kuphunziridwa pakupanga mafakitale makamaka ndi Sb, Ge, ndi Ti series compounds. Kafukufuku wambiri wasonyeza kuti: Zoyambitsa Ge zimakhala ndi zotsatira zochepa ndipo zimapanga PET yapamwamba kwambiri, koma ntchito yawo si yayikulu, ndipo ili ndi zinthu zochepa ndipo ndi yokwera mtengo; Ma catalyst opangidwa ndi Ti ali ndi ntchito zambiri komanso liwiro la reaction, koma ma catalytic side reaction awo ndi odziwikiratu, zomwe zimapangitsa kuti kutentha kusayende bwino komanso mtundu wachikasu wa chinthucho, ndipo nthawi zambiri angagwiritsidwe ntchito popanga PBT, PTT, PCT, ndi zina zotero; ma catalyst opangidwa ndi Sb sagwira ntchito kwambiri. Ubwino wa chinthucho ndi wapamwamba chifukwa ma catalyst opangidwa ndi Sb ndi ogwira ntchito kwambiri, ali ndi ma catalyst ochepa, komanso ndi otsika mtengo. Chifukwa chake, akhala akugwiritsidwa ntchito kwambiri. Pakati pawo, ma catalyst opangidwa ndi Sb omwe amagwiritsidwa ntchito kwambiri ndi antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), ndi zina zotero.
Poyang'ana mbiri ya chitukuko cha makampani opanga ma polyester, titha kupeza kuti zomera zopitilira 90% za polyester padziko lonse lapansi zimagwiritsa ntchito mankhwala a antimoni ngati ma catalyst. Pofika mu 2000, China idayambitsa zomera zingapo za polyester, zomwe zonse zidagwiritsa ntchito mankhwala a antimoni ngati ma catalyst, makamaka Sb2O3 ndi Sb(CH3COO)3. Kudzera mu mgwirizano wa kafukufuku wasayansi waku China, mayunivesite, ndi madipatimenti opanga, ma catalyst awiriwa tsopano apangidwa mokwanira mdziko muno.
Kuyambira mu 1999, kampani ya mankhwala yaku France ya Elf yatulutsa chothandizira cha antimony glycol [Sb2 (OCH2CH2CO) 3] ngati chinthu chopangidwa ndi zinthu zotsitsimutsa zachikhalidwe. Ma polyester chips opangidwa ali ndi kuyera kwambiri komanso kuthekera kozungulira bwino, zomwe zakopa chidwi chachikulu kuchokera ku mabungwe ofufuza za catalyst akunyumba, mabizinesi, ndi opanga ma polyester ku China.
I. Kafukufuku ndi kugwiritsa ntchito antimoni trioxide
Dziko la United States ndi limodzi mwa mayiko oyambirira kupanga ndi kugwiritsa ntchito Sb2O3. Mu 1961, kugwiritsidwa ntchito kwa Sb2O3 ku United States kunafika matani 4,943. M'zaka za m'ma 1970, makampani asanu ku Japan amapanga Sb2O3 yokhala ndi mphamvu yonse yopangira matani 6,360 pachaka.
Magulu akuluakulu ofufuza ndi chitukuko cha Sb2O3 ku China makamaka amapangidwa ndi makampani akale a boma ku Hunan Province ndi Shanghai. UrbanMines Tech. Limited yakhazikitsanso kampani yopanga zinthu zaukadaulo ku Hunan Province.
(I). Njira yopangira antimoni trioxide
Kupanga Sb2O3 nthawi zambiri kumagwiritsa ntchito miyala ya antimony sulfide ngati zinthu zopangira. Antimony yachitsulo imakonzedwa kaye, kenako Sb2O3 imapangidwa pogwiritsa ntchito antimony yachitsulo ngati zinthu zopangira.
Pali njira ziwiri zazikulu zopangira Sb2O3 kuchokera ku antimoni yachitsulo: kusungunuka mwachindunji ndi kuwonongeka kwa nayitrogeni.
1. Njira yowotchera mwachindunji
Antimoni yachitsulo imakumana ndi mpweya womwe ukutenthedwa ndikupanga Sb2O3. Njira yochitira izi ndi iyi:
4Sb＋3O2＝＝2Sb2O3
2. Kuchuluka kwa madzi m'thupi (Ammolysis)
Chitsulo cha antimony chimakumana ndi chlorine kuti apange antimony trichloride, yomwe kenako imasungunuka, imathiridwa ndi hydrolyzed, imasungunuka ndi ammonolyzed, imatsukidwa, ndikuumitsidwa kuti ipeze chinthu chomalizidwa cha Sb2O3. Equation yoyambira ya reaction ndi iyi:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Ntchito za antimoni trioxide
Kugwiritsa ntchito kwakukulu kwa antimony trioxide ndiko kuyambitsa polymerase komanso choletsa moto pazinthu zopangidwa.
Mu makampani opanga ma polyester, Sb2O3 idagwiritsidwa ntchito koyamba ngati chothandizira. Sb2O3 imagwiritsidwa ntchito makamaka ngati chothandizira cha polycondensation cha njira ya DMT ndi njira yoyambirira ya PTA ndipo nthawi zambiri imagwiritsidwa ntchito limodzi ndi H3PO4 kapena ma enzyme ake.
(III). Mavuto ndi antimoni trioxide
Sb2O3 ili ndi kusungunuka kochepa mu ethylene glycol, yokhala ndi kusungunuka kwa 4.04% yokha pa 150°C. Chifukwa chake, ethylene glycol ikagwiritsidwa ntchito kukonzekera chothandizira, Sb2O3 imakhala ndi kusungunuka kochepa, komwe kungayambitse mosavuta chothandizira kwambiri mu dongosolo la polymerization, kupanga ma trimmers okwera kwambiri, ndikubweretsa zovuta pakuzungulira. Pofuna kukonza kusungunuka ndi kufalikira kwa Sb2O3 mu ethylene glycol, nthawi zambiri amagwiritsidwa ntchito kugwiritsa ntchito ethylene glycol yambiri kapena kuwonjezera kutentha kwa kusungunuka kufika pa 150°C. Komabe, pamwamba pa 120°C, Sb2O3 ndi ethylene glycol zimatha kupanga ethylene glycol antimony precipitation zikagwira ntchito limodzi kwa nthawi yayitali, ndipo Sb2O3 ikhoza kuchepetsedwa kukhala metallic antimony mu polycondensation reaction, zomwe zingayambitse "chifunga" mu polyester chips ndikukhudza ubwino wa malonda.
II. Kafukufuku ndi kugwiritsa ntchito antimoni acetate
Njira yokonzekera antimoni acetate
Poyamba, antimony acetate inkakonzedwa pophatikizana ndi antimony trioxide ndi acetic acid, ndipo acetic anhydride inkagwiritsidwa ntchito ngati chotsukira madzi kuti itenge madzi opangidwa ndi yankho. Ubwino wa chinthu chomalizidwa chomwe chinapezedwa ndi njira iyi sunali wapamwamba, ndipo zinatenga maola opitilira 30 kuti antimony trioxide isungunuke mu acetic acid. Pambuyo pake, antimony acetate inakonzedwa pophatikizana ndi antimony yachitsulo, antimony trichloride, kapena antimony trioxide ndi acetic anhydride, popanda kufunikira chotsukira madzi.
1. Njira ya antimoni trichloride
Mu 1947, H. Schmidt ndi anzake ku West Germany adapanga Sb(CH3COO)3 pochita SbCl3 ndi acetic anhydride. Fomula ya reaction ndi iyi:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Njira yachitsulo cha antimoni
Mu 1954, TPaybea wa ku Soviet Union wakale adapanga Sb(CH3COO)3 pochita antimony yachitsulo ndi peroxyacetyl mu yankho la benzene. Njira yochitira izi ndi iyi:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Njira ya antimoni trioxide
Mu 1957, F. Nerdel wa ku West Germany adagwiritsa ntchito Sb2O3 kuti agwirizane ndi acetic anhydride kuti apange Sb(CH3COO)3.
Sb2O3(CH3CO)(CH3CO)2O(2Sb)(CH3COO)3
Vuto la njira iyi ndilakuti makhiristo nthawi zambiri amasonkhana m'zidutswa zazikulu ndikumamatira mwamphamvu kukhoma lamkati la reactor, zomwe zimapangitsa kuti mtundu ndi khalidwe la zinthu zisaoneke bwino.
4. Njira yosungunulira ya antimoni trioxide
Kuti athetse zofooka za njira yomwe ili pamwambapa, chosungunulira chosalowerera nthawi zambiri chimawonjezedwa panthawi ya Sb2O3 ndi acetic anhydride. Njira yeniyeni yokonzekera ndi iyi:
(1) Mu 1968, R. Thoms wa ku American Mosun Chemical Company adasindikiza patent yokhudza kukonzekera antimony acetate. Patentyo idagwiritsa ntchito xylene (o-, m-, p-xylene, kapena chisakanizo chake) ngati chosungunulira chopanda mpweya kuti apange makhiristo abwino a antimony acetate.
(2) Mu 1973, dziko la Czech Republic linapanga njira yopangira antimony acetate pogwiritsa ntchito toluene ngati chosungunulira.
III. Kuyerekeza kwa ma catalyst atatu okhala ndi antimoni
| Antimoni Trioxide | Antimoni aseteti | Antimoni Glycolate | |
| Katundu Woyambira | Yodziwika bwino monga antimony woyera, molecular formula Sb2O3, molecular weight 291.51, white powder, melting point 656℃. Theory antimony content is about 83.53%. Relativity density 5.20g/ml. Sungunuka mu concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, tartaric acid ndi alkali solution, osasungunuka m'madzi, mowa, diluted sulfuric acid. | Fomula ya molekyulu Sb(AC) 3, kulemera kwa molekyulu 298.89, kuchuluka kwa antimoni pafupifupi 40.74%, malo osungunuka 126-131℃, kuchuluka kwa 1.22g/ml (25℃), ufa woyera kapena wosakhala woyera, wosungunuka mosavuta mu ethylene glycol, toluene ndi xylene. | Fomula ya molekyulu Sb 2 (EG) 3, Kulemera kwa molekyulu ndi pafupifupi 423.68, malo osungunuka ndi ＞ 100℃ (dec.), kuchuluka kwa antimony komwe kumadziwika ndi pafupifupi 57.47%, mawonekedwe ake ndi oyera ngati kristalo olimba, osakhala ndi poizoni komanso osakoma, osavuta kuyamwa chinyezi. Amasungunuka mosavuta mu ethylene glycol. |
| Njira Yopangira ndi Ukadaulo | Amapangidwa makamaka pogwiritsa ntchito 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 / Iron Ore / Limestone → Kutentha ndi Kutulutsa Fungo → Kusonkhanitsa | Makampaniwa amagwiritsa ntchito kwambiri njira ya Sb 2 O 3 -solvent popanga: Sb2O3 ＋ 3 (CH3CO) 2O→ 2Sb(AC) 3Njira: kutentha reflux → hot filtration → crystallization → vacuum drying → productZindikirani: Sb(AC) 3 imasungunuka mosavuta, kotero toluene kapena xylene yosungunuka yosalowerera ndale yomwe imagwiritsidwa ntchito iyenera kukhala yopanda madzi, Sb 2 O 3 singakhale yonyowa, ndipo zida zopangira ziyeneranso kukhala zouma. | Makampaniwa amagwiritsa ntchito kwambiri njira ya Sb 2 O 3 popanga: Sb 2 O 3 +3EG→Sb 2 (EG) 3 +3H 2 O Njira: Kudyetsa (Sb 2 O 3, zowonjezera ndi EG) → kutentha ndi kukakamiza → kuchotsa slag, zinyalala ndi madzi → kusintha mtundu → kusefa kotentha → kuzizira ndi kupanga makristalo → kulekanitsa ndi kuumitsa → mankhwala Zindikirani: Njira yopangira iyenera kuchotsedwa m'madzi kuti ipewe hydrolysis. Izi zimachitika chifukwa cha kusinthasintha, ndipo nthawi zambiri mankhwalawa amalimbikitsidwa pogwiritsa ntchito ethylene glycol yochulukirapo ndikuchotsa madzi a mankhwalawo. |
| Ubwino | Mtengo wake ndi wotsika mtengo, ndi wosavuta kugwiritsa ntchito, uli ndi mphamvu yochepetsera kutentha komanso nthawi yochepa yoziziritsa. | Antimony acetate ili ndi kusungunuka bwino mu ethylene glycol ndipo imafalikira mofanana mu ethylene glycol, zomwe zingathandize kuti antimony igwiritsidwe ntchito bwino; Antimony acetate ili ndi mphamvu zambiri zoyambitsa, kuchepa kwa kuwonongeka, kukana kutentha bwino komanso kukhazikika kwa kukonza; Nthawi yomweyo, kugwiritsa ntchito antimony acetate ngati chothandizira sikutanthauza kuwonjezera co-catalyst ndi stabilizer. Kachitidwe ka antimony acetate catalytic system kamakhala kofatsa, ndipo mtundu wa chinthucho ndi wapamwamba, makamaka mtundu wake, womwe ndi wabwino kuposa wa antimony trioxide (Sb2O3). | Chothandizirachi chimakhala ndi kusungunuka kwakukulu mu ethylene glycol; zero-valent antimony imachotsedwa, ndipo zonyansa monga mamolekyu achitsulo, ma chloride ndi ma sulfate omwe amakhudza polycondensation amachepetsedwa kufika pamlingo wotsika kwambiri, kuthetsa vuto la dzimbiri la acetate ion pazida; Sb 3+ mu Sb 2 (EG) 3 ndi yokwera kwambiri, zomwe zitha kukhala chifukwa kusungunuka kwake mu ethylene glycol pa kutentha kwa reaction ndikokulirapo kuposa kwa Sb 2 O 3 Poyerekeza ndi Sb(AC) 3, kuchuluka kwa Sb 3+ komwe kumagwira ntchito yothandiza kwambiri ndi kwakukulu. Mtundu wa chinthu cha polyester chopangidwa ndi Sb 2 (EG) 3 ndi wabwino kuposa wa Sb 2 O 3 Chokwera pang'ono kuposa choyambirira, zomwe zimapangitsa kuti chinthucho chiwoneke chowala komanso choyera; |
| Kulephera | Kusungunuka kwa ethylene glycol ndi koipa, ndi 4.04% yokha pa 150°C. M'machitidwe, ethylene glycol ndi yochulukirapo kapena kutentha kwa kusungunuka kumawonjezeka kufika pa 150°C. Komabe, pamene Sb 2O3 ichitapo kanthu ndi ethylene glycol kwa nthawi yayitali pa 120°C, mvula ya ethylene glycol antimony ingachitike, ndipo Sb 2O3 ikhoza kuchepetsedwa kukhala makwerero achitsulo mu polycondensation reaction, zomwe zingayambitse "chifunga cha imvi" mu polyester chips ndikukhudza ubwino wa mankhwala. Chochitika cha polyvalent antimony oxides chimachitika panthawi yokonzekera Sb 2O3, ndipo kuyera kwa antimony kumakhudzidwa. | Kuchuluka kwa antimony mu catalyst ndi kochepa; zinyalala za acetic acid zomwe zimayambitsa kuwononga zida, zimaipitsa chilengedwe, ndipo sizimalola kukonzedwa ndi madzi otayira; njira yopangira ndi yovuta, mikhalidwe ya malo ogwirira ntchito ndi yoipa, pali kuipitsidwa, ndipo chinthucho n'chosavuta kusintha mtundu. N'zosavuta kuwola chikatenthedwa, ndipo zinthu za hydrolysis ndi Sb2O3 ndi CH3COOH. Nthawi yokhalamo kwa zinthuzo ndi yayitali, makamaka mu gawo lomaliza la polycondensation, lomwe ndi lalikulu kwambiri kuposa dongosolo la Sb2O3. | Kugwiritsa ntchito Sb 2 (EG) 3 kumawonjezera mtengo wa chothandizira cha chipangizocho (kukwera kwa mtengo kungachepetsedwe pokhapokha ngati 25% ya PET ikugwiritsidwa ntchito podzizungulira yokha). Kuphatikiza apo, b ya mtundu wa chinthucho imawonjezeka pang'ono. |