Zaren Polyester (PET) shine mafi girman nau'in zaren roba. Tufafin da aka yi da zaren polyester suna da daɗi, suna da laushi, suna da sauƙin wankewa, kuma suna da sauri bushewa. Ana kuma amfani da polyester sosai a matsayin kayan da aka yi amfani da su don marufi, zaren masana'antu, da kuma robobi na injiniya. Sakamakon haka, polyester ya bunƙasa cikin sauri a duk duniya, yana ƙaruwa a matsakaicin adadin shekara-shekara na kashi 7% kuma tare da babban fitarwa.
Ana iya raba samar da Polyester zuwa hanyar dimethyl terephthalate (DMT) da hanyar terephthalic acid (PTA) dangane da hanyar aiwatarwa kuma ana iya raba su zuwa tsari mai rikitarwa da tsari mai ci gaba dangane da aiki. Ko da kuwa hanyar aiwatar da samarwa da aka ɗauka, amsawar polycondensation tana buƙatar amfani da mahaɗan ƙarfe azaman masu haɓaka. Haɗakar polycondensation muhimmin mataki ne a cikin tsarin samar da polyester, kuma lokacin polycondensation shine matsala don inganta yawan amfanin ƙasa. Inganta tsarin mai haɓaka abu ne mai mahimmanci wajen inganta ingancin polyester da rage lokacin polycondensation.
UrbanMines Tech. Limited babban kamfani ne na kasar Sin wanda ya kware a fannin bincike da samar da sinadarai masu kara kuzari na polyester, antimony acetate, da kuma antimony glycol. Mun gudanar da bincike mai zurfi kan wadannan kayayyakin - sashen bincike da ci gaba na UrbanMines yanzu ya takaita bincike da amfani da sinadaran kara kuzari na antimony a cikin wannan labarin don taimakawa abokan cinikinmu wajen amfani da su cikin sassauci, inganta hanyoyin samarwa, da kuma samar da cikakken gasa na kayayyakin fiber na polyester.
Masana na cikin gida da na ƙasashen waje gabaɗaya sun yi imanin cewa polyester polycondensation wani abu ne na faɗaɗa sarka, kuma tsarin catalytic yana cikin haɗin chelation, wanda ke buƙatar atom ɗin ƙarfe mai haɓaka don samar da orbitals mara komai don daidaitawa da arc biyu na electrons na carbonyl oxygen don cimma manufar catalysis. Don polycondensation, tunda yawan gajimare na carbonyl oxygen a cikin rukunin hydroxyethyl ester yana da ƙarancin yawa, electronegativity na ions na ƙarfe yana da yawa yayin daidaitawa, don sauƙaƙe daidaitawa da faɗaɗa sarka.
Ana iya amfani da waɗannan a matsayin masu haɓaka sinadarai na 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 da sauran ƙarfe oxides, alcoholates, carboxylates, borates, halides da amines, ureas, guanidines, mahadi masu ɗauke da sulfur. Duk da haka, masu haɓaka sinadarai waɗanda ake amfani da su a yanzu kuma ake nazari a kansu a masana'antu galibi sune mahaɗan Sb, Ge, da Ti. Yawancin bincike sun nuna cewa: Masu haɓaka sinadarai masu tushen Ge suna da ƙarancin halayen gefe kuma suna samar da PET mai inganci, amma ayyukansu ba su da yawa, kuma suna da ƙarancin albarkatu kuma suna da tsada; Masu haɓaka sinadarin Ti suna da babban aiki da saurin amsawa da sauri, amma halayensu na catalytic sun fi bayyana, wanda ke haifar da rashin kwanciyar hankali na zafi da launin rawaya na samfurin, kuma gabaɗaya ana iya amfani da su ne kawai don haɗa PBT, PTT, PCT, da sauransu; Masu haɓaka sinadarin Sb ba wai kawai suna da ƙarfi ba. Ingancin samfurin yana da girma saboda masu haɓaka sinadarin Sb suna da ƙarfi, suna da ƙarancin amsawar gefe, kuma suna da rahusa. Saboda haka, an yi amfani da su sosai. Daga cikinsu, masu haɓaka sinadarin Sb da aka fi amfani da su sune antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), da sauransu.
Idan muka duba tarihin ci gaban masana'antar polyester, za mu ga cewa sama da kashi 90% na masana'antar polyester a duniya suna amfani da sinadaran antimony a matsayin masu kara kuzari. Zuwa shekarar 2000, kasar Sin ta gabatar da wasu masana'antun polyester, wadanda dukkansu suka yi amfani da sinadaran antimony a matsayin masu kara kuzari, galibi Sb2O3 da Sb(CH3COO)3. Ta hanyar hadin gwiwar binciken kimiyya na kasar Sin, jami'o'i, da sassan samar da kayayyaki, yanzu an samar da wadannan sinadaran guda biyu a cikin gida.
Tun daga shekarar 1999, kamfanin sinadarai na Faransa Elf ya ƙaddamar da wani maganin hana kumburi [Sb2 (OCH2CH2CO) 3] a matsayin ingantaccen samfurin maganin hana kumburi na gargajiya. Kwakwalwar polyester da aka samar suna da farin jini sosai da kuma kyakkyawan juyi, wanda ya jawo hankali sosai daga cibiyoyin bincike na catalyst na cikin gida, kamfanoni, da masana'antun polyester a China.
I. Bincike da amfani da antimony trioxide
Amurka tana ɗaya daga cikin ƙasashen farko da suka samar da kuma amfani da Sb2O3. A shekarar 1961, yawan amfani da Sb2O3 a Amurka ya kai tan 4,943. A shekarun 1970, kamfanoni biyar a Japan suna samar da Sb2O3 tare da jimillar ƙarfin samarwa na tan 6,360 a kowace shekara.
Manyan sassan bincike da ci gaban Sb2O3 na kasar Sin galibi suna cikin tsoffin kamfanonin gwamnati a Lardin Hunan da Shanghai. UrbanMines Tech. Limited kuma ta kafa layin samarwa na ƙwararru a Lardin Hunan.
(I). Hanyar samar da antimony trioxide
Ana yin Sb2O3 yawanci ta amfani da ma'adinin antimony sulfide a matsayin kayan aiki. Da farko ana shirya antimony na ƙarfe, sannan a samar da Sb2O3 ta amfani da antimony na ƙarfe a matsayin kayan aiki.
Akwai manyan hanyoyi guda biyu don samar da Sb2O3 daga antimony na ƙarfe: iskar shaka kai tsaye da kuma rugujewar nitrogen.
1. Hanyar hada iskar shaka kai tsaye
Antimony na ƙarfe yana amsawa da iskar oxygen a lokacin dumama don samar da Sb2O3. Tsarin amsawar shine kamar haka:
4Sb＋3O2＝＝2Sb2O3
2. Ammolysis
Antimony metal yana yin aiki tare da chlorine don haɗa antimony trichloride, wanda daga nan ake tace shi, a narkar da shi, ammonolyzed, a wanke shi, sannan a busar da shi don samun samfurin Sb2O3 da aka gama. Tsarin amsawar asali shine:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Amfani da antimony trioxide
Babban amfani da antimony trioxide shine a matsayin mai kara kuzari ga polymerase da kuma mai hana harshen wuta ga kayan roba.
A masana'antar polyester, an fara amfani da Sb2O3 a matsayin mai kara kuzari. Ana amfani da Sb2O3 galibi a matsayin mai kara kuzari ga hanyar DMT da kuma hanyar PTA ta farko kuma galibi ana amfani da ita tare da H3PO4 ko enzymes dinta.
(III). Matsalolin da ke tattare da antimony trioxide
Sb2O3 yana da ƙarancin narkewa a cikin ethylene glycol, tare da narkewar kashi 4.04% kawai a 150°C. Saboda haka, lokacin da ake amfani da ethylene glycol don shirya mai kara kuzari, Sb2O3 yana da ƙarancin wargajewa, wanda zai iya haifar da mai kara kuzari mai yawa a cikin tsarin polymerization cikin sauƙi, yana samar da masu gyara cyclic masu yawan narkewa, kuma yana kawo wahaloli ga juyawa. Don inganta narkewa da wargajewar Sb2O3 a cikin ethylene glycol, galibi ana amfani da shi don amfani da ethylene glycol mai yawa ko ƙara zafin narkewa zuwa sama da 150°C. Duk da haka, sama da 120°C, Sb2O3 da ethylene glycol na iya samar da hazo na ethylene glycol antimony lokacin da suka yi aiki tare na dogon lokaci, kuma Sb2O3 na iya ragewa zuwa antimony na ƙarfe a cikin amsawar polycondensation, wanda zai iya haifar da "hazo" a cikin kwakwalwan polyester kuma yana shafar ingancin samfur.
II. Bincike da amfani da antimony acetate
Hanyar shiri na antimony acetate
Da farko, an shirya antimony acetate ta hanyar yin maganin antimony trioxide tare da acetic acid, kuma an yi amfani da acetic anhydride a matsayin maganin bushewa don shanye ruwan da amsawar ta haifar. Ingancin samfurin da aka gama da aka samu ta wannan hanyar bai yi yawa ba, kuma ya ɗauki fiye da awanni 30 kafin antimony trioxide ya narke a cikin acetic acid. Daga baya, an shirya antimony acetate ta hanyar yin maganin antimony metal, antimony trichloride, ko antimony trioxide tare da acetic anhydride, ba tare da buƙatar maganin bushewar ruwa ba.
1. Hanyar Antimony trichloride
A shekarar 1947, H. Schmidt da abokan aikinsa a Yammacin Jamus sun shirya Sb(CH3COO)3 ta hanyar yin maganin SbCl3 da acetic anhydride. Tsarin maganin shine kamar haka:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Hanyar ƙarfe ta Antimony
A shekarar 1954, TAPaybea na tsohuwar Tarayyar Soviet ta shirya Sb(CH3COO)3 ta hanyar yin maganin antimony na ƙarfe da peroxyacetyl a cikin maganin benzene. Tsarin amsawar shine:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Hanyar antimony trioxide
A shekarar 1957, F. Nerdel na Yammacin Jamus ya yi amfani da Sb2O3 don yin martani da acetic anhydride don samar da Sb(CH3COO)3.
Sb2O3＋3（CH3CO）2O＝＝2Sb（CH3COO）3
Rashin kyawun wannan hanyar ita ce lu'ulu'u suna taruwa zuwa manyan guntu kuma suna mannewa sosai a bangon ciki na reactor, wanda ke haifar da rashin ingancin samfurin da launi mara kyau.
4. Hanyar maganin antimony trioxide
Domin shawo kan kurakuran hanyar da ke sama, yawanci ana ƙara wani sinadari mai tsaka-tsaki yayin amsawar Sb2O3 da acetic anhydride. Takamaiman hanyar shiri ita ce kamar haka:
(1) A shekarar 1968, R. Thoms na Kamfanin Sinadaran Mosun na Amurka ya buga takardar izinin mallaka kan shirya maganin antimony acetate. Takardar izinin mallakar ta yi amfani da xylene (o-, m-, p-xylene, ko cakuda su) a matsayin maganin da ba shi da sinadarai masu tsaka tsaki don samar da kyawawan lu'ulu'u na maganin antimony acetate.
(2) A shekarar 1973, Jamhuriyar Czech ta ƙirƙiro wata hanya ta samar da sinadarin antimony acetate mai kyau ta amfani da toluene a matsayin mai narkewa.
III. Kwatanta abubuwa uku masu amfani da antimony
| Antimony Trioxide | Antimony Acetate | Antimony Glycolate | |
| Kayayyakin Asali | An fi sani da farin antimony, tsarin kwayoyin halitta Sb2O3, nauyin kwayoyin halitta 291.51, farin foda, wurin narkewa 656℃. Yawan antimony na ka'ida shine kusan 83.53%. Yawan dangi shine 5.20g/ml. Yana narkewa a cikin sinadarin hydrochloric mai yawa, sinadarin sulfuric mai yawa, sinadarin nitric mai yawa, sinadarin tartaric da maganin alkali, wanda ba ya narkewa a cikin ruwa, barasa, da kuma sinadarin sulfuric mai narkewa. | Tsarin kwayoyin halitta Sb(AC) 3, nauyin kwayoyin halitta 298.89, abun ciki na antimony na ka'ida kusan 40.74%, wurin narkewa 126-131℃, yawa 1.22g/ml (25℃), foda fari ko mara fari, mai narkewa cikin sauƙi a cikin ethylene glycol, toluene da xylene. | Tsarin kwayoyin halitta Sb 2 (EG) 3, Nauyin kwayoyin halitta yana da kusan 423.68, wurin narkewa shine ＞ 100℃ (disamba), abun da ke cikin ka'idar antimony shine kusan 57.47%, bayyanar yana da farin kristal mai ƙarfi, ba shi da guba kuma ba shi da ɗanɗano, yana da sauƙin sha danshi. Yana narkewa cikin sauƙi a cikin ethylene glycol. |
| Hanyar Haɗawa da Fasaha | An haɗa shi da tsarin stibnite mafi yawa: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 3Lura: Stibnite / Ma'adinan ƙarfe / Dutse mai laushi → Dumama da hayaki → Tarin | Masana'antar galibi tana amfani da hanyar Sb2O3 -mai narkewa don haɗawa:Sb2O3 ＋ 3 (CH3CO) 2O → 2Sb(AC) 3Tsarin aiki: dumama reflux → tace zafi → crystallization → busar da injin → samfurLura: Sb(AC) 3 yana da sauƙin hydrolyzed, don haka toluene ko xylene mai narkewa mai tsaka tsaki da ake amfani da shi dole ne ya kasance mara ruwa, Sb2O3 ba zai iya kasancewa cikin danshi ba, kuma kayan aikin samarwa dole ne su bushe. | Masana'antar galibi tana amfani da hanyar Sb 2 O 3 don haɗa:Sb 2 O 3 +3EG→Sb 2 (EG) 3 +3H 2 OProcess: Ciyarwa (Sb 2 O 3, ƙari da EG) → ɗumamawa da amsawar matsi → cire tarkace, ƙazanta da ruwa → canza launi → tacewa mai zafi → sanyaya da lu'ulu'u → rabuwa da bushewa → samfurLura: Tsarin samarwa yana buƙatar a ware shi daga ruwa don hana hydrolysis. Wannan amsawar amsawa ce mai jurewa, kuma gabaɗaya ana haɓaka amsawar ta hanyar amfani da wuce gona da iri na ethylene glycol da cire ruwan samfurin. |
| Riba | Farashin yana da arha sosai, yana da sauƙin amfani, yana da matsakaicin aikin catalytic da ɗan gajeren lokacin polycondensation. | Antimony acetate yana da kyakkyawan narkewa a cikin ethylene glycol kuma an rarraba shi daidai gwargwado a cikin ethylene glycol, wanda zai iya inganta ingancin amfani da antimony; Antimony acetate yana da halaye na babban aikin catalytic, ƙarancin amsawar lalacewa, juriya mai kyau ga zafi da kwanciyar hankali na sarrafawa; A lokaci guda, amfani da antimony acetate a matsayin mai kara kuzari ba ya buƙatar ƙara mai kara kuzari da mai daidaita kuzari. Amsar tsarin antimony acetate catalytic yana da sauƙi, kuma ingancin samfurin yana da girma, musamman launi, wanda ya fi na tsarin antimony trioxide (Sb2O3) kyau. | Mai kara kuzari yana da yawan narkewa a cikin ethylene glycol; ana cire antimony mai sifili, kuma an rage datti kamar ƙwayoyin ƙarfe, chlorides da sulfates waɗanda ke shafar polycondensation zuwa mafi ƙasƙanci, yana kawar da matsalar lalata ion acetate akan kayan aiki; Sb 3+ a cikin Sb 2 (EG) 3 yana da yawa, wanda wataƙila saboda narkewarsa a cikin ethylene glycol a zafin amsawa ya fi na Sb 2 O 3 Idan aka kwatanta da Sb (AC) 3, adadin Sb 3+ wanda ke taka rawar catalytic ya fi girma. Launin samfurin polyester da Sb 2 (EG) 3 ya samar ya fi na Sb 2 O 3 kyau. Ya fi na asali girma kaɗan, yana sa samfurin ya yi kama da haske da fari; |
| Rashin amfani | Narkewar ethylene glycol ba ta da kyau, kashi 4.04% ne kawai a 150°C. A aikace, ethylene glycol ya yi yawa ko kuma zafin narkewar ya ƙaru zuwa sama da 150°C. Duk da haka, lokacin da Sb2O3 ya yi hulɗa da ethylene glycol na dogon lokaci a sama da 120°C, ruwan sama na ethylene glycol na iya faruwa, kuma Sb2O3 na iya raguwa zuwa tsani na ƙarfe a cikin amsawar polycondensation, wanda zai iya haifar da "hazo mai launin toka" a cikin kwakwalwan polyester kuma yana shafar ingancin samfur. Abin da ke faruwa na polyvalent antimony oxides yana faruwa yayin shirya Sb2O3, kuma ingancin tsarkin antimony yana shafar. | Abubuwan da ke cikin sinadarin antimony na mai kara kuzari ba su da yawa; ƙazanta na acetic acid sun haifar da lalata kayan aiki, suna gurɓata muhalli, kuma ba sa taimakawa wajen magance ruwan shara; tsarin samarwa yana da rikitarwa, yanayin yanayin aiki ba shi da kyau, akwai gurɓatawa, kuma samfurin yana da sauƙin canza launi. Yana da sauƙin ruɓewa lokacin da aka dumama shi, kuma samfuran hydrolysis sune Sb2O3 da CH3COOH. Lokacin zama na kayan yana da tsawo, musamman a matakin ƙarshe na polycondensation, wanda ya fi tsarin Sb2O3 girma sosai. | Amfani da Sb 2 (EG) 3 yana ƙara farashin mai kara kuzari na na'urar (ƙarin farashi za a iya rage shi ne kawai idan an yi amfani da kashi 25% na PET don juya kai tsaye na zare). Bugu da ƙari, ƙimar b na launin samfurin yana ƙaruwa kaɗan. |