Ifayibha yePolyester (PET) yeyona ininzi yefayibha yokwenziwa. Iimpahla ezenziwe ngefayibha yePolyester zikhululekile, ziqinile, kulula ukuzihlamba, kwaye zomile ngokukhawuleza. IPolyester ikwasetyenziswa kakhulu njengezinto zokupakisha, imisonto yemizi-mveliso, kunye neeplastiki zobunjineli. Ngenxa yoko, i-polyester ikhule ngokukhawuleza kwihlabathi liphela, inyuka ngesantya sonyaka se-7% kwaye ivelisa imveliso enkulu.
Imveliso yePolyester inokwahlulwa ibe yindlela ye-dimethyl terephthalate (DMT) kunye nendlela ye-terephthalic acid (PTA) ngokwendlela yenkqubo kwaye inokwahlulwa ibe yinkqubo eqhubekayo kunye nenkqubo eqhubekayo ngokwendlela yokusebenza. Nokuba yeyiphi na indlela yenkqubo yemveliso eyamkelweyo, i-polycondensation reaction ifuna ukusetyenziswa kweekhompawundi zesinyithi njengee-catalysts. I-polycondensation reaction linyathelo elibalulekileyo kwinkqubo yemveliso ye-polyester, kwaye ixesha le-polycondensation liyingxaki yokuphucula isivuno. Ukuphuculwa kwenkqubo ye-catalyst yinto ebalulekileyo ekuphuculeni umgangatho we-polyester kunye nokunciphisa ixesha le-polycondensation.
I-UrbanMines Tech. Limited yinkampani ephambili yaseTshayina egxile kwi-R&D, ukuveliswa, kunye nokunikezelwa kwe-antimony trioxide ye-polyester catalyst-grade, i-antimony acetate, kunye ne-antimony glycol. Senze uphando olunzulu ngezi mveliso—isebe le-R&D le-UrbanMines ngoku lishwankathela uphando kunye nokusetyenziswa kwe-antimony catalysts kweli nqaku ukunceda abathengi bethu ukuba basebenzise ngokulula, baphucule iinkqubo zemveliso, kwaye banikezele ngokukhuphisana okupheleleyo kweemveliso ze-polyester fiber.
Izazinzulu zasekhaya nezangaphandle ngokubanzi zikholelwa ukuba i-polyester polycondensation yi-chain extension reaction, kwaye indlela yokwenza i-catalytic ixhomekeke kwi-chelation coordination, efuna i-catalyst metal atom ukuba inike ii-orbitals ezingenanto ukuze zihambelane ne-arc pair yee-electron ze-carbonyl oxygen ukufezekisa injongo ye-catalysis. Kwi-polycondensation, ekubeni i-electron cloud density ye-carbonyl oxygen kwiqela le-hydroxyethyl ester iphantsi kakhulu, i-electronegativity yee-ion zesinyithi iphezulu kakhulu ngexesha lokulungelelanisa, ukuze kube lula ukulungelelanisa kunye nokwandiswa kwe-chain.
Ezi zilandelayo zingasetyenziswa njengee-catalysts ze-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 kunye nezinye ii-metal oxides, alcoholates, carboxylates, borates, halides kunye ne-amines, ureas, guanidines, organic compounds. Nangona kunjalo, ii-catalysts ezisetyenziswayo nezifundwayo kwimveliso yemizi-mveliso ikakhulu zii-compounds ze-Sb, Ge, kunye ne-Ti series. Inani elikhulu lezifundo libonise ukuba: Ii-catalysts ezisekelwe kwi-Ge zine-side reactions ezimbalwa kwaye zivelisa i-PET esemgangathweni ophezulu, kodwa umsebenzi wazo awuphezulu, kwaye zinezixhobo ezimbalwa kwaye zibiza kakhulu; Ii-catalysts ezisekelwe kwi-Ti zinomsebenzi ophezulu kunye nesantya sokuphendula esikhawulezayo, kodwa iimpendulo zazo ezichaseneyo nezibangela ukuxinana zibonakala ngakumbi, nto leyo ebangela ukuba imveliso ingazinzi kakuhle kubushushu kunye nombala otyheli, kwaye ngokubanzi zinokusetyenziselwa kuphela ukwenziwa kwe-PBT, PTT, PCT, njl.njl.; Ii-catalysts ezisekelwe kwi-Sb azisebenzi nje kuphela. Umgangatho wemveliso uphezulu kuba ii-catalysts ezisekelwe kwi-Sb zisebenza ngakumbi, zineziphumo ezimbalwa ezichaseneyo, kwaye zingabizi kakhulu. Ke ngoko, zisetyenziswe kakhulu. Phakathi kwazo, ii-catalysts ezisekelwe kwi-Sb ezisetyenziswa kakhulu yi-antimony trioxide (Sb2O3), i-antimony acetate (Sb(CH3COO)3), njl.njl.
Xa sijonga imbali yophuhliso lweshishini le-polyester, singafumanisa ukuba ngaphezulu kwama-90% ezityalo ze-polyester ehlabathini zisebenzisa ii-antimony compounds njengee-catalysts. Ngowama-2000, iTshayina yayisele ingenise izityalo ezininzi ze-polyester, zonke ezazisebenzisa ii-antimony compounds njengee-catalysts, ikakhulu i-Sb2O3 kunye ne-Sb(CH3COO)3. Ngemizamo edibeneyo yophando lwezenzululwazi lwaseTshayina, iiyunivesithi, kunye namasebe emveliso, ezi catalysts zimbini ngoku ziye zaveliswa ngokupheleleyo ekhaya.
Ukususela ngo-1999, inkampani yaseFransi yeekhemikhali i-Elf iqalise i-antimony glycol [Sb2 (OCH2CH2CO) 3] catalyst njengemveliso ephuculweyo yee-catalysts zemveli. Iitships ze-polyester eziveliswayo zimhlophe kakhulu kwaye ziyakwazi ukujikeleza kakuhle, nto leyo ethe yatsala ingqalelo enkulu kumaziko ophando lwe-catalyst zasekhaya, amashishini kunye nabavelisi be-polyester eTshayina.
I. Uphando kunye nokusetyenziswa kwe-antimony trioxide
I-United States yenye yamazwe okuqala ukuvelisa nokusebenzisa i-Sb2O3. Ngo-1961, ukusetyenziswa kwe-Sb2O3 e-United States kwafikelela kwiitoni ezingama-4,943. Ngeminyaka yoo-1970, iinkampani ezintlanu eJapan zavelisa i-Sb2O3 enomthamo wemveliso iyonke weetoni ezingama-6,360 ngonyaka.
Iiyunithi eziphambili zophando nophuhliso ze-Sb2O3 zaseTshayina zigxile kakhulu kwiinkampani zangaphambili eziphantsi kukarhulumente kwiPhondo laseHunan naseShanghai. I-UrbanMines Tech. Limited ikwaseke umgca wemveliso yobungcali kwiPhondo laseHunan.
(I). Indlela yokuvelisa i-antimony trioxide
Ukwenziwa kwe-Sb2O3 kudla ngokusebenzisa i-antimony sulfide ore njengezinto eziluhlaza. I-antimony yesinyithi iyalungiswa kuqala, ize emva koko i-Sb2O3 iveliswe kusetyenziswa i-antimony yesinyithi njengezinto eziluhlaza.
Kukho iindlela ezimbini eziphambili zokuvelisa i-Sb2O3 kwi-antimony yesinyithi: i-oxidation ethe ngqo kunye nokubola kwe-nitrogen.
1. Indlela yokufunxa ngqo
I-antimony yesinyithi iphendula nge-oxygen phantsi kobushushu ukuze yenze i-Sb2O3. Inkqubo yokusabela yile ilandelayo:
4Sb＋3O2＝＝2Sb2O3
2. I-Ammolysis
I-Antimony metal idibana ne-chlorine ukuze ivelise i-antimony trichloride, emva koko inyibilikiswe, i-hydrolyzed, i-ammonolyzed, ihlanjwe, ize yomiswe ukuze kufunyanwe imveliso ye-Sb2O3 egqityiweyo. I-equation esisiseko yempendulo yile:
2Sb＋3Cl2＝＝2SbCl3
I-SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Ukusetyenziswa kwe-antimony trioxide
Eyona ndlela iphambili yokusebenzisa i-antimony trioxide kukwenza i-polymerase ibe yinto ethintela ilangatye kwizinto ezenziwe ngokwenziwa.
Kwishishini le-polyester, i-Sb2O3 yaqala ukusetyenziswa njenge-catalyst. I-Sb2O3 isetyenziswa kakhulu njenge-polycondensation catalyst kwindlela ye-DMT kunye nendlela yokuqala ye-PTA kwaye isetyenziswa ngokubanzi kunye ne-H3PO4 okanye ii-enzymes zayo.
(III). Iingxaki nge-antimony trioxide
I-Sb2O3 ayinakunyibilika kakuhle kwi-ethylene glycol, kwaye inyibilika yi-4.04% kuphela kwi-150°C. Ke ngoko, xa i-ethylene glycol isetyenziselwa ukulungiselela i-catalyst, i-Sb2O3 ayinakunyibilika kakuhle, nto leyo enokubangela i-catalyst eninzi kwinkqubo ye-polymerization, ivelise ii-cyclic trimers ezinyibilikayo kakhulu, kwaye izise ubunzima ekujikelezeni. Ukuphucula ukunyibilika kunye nokusasazeka kwe-Sb2O3 kwi-ethylene glycol, ngokuqhelekileyo kusetyenziswa i-ethylene glycol eninzi okanye ukunyusa ubushushu bokunyibilika ukuya kuthi ga kwi-150°C. Nangona kunjalo, ngaphezulu kwe-120°C, i-Sb2O3 kunye ne-ethylene glycol zinokuvelisa i-ethylene glycol antimony precipitation xa zisebenza kunye ixesha elide, kwaye i-Sb2O3 inokwehliswa ibe yi-metallic antimony kwi-polycondensation reaction, enokubangela "inkungu" kwiitships ze-polyester kwaye ichaphazele umgangatho wemveliso.
II. Uphando kunye nokusetyenziswa kwe-antimony acetate
Indlela yokulungiselela i-antimony acetate
Ekuqaleni, i-antimony acetate yayilungiswa ngokuphendula i-antimony trioxide ne-acetic acid, kwaye i-acetic anhydride yayisetyenziswa njenge-arhente yokufunxa amanzi ukuze kufunxwe amanzi aveliswa yi-reaction. Umgangatho wemveliso egqityiweyo efunyenwe ngale ndlela wawungekho phezulu, kwaye kwathatha iiyure ezingaphezu kwama-30 ukuba i-antimony trioxide inyibilike kwi-acetic acid. Kamva, i-antimony acetate yalungiswa ngokuphendula i-antimony yesinyithi, i-antimony trichloride, okanye i-antimony trioxide ne-acetic anhydride, ngaphandle kwesidingo se-arhente yokufunxa amanzi.
1. Indlela ye-antimony trichloride
Ngo-1947, u-H. Schmidt nabanye eNtshona Jamani balungiselela i-Sb(CH3COO)3 ngokuphendula i-SbCl3 nge-acetic anhydride. Ifomula yokusabela yile ilandelayo:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Indlela yesinyithi se-antimony
Ngo-1954, i-TAPaybea yeSoviet Union yangaphambili yalungisa i-Sb(CH3COO)3 ngokuphendula i-antimony yesinyithi kunye ne-peroxyacetyl kwisisombululo se-benzene. Ifomyula yokusabela yile:
I-Sb＋(CH3COO)2==I-Sb(CH3COO)3
3. Indlela ye-antimony trioxide
Ngo-1957, uF. Nerdel waseNtshona Jamani wasebenzisa i-Sb2O3 ukusabela kwi-acetic anhydride ukuvelisa i-Sb(CH3COO)3.
Sb2O3＋3(CH3CO)2O＝(2Sb(CH3COO)3
Ingxaki yale ndlela kukuba iikristale zihlala zihlangana zibe ziingceba ezinkulu kwaye zinamathele ngokuqinileyo eludongeni lwangaphakathi lwe-reactor, nto leyo ebangela umgangatho wemveliso kunye nombala ophantsi.
4. Indlela yesinyibilikisi se-antimony trioxide
Ukuze koyiswe iziphene zale ndlela ingentla, kudla ngokufakwa isinyibilikisi esingathathi cala ngexesha lokusabela kwe-Sb2O3 kunye ne-acetic anhydride. Indlela ethile yokulungiselela yile ilandelayo:
(1) Ngo-1968, u-R. Thoms we-American Mosun Chemical Company wapapasha ilungelo lomenzi malunga nokulungiswa kwe-acetate ye-antimony. Ilungelo lomenzi lisebenzise i-xylene (o-, m-, p-xylene, okanye umxube wayo) njengesinyibilikisi esingathathi cala ukuvelisa iikristale ezintle ze-acetate ye-antimony.
(2) Ngo-1973, iRiphabliki yaseCzech yasungula indlela yokuvelisa i-acetate entle ye-antimony kusetyenziswa i-toluene njengesinyibilikisi.
III. Ukuthelekiswa kweekhatalyst ezintathu ezisekelwe kwi-antimony
| I-Antimony Trioxide | I-Antimony Acetate | I-Antimony Glycolate | |
| Iipropati eziSiseko | Eyaziwa kakhulu ngokuba yi-antimony emhlophe, i-molecular formula Sb2O3, ubunzima be-molecular 291.51, umgubo omhlophe, iqondo lokunyibilika 656℃. Umxholo we-antimony wethiyori umalunga ne-83.53%. Uxinano oluhambelanayo yi-5.20g/ml. Inyibilika kwi-hydrochloric acid exineneyo, i-sulfuric acid exineneyo, i-nitric acid exineneyo, i-tartaric acid kunye nesisombululo se-alkali, ayinyibiliki emanzini, i-alcohol, i-sulfuric acid enyibilikisiweyo. | Ifomula yemolekyuli i-Sb(AC) 3, ubunzima bemolekyuli yi-298.89, umxholo we-antimony oqikelelweyo malunga ne-40.74%, indawo yokunyibilika yi-126-131℃, uxinano yi-1.22g/ml (25℃), umgubo omhlophe okanye ongekho mhlophe, onyibilikayo lula kwi-ethylene glycol, i-toluene kunye ne-xylene. | Ifomula yemolekyuli Sb 2 (EG) 3, Ubunzima bemolekyuli bumalunga ne-423.68, indawo yokunyibilika yi ＞ 100℃ (dec.), umxholo we-antimony wethiyori umalunga ne-57.47%, imbonakalo yayo imhlophe njengekristale eqinileyo, ayinatyhefu kwaye ayinancasa, kulula ukuyifunxa umswakama. Inyibilika lula kwi-ethylene glycol. |
| Indlela yokwenziwa kunye neTekhnoloji | Yenziwe kakhulu ngendlela ye-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 3Qaphela: I-Stibnite / Iron Ore / I-Limestone → Ukufudumeza kunye nokuFutha → Ukuqokelelwa | Olu shishino lusebenzisa kakhulu indlela ye-Sb 2 O 3 -solvent yokwenza i-synthesis:Sb2O3 ＋ 3 (CH3CO) 2O→ 2Sb(AC) 3Inkqubo: ukufudumala i-reflux → ukuhluza okushushu → i-crystallization → ukomisa nge-vacuum → imvelisoQaphela: I-Sb(AC) 3 i-hydrolyzed lula, ngoko ke i-solvent engathathi hlangothi ye-toluene okanye i-xylene esetyenzisiweyo kufuneka ibe yi-anhydrous, i-Sb 2 O 3 ayinakuba kwimeko yokumanzisa, kwaye izixhobo zemveliso nazo kufuneka zome. | Olu shishino lusebenzisa kakhulu indlela ye-Sb 2 O 3 ukwenza i-synthesis: Sb 2 O 3 +3EG→Sb 2 (EG) 3 +3H 2 OPcess: Ukondla (Sb 2 O 3 , izongezo kunye ne-EG) → ukufudumala kunye ne-pressurizing reaction → ukususa i-slag, ukungcola kunye namanzi → ukususwa kombala → ukuhluzwa okushushu → ukupholisa kunye ne-crystallization → ukwahlukana kunye nokomisa → imvelisoQaphela: Inkqubo yemveliso kufuneka yahlulwe emanzini ukuthintela i-hydrolysis. Le reaction yi-reaction eguqukayo, kwaye ngokubanzi i-reaction ikhuthazwa ngokusebenzisa i-ethylene glycol engaphezulu kunye nokususa amanzi emveliso. |
| Inzuzo | Ixabiso liphantsi kakhulu, kulula ukulisebenzisa, linomsebenzi ophakathi wokutsala amandla kunye nexesha elifutshane lokufunxa amanzi. | I-Antimony acetate inokunyibilika kakuhle kwi-ethylene glycol kwaye isasazwa ngokulinganayo kwi-ethylene glycol, nto leyo enokuphucula ukusebenza kakuhle kwe-antimony; I-Antimony acetate ineempawu zomsebenzi ophezulu we-catalytic, impendulo encinci yokuwohloka, ukumelana nobushushu okuhle kunye nozinzo lokucubungula; Kwangaxeshanye, ukusebenzisa i-antimony acetate njenge-catalyst akudingi kongezwa kwe-co-catalyst kunye ne-stabilizer. Indlela esebenza ngayo inkqubo ye-antimony acetate catalytic ithambile, kwaye umgangatho wemveliso uphezulu, ingakumbi umbala, ongcono kunowenkqubo ye-antimony trioxide (Sb2O3). | I-catalyst inonyibiliko oluphezulu kwi-ethylene glycol; i-antimony ye-zero-valent iyasuswa, kwaye ukungcola okufana neemolekyuli zesinyithi, ii-chloride kunye nee-sulfates ezichaphazela i-polycondensation kuyancitshiswa ukuya kwinqanaba eliphantsi, okususa ingxaki yokugqwala kwe-acetate ion kwizixhobo; i-Sb 3+ kwi-Sb 2 (EG) 3 iphezulu kakhulu, oku kusenokuba kungenxa yokuba ukunyibilika kwayo kwi-ethylene glycol kubushushu bokusabela kungaphezulu kunokwe-Sb 2 O 3 Xa kuthelekiswa ne-Sb(AC) 3, ubungakanani be-Sb 3+ obudlala indima ye-catalytic bukhulu. Umbala wemveliso ye-polyester eyenziwe yi-Sb 2 (EG) 3 ungcono kunowe-Sb 2 O 3 Iphezulu kancinci kuneyokuqala, okwenza imveliso ibonakale ikhanya kwaye imhlophe ngakumbi; |
| Ububi | Ukunyibilika kwi-ethylene glycol akukuhle, yi-4.04% kuphela kwi-150°C. Ngokwesiqhelo, i-ethylene glycol igqithisile okanye ubushushu bokunyibilika bunyuswa bube ngaphezu kwe-150°C. Nangona kunjalo, xa i-Sb2O3 isabela ne-ethylene glycol ixesha elide ngaphezulu kwe-120°C, i-ethylene glycol antimony precipitation inokwenzeka, kwaye i-Sb2O3 inokuncitshiswa ibe yi-metal ladder kwi-polycondensation reaction, enokubangela "i-grey fog" kwi-polyester chips kwaye ichaphazele umgangatho wemveliso. Imeko ye-polyvalent antimony oxides yenzeka ngexesha lokulungiselela i-Sb2O3, kwaye ubumsulwa obusebenzayo be-antimony buyachaphazeleka. | Umxholo we-antimony we-catalyst uphantsi kakhulu; ukungcola kwe-acetic acid okuzisa izixhobo zokubola, kungcolisa okusingqongileyo, kwaye akulungelanga ukunyangwa kwamanzi amdaka; inkqubo yemveliso iyinkimbinkimbi, iimeko zokusebenza azintle, kukho ungcoliseko, kwaye imveliso kulula ukuyitshintsha umbala. Kulula ukubola xa ishushu, kwaye iimveliso ze-hydrolysis yi-Sb2O3 kunye ne-CH3COOH. Ixesha lokuhlala kwezinto lide, ngakumbi kwinqanaba lokugqibela le-polycondensation, eliphezulu kakhulu kunenkqubo ye-Sb2O3. | Ukusetyenziswa kwe-Sb 2 (EG) 3 kwandisa ixabiso le-catalyst yesixhobo (ukunyuka kwexabiso kunokulungiswa kuphela ukuba i-25% ye-PET isetyenziselwa ukuzijikelezisa kwe-filaments). Ukongeza, ixabiso le-b lombala wemveliso liyanda kancinci. |