Polyester (PET) fiber waa noocyada ugu badan ee fiber synthetic. Dharka laga sameeyay fiber polyester-ka ayaa ah mid raaxo leh, qallafsan, si sahlan loo dhaqi karo, waana dhakhso loo engegaa. Polyester-ka ayaa sidoo kale si weyn loogu isticmaalaa sida alaabta ceeriin ee baakadaha, dunnooyinka warshadaha, iyo balaastikada injineernimada. Natiijo ahaan, polyester-ka ayaa si degdeg ah u horumaray adduunka oo dhan, isaga oo kordhay celcelis ahaan heerka sannadlaha ah ee 7% iyo wax soo saar ballaadhan.
Wax-soo-saarka Polyester-ka waxa loo qaybin karaa dariiqa dimethyl terephthalate (DMT) iyo dariiqa terephthalic acid (PTA) marka loo eego dariiqa geedi socodka waxaana loo qaybin karaa habsocod dhex-dhexaad ah iyo habsocod joogto ah marka la eego shaqada. Iyadoo aan loo eegin dariiqa wax soo saarka ee la qaatay, falcelinta polycondensation-ka waxay u baahan tahay isticmaalka ka samaysan birta sidii kicin. Dareen-celinta polyester-ka ayaa ah tallaabo muhiim ah oo ku socota habka wax-soo-saarka polyester-ka, iyo wakhtiga qaboojinta polyester-ka ayaa ah cidhiidhiga horumarinta wax-soo-saarka. Hagaajinta nidaamka kicinta ayaa ah arrin muhiim ah oo lagu hagaajinayo tayada polyester-ka iyo soo gaabinaysa wakhtiga qaboojinta.
UrbanMines Tech. Limited waa shirkad hormuud ah oo Shiinees ah oo ku takhasustay R&D, wax soo saarka, iyo sahayda polyester-ka-fasalka antimony trioxide, antimony acetate, iyo antimony glycol. Waxaan samaynay cilmi-baaris qoto dheer oo ku saabsan alaabtan - waaxda R & D ee UrbanMines hadda waxay soo koobeysaa cilmi-baarista iyo codsiga antimony-ka ee qodobkan si ay uga caawiso macaamiisheena inay si dabacsanaan leh u codsadaan, kor u qaadaan hababka wax soo saarka, iyo bixinta tartan dhamaystiran oo ah alaabta fiber polyesterka.
Aqoonyahanada gudaha iyo kuwa ajnabiga ah guud ahaan waxay aaminsan yihiin in polyester polyester ay tahay falcelinta silsiladda fidinta, iyo habka catalytic waxaa iska leh isuduwidda chelation, kaas oo u baahan atomka birta ee kicinta si uu u bixiyo orbitals madhan si uu ula socdo lammaanaha arc ee elektarooniga ah ee carbonyl oxygen si loo gaaro ujeedada catalysis. Polycondensation-ka, maadaama cufnaanta daruuriga elektarooniga ah ee ogsijiinta karbonyl ee kooxda hydroxyethyl ester ay aad u hooseyso, koronto-siinta ion birta ayaa aad u sareysa inta lagu jiro isuduwidda, si loo fududeeyo isuduwidda iyo fidinta silsiladda.
Kuwa soo socda ayaa loo isticmaali karaa kicinta polyester-ka: 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 iyo oksaydhyada kale ee biraha, alcoholates, karboksylates, borates, halides iyo amines, ureas, guanidines, xeryahooda organic ka kooban baaruud. Si kastaba ha ahaatee, kicinta hadda la isticmaalo laguna daraaseeyo wax soo saarka warshadaha ayaa u badan xeryahooda taxanaha Sb, Ge, iyo Ti. Tiro badan oo daraasado ah ayaa muujiyay in: Ge-based catalysts ay leeyihiin falcelin-celin yar oo soo saara PET tayo sare leh, laakiin hawlahooda maaha mid sarreeya, oo waxay haystaan ilo yar oo qaali ah; Ti-ku-salaysan waxay leeyihiin firfircooni sare iyo xawaare falcelin degdeg ah, laakiin falcelintooda dhinaca catalytic ayaa aad u cad, taasoo keentay xasillooni kuleyl xumo iyo midabka jaalaha ah ee badeecadda, guud ahaanna waxaa loo isticmaali karaa oo keliya isku-darka PBT, PTT, PCT, iwm; Kataliyeyaasha Sb-ku-salaysan maaha oo kaliya kuwo firfircoon. Tayada alaabadu aad bay u sarraysaa sababtoo ah kicinta Sb-ku salaysan ayaa aad u firfircoon, waxay leeyihiin falcelin dhinaca dhinac ah, wayna ka jaban yihiin. Sidaa darteed, si weyn ayaa loo isticmaalay. Waxaa ka mid ah, kicinta ku saleysan Sb ee inta badan la isticmaalo waa antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), iwm.
Marka la eego taariikhda horumarinta warshadaha polyester-ka, waxaan ogaan karnaa in in ka badan 90% dhirta polyester-ka ee adduunka ay isticmaalaan xeryahooda antimony sida kicinta. Sannadkii 2000-kii, Shiinuhu waxa uu soo saaray dhowr geedo polyester-ka ah, kuwaas oo dhammaantood u isticmaalay xeryahooda antimony si ay u kiciyaan, gaar ahaan Sb2O3 iyo Sb(CH3COO)3. Dadaalka wadajirka ah ee cilmi-baarista sayniska ee Shiinaha, jaamacadaha, iyo waaxaha wax-soo-saarka, labadan kicin ayaa hadda si buuxda loo soo saaray gudaha.
Tan iyo 1999kii, shirkadda Faransiiska ee Elf waxay soo saartay antimony glycol [Sb2 (OCH2CH2CO) 3] kicinta sida badeecada la cusboonaysiiyay ee kicinta dhaqameed. Chips-ka polyester-ka ee la soo saaray waxay leeyihiin caddaan sare iyo is-midaaminta wanaagsan, taas oo soo jiidatay dareen weyn machadyada cilmi-baarista kicinta gudaha, shirkadaha, iyo soo-saareyaasha polyester-ka ee Shiinaha.
I. Cilmi-baarista iyo adeegsiga antimony trioxide
Maraykanku waa mid ka mid ah wadamada ugu horreeya ee soo saara oo lagu dabaqo Sb2O3. Sannadkii 1961-kii, isticmaalka Sb2O3 ee Maraykanka wuxuu gaadhay 4,943 tan. Sannadihii 1970-aadkii, shan shirkadood oo Japan ku yaalla ayaa soo saaray Sb2O3 oo wadarta awoodda wax-soo-saarka 6,360 tan sannadkii.
Unugyada cilmi-baarista iyo horumarinta ee Sb2O3 ee ugu weyn Shiinaha waxay inta badan ku urursan yihiin ganacsiyadii hore ee ay dawladdu lahayd ee ku yaal Gobolka Hunan iyo Shanghai. UrbanMines Tech. Limited waxa kale oo ay ka dhistay khad wax soo saar xirfad leh gudaha Gobolka Hunan.
(I). Habka loo soo saaro antimony trioxide
Samaynta Sb2O3 waxay caadi ahaan u isticmaashaa maadada antimony sulfide sida walxo ceeriin ah. Antimony bir ah ayaa marka hore la diyaariyaa, ka dibna Sb2O3 ayaa la soo saaraa iyadoo la isticmaalayo antimony birta ah sida alaabta ceeriin.
Waxaa jira laba hab oo waaweyn oo loo soo saaro Sb2O3 laga bilaabo antimony bir ah: oksaydhka tooska ah iyo kala-goynta nitrogen.
1. Habka oksaydhka tooska ah
Birta antimony waxay la falgashaa ogsijiin kuleylinta hoosteeda si ay u sameyso Sb2O3. Habka falcelinta waa sida soo socota:
4Sb＋3O2＝2Sb2O3
2. Ammonolysis
Birta Antimony waxay la falgashaa koloriin si ay u abuurto antimony trichloride, ka dibna la nadiifiyo, hydrolyzed, ammonolyzed, la dhaqo, oo la qalajiyo si loo helo badeecada Sb2O3 dhammaatay. Isla'egta falcelinta aasaasiga ah waa:
2Sb＋3Cl2＝2SbCl3
SbCl3＋H2O＝SbOCl＋2HCl
4SbOCl＋H2O＝
Sb2O3·2SbOCl —OH＝2Sb2O3＋2NH4Cl＋H2O
(II). Isticmaalka antimony trioxide
Isticmaalka ugu muhiimsan ee antimony trioxide waa sida kicinta polymerase iyo ololka dib u celinta alaabta synthetic.
Warshadaha polyester-ka, Sb2O3 ayaa markii ugu horreysay loo adeegsaday kicin ahaan. Sb2O3 waxaa inta badan loo isticmaalaa sidii kicinta kondensation-ka ee dariiqa DMT iyo dariiqa hore ee PTA waxaana guud ahaan loo isticmaalaa marka lagu daro H3PO4 ama enzymeskeeda.
(III). Dhibaatooyinka antimony trioxide
Sb2O3 waxay leedahay milmayn liidata ee ethylene glycol, oo leh milmi 4.04% oo keliya 150°C. Sidaa darteed, marka ethylene glycol loo isticmaalo diyaarinta kicinta, Sb2O3 waxay leedahay kala firdhisanaan liidata, taas oo si sahlan u keeni karta kicinta xad-dhaafka ah ee nidaamka polymerization, waxay dhalinaysaa trimers-wareeg heer sare ah oo wareeg ah, oo keenaya dhibaatooyin si wareeg ah. Si loo hagaajiyo milanka iyo kala firdhinta Sb2O3 ee ethylene glycol, waxaa guud ahaan la qaatay in la isticmaalo glycol ethylene xad-dhaaf ah ama la kordhiyo heerkulka kala dirida ilaa 150 ° C. Si kastaba ha noqotee, ka sarreeya 120 ° C, Sb2O3 iyo ethylene glycol waxay soo saari karaan roobabka ethylene glycol antimony marka ay isla dhaqmaan muddo dheer, Sb2O3 waxaa laga yaabaa in lagu yareeyo antimony birta ah ee falcelinta polycondensation, taas oo keeni karta "ceeryo" jajabyada polyesterka waxayna saameynayaan tayada alaabta.
II. Cilmi-baarista iyo codsiga antimony acetate
Habka diyaarinta ee antimony acetate
Markii hore, antimony acetate ayaa la diyaariyey iyada oo ka falcelinaysa antimony trioxide oo leh acetic acid, iyo acetic anhydride ayaa loo isticmaalay wakiilka fuuq-baxa si ay u nuugaan biyaha ka dhashay falcelinta. Tayada alaabta la dhammeeyey ee lagu helay habkani ma ahayn mid sare, waxayna qaadatay in ka badan 30 saacadood in antimony trioxide ay ku milanto acetic acid. Ka dib, antimony acetate ayaa la diyaariyey iyada oo ka falcelinaysa antimony birta, antimony trichloride, ama antimony trioxide leh acetic anhydride, iyada oo aan loo baahnayn wakiilka fuuqbaxa.
1. Habka antimony trichloride
Sannadkii 1947, H. Schmidt et al. Galbeedka Jarmalka waxay diyaariyeen Sb(CH3COO)3 iyagoo ka falcelinaya SbCl3 oo leh anhydride acetic. Habka falcelinta waa sida soo socota:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Habka birta Antimony
Sanadkii 1954, TAPaybea oo ka tirsan Midowga Soofiyeeti hore waxay diyaarisay Sb (CH3COO) 3 iyada oo ka falcelinaysa antimony birta ah iyo peroxyacetyl ee xalka benzene. Habka falcelinta waa:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Habka antimony trioxide
Sannadkii 1957-kii, F. Nerdel oo reer Jarmal ah ayaa isticmaalay Sb2O3 si ay uga falceliso anhydride-ka acetic si ay u soo saarto Sb(CH3COO)3.
Sb2O3＋3（CH3CO）2O＝＝2Sb（CH3COO）3
Khasaaraha habkani waa in crystals u muuqdaan in ay isu geeyaan qaybo waaweyn oo si adag ugu dheggan gidaarka gudaha ee reactor, taasoo keentay tayada alaabta iyo midabka liidata.
4. Habka dareeraha antimony trioxide
Si looga gudbo cilladaha habka kor ku xusan, dareere dhexdhexaad ah ayaa badanaa lagu daraa inta lagu jiro falcelinta Sb2O3 iyo acetic anhydride. Habka diyaarinta gaarka ah waa sida soo socota:
(1) Sannadkii 1968-kii, R. Thoms oo ka tirsan Shirkadda Kiimikada Maraykanka ee Mosun ayaa daabacday shati ku saabsan diyaarinta antimony acetate. Patent-ku wuxuu isticmaalay xylene (o-, m-, p-xylene, ama isku darkooda) sidii dareere dhexdhexaad ah si loo soo saaro kirismasyada wanaagsan ee antimony acetate.
(2) Sannadkii 1973-kii, jamhuuriyadda Czech waxa ay ikhtiraacday hab lagu soo saaro antimony acetate wanaagsan iyadoo la isticmaalayo toluene sida dareere.
III. Isbarbardhigga seddexda kiciyayaal antimony ku salaysan
| Antimony Trioxide | Antimony acetate | Antimony Glycolate | |
| Guryaha aasaasiga ah | Caadi ahaan loo yaqaan antimony cad, caanaha molecular Sb 2 O 3, miisaanka kelli 291.51, budada cad, barta dhalaalka 656 ℃. Waxa ku jira antimony-ka aragtida waa qiyaastii 83.53 %. Cufnaanta qaraabada 5.20g/ml . Ku milmay hydrochloric acid, sulfuric acid xoog leh, nitric acid, tartaric acid iyo xalalka alkali, oo aan lagu milmin biyaha, khamriga, milo sulfuric acid. | Qaaciddada molecular Sb (AC) 3, miisaanka kelli 298.89, content antimony theoretical oo ku saabsan 40.74%, barta dhalaalay 126-131 ℃, cufnaanta 1.22g / ml (25 ℃), caddaan ama cad-cad budo, si fudud u milmay in glycol ethylene. iyo xylene. | Qaaciddada molecular Sb 2 (EG) 3, Miisaanka kelliku wuxuu ku saabsan yahay 423.68, barta dhalaalidu waa ＞ 100 ℃ (dec.) , content antimony theoretical waa qiyaastii 57.47 %, muuqaalku waa crystalline cad oo adag, aan sun ahayn oo aan dhadhan lahayn, fududahay in la nuugo qoyaanka. Waxay si fudud ugu milmi kartaa ethylene glycol. |
| Habka Synthesis iyo Technology | Inta badan waxaa lagu farsameeyay habka stibnite:2Sb 2 S 3 +9O 2 →2Sb 2 O 3 +6SO 2 ↑Sb 2 O 3 +3C→2Sb+3CO↑ 4Sb+O 2 Kuleylinta iyo qiiqa → Ururinta | Wershadaha inta badan waxay isticmaalaan Sb 2 O 3 -habka milmaha si ay isugu keenaan:Sb2O3 si sahlan loo hydrolyzed, markaa dareeraha dhexdhexaadka ah ee toluene ama xylene ee la isticmaalo waa inuu noqdaa mid aan biyo lahayn. | Warshadaha inta badan waxay adeegsadaan habka Sb 2 O 3 si ay isugu keenaan:Sb 2 O 3 +3EG→Sb 2 (EG) 3 +3H 2 Oprocess: Quudin (Sb 2 O 3, additives iyo EG) → kululaynta iyo falcelinta cadaadiska , wasakhda iyo biyaha → midabaynta → sifaynta kulul → qaboojinta iyo crystallization → kala soocida iyo qalajinta → ProductFiiro gaar ah: Geedi socodka wax soo saarka wuxuu u baahan yahay in laga sooco biyaha si looga hortago biyo. Dareen-celintani waa fal-celin dib loo rogi karo, guud ahaan fal-celinta waxaa lagu hormariyaa iyadoo la isticmaalayo ethylene glycol oo dheeraad ah oo laga saaro biyaha alaabta. |
| Faa'iidada | qiimuhu waa raqiis, way fududahay in la isticmaalo, waxa uu leeyahay firfircooni firfircooni dhexdhexaad ah iyo wakhti gaaban oo biyo-qaboojin ah. | Antimony acetate waxay leedahay solubility wanaagsan ee ethylene glycol waxayna si siman u kala firdhisaa ethylene glycol, taas oo hagaajin karta waxtarka isticmaalka antimony; Isla mar ahaantaana, isticmaalka antimony acetate sida kicinta uma baahna in lagu daro co-catalyst iyo xasiliye. Dareen-celinta antimony acetate catalytic system waa mid khafiif ah, tayada badeecaduna waa mid sareysa, gaar ahaan midabka, taas oo ka fiican nidaamka antimony trioxide (Sb 2 O 3). | Kiciyahu waxa uu leeyahay milmi sare oo ethylene glycol ah; eber-valent antimony waa la saaraa, iyo wasakhda sida molecules birta, chlorides iyo sulfates ee saameeya polycondensation ayaa hoos loo dhigaa meesha ugu hooseysa, taas oo meesha ka saaraysa dhibaatada daxalka acetate ion ee qalabka; Sb 3+ ee Sb 2 (EG) 3 waa mid aad u sarreeya. , taas oo laga yaabo inay tahay sababtoo ah milmaheeda ethylene glycol ee heerkulka falcelinta ayaa ka weyn Sb 2 O 3 Marka loo eego Sb(AC) 3, qadarka Sb 3+ ee ka ciyaara doorka kicinta ayaa ka weyn. Midabka polyester-ka ee ay soo saarto Sb 2 (EG) 3 ayaa ka fiican kan Sb 2 O 3 In yar ka sarreeya kan asalka ah, taas oo ka dhigaysa alaabtu mid ifaysa oo cad; |
| Khasaaro | Solubility ee ethylene glycol waa liidata, kaliya 4.04% at 150 ° C. Ficil ahaan, ethylene glycol ayaa xad dhaaf ah ama heerkulka kala diriddu waa la kordhiyaa oo ka sarreeya 150 ° C. Si kastaba ha noqotee, marka Sb 2 O 3 ay la falgasho ethylene glycol muddo dheer oo ka sarreysa 120 ° C, ethylene glycol antimony ayaa laga yaabaa inay dhacdo, Sb 2 O 3 waxaa laga yaabaa in lagu yareeyo jaranjarada birta ee falcelinta polycondensation, taas oo keeni karta "ceeryaamo cawl " ee chips polyester-ka waxayna saameeyaan tayada alaabta. Ifafaalaha polyvalent antimony oxides waxay dhacdaa inta lagu jiro diyaarinta Sb 2 O 3, iyo nadiifinta waxtarka leh ee antimony waa la saameeyaa. | Waxa ku jira antimony ee kicinta waa mid aad u hooseeya; wasakhda acetic acid waxay soo bandhigtay qalabka daxalka, wasakheeya deegaanka, oo aan ku haboonayn daaweynta biyaha wasakhda ah; habka wax soo saarku waa mid adag, xaaladaha jawiga shaqada waa liitaa, waxaa jira wasakh, iyo alaabtu way fududahay in la beddelo midabka. Way fududahay in la dumiyo marka la kululeeyo, iyo alaabada hydrolysis waa Sb2O3 iyo CH3COOH . Waqtiga degenaanshaha maaddadu waa mid dheer, gaar ahaan heerka ugu dambeeya ee polycondensation, kaas oo aad uga sarreeya nidaamka Sb2O3. | Isticmaalka Sb 2 (EG) 3 waxay kordhisaa qiimaha qalabka (kor u kaca kharashka waxa kaliya oo la dhimi karaa haddii 25% PET loo isticmaalo is miiqinta fiilooyinka). Intaa waxaa dheer, qiimaha b ee midabka alaabta ayaa kor u kaca wax yar. |