Fiber yepolyester (PET) ndiyo mhando yakakura kwazvo yefiber yekugadzira. Zvipfeko zvakagadzirwa nefiber yepolyester zvinonyaradza, zvinotsvedzerera, zviri nyore kuwacha, uye zvinokurumidza kuoma. Polyester inoshandiswawo zvakanyanya sezvinhu zvekugadzira, shinda dzemaindasitiri, uye mapurasitiki einjiniya. Nekuda kweizvozvo, polyester yakura nekukurumidza pasi rese, ichiwedzera ne7% pagore uye ichiburitsa zvakawanda.
Kugadzirwa kwepolyester kunogona kukamurwa kuita nzira ye dimethyl terephthalate (DMT) uye nzira ye terephthalic acid (PTA) maererano nenzira yekushanda uye kunogona kukamurwa kuita nzira yepakati nepakati uye nzira yekushanda. Pasinei nenzira yekugadzirwa yakagamuchirwa, polycondensation reaction inoda kushandiswa kwesimbi se catalysts. Polycondensation reaction idanho guru mukugadzirwa kwepolyester, uye nguva ye polycondensation ndiyo dambudziko rekuvandudza goho. Kuvandudzwa kwe catalyst system chinhu chakakosha mukuvandudza mhando yepolyester uye kupfupisa nguva ye polycondensation.
UrbanMines Tech. Limited ikambani inotungamira yekuChina inonyanya kugadzira R&D, kugadzira, uye kugovera polyester catalyst-grade antimony trioxide, antimony acetate, uye antimony glycol. Takaita tsvakiridzo yakadzama pazvigadzirwa izvi—dhipatimendi reR&D reUrbanMines ikozvino rinopfupikisa tsvakiridzo nekushandiswa kweantimony catalysts muchinyorwa chino kubatsira vatengi vedu kushandisa, kugadzirisa maitiro ekugadzira, uye kupa makwikwi akazara ezvigadzirwa zvepolyester fiber.
Nyanzvi dzemuno nedzekunze dzinotenda kuti polyester polycondensation iketani yekuwedzera, uye nzira ye catalytic ndeye chelation coordinate, iyo inoda kuti catalyst metal atomu ipe ma empty orbitals kuti aenderane ne arc pair yema electron e carbonyl oxygen kuti azadzise chinangwa che catalysis. Kune polycondensation, sezvo density yema electron e carbonyl oxygen mu hydroxyethyl ester group yakaderera, electronegativity yema ions esimbi yakakwira panguva ye coordinate, kuti zvive nyore coordinate uye chain extension.
Zvinotevera zvinogona kushandiswa sezvinhu zvinokonzeresa makemikari zvepolyester: 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 nedzimwe metal oxides, alcoholates, carboxylates, borates, halides uye amines, ureas, guanidines, organic compounds. Zvisinei, zvinhu zvinoshandiswa uye zvinodzidzwa mukugadzirwa kwemaindasitiri zvinonyanya kuve Sb, Ge, uye Ti series compounds. Ongororo dzakawanda dzakaratidza kuti: Zvinhu zvinokonzeresa makemikari zveGe zvine side reaction shoma uye zvinogadzira PET yepamusoro, asi basa razvo harisi rakawanda, uye zvine zviwanikwa zvishoma uye zvinodhura; Ma catalysts anobva kuTi ane basa guru uye anokurumidza kukurumidza kuita, asi maitiro avo e catalytic side anonyatsooneka, zvichikonzera kusagadzikana kwekupisa uye ruvara rweyero rwechigadzirwa, uye anogona kushandiswa chete pakugadzira PBT, PTT, PCT, nezvimwewo; ma catalysts anobva kuSb haangoshandi chete. Hunhu hwechigadzirwa hwakakwirira nekuti ma catalysts anobva kuSb anoshanda zvakanyanya, ane side reaction shoma, uye akachipa. Nokudaro, akashandiswa zvakanyanya. Pakati pawo, ma catalysts anonyanya kushandiswa eSb ndeaya antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), nezvimwewo.
Tichitarisa nhoroondo yekuvandudzwa kweindasitiri yepolyester, tinogona kuona kuti zvinopfuura 90% yezvirimwa zvepolyester pasi rose zvinoshandisa mishonga yeantimony semacatalysts. Pakazosvika 2000, China yakanga yatanga zvirimwa zvepolyester zvakawanda, zvese zvaishandisa mishonga yeantimony semacatalysts, kunyanya Sb2O3 neSb(CH3COO)3. Kuburikidza nekushanda pamwe chete kwekutsvaga kwesainzi yeChina, mayunivhesiti, nemadhipatimendi ekugadzira, macatalysts maviri aya ikozvino agadzirwa zvizere munyika.
Kubva muna 1999, kambani yemakemikari yekuFrance inonzi Elf yakatanga mushonga we antimony glycol [Sb2 (OCH2CH2CO) 3] semushonga wekuvandudza we catalysts dzechinyakare. Machipisi e polyester anogadzirwa ane kuchena kwakanyanya uye kugona kutenderera zvakanaka, izvo zvakakwezva kutariswa kukuru kubva kumasangano ekutsvagisa catalyst emuno, mabhizinesi, uye vagadziri ve polyester muChina.
I. Kutsvaga nekushandisa antimony trioxide
United States ndeimwe yenyika dzekutanga kugadzira nekushandisa Sb2O3. Muna 1961, kushandiswa kweSb2O3 muUnited States kwakasvika matani 4,943. Muma1970, makambani mashanu muJapan aigadzira Sb2O3 ine huwandu hwematani 6,360 pagore.
Mayuniti makuru ekutsvagisa nekusimudzira eSb2O3 muChina anonyanya kutarisisa makambani aimbova ehurumende muHunan Province neShanghai. UrbanMines Tech. Limited yakagadzirawo kambani yekugadzira zvinhu zvehunyanzvi muHunan Province.
(I). Nzira yekugadzira antimony trioxide
Kugadzirwa kweSb2O3 kunowanzo shandisa maori eantimony sulfide sezvinhu zvisina kugadzirwa. Antimony yesimbi inotanga yagadzirwa, uye Sb2O3 inogadzirwa uchishandisa antimony yesimbi sezvinhu zvisina kugadzirwa.
Kune nzira mbiri huru dzekugadzira Sb2O3 kubva kusimbi antimony: oxidation yakananga uye kuora kwenitrogen.
1. Nzira yekuoxidation yakananga
Antimony yesimbi inosangana neokisijeni iri kudziya kuti igadzire Sb2O3. Maitiro ekuita izvi ndeekuti:
4Sb＋3O2＝＝2Sb2O3
2. Kubviswa kweropa kubva muropa
Simbi yeAntimony inosangana nechlorine kugadzira antimony trichloride, iyo inobva yanyungudutswa, yozonyungudutswa, yozoiswa ammonolyzed, yogezwa, yozoomeswa kuti iwane chigadzirwa cheSb2O3 chapera. Equation yekutanga yemhinduro ndeiyi:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Mashandisirwo eantimony trioxide
Kushandiswa kukuru kweantimony trioxide ndiko kunokonzera polymerase uye chinhu chinodzivirira moto pazvinhu zvakagadzirwa.
Muindasitiri yepolyester, Sb2O3 yakatanga kushandiswa sechinhu chinobatsira pakuumbwa kwesimbi. Sb2O3 inonyanya kushandiswa sechinhu chinobatsira pakuumbwa kwesimbi (polycondensation catalyst) chenzira yeDMT uye nzira yekutanga yePTA uye inowanzo shandiswa pamwe chete neH3PO4 kana ma enzyme ayo.
(III). Matambudziko ne antimony trioxide
Sb2O3 haina kunyungudika kwakawanda mu ethylene glycol, ine kunyungudika kwe4.04% chete pa150°C. Saka, kana ethylene glycol ikashandiswa kugadzira catalyst, Sb2O3 haina kunyungudika kwakawanda, izvo zvinogona kukonzera catalyst yakawandisa mu polymerization system, kugadzira high-melting-point cyclic trimers, uye kuunza matambudziko ekutenderera. Kuti Sb2O3 ive inonyungudika uye kupararira kwayo mu ethylene glycol, inowanzo shandiswa kushandisa ethylene glycol yakawandisa kana kuwedzera tembiricha yekunyungudika kusvika pamusoro pe150°C. Zvisinei, pamusoro pe120°C, Sb2O3 ne ethylene glycol zvinogona kugadzira ethylene glycol antimony precipitation kana zvikashanda pamwe chete kwenguva yakareba, uye Sb2O3 inogona kuderedzwa kuita metallic antimony mu polycondensation reaction, izvo zvinogona kukonzera "fog" mu polyester chips uye kukanganisa kunaka kwechigadzirwa.
II. Kutsvaga nekushandisa antimony acetate
Nzira yekugadzirira antimony acetate
Pakutanga, antimony acetate yaigadzirwa nekuita antimony trioxide neacetic acid, uye acetic anhydride yakashandiswa senzira yekunyudza mvura inogadzirwa nekuita. Hunhu hwechigadzirwa chakapedzwa chakawanikwa nenzira iyi hwaive husina kukwira, uye zvakatora maawa anopfuura makumi matatu kuti antimony trioxide inyungudike muacetic acid. Gare gare, antimony acetate yakagadzirwa nekuita antimony yesimbi, antimony trichloride, kana antimony trioxide neacetic anhydride, pasina chikonzero chechinhu chinonyungudutsa mvura.
1. Nzira yeAntimony trichloride
Muna 1947, H. Schmidt nevamwe vake kuWest Germany vakagadzira Sb(CH3COO)3 nekushandisa SbCl3 neacetic anhydride. Nzira yekuita nayo iyi inotevera:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Nzira yesimbi yeantimoni
Muna 1954, TPaybea yeyaimbova Soviet Union yakagadzira Sb(CH3COO)3 nekugadzira antimony yesimbi uye peroxyacetyl mumushonga webenzene. Nzira yekugadzirira mhinduro ndeiyi:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Nzira yeAntimony trioxide
Muna 1957, F. Nerdel wekuWest Germany akashandisa Sb2O3 kuita mubatanidzwa neacetic anhydride kugadzira Sb(CH3COO)3.
Sb2O3＋3(CH3CO)2O(2O)(2Sb)(CH3COO)3
Dambudziko renzira iyi nderekuti makristaro anowanzo ungana kuita zvidimbu zvakakura uye anonamira zvakasimba pamadziro emukati me reactor, zvichikonzera kunaka kwemhando yechigadzirwa uye ruvara rwakashata.
4. Nzira yekunyungudutsa yeAntimony trioxide
Kuti zvisave nemhedzisiro yenzira iri pamusoro apa, chinhu chinonyungudutsa chinowanzo wedzerwa panguva yeSb2O3 uye acetic anhydride. Nzira chaiyo yekugadzirira ndeiyi inotevera:
(1) Muna 1968, R. Thoms weAmerican Mosun Chemical Company akaburitsa patent pakugadzira antimony acetate. Patent iyi yakashandisa xylene (o-, m-, p-xylene, kana musanganiswa wayo) sechinhu chinonyungudutsa chisina kusimba kugadzira makristaro akanaka eantimony acetate.
(2) Muna 1973, Czech Republic yakagadzira nzira yekugadzira antimony acetate yakanaka ichishandisa toluene semusanganiswa.
III. Kuenzaniswa kwezvinokonzera simba zvitatu zve antimony
| Antimony Trioxide | Antimony Acetate | Antimony Glycolate | |
| Zvivako Zvikuru | Inozivikanwa seye antimony chena, molecular formula Sb2O3, molecular weight 291.51, chena powder, melting point 656℃. Theorytical antimony content inenge 83.53%. Relative density 5.20g/ml. Inonyungudika mu concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, tartaric acid uye alkali solution, hainyungudike mumvura, alcohol, diluted sulfuric acid. | Fomura yeMolecular Sb(AC) 3, huremu hweMolecular 298.89, huwandu hweantimoni hwedzidziso hunosvika 40.74%, poindi yekunyunguduka 126-131℃, huwandu hwe1.22g/ml (25℃), upfu huchena kana husina kuchena, hunonyungudika nyore nyore mu ethylene glycol, toluene uye xylene. | Fomura yeMolecular Sb 2 (EG) 3, Huremu hweMolecular hunosvika 423.68, poindi yekunyunguduka iri ＞ 100℃ (Dec.), huwandu hweantimony hwedzidziso hunosvika 57.47%, chitarisiko chayo chakaita secrystalline chena, hachina chepfu uye hachina kunaka, chiri nyore kunyunguduka. Inonyungudika nyore nyore mu ethylene glycol. |
| Nzira yeKugadzira uye Tekinoroji | Yakagadzirwa zvakanyanya nenzira 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 3Cherechedza: Stibnite / Iron Ore / Limestone → Kupisa uye Kupisa Fuming → Kuunganidza | Indasitiri iyi inonyanya kushandisa nzira yeSb 2 O 3 -solvent yekugadzira:Sb2O3 ＋ 3 (CH3CO) 2O→ 2Sb(AC) 3Maitiro: kupisa reflux → kupisa kupisa → kucheneswa kwemvura → kucheneswa kwemvura → kuomesa kwevacuum → chigadzirwaCherechedza: Sb(AC) 3 inonyungudika nyore nyore, saka toluene kana xylene inoshandiswa inofanira kunge isina mvura, Sb 2 O 3 haigone kunge yakanyorova, uye michina yekugadzira inofanirawo kunge yakaoma. | Indasitiri iyi inonyanya kushandisa nzira yeSb 2 O 3 kugadzira:Sb 2 O 3 +3EG→Sb 2 (EG) 3 +3H 2 OMaitiro: Kudyisa (Sb 2 O 3, zvinowedzerwa uye EG) → kupisa nekumanikidza → kubvisa tsvina, tsvina nemvura → kubvisa ruvara → kupisa kunopisa → kutonhora nekuita makristaro → kupatsanurwa nekuomeswa → chigadzirwaCherechedza: Maitiro ekugadzira anofanirwa kuparadzaniswa nemvura kudzivirira hydrolysis. Kuita uku kunowanzo gadziriswa, uye kazhinji maitiro acho anokurudzirwa nekushandisa ethylene glycol yakawandisa nekubvisa mvura yechigadzirwa. |
| Zvakanakira | Mutengo wacho wakachipa, uri nyore kushandisa, une basa rekugadzirisa zvinhu zviri pakati nepakati uye nguva pfupi yekupisa zvinhu. | Antimony acetate ine kunyungudika kwakanaka mu ethylene glycol uye inopararira zvakaenzana mu ethylene glycol, izvo zvinogona kuvandudza mashandiro e antimony; Antimony acetate ine hunhu hwe catalytic activity yakanyanya, kuita kushoma kwekuora, kuramba kupisa zvakanaka uye kugadzikana kwekugadzirisa; Panguva imwe chete, kushandisa antimony acetate se catalyst hazvidi kuwedzerwa co-catalyst uye stabilizer. Maitiro e antimony acetate catalytic system haana kunyanya kusimba, uye mhando yechigadzirwa chacho yakanyanya kunaka, kunyanya ruvara, rwuri nani pane rwe antimony trioxide (Sb2O3) system. | Catalyst ine kunyungudika kwakanyanya mu ethylene glycol; zero-valent antimony inobviswa, uye tsvina dzakadai semamorekuru esimbi, machloride nemasulfates anokanganisa polycondensation inoderedzwa kusvika padanho rakaderera, zvichibvisa dambudziko re acetate ion corrosion pamidziyo; Sb 3+ mu Sb 2 (EG) 3 yakakwira zvakanyanya, izvo zvinogona kunge zvichikonzerwa nekuti kunyungudika kwayo mu ethylene glycol patembiricha ye reaction yakakura kupfuura iyo ye Sb 2 O 3 Zvichienzaniswa ne Sb(AC) 3, huwandu hwe Sb 3+ hunoita basa re catalytic hwakakura. Ruvara rwechigadzirwa che polyester chinogadzirwa ne Sb 2 (EG) 3 rwuri nani pane rwe Sb 2 O 3 Rwakakwira zvishoma pane rwepakutanga, zvichiita kuti chigadzirwa chitaridzike chakajeka uye chichena; |
| Kusagadzikana | Kunyungudika kwe ethylene glycol hakuna kunaka, 4.04% chete pa150°C. Mukuita, ethylene glycol yakawandisa kana kuti tembiricha yekunyungudika inowedzerwa kusvika pamusoro pe150°C. Zvisinei, kana Sb2O3 ikaita ne ethylene glycol kwenguva yakareba pamusoro pe120°C, mvura inogona kudonha kubva mu ethylene glycol antimony, uye Sb2O3 inogona kuderedzwa kuita simbi ladder mu polycondensation reaction, izvo zvinogona kukonzera "grey fog" mu polyester chips uye kukanganisa kunaka kwechigadzirwa. Chiitiko che polyvalent antimony oxides chinoitika panguva yekugadzirira Sb2O3, uye kuchena kwe antimony kunokanganisa. | Hunhu hweantimony mu catalyst hwakaderera; tsvina yeacetic acid yakaunza ngura mumidziyo, inosvibisa nharaunda, uye haikodzeri kurapwa kwemvura yakasviba; maitiro ekugadzira akaomarara, mamiriro ekushanda kwenzvimbo haana kunaka, kune kusvibiswa, uye chigadzirwa chiri nyore kuchinja ruvara. Zviri nyore kuora kana zvapiswa, uye zvigadzirwa zve hydrolysis ndezve Sb2O3 ne CH3COOH. Nguva yekugara kwezvinhu yakareba, kunyanya muchikamu chekupedzisira che polycondensation, icho chakakwira zvakanyanya kupfuura Sb2O3 system. | Kushandiswa kweSb 2 (EG) 3 kunowedzera mutengo we catalyst wemudziyo (kuwedzera kwemutengo kunogona kugadziriswa chete kana 25% yePET ikashandiswa kuzvitenderedza kwe filaments). Pamusoro pezvo, b kukosha kweruvara rwechigadzirwa kunowedzera zvishoma. |