Polyester (PET) faibha ndiyo yakakura siyana yesynthetic fiber. Mbatya dzakagadzirwa nepolyester fiber dzakagadzikana, dzakatsetseka, dziri nyore kugeza, uye dzinokurumidza kuoma. Polyester inoshandiswawo zvakanyanya sechinhu chakabikwa chekurongedza, tambo dzemaindasitiri, uye mainjiniya epurasitiki. Nekuda kweizvozvo, polyester yakasimukira nekukurumidza pasi rose, ichiwedzera paavhareji yegore re7% uye nekubuda kukuru.
Kugadzirwa kwepolyester kunogona kukamurwa kuita dimethyl terephthalate (DMT) nzira uye terephthalic acid (PTA) nzira maererano nemaitiro nzira uye inogona kukamurwa kuita inopindirana maitiro uye inoenderera maitiro maererano nekushanda. Kunyangwe nzira yekugadzira yakagamuchirwa, iyo polycondensation reaction inoda kushandiswa kwesimbi komisheni sezvinokonzeresa. Iyo polycondensation reaction inhanho yakakosha mukugadzirwa kwepolyester, uye nguva yepolycondensation ndiyo bhodhoro rekuvandudza goho. Kuvandudzwa kweiyo catalyst system chinhu chakakosha mukuvandudza kunaka kwepolyester uye kupfupisa nguva yepolycondensation.
UrbanMines Tech. Limited ikambani inotungamira yekuChina inoshanda muR&D, kugadzira, uye kupa polyester catalyst-giredhi antimony trioxide, antimony acetate, uye antimony glycol. Takaita tsvakiridzo yakadzama pamusoro pezvigadzirwa izvi-Dhipatimendi reR&D reUrbanMines rave kupfupisa kutsvagisa nekushandiswa kweantimony catalysts muchinyorwa chino kubatsira vatengi vedu kushandisa zviri nyore, kugadzirisa magadzirirwo ekugadzira, uye kupa kukwikwidza kwakadzama kwezvigadzirwa zvepolyester fiber.
Nyanzvi dzemudzimba nedzekunze dzinowanzotenda kuti polyester polycondensation iketani yekuwedzera maitiro, uye iyo catalytic mashandiro ndeye chelation coordination, iyo inoda iyo catalyst simbi atomu kuti ipe ma orbitals asina chinhu kuti aenderane nearc peya yema electrons ecarbonyl okisijeni kuzadzisa chinangwa catalysis. Zvepolycondensation, sezvo electron cloud density ye carbonyl oxygen muboka re hydroxyethyl ester yakadzikira, electronegativity yemaoni esimbi yakakwira zvakanyanya panguva yekubatana, kufambisa kurongeka uye kuwedzera cheni.
Izvi zvinotevera zvinogona kushandiswa se polyester catalysts: 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 uye mamwe masimbi oxides, alcoholates, carboxylates, borates, halides uye amines, ureas, guanidines, sulfur-containing organic compounds. Nekudaro, izvo zvinokonzeresa izvo zvino kushandiswa uye kudzidzwa mukugadzirwa kwemaindasitiri zvakanyanya Sb, Ge, uye Ti akatevedzana makomisheni. Nhamba huru yezvidzidzo zvakaratidza kuti: Ge-based catalysts ine zvishoma zvishoma zvinogadziriswa uye inobudisa PET yepamusoro, asi basa ravo harina kukwirira, uye vane zvishoma uye zvinodhura; Ti-based catalysts ine yakakwira chiitiko uye nekukurumidza kuita kukurumidza, asi maitiro avo anokonzeresa ari pachena, zvichikonzera kusagadzikana kwemafuta uye yero ruvara rwechigadzirwa, uye anogona kazhinji kushandiswa chete kubatanidzwa kwePBT, PTT, PCT, etc.; Sb-based catalysts haisi kungoshanda chete. Hunhu hwechigadzirwa hwakakwira nekuti Sb-based catalysts inoshanda zvakanyanya, ine mashoma emativi maitiro, uye yakachipa. Nokudaro, dzakashandiswa zvikuru. Pakati pavo, iyo inonyanya kushandiswa Sb-based catalysts ndeye antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), nezvimwewo.
Tichitarisa nhoroondo yebudiriro yeindasitiri yepolyester, tinogona kuona kuti inopfuura 90% yemiti yepolyester munyika inoshandisa antimony compounds sezvinokonzera. Pakazosvika gore ra2000, China yakanga yaunza zvirimwa zvepolyester zvakati wandei, zvese zvaishandisa mishonga yeantimony sezvinokonzeresa, zvikuru Sb2O3 neSb(CH3COO)3. Kuburikidza nekuedza kwakabatana kweChinese sainzi kutsvagisa, mayunivhesiti, uye madhipatimendi ekugadzira, izvi zviviri zvinokonzeresa zvave kugadzirwa zvizere mudzimba.
Kubva 1999, kambani yemakemikari yeFrance Elf yakatanga antimony glycol [Sb2 (OCH2CH2CO) 3] catalyst sechigadzirwa chakakwidziridzwa chezvinokonzeresa zvechinyakare. Iwo machipisi epolyester anogadzirwa ane kuchena kwakanyanya uye kunaka kutenderera, izvo zvakwezva kutarisisa kukuru kubva kudzimba dzinokurudzira tsvagiridzo masangano, mabhizinesi, uye vagadziri vepolyester muChina.
I. Tsvakurudzo uye kushandiswa kweantimony trioxide
United States ndiyo imwe yenyika dzekutanga kugadzira nekushandisa Sb2O3. Muna 1961, kushandiswa kweSb2O3 muUnited States kwakasvika 4,943 matani. Mumakore ekuma1970, makambani mashanu muJapan akagadzira Sb2O3 ine huwandu hwekugadzira huwandu hwematani 6,360 pagore.
MaChina makuru eSb2O3 ekutsvagisa nekusimudzira zvikamu anonyanya kutariswa mune aimbove mabhizinesi ehurumende muHunan Province neShanghai. UrbanMines Tech. Limited zvakare yakagadzira nyanzvi yekugadzira mutsara muHunan Province.
(I). Nzira yekugadzira antimony trioxide
Kugadzirwa kweSb2O3 kunowanzo shandisa antimony sulfide ore seyakabikwa. Metal antimony inotanga kugadzirirwa, uye ipapo Sb2O3 inogadzirwa uchishandisa antimony yesimbi seyakagadzirwa.
Pane nzira mbiri huru dzekugadzira Sb2O3 kubva kusimbi antimony: yakananga oxidation uye nitrogen decomposition.
1. Yakananga oxidation nzira
Metal antimony inopindirana neokisijeni pasi pekudziya kuita Sb2O3. The reaction process ndeiyi:
4Sb＋3O2＝＝2Sb2O3
2. Ammonolysis
Antimony metal inopindirana neklorini kuti igadzire antimony trichloride, iyo inobva yanyungudutswa, hydrolyzed, ammonolyzed, yakashambidzwa, uye yakaomeswa kuti iwane yakagadzirwa Sb2O3 chigadzirwa. The basic reaction equation ndeiyi:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Kushandisa antimony trioxide
Iko kushandiswa kukuru kweantimony trioxide senge inokonzeresa yepolymerase uye murazvo unodzora zvinhu zvekugadzira.
Muindasitiri yepolyester, Sb2O3 yakatanga kushandiswa sechinhu chinokonzeresa. Sb2O3 inonyanya kushandiswa se polycondensation catalyst yeDMT nzira uye yekutanga PTA nzira uye inowanzoshandiswa pamwe chete neH3PO4 kana ma enzymes ayo.
(III). Matambudziko ane antimony trioxide
Sb2O3 ine kunyungudika kwakashata mu ethylene glycol, ine solubility ye 4.04% chete pa 150°C. Naizvozvo, kana ethylene glycol inoshandiswa kugadzirira iyo catalyst, Sb2O3 ine urombo dispersibility, iyo inogona nyore kukonzera yakawandisa catalyst mu polymerization system, inogadzira yakakwirira-melting-point cyclic trimers, uye inounza matambudziko ekutenderera. Kuvandudza kunyungudika uye kupararira kweSb2O3 mu ethylene glycol, inowanzogamuchirwa kushandisa yakawandisa ethylene glycol kana kuwedzera tembiricha yekunyungudika kusvika pamusoro pe150 ° C. Zvisinei, pamusoro pe120 ° C, Sb2O3 uye ethylene glycol inogona kubudisa ethylene glycol antimony precipitation pavanenge vachiita pamwe chete kwenguva yakareba, uye Sb2O3 inogona kuderedzwa kuva antimony yesimbi mu polycondensation reaction, iyo inogona kukonzera "mhute" mu polyester chips uye kukanganisa. chigadzirwa chemhando.
II. Tsvagiridzo uye kushandiswa kweantimony acetate
Kugadzirira nzira ye antimony acetate
Pakutanga, antimony acetate yakagadzirwa nekuita antimony trioxide neacetic acid, uye acetic anhydride yakashandiswa semushonga wekudzikisa mvura kuti utore mvura inogadzirwa nemhinduro. Unhu hwechigadzirwa chakapedzwa chakawanikwa nenzira iyi hwakanga husina kukwirira, uye zvakatora maawa anopfuura makumi matatu kuti antimony trioxide iparare muacetic acid. Gare gare, antimony acetate yakagadzirwa nekuita antimony yesimbi, antimony trichloride, kana antimony trioxide ine acetic anhydride, pasina kudiwa kweanopedza mvura.
1. Antimony trichloride nzira
Muna 1947, H. Schmidt et al. muWest Germany yakagadzirira Sb(CH3COO)3 nekuita SbCl3 neacetic anhydride. Iyo reaction formula ndeyotevera:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Antimony simbi nzira
Muna 1954, TAPaybea yeyaimbova Soviet Union yakagadzira Sb(CH3COO)3 nekuita metallic antimony uye peroxyacetyl mumushonga webenzene. Iyo reaction formula ndeye:
Sb(CH3COO)2==Sb(CH3COO)3
3. Antimony trioxide nzira
Muna 1957, F. Nerdel wekuWest Germany akashandisa Sb2O3 kuita neacetic anhydride kugadzira Sb(CH3COO)3.
Sb2O3＋3(CH3CO)2O(2O)(2Sb(CH3COO)3
Izvo zvakashata zveiyi nzira ndezvekuti makristasi anowanzo kuunganidza muzvidimbu zvakakura uye anonamatira zvakasimba kumadziro emukati eiyo reactor, zvichikonzera hurombo hwechigadzirwa kunaka uye ruvara.
4. Antimony trioxide solvent nzira
Kuti ukunde kukanganisa kweiyo nzira iri pamusoro, inogadziriswa inogadziriswa inowanzowedzerwa panguva yekuita kweSb2O3 uye acetic anhydride. Iyo chaiyo nzira yekugadzirira ndeyotevera:
(1) Muna 1968, R. Thoms weAmerican Mosun Chemical Company yakabudisa patent pamusoro pekugadzirwa kweantimony acetate. Patent yakashandisa xylene (o-, m-, p-xylene, kana musanganiswa wayo) sechinhu chisina kwacho chinonyungudutsa kugadzira makristasi akanaka eantimony acetate.
(2) Muna 1973, Czech Republic yakagadzira nzira yekugadzira yakanaka antimony acetate vachishandisa toluene sechinhu chinonyungudutsa.
III. Kuenzanisa matatu antimony-based catalysts
| Antimony Trioxide | Antimony Acetate | Antimony Glycolate | |
| Basic Properties | Inowanzozivikanwa se antimony white, molecular formula Sb 2 O 3, molecular weight 291.51, white powder, melting point 656 ℃. Theoretical antimony content inosvika 83.53 %. Hukama density 5.20g/ml. Soluble in concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, tartaric acid uye alkali solution, isinganyunguriki mumvura, doro, dilute sulfuric acid. | Molecular formula Sb(AC) 3, molecular weight 298.89, theoretical antimony content about 40.74%, melting point 126-131℃, density 1.22g/ml (25℃), white or off-white powder, inonyungudika zviri nyore muethyleneglycol. uye xylene. | Molecular formula Sb 2 (EG) 3, Huremu hwema molecular huremu hunosvika 423.68, panonyungudika ＞ 100℃(dec.), theoretical antimony content inenge 57.47%, chitarisiko chakachena crystalline yakasimba, isina chepfu uye isina kunaka, nyore kutora unyoro. Inonyungudika nyore mu ethylene glycol. |
| Synthesis Method uye Technology | Inonyanyogadzirwa nenzira yestibnite: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 / Lime Iron Ore Kupisa uye Kupfuta → Kuunganidza | Indasitiri inonyanya kushandisa nzira yeSb 2 O 3 -solvent ye synthesis:Sb2O3 ＋ 3 ( CH3CO ) 2O→ 2Sb(AC) 3Maitiro: kudziyisa reflux → kupisa kusefa → crystallization → vacuum drying → chigadzirwaCherechedza: Sb(AC) 3 is iri nyore hydrolyzed, saka iyo isina kwayakarerekera solvent toluene kana xylene inoshandiswa inofanira kunge iine anhydrous, Sb 2 O 3 haigone kunge iri mukunyorova, uye michina yekugadzira inofanirawo kunge yakaoma. | Indasitiri inonyanya kushandisa nzira yeSb 2 O 3 kugadzira:Sb 2 O 3 +3EG→Sb 2 (EG) 3 +3H 2 OProcess: Kudyisa (Sb 2 O 3 , additives uye EG) → kudziyisa nekumanikidza kuita → kubvisa slag , tsvina nemvura → decolorization → kupisa kusefa → kutonhora uye crystallization → kupatsanura nekuomesa → chigadzirwaCherechedza: Maitiro ekugadzira anoda kuparadzaniswa nemvura kudzivirira hydrolysis. Kuita uku kudzokororwa, uye kazhinji maitiro anosimudzirwa nekushandisa yakawandisa ethylene glycol uye kubvisa chigadzirwa mvura. |
| Advantage | Mutengo wacho wakachipa, uri nyore kushandisa, une mwero catalytic chiitiko uye ipfupi polycondensation nguva. | Antimony acetate ine yakanaka solubility mu ethylene glycol uye yakaparadzirwa zvakaenzana mu ethylene glycol, iyo inogona kuvandudza kushandiswa kweantimony; Antimony acetate ine maitiro epamusoro-catalytic chiitiko, kuderera kuderera kwekuita, kunaka kwekupisa uye kugadzikana kwekugadzirisa; Panguva imwecheteyo, kushandisa antimony acetate sechinhu chinokonzera hazvidi kuwedzera kwe-co-catalyst uye stabilizer. Maitiro e antimony acetate catalytic system ane unyoro, uye mhando yechigadzirwa yakakwirira, kunyanya ruvara, iyo iri nani pane iyo antimony trioxide (Sb 2 O 3) system. | Iyo catalyst ine yakanyanya solubility mu ethylene glycol; zero-valent antimony inobviswa, uye tsvina yakaita sesimbi molecules, chlorides uye sulfates inokanganisa polycondensation inoderedzwa kusvika yakaderera, kubvisa dambudziko reacetate ion corrosion pamichina;Sb 3+ muSb 2 (EG) 3 yakakwirira kwazvo. , iyo inogona kunge iri nokuti kunyungudika kwayo mu ethylene glycol pakupisa kwekuita kwakakura kudarika kweSb 2 O 3 Kuenzaniswa neSb (AC) 3, huwandu hweSb 3+ hunoita basa rekugadzirisa hukuru. Rudzi rwechigadzirwa chepolyester chinogadzirwa neSb 2 (EG) 3 chiri nani kupfuura cheSb 2 O 3 Chinokwira zvishoma kudarika chepakutanga, zvichiita kuti chigadzirwa chive chakajeka uye chichena; |
| Kukanganisa | Solubility mu ethylene glycol yakashata, chete 4.04% pa 150 ° C. Mukuita, ethylene glycol yakanyanyisa kana kupisa kwekuparara kunowedzera kusvika pamusoro pe150 ° C. Zvisinei, apo Sb 2 O 3 inopindirana ne ethylene glycol kwenguva yakareba iri pamusoro pe 120 ° C, ethylene glycol antimony precipitation inogona kuitika, uye Sb 2 O 3 inogona kuderedzwa kusvika kumatare ematare mu polycondensation reaction, iyo inogona kukonzera "grey fog. " mumachipisi epolyester uye anokanganisa kunaka kwechigadzirwa. Chiitiko chepolyvalent antimony oxides chinoitika panguva yekugadzirira Sb 2 O 3, uye kuchena kunobudirira kweantimony kunokanganisa. | Iyo antimony yemukati yecatalyst yakaderera; iyo acetic acid tsvina yakaunza corrode midziyo, inosvibisa nharaunda, uye haikodzeri kuchenesa mvura; nzira yekugadzira yakaoma, mamiriro ekunze ekushanda haana kunaka, kune kusvibiswa, uye chigadzirwa chiri nyore kuchinja ruvara. Zviri nyore kuora kana kupisa, uye zvigadzirwa zve hydrolysis ndeye Sb2O3 uye CH3COOH. Nguva yekugara yezvinhu yakareba, kunyanya muchikamu chekupedzisira chepolycondensation, iyo yakanyanya kukwirira kupfuura iyo Sb2O3 system. | Kushandiswa kweSb 2 (EG) 3 kunowedzera mari inokonzera chigadziro (kuwedzerwa kwemari kunogona kugadziriswa chete kana 25% yePET inoshandiswa pakuzvitsvaga kwefilaments). Mukuwedzera, iyo b kukosha kwechigadzirwa hue inowedzera zvishoma. |