ʻO ka fiber polyester (PET) ka nui loa o ka fiber synthetic. ʻO nā lole i hana ʻia me ka fiber polyester he ʻoluʻolu, ʻoluʻolu, maʻalahi e holoi, a wikiwiki hoʻi e maloʻo. Hoʻohana nui ʻia ka polyester ma ke ʻano he mea maka no ka hoʻopili ʻana, nā wili ʻoihana, a me nā plastic engineering. ʻO ka hopena, ua ulu wikiwiki ka polyester ma ka honua holoʻokoʻa, e hoʻonui ana i ka awelika makahiki o 7% a me ka puka nui.
Hiki ke hoʻokaʻawale ʻia ka hana polyester i ke ala dimethyl terephthalate (DMT) a me ka terephthalic acid (PTA) ala e pili ana i ke ala kaʻina hana a hiki ke hoʻokaʻawale ʻia i ke kaʻina intermittent a me ke kaʻina hana mau e pili ana i ka hana. Ma waho o ke ala kaʻina hana i hoʻohana ʻia, pono ka hopena polycondensation i ka hoʻohana ʻana i nā pūhui metala ma ke ʻano he catalysts. ʻO ka hopena polycondensation kahi hana nui i ke kaʻina hana polyester, a ʻo ka manawa polycondensation ka bottleneck no ka hoʻomaikaʻi ʻana i ka hua. ʻO ka hoʻomaikaʻi ʻana i ka ʻōnaehana catalyst kahi mea nui i ka hoʻomaikaʻi ʻana i ka maikaʻi o ka polyester a me ka pōkole o ka manawa polycondensation.
ʻenehana UrbanMines. ʻO Limited kahi hui Kina koʻikoʻi i ka R&D, hana, a me ka hoʻolako ʻana i ka polyester catalyst-grade antimony trioxide, antimony acetate, a me ka antimony glycol. Ua hana mākou i ka noiʻi hohonu e pili ana i kēia mau huahana—ua hōʻuluʻulu ke keʻena R&D o UrbanMines i ka noiʻi a me ka hoʻohana ʻana i nā catalysts antimony i kēia ʻatikala e kōkua i kā mākou mea kūʻai aku e hoʻopili maʻalahi, hoʻomaikaʻi i nā kaʻina hana, a hāʻawi i ka hoʻokūkū piha o nā huahana polyester fiber.
Manaʻo ka poʻe ʻepekema kūloko a me nā haole ʻo ka polyester polycondensation kahi hopena hoʻonui kaulahao, a ʻo ke ʻano catalytic no ka chelation coordination, kahi e koi ai i ka catalyst metal atom e hāʻawi i nā orbitals ʻole e hoʻohui me nā arc o nā electrons o carbonyl oxygen e hoʻokō i ke kumu o hoʻopalekana. No ka polycondensation, no ka mea he haʻahaʻa loa ke ʻano o ke ao electron o carbonyl oxygen i loko o ka pūʻulu hydroxyethyl ester, ʻoi aku ka kiʻekiʻe o ka electronegativity o nā ion metala i ka wā hoʻohui, e hoʻomaʻamaʻa i ka hoʻohui ʻana a me ka hoʻonui ʻana i ke kaulahao.
Hiki ke hoʻohana ʻia kēia mau mea ma ke ʻano he 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 a me na mea e ae metala, alcoholates, carboxylates, borates, halides and amines, ureas, guanidines, sulfur-containing organic compounds. Eia nō naʻe, ʻo nā catalysts i hoʻohana ʻia a aʻo ʻia i ka hana ʻoihana ʻo ia ka nui o nā pūhui Sb, Ge, a me Ti. Ua hōʻike ʻia ka helu nui o nā haʻawina: He liʻiliʻi nā hopena ʻaoʻao o Ge-based a hoʻopuka i ka PET kiʻekiʻe, akā ʻaʻole kiʻekiʻe kā lākou hana, a he liʻiliʻi kā lākou waiwai a he pipiʻi; He kiʻekiʻe ka hana a me ka wikiwiki o ka hopena o nā catalysts, akā ʻoi aku ka maopopo o kā lākou catalytic ʻaoʻao, ka hopena i ka maikaʻi ʻole o ka wela a me ka kala melemele o ka huahana, a hiki ke hoʻohana wale ʻia no ka synthesis o PBT, PTT, PCT, etc.; ʻAʻole ʻoi aku ka ikaika o nā catalysts ma muli o Sb. He kiʻekiʻe ka maikaʻi o ka huahana no ka mea ʻoi aku ka ikaika o nā catalysts-based Sb, liʻiliʻi nā hopena ʻaoʻao, a ʻoi aku ka liʻiliʻi. No laila, ua hoʻohana nui ʻia lākou. Ma waena o lākou, ʻo ka mea hoʻohana maʻamau Sb-based catalysts he antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), etc.
Ke nānā nei i ka mōʻaukala hoʻomohala o ka ʻoihana polyester, hiki iā mākou ke ʻike ma mua o 90% o nā mea kanu polyester i ka honua e hoʻohana i nā pūhui antimony e like me nā catalysts. Ma ka makahiki 2000, ua hoʻolauna ʻo Kina i kekahi mau mea kanu polyester, ua hoʻohana lākou a pau i nā pūhui antimony ma ke ʻano he catalysts, ʻo ia hoʻi ʻo Sb2O3 a me Sb(CH3COO)3. Ma o ka hui pū ʻana o ka noiʻi ʻepekema Kina, nā kulanui, a me nā keʻena hana, ua hoʻopuka piha ʻia kēia mau catalysts ʻelua ma ka home.
Mai ka makahiki 1999, ua hoʻokumu ʻo Elf hui kemika Palani i kahi catalyst antimony glycol [Sb2 (OCH2CH2CO) 3] ma ke ʻano he huahana hoʻomaikaʻi o nā catalysts kuʻuna. He keʻokeʻo kiʻekiʻe a me ka spinnability maikaʻi nā pahu polyester i hana ʻia, ka mea i huki nui ʻia mai nā hale noiʻi catalyst home, nā ʻoihana, a me nā mea hana polyester ma Kina.
I. Ka noiʻi a me ka hoʻohana ʻana i ka antimony trioxide
ʻO ʻAmelika Hui Pū ʻIa kekahi o nā ʻāina mua loa i hana a hoʻohana iā Sb2O3. I ka makahiki 1961, hiki i ka 4,943 tons ka hoʻohana ʻana o Sb2O3 ma ʻAmelika Hui Pū ʻIa. I nā makahiki 1970, ʻelima mau hui ma Iapana i hoʻopuka i ka Sb2O3 me ka nui o ka mana hana o 6,360 tons i kēlā me kēia makahiki.
ʻO nā ʻāpana noiʻi a me ka hoʻomohala ʻana o Sb2O3 koʻikoʻi o Kina ka mea nui i nā ʻoihana aupuni mua ma Hunan Province a me Shanghai. ʻenehana UrbanMines. Ua hoʻokumu pū ʻo Limited i kahi laina hana ʻoihana ma Hunan Province.
(I). Ke ala no ka hana ʻana i ka antimony trioxide
Hoʻohana maʻamau ka hana ʻana o Sb2O3 i ka antimony sulfide ore ma ke ʻano he mea maka. Hoʻomākaukau mua ʻia ka antimony metala, a laila hana ʻia ʻo Sb2O3 me ka hoʻohana ʻana i ka antimony metala ma ke ʻano he mea maka.
ʻElua mau ala nui no ka hana ʻana i ka Sb2O3 mai ka antimony metala: ka hoʻokahe pololei a me ka decomposition nitrogen.
1. Keʻano hoʻokahe pololei
Hoʻopili ka antimony metala me ka oxygen ma lalo o ka hoʻomehana ʻana e hana i ka Sb2O3. Penei ke kaʻina hana.
4Sb＋3O2＝＝2Sb2O3
2. Ammonolysis
Hoʻopili ka metala Antimony me ka chlorine e synthesize antimony trichloride, a laila hoʻoheheʻe ʻia, hydrolyzed, ammonolyzed, holoi ʻia, a maloʻo no ka loaʻa ʻana o ka huahana Sb2O3. ʻO ka hoʻohālikelike hoʻohālikelike kumu:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Hoʻohana i ka antimony trioxide
ʻO ka hoʻohana nui ʻana o ka antimony trioxide ma ke ʻano he catalyst no ka polymerase a me ka pale ahi no nā mea synthetic.
I ka ʻoihana polyester, ua hoʻohana mua ʻia ʻo Sb2O3 ma ke ʻano he catalyst. Hoʻohana nui ʻia ʻo Sb2O3 ma ke ʻano he polycondensation catalyst no ke ala DMT a me ke ala PTA mua a hoʻohana pinepine ʻia me ka H3PO4 a i ʻole kāna mau enzymes.
(III). Nā pilikia me ka antimony trioxide
He haʻahaʻa ko Sb2O3 i ka ethylene glycol, me ka solubility o 4.04% wale nō ma 150°C. No laila, ke hoʻohana ʻia ka ethylene glycol no ka hoʻomākaukau ʻana i ka mea hoʻoheheʻe, ʻo Sb2O3 ʻino ka dispersibility, hiki ke hana maʻalahi i ka catalyst kiʻekiʻe i ka ʻōnaehana polymerization, hoʻohua i nā trimers cyclic kiʻekiʻe heheʻe, a lawe mai i nā pilikia i ka wili. No ka hoʻomaikaʻi ʻana i ka solubility a me ka hoʻopuehu ʻana o Sb2O3 i loko o ka ethylene glycol, hoʻohana maʻamau ia e hoʻohana i ka ethylene glycol kiʻekiʻe a i ʻole e hoʻonui i ka wela hoʻoheheʻe ʻana ma luna o 150°C. Eia nō naʻe, ma luna o 120°C, hiki i ka Sb2O3 a me ka ethylene glycol ke hana i ka ethylene glycol antimony precipitation ke hana like lākou no ka manawa lōʻihi, a hiki ke hoʻemi ʻia ʻo Sb2O3 i ka antimony metallic i ka hopena polycondensation, hiki ke hoʻoulu i ka "fog" i nā ʻāpana polyester a pili. maikaʻi huahana.
II. Ka noiʻi a me ka hoʻohana ʻana i ka antimony acetate
ʻO ke ʻano hoʻomākaukau o ka antimony acetate
I ka wā mua, ua hoʻomākaukau ʻia ka antimony acetate ma ka hana ʻana i ka antimony trioxide me ka acetic acid, a ua hoʻohana ʻia ka anhydride acetic ma ke ʻano he mea hoʻoheheʻe wai e hoʻomoʻa i ka wai i hana ʻia e ka hopena. ʻAʻole kiʻekiʻe ka maikaʻi o ka huahana i hoʻopau ʻia ma kēia ʻano, a ʻoi aku ma mua o 30 mau hola no ka antimony trioxide e hoʻoheheʻe i ka acetic acid. Ma hope mai, ua hoʻomākaukau ʻia ka antimony acetate ma ka hana ʻana i ka antimony metala, antimony trichloride, a i ʻole antimony trioxide me ka acetic anhydride, me ka ʻole o kahi mea hoʻoheheʻe wai.
1. Antimony trichloride ala
I ka makahiki 1947, H. Schmidt et al. ma Kelemānia Komohana i hoʻomākaukau iā Sb(CH3COO)3 ma ka hana ʻana iā SbCl3 me ka acetic anhydride. Penei ke ano o ka pane.
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Keʻano metala Antimony
I ka makahiki 1954, ua hoʻomākaukau ʻo TAPaybea o ka Soviet Union mua iā Sb(CH3COO)3 ma ka hana ʻana i ka antimony metala a me ka peroxyacetyl i loko o kahi solution benzene. ʻO ke kumu hoʻohālikelike:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Antimony trioxide ala
I ka makahiki 1957, ua hoʻohana ʻo F. Nerdel o Kelemānia Komohana iā Sb2O3 e hana me ka acetic anhydride e hana ai i ka Sb(CH3COO)3.
Sb2O3＋3（CH3CO）2O＝＝2Sb（CH3COO）3
ʻO ka hemahema o kēia ʻano hana, ʻo ia ka mea e hōʻuluʻulu ʻia nā kristal i loko o nā ʻāpana nui a paʻa paʻa i ka paia o loko o ka reactor, e hopena i ka maikaʻi o ka huahana a me ke kala.
4. Anatimony trioxide solvent ala
No ka lanakila ʻana i nā hemahema o ke ʻano i luna, hoʻohui pinepine ʻia kahi solvent kūʻokoʻa i ka wā o ka hopena o Sb2O3 a me ka acetic anhydride. ʻO ke ʻano hoʻomākaukau kūikawā penei:
(1) I ka makahiki 1968, ua paʻi ʻo R. Thoms o ka American Mosun Chemical Company i kahi patent no ka hoʻomākaukau ʻana i ka antimony acetate. Ua hoʻohana ka patent i ka xylene (o-, m-, p-xylene, a i ʻole ka hui ʻana o ia mea) ma ke ʻano he mea hoʻoheheʻe kūʻokoʻa e hana i nā kristal maikaʻi o ka antimony acetate.
(2) I ka makahiki 1973, ua hana ʻo Czech Republic i kahi ala no ka hana ʻana i ka acetate antimony maikaʻi me ka hoʻohana ʻana i ka toluene ma ke ʻano he solvent.
III. Hoʻohālikelike o ʻekolu mau mea hoʻoheheʻe antimony
| Antimony Trioxide | Antimony Acetate | Antimony Glycolate | |
| Na Waiwai Kumu | ʻIke maʻamau ʻo antimony white, molecular formula Sb 2 O 3 , molecular weight 291.51 , keʻokeʻo pauda, melting point 656℃ . ʻO ka manaʻo antimony ma kahi o 83.53%. 5.20g/ml . Hiki ke hoʻoheheʻe ʻia i loko o ka waikawa hydrochloric concentrated, concentrated sulfuric acid, concentrated nitric acid, tartaric acid and alkali solution, insoluble in water, alcohol, dilute sulfuric acid. | Molecular formula Sb(AC) 3 , molecular kaumaha 298.89 , theoretical antimony content e pili ana i 40.74 %, melting point 126-131 ℃ , density 1.22g/ml (25 ℃), keʻokeʻo a i ʻole keʻokeʻo pauka, hiki ke hoʻoheheʻe ʻia i ka ethylene glycol, toluene. a me ka xylene. | ʻO ka molecular formula Sb 2 (EG) 3, ʻO ke kaumaha o ka molekala e pili ana i 423.68, ʻo ka helu hoʻoheheʻe he ＞ 100 ℃ (dec.), ʻo ka manaʻo antimony ma kahi o 57.47%, ʻo ke ʻano he keʻokeʻo keʻokeʻo keʻokeʻo, ʻaʻohe mea ʻawaʻawa a me ka ʻono, maʻalahi e komo i ka maʻamau. Hiki ke hoʻoheheʻe ʻia i ka ethylene glycol. |
| Hana Hana a me ʻenehana | Hoʻohui nui ʻia e ke ʻano 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 3Note: Stibnite / Iron Ore / Limestone ʻO ka hoʻomehana a me ka puhi ʻana → Ohi | Hoʻohana nui ka ʻoihana i ke ʻano Sb 2 O 3 -solvent no ka synthesis: Sb2O3 ＋ 3 ( CH3CO ) 2O→ 2Sb(AC) 3 Kaʻina: reflux wela → kānana wela → crystallization → maloʻo maloʻo → huahanaNote: Sb(AC) 3 maʻalahi ka hydrolyzed, no laila, ʻo ka toluene a i ʻole xylene solvent i hoʻohana ʻia he anhydrous, ʻaʻole hiki i ka Sb 2 O 3 ke maloʻo, a pono e maloʻo nā lako hana. | Hoʻohana nui ka ʻoihana i ke ʻano Sb 2 O 3 e synthesize: Sb 2 O 3 + 3EG → Sb 2 (EG) 3 + 3H 2 OKe kaʻina hana: hānai (Sb 2 O 3, additives a me EG) → hoʻomehana a me ka hoʻoulu ʻana → wehe i ka slag. , haumia a me ka wai → decolorization → kānana wela → hoʻoluʻu a me ka crystallization → hoʻokaʻawale a maloʻo → huahanaNote: Pono ke kaʻina hana e hoʻokaʻawale i ka wai e pale i ka hydrolysis. He hopena hiki ke hoʻohuli ʻia kēia pane, a ma ke ʻano maʻamau, hoʻonui ʻia ka hopena ma o ka hoʻohana ʻana i ka ethylene glycol a me ka wehe ʻana i ka wai huahana. |
| Pōmaikaʻi | He maʻalahi ke kumukūʻai, maʻalahi ka hoʻohana ʻana, loaʻa ka hana catalytic haʻahaʻa a me ka manawa polycondensation pōkole. | ʻO ka Antimony acetate ka mea hiki ke hoʻoheheʻe maikaʻi ʻia i ka ethylene glycol a ua hoʻopuehu ʻia i ka ethylene glycol, hiki ke hoʻomaikaʻi i ka hoʻohana ʻana o ka antimony; I ka manawa like, ʻo ka hoʻohana ʻana i ka antimony acetate ma ke ʻano he catalyst ʻaʻole pono e hoʻohui i kahi co-catalyst a me kahi stabilizer. ʻO ka hopena o ka'ōnaehana catalytic antimony acetate he mea maʻalahi, a he kiʻekiʻe ka maikaʻi o ka huahana,ʻoi aku ka maikaʻi o ke kala,ʻoi aku ka maikaʻi ma mua o ka pūnaewele antimony trioxide (Sb 2 O 3). | He kiʻekiʻe ka solubility o ka catalyst i ka ethylene glycol; Hoʻopau ʻia ka antimony zero-valent, a hoʻemi ʻia nā mea haumia e like me nā molekole hao, chlorides a me nā sulfate e pili ana i ka polycondensation i kahi haʻahaʻa loa, e hoʻopau ana i ka pilikia o ka acetate ion corrosion ma nā mea hana; Sb 3+ i Sb 2 (EG) 3 he kiʻekiʻe. , no ka mea, ua oi aku ka nui o kona solubility i loko o ka ethylene glycol ma ka wela o ka hopena ma mua o ko Sb 2 O 3 I ka hoohalikeia me Sb(AC) 3, ua oi aku ka nui o ka Sb 3+ e hana ana i ka hana catalytic. ʻOi aku ka maikaʻi o ka waihoʻoluʻu o ka huahana polyester i hana ʻia e Sb 2 (EG) 3 ma mua o ka Sb 2 O 3 ʻoi aku ka kiʻekiʻe ma mua o ka mea kumu, e ʻoi aku ka nani a me ke keʻokeʻo o ka huahana; |
| Ka pōʻino | He ʻilihune ka solubility i ka ethylene glycol, he 4.04% wale nō ma 150°C. I ka hoʻomaʻamaʻa, ʻoi aku ka nui o ka ethylene glycol a i ʻole ke hoʻonui ʻia ka mahana hoʻoheheʻe ma luna o 150°C. Eia nō naʻe, ke hana ʻia ʻo Sb 2 O 3 me ka ethylene glycol no ka manawa lōʻihi ma luna o 120°C, hiki mai ka ethylene glycol antimony precipitation, a hiki ke hoʻemi ʻia ʻo Sb 2O 3 i alapiʻi metala i ka hopena polycondensation, hiki ke hoʻoulu i ka "poe hina. " i nā ʻāpana polyester a pili i ka maikaʻi o ka huahana. ʻO ke ʻano o ka polyvalent antimony oxides i ka wā o ka hoʻomākaukau ʻana o Sb 2 O 3, a pili ka maʻemaʻe o ka antimony. | He haʻahaʻa ka ʻike antimony o ka catalyst; ʻO nā mea haumia acetic acid i hoʻokomo i nā mea ʻino, hoʻohaumia i ke kaiapuni, a ʻaʻole kūpono i ka mālama ʻana i ka wai ʻino; paʻakikī ke kaʻina hana, ʻilihune nā kūlana o ka hana, aia ka pollution, a maʻalahi ka huahana e hoʻololi i ke kala. He maʻalahi ke hoʻoheheʻe i ka wā i wela ai, a ʻo nā huahana hydrolysis ʻo Sb2O3 a me CH3COOH. He lōʻihi ka manawa noho, ʻoi aku ka nui ma ka pae polycondensation hope, ʻoi aku ka kiʻekiʻe ma mua o ka ʻōnaehana Sb2O3. | ʻO ka hoʻohana ʻana iā Sb 2 (EG) 3 e hoʻonui i ke kumukūʻai catalyst o ka mīkini (hiki ke hoʻonui ʻia ke kumukūʻai inā hoʻohana ʻia ka 25% o PET no ka wili ponoʻī o nā filament). Eia kekahi, piʻi iki ka waiwai b o ka hue huahana. |