Polyester (PET) eriri bụ nke kasị ukwuu ụdị sịntetik eriri. Uwe e ji eriri polyester mee na-adị mma, na-egbuke egbuke, dị mfe ịsacha, na-adị ngwa ịkpọ nkụ. A na-ejikwa polyester n'ọtụtụ ebe dị ka akụrụngwa maka nkwakọ ngwaahịa, yarn ụlọ ọrụ, na plastik injinịa. N'ihi ya, polyester etolitela ngwa ngwa n'ụwa nile, na-abawanye na nkezi ọnụego kwa afọ nke 7% yana nnukwu mmepụta.
Enwere ike kewaa mmepụta polyester n'ime ụzọ dimethyl terephthalate (DMT) na ụzọ terephthalic acid (PTA) na usoro nke usoro usoro ma nwee ike kewaa n'ime usoro nkwụsịtụ na usoro na-aga n'ihu na usoro ọrụ. N'agbanyeghị ụzọ usoro mmepụta ihe a nakweere, mmeghachi omume polycondensation chọrọ iji ogige ígwè dị ka ihe na-akpali akpali. Mmeghachi omume polycondensation bụ isi ihe dị mkpa na usoro mmepụta polyester, na oge condensation bụ ihe mgbochi maka imeziwanye mkpụrụ. Ọganihu nke usoro ihe na-akpata bụ ihe dị mkpa na-eme ka mma nke polyester dị mma ma na-ebelata oge polycondensation.
Ụlọ ọrụ UrbanMines Tech. Limited bụ ụlọ ọrụ China na-eduga ọkachamara na R&D, mmepụta na ọkọnọ nke polyester catalyst-grade antimony trioxide, antimony acetate, na antimony glycol. Anyị emeela nyocha miri emi na ngwaahịa ndị a - ngalaba R&D nke UrbanMines ugbu a na-achikota nyocha na ngwa nke antimony catalysts n'isiokwu a iji nyere ndị ahịa anyị aka itinye mgbanwe n'ọrụ, kwalite usoro mmepụta, ma nye asọmpi zuru oke nke ngwaahịa polyester fiber.
Ndị ọkà mmụta ụlọ na ndị si mba ọzọ kwenyere n'ozuzu na polyester polycondensation bụ mmeghachi omume ndọtị agbụ, na usoro catalytic bụ nke nhazi chelation, nke chọrọ ka atom metal catalyst na-enye orbitals efu iji jikọta ya na arc ụzọ nke electrons nke carbonyl oxygen iji mezuo ebumnuche nke catalysis. Maka polycondensation, ebe njupụta igwe ojii nke carbonyl oxygen na hydroxyethyl ester otu dị ntakịrị, electronegativity nke ion metal dị oke elu n'oge nhazi, iji kwado nhazi na ndọtị agbụ.
Enwere ike iji ihe ndị a dị ka ihe ndị na-emepụta 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 na ndị ọzọ metal oxides, alcoholates, carboxylates, borates, halides na amines, ureas, guanidines, sọlfọ-nwere organic ogige. Otú ọ dị, ihe na-akpali akpali nke a na-eji ugbu a ma na-amụ na mmepụta mmepụta ihe bụ nke kachasị Sb, Ge, na Ti series compounds. Ọnụ ọgụgụ dị ukwuu nke ọmụmụ egosila na: Ge-based catalysts nwere ntakịrị mmeghachi omume n'akụkụ ma na-emepụta PET dị elu, ma ọrụ ha adịghị elu, na ha nwere ihe onwunwe ole na ole ma dị oke ọnụ; Ti-based catalysts nwere elu ọrụ na ngwa ngwa mmeghachi omume ọsọ, ma ha catalytic akụkụ mmeghachi omume bụ ihe doro anya, na-akpata na-adịghị mma thermal kwụsie ike na-acha odo odo na agba nke ngwaahịa, na ha nwere ike n'ozuzu naanị ga-eji maka njikọ nke PBT, PTT, PCT, wdg; Ihe na-eme ka Sb na-eme ka ọ bụghị naanị na-arụ ọrụ. Ogo ngwaahịa a dị elu n'ihi na ihe ndị na-eme ka Sb na-arụ ọrụ na-arụsi ọrụ ike, na-enwe mmeghachi omume n'akụkụ ole na ole, ma dị ọnụ ala. Ya mere, a na-eji ha eme ihe n'ọtụtụ ebe. N'ime ha, ihe ndị na-eme ka Sb na-ejikarị eme ihe bụ antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), wdg.
N'ileghachi anya na akụkọ mmepe nke ụlọ ọrụ polyester, anyị nwere ike ịhụ na ihe karịrị 90% nke osisi polyester dị n'ụwa na-eji ogige antimony eme ihe dị ka ihe na-akpali akpali. Ka ọ na-erule afọ 2000, China ewebatala ọtụtụ osisi polyester, ha niile na-eji ogige antimony dị ka ihe na-akpali akpali, ọkachasị Sb2O3 na Sb(CH3COO)3. Site na njikọ aka nke nyocha sayensị ndị China, mahadum, na ngalaba mmepụta ihe, emepụtala ihe abụọ a na-akpata ugbu a n'ụzọ zuru oke n'ụlọ.
Kemgbe 1999, ụlọ ọrụ kemịkalụ France bụ Elf ewepụtala antimony glycol [Sb2 (OCH2CH2CO) 3] katalyt dị ka ngwaahịa emelitere nke ihe mkpali ọdịnala. Mpempe akwụkwọ polyester emepụtara nwere nnukwu ọcha yana ezigbo spinnability, bụ nke dọtara mmasị dị ukwuu site na ụlọ ọrụ nyocha nke ụlọ, ụlọ ọrụ, na ndị na-emepụta polyester na China.
I. Nchọpụta na ntinye nke antimony trioxide
United States bụ otu n'ime mba izizi imepụta na itinye Sb2O3. Na 1961, oriri nke Sb2O3 na United States ruru 4,943 tọn. N'afọ ndị 1970, ụlọ ọrụ ise na Japan na-emepụta Sb2O3 nwere ikike mmepụta nke 6,360 tọn kwa afọ.
Ngalaba nyocha na mmepe nke Sb2O3 nke China bụ nke etinyere na ụlọ ọrụ gọọmentị mbụ nwere na Hunan Province na Shanghai. Ụlọ ọrụ UrbanMines Tech. Limited nwekwara guzobe a ọkachamara mmepụta ahịrị na Hunan Province.
(M). Usoro maka imepụta antimony trioxide
Nrụpụta nke Sb2O3 na-ejikarị antimony sulfide ore dị ka akụrụngwa. A na-ebu ụzọ kwadebe antimony metal, wee mepụta Sb2O3 site na iji antimony metal dị ka akụrụngwa.
Enwere ụzọ abụọ bụ isi maka imepụta Sb2O3 site na antimony ọla: oxidation kpọmkwem na ire nitrogen.
1. Direct oxidation usoro
Metal antimony na-emeghachi omume na oxygen n'okpuru kpo oku iji mepụta Sb2O3. Usoro mmeghachi omume bụ nke a:
4Sb＋3O2＝2Sb2O3
2. Ammonolysis
Antimony metal na-emeghachi omume na chlorine iji mepụta antimony trichloride, nke a na-agbaze, hydrolyzed, ammonolyzed, sachaa, na akpọnwụ iji nweta ngwaahịa Sb2O3 emechara. Usoro mmeghachi omume bụ isi bụ:
2Sb＋3Cl2＝2SbCl3
SbCl3＋H2O＝SbOCl＋2HCl
4SbOCl＋H2O＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl OH＝2Sb2O3＋2NH4Cl＋H2O
(II). A na-eji antimony trioxide eme ihe
Isi ojiji nke antimony trioxide bụ ihe na-eme ka polymerase na ihe na-egbochi ire ọkụ maka ihe sịntetik.
N'ime ụlọ ọrụ polyester, a na-eji Sb2O3 mee ihe na mbụ. A na-ejikarị Sb2O3 eme ihe dị ka ihe na-akpata polycondensation maka ụzọ DMT na ụzọ PTA mbụ ma na-ejikarị ya na H3PO4 ma ọ bụ enzymes ya.
(III). Nsogbu na antimony trioxide
Sb2O3 nwere adịghị ike solubility na ethylene glycol, na solubility nke naanị 4.04% na 150 ° C. Ya mere, mgbe a na-eji ethylene glycol akwadebe ihe na-emepụta ihe, Sb2O3 enweghị mgbasa ozi na-adịghị mma, nke nwere ike ime ka ọ dịkwuo mfe na usoro polymerization, na-emepụta ihe na-agbaze cyclic trimers dị elu, ma na-eweta ihe isi ike na ntụgharị. Iji melite solubility na dispersibility nke Sb2O3 na ethylene glycol, a na-emekarị nakweere iji oke ethylene glycol ma ọ bụ mee ka mgbaze okpomọkụ ruo n'elu 150 ° C. Otú ọ dị, n'elu 120 ° C, Sb2O3 na ethylene glycol nwere ike ịmepụta ethylene glycol antimony mmiri ozuzo mgbe ha na-emekọ ọnụ ruo ogologo oge, na Sb2O3 nwere ike belata na antimony dara na mmeghachi omume polycondensation, nke nwere ike ime ka "fog" na ibe polyester ma na-emetụta ya. àgwà ngwaahịa.
II. Nnyocha na ntinye nke antimony acetate
Usoro nkwadebe nke antimony acetate
Na mbụ, a kwadebere antimony acetate site n'imeghachi antimony trioxide na acetic acid, a na-ejikwa acetic anhydride dị ka ihe na-eme ka mmiri na-ekpo ọkụ na-amịkọrọ mmiri nke mmeghachi omume ahụ na-emepụta. Ogo nke ngwaahịa emechara enwetara site na usoro a adịghị elu, ọ were ihe karịrị awa 30 maka antimony trioxide ịgbaze na acetic acid. Mgbe e mesịrị, a kwadebere antimony acetate site n'imeghachi omume antimony metal, antimony trichloride, ma ọ bụ antimony trioxide na acetic anhydride, na-enweghị mkpa maka ihe na-ekpochapụ mmiri.
1. Antimony trichloride usoro
Na 1947, H. Schmidt et al. na West Germany kwadebere Sb (CH3COO) 3 site na imeghachi SbCl3 na acetic anhydride. Usoro mmeghachi omume bụ nke a:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Antimony metal usoro
Na 1954, TAPaybea nke bụbu Soviet Union kwadebere Sb (CH3COO) 3 site n'imeghachi omume antimony ọla na peroxyacetyl na ngwọta benzene. Usoro mmeghachi omume bụ:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Antimony trioxide usoro
Na 1957, F. Nerdel nke West Germany ji Sb2O3 meghachi omume na acetic anhydride iji mepụta Sb (CH3COO) 3.
Sb2O3＋3（CH3CO）2O＝＝2Sb（CH3COO）3
Mwepu nke usoro a bụ na kristal na-agbakọta ọnụ n'ime nnukwu iberibe ma rapara n'ahụ mgbidi dị n'ime nke reactor, na-akpata adịghị mma ngwaahịa na agba.
4. Antimony trioxide mgbaze usoro
Iji merie adịghị ike nke usoro ahụ dị n'elu, a na-agbakwụnye ihe mgbaze na-anọpụ iche n'oge mmeghachi omume nke Sb2O3 na acetic anhydride. Usoro nkwadebe kpọmkwem bụ nke a:
(1) Na 1968, R. Thoms nke American Mosun Chemical Company bipụtara patent na nkwadebe nke antimony acetate. Patent eji xylene (o-, m-, p-xylene, ma ọ bụ ngwakọta ya) dị ka ihe mgbaze na-anọpụ iche iji mepụta kristal dị mma nke antimony acetate.
(2) Na 1973, Czech Republic chepụtara usoro maka imepụta ezigbo antimony acetate na-eji toluene dị ka ihe mgbaze.
III. Ntụle nke atọ antimony dabeere catalysts
| Antimony Trioxide | Antimony acetate | Antimony Glycolate | |
| Njirimara ndị bụ isi | A na-akpọkarị antimony ọcha, usoro ihe omimi Sb 2 O 3, arọ molecular 291.51, ntụ ntụ ọcha, ebe mgbaze 656 ℃. Theoretical antimony ọdịnaya bụ ihe dịka 83.53 %. Njupụta nke ikwu 5.20g/ml . Soluble na concentrated hydrochloric acid, ndọkwasị sulfuric acid, ndọkwasị nitric acid, tartaric acid na alkali ngwọta, insoluble na mmiri, mmanya, itughari sulfuric acid. | Usoro ihe omimi Sb (AC) 3, molecular arọ 298.89, theoretical antimony ọdịnaya banyere 40.74%, agbaze ebe 126-131 ℃, njupụta 1.22g / ml (25 ℃), na-acha ọcha ma ọ bụ na-acha ọcha ntụ ntụ, mfe soluble na ethylene glycol. na xylene. | Usoro molecular Sb 2 (EG) 3 , The molecular arọ bụ banyere 423.68 , na-agbaze ebe bụ ＞ 100 ℃ (dec.) , theoretical antimony ọdịnaya bụ banyere 57.47 %, ọdịdị bụ ọcha crystalline siri ike, na-adịghị egbu egbu na keenweghiuto, mfe itinye mmiri mmiri. Ọ na-adị mfe mgbaze na ethylene glycol. |
| Usoro synthesis na teknụzụ | Ejiri usoro stibnite mebere nke ọma: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 3 Cheta: Stibnite / Iron Ore / limestone Na-ekpo ọkụ na ọkụ → mkpokọta | Ụlọ ọrụ ahụ na-ejikarị Sb 2 O 3 - usoro mgbaze maka njikọ: Sb2O3 ＋ 3 ( CH3CO ) 2O → 2Sb (AC) 3 Usoro: kpo oku reflux → ọkụ filtration → crystallization → agụụ ihicha → ProductNote: Sb(AC) 3 bụ dị mfe hydrolyzed, ya mere, ihe mgbaze na-anọpụ iche toluene ma ọ bụ xylene eji eme ihe ga-abụ ihe na-adịghị mma, Sb 2 O 3 enweghị ike ịnọ n'ọnọdụ mmiri, na akụrụngwa mmepụta ahụ aghaghịkwa nkụ. | Ụlọ ọrụ ahụ na-ejikarị usoro Sb 2 O 3 mee ihe: Sb 2 O 3 + 3EG → Sb 2 (EG) 3 + 3H 2 OProcess: Nri (Sb 2 O 3, mgbakwunye na EG) → kpo oku na nrụgide mmeghachi omume → wepụ slag , adịghị ọcha na mmiri → decolorization → ọkụ filtration → jụrụ oyi na crystallization → nkewa na ihicha → ngwaahịa Rịba ama: Usoro mmepụta kwesịrị ka ọ dịpụrụ adịpụ na mmiri iji gbochie hydrolysis. Mmeghachi omume a bụ mmeghachi omume na-agbanwe agbanwe, na n'ozuzu, a na-akwalite mmeghachi omume site na iji ethylene glycol ngafe na iwepu mmiri ngwaahịa. |
| Uru | Ọnụahịa ahụ dị ọnụ ala, ọ dị mfe iji, nwere ọrụ catalytic na-agafeghị oke na obere oge polycondensation. | Antimony acetate nwere ezigbo solubility na ethylene glycol ma na-agbasasịkwa na ethylene glycol, nke nwere ike imeziwanye arụmọrụ nke antimony; Antimony acetate nwere njirimara nke ọrụ catalytic dị elu, mmeghachi omume na-adịghị ala ala, ezigbo nkwụsị ọkụ na nhazi nhazi; N'otu oge ahụ, iji antimony acetate dị ka onye na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ dịkwuo mma, ọ dịghị mkpa ka mgbakwunye nke onye na-eme ihe na-eme ka ọ dịkwuo mma. Mmeghachi omume nke usoro antimony acetate catalytic dị ntakịrị, na àgwà ngwaahịa dị elu, karịsịa agba, nke dị mma karịa nke usoro antimony trioxide (Sb 2 O 3). | Ihe na-akpali akpali nwere nnukwu solubility na ethylene glycol; A na-ewepụ antimony efu-valent, na adịghị ọcha dị ka ígwè molecules, chlorides na sulfates nke na-emetụta polycondensation na-ebelata ruo ebe kachasị ala, na-ewepụ nsogbu nke acetate ion corrosion na ngwá ọrụ; Sb 3+ na Sb 2 (EG) 3 dị oke elu. , nke nwere ike ịbụ n'ihi na solubility ya na ethylene glycol na mmeghachi omume okpomọkụ dị ukwuu karịa nke Sb 2 O 3 Tụnyere Sb (AC) 3, ọnụọgụ Sb 3+ na-arụ ọrụ catalytic dị ukwuu. Agba nke ngwaahịa polyester nke Sb 2 (EG) 3 na-emepụta dị mma karịa nke Sb 2 O 3 Dị elu karịa nke mbụ, na-eme ka ngwaahịa ahụ na-egbuke egbuke ma na-acha ọcha; |
| Mwepu | Solubility na ethylene glycol adịghị mma, naanị 4.04% na 150 ° C. Na omume, ethylene glycol karịrị akarị ma ọ bụ na-abawanye okpomọkụ nke mgbasa ruo n'elu 150 ° C. Otú ọ dị, mgbe Sb 2 O 3 na-emeghachi omume na ethylene glycol ruo ogologo oge n'elu 120 ° C, ethylene glycol antimony mmiri ozuzo nwere ike ime, na Sb 2 O 3 nwere ike belata n'ọkwá ígwè na mmeghachi omume polycondensation, nke nwere ike ime ka "igwe ojii na-acha ntụ ntụ". "na polyester ibe ma na-emetụta àgwà ngwaahịa. Ihe omume nke polyvalent antimony oxides na-eme n'oge nkwadebe nke Sb 2 O 3, na-emetụta ịdị ọcha nke antimony dị irè. | Ọdịnaya antimony nke ihe na-akpata dị ntakịrị; ihe ndị na-adịghị ọcha nke acetic acid webatara ngwá ọrụ ndị na-emebi emebi, na-emetọ gburugburu ebe obibi, na-adịghịkwa mma maka ọgwụgwọ mmiri mkpofu; usoro mmepụta ihe dị mgbagwoju anya, ọnọdụ ọrụ gburugburu ebe obibi adịghị mma, enwere mmetọ, na ngwaahịa dị mfe ịgbanwe agba. Ọ dị mfe ire ere mgbe a na-ekpo ọkụ, na ngwaahịa hydrolysis bụ Sb2O3 na CH3COOH . Oge obibi ihe onwunwe dị ogologo, karịsịa na njedebe polycondensation ikpeazụ, nke dị elu karịa usoro Sb2O3. | Ojiji nke Sb 2 (EG) 3 na-abawanye ọnụ ahịa nke ngwa ngwa (mmụba ọnụ ahịa nwere ike ịkwụsị ma ọ bụrụ na 25% nke PET na-eji onwe ya na-agbapụta filaments). Na mgbakwunye, uru b nke hue ngwaahịa na-abawanye ntakịrị. |