Eriri Polyester (PET) bụ ụdị eriri sịntetik kachasị ukwuu. Uwe e ji eriri polyester mee dị mma, dị nro, dị mfe ịsa, ma kpọọ nkụ ngwa ngwa. A na-ejikwa polyester eme ihe nke ukwuu dị ka ihe eji eme nkwakọ ngwaahịa, eriri ụlọ ọrụ mmepụta ihe, na plastik injinia. N'ihi ya, polyester etolitela ngwa ngwa n'ụwa niile, na-amụba na nkezi ọnụego kwa afọ nke 7% ma nwee nnukwu mmepụta.
Enwere ike kewaa mmepụta polyester ụzọ dimethyl terephthalate (DMT) na ụzọ terephthalic acid (PTA) n'ihe gbasara ụzọ usoro, enwere ike kewaa ya n'ime usoro na-aga n'ihu na usoro na-aga n'ihu n'ihe gbasara ọrụ. N'agbanyeghị ụzọ usoro mmepụta ejiri, mmeghachi omume polycondensation chọrọ iji ngwakọta ígwè dị ka ihe na-akpali akpali. Mmeghachi omume polycondensation bụ nzọụkwụ dị mkpa na usoro mmepụta polyester, oge polycondensation bụkwa ihe mgbochi maka imeziwanye mmepụta. Mmezi nke sistemụ catalyst bụ ihe dị mkpa n'imeziwanye mma nke polyester na ime ka oge polycondensation dị mkpụmkpụ.
UrbanMines Tech. Limited bụ ụlọ ọrụ China kachasị elu nke na-ahụ maka nyocha na mmepe, mmepụta, na inye polyester catalyst-grade antimony trioxide, antimony acetate, na antimony glycol. Anyị emeela nnyocha miri emi na ngwaahịa ndị a - ngalaba nyocha na mmepe nke UrbanMines na-achịkọta nyocha na ojiji nke antimony catalyst n'isiokwu a iji nyere ndị ahịa anyị aka itinye, melite usoro mmepụta, na inye asọmpi zuru oke nke ngwaahịa eriri polyester.
Ndị ọkà mmụta obodo na ndị mba ọzọ kwenyere na polyester polycondensation bụ mmeghachi omume ndọtị nke yinye, usoro catalytic bụ nke nhazi chelation, nke chọrọ ka atọm ígwè catalyst nye orbitals efu iji jikọta ya na arc pair of electrons nke carbonyl oxygen iji mezuo ebumnuche nke catalysis. Maka polycondensation, ebe ọ bụ na njupụta igwe ojii electron nke carbonyl oxygen dị na otu hydroxyethyl ester dị obere, electronegativity nke ion ígwè dị elu n'oge nhazi, iji mee ka nhazi na ịgbatị yinye dị mfe.
A pụrụ iji ihe ndị a mee ihe dị ka ihe na-akpali 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 ihe ndị ọzọ dị na metal oxides, alcoholates, carboxylates, borates, halides na amines, ureas, guanidines, ihe ndị dị na organic nwere sulfur. Agbanyeghị, ihe ndị na-akpali akpali nke a na-eji ugbu a ma na-amụ na mmepụta ụlọ ọrụ bụ isi ihe ndị na-akpali akpali Sb, Ge, na Ti. Ọtụtụ ọmụmụ egosila na: Ihe ndị na-akpali akpali dabere na Ge nwere obere mmeghachi omume n'akụkụ ma na-emepụta PET dị elu, mana ọrụ ha adịghị elu, ha enweghịkwa akụrụngwa ole na ole ma dị oke ọnụ; Ihe mkpali dabere na Ti nwere nnukwu ọrụ na ọsọ mmeghachi omume ngwa ngwa, mana mmeghachi omume mmetụta ha na-apụta ìhè karịa, na-ebute nkwụsi ike okpomọkụ na agba odo nke ngwaahịa ahụ, a pụkwara iji ha naanị maka imepụta PBT, PTT, PCT, wdg.; Ihe mkpali dabere na Sb abụghị naanị na ọ na-arụ ọrụ karịa. Ogo ngwaahịa ahụ dị elu n'ihi na ihe mkpali dabere na Sb na-arụ ọrụ karịa, na-enwe obere mmeghachi omume n'akụkụ, ma dị ọnụ ala. Ya mere, ejirila ha nke ukwuu. N'ime ha, ihe mkpali dabere na Sb kachasị eji bụ antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), wdg.
N'ileba anya n'akụkọ mmepe nke ụlọ ọrụ polyester, anyị nwere ike ịchọpụta na ihe karịrị 90% nke osisi polyester n'ụwa na-eji ngwakọta antimony dị ka ihe na-akpali akpali. Ka ọ na-erule afọ 2000, China ewebatala ọtụtụ osisi polyester, ha niile jiri ngwakọta antimony dị ka ihe na-akpali akpali, ọkachasị Sb2O3 na Sb(CH3COO)3. Site na mbọ nke nyocha sayensị China, mahadum, na ngalaba mmepụta, emepụtala ihe na-akpali akpali abụọ a n'ime obodo.
Kemgbe afọ 1999, ụlọ ọrụ kemịkalụ French bụ Elf ewepụtala ihe na-akpali antimony glycol [Sb2 (OCH2CH2CO) 3] dị ka ihe na-akwalite mmepụta nke ihe na-akpali akpali ọdịnala. Mpekere polyester ndị a na-emepụta nwere nnukwu ọcha na ezigbo ntụgharị, nke dọtara mmasị dị ukwuu site n'aka ụlọ ọrụ nyocha ihe na-akpali akpali nke obodo, ụlọ ọrụ, na ndị na-emepụta polyester na China.
I. Nnyocha na itinye antimony trioxide n'ọrụ
Mba Amerịka bụ otu n'ime mba mbụ mepụtara ma tinye Sb2O3 n'ọrụ. Na 1961, oriri Sb2O3 na mba Amerịka ruru tọn 4,943. N'afọ 1970, ụlọ ọrụ ise na Japan mepụtara Sb2O3 nke nwere ikike mmepụta zuru oke nke tọn 6,360 kwa afọ.
Isi ngalaba nyocha na mmepe Sb2O3 nke China na-elekwasị anya na ụlọ ọrụ gọọmentị nweburu na Hunan Province na Shanghai. UrbanMines Tech. Limited eguzobekwala usoro mmepụta ọkachamara na Hunan Province.
(I). Ụzọ e si emepụta antimony trioxide
A na-ejikarị antimony sulfide ore emepụta Sb2O3. A na-ebu ụzọ kwadebe antimony metal, e mesịa, a na-eji antimony metal emepụta Sb2O3.
E nwere ụzọ abụọ isi esi emepụta Sb2O3 site na antimony metal: oxidation ozugbo na mmebi nitrogen.
1. Usoro oxidation kpọmkwem
Antimony ígwè na-emeghachi omume na ikuku oxygen mgbe a na-ekpo ọkụ iji mepụta Sb2O3. Usoro mmeghachi omume bụ dịka ndị a:
4Sb＋3O2＝＝2Sb2O3
2. Ammonolysis
Antimony metal na-emeghachi omume na chlorine iji mepụta antimony trichloride, nke a na-ewepụ mmiri, na-eme ka ọ dị ọcha, na-eme ka ọ dị ọcha, na-asa ya, na-asa ya, ma kpọọ nkụ 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). Ojiji nke antimony trioxide
Ojiji bụ isi nke antimony trioxide bụ ihe na-akpali polymerase na ihe na-egbochi ire ọkụ maka ihe ndị e ji emepụta ihe.
N'ụlọ ọrụ polyester, e ji Sb2O3 mee ihe na mbụ dị ka ihe na-akpali akpali. A na-ejikarị Sb2O3 eme ihe dị ka ihe na-akpali akpali maka ụzọ DMT na ụzọ PTA mbụ, a na-ejikarịkwa ya eme ihe na H3PO4 ma ọ bụ enzymes ya.
(III). Nsogbu na antimony trioxide
Sb2O3 enweghị ike ịgbaze na ethylene glycol, yana naanị 4.04% na 150°C. Ya mere, mgbe ejiri ethylene glycol kwadebe ihe na-akpali akpali, Sb2O3 enweghị ike ịgbaze nke ọma, nke nwere ike ibute nnukwu ihe na-akpali akpali na sistemụ polymerization, mepụta ihe na-agbaze nke nwere ebe dị elu, ma weta nsogbu na ntụgharị. Iji melite ịgbaze na ịgbaze nke Sb2O3 na ethylene glycol, a na-ejikarị ya eme ihe iji oke ethylene glycol ma ọ bụ mee ka okpomọkụ ịgbaze ruo karịa 150°C. Agbanyeghị, karịa 120°C, Sb2O3 na ethylene glycol nwere ike imepụta mmiri ozuzo ethylene glycol antimony mgbe ha na-arụkọ ọrụ ruo ogologo oge, Sb2O3 nwekwara ike ibelata ka ọ bụrụ antimony metal na mmeghachi omume polycondensation, nke nwere ike ibute "fog" na ibe polyester ma metụta mma ngwaahịa.
II. Nnyocha na itinye antimony acetate n'ọrụ
Usoro nkwadebe nke antimony acetate
Na mbụ, a na-eji antimony acetate emeghachi omume na antimony trioxide na acetic acid, a na-ejikwa acetic anhydride eme ihe dị ka ihe na-eme ka mmiri ghara ịdị ọcha iji mịpụta mmiri sitere na mmeghachi omume ahụ. Ọdịdị nke ngwaahịa emechara site na usoro a adịghị elu, o were ihe karịrị awa iri atọ ka antimony trioxide gbazee na acetic acid. Mgbe e mesịrị, a kwadebere antimony acetate site na iji metal antimony, antimony trichloride, ma ọ bụ antimony trioxide na acetic anhydride, na-enweghị mkpa maka ihe na-eme ka mmiri ghara ịdị ọcha.
1. Usoro Antimony trichloride
Na 1947, H. Schmidt na ndị otu ya na West Germany kwadebere Sb(CH3COO)3 site na iji acetic anhydride meghachi omume na SbCl3. Usoro mmeghachi omume ahụ bụ dịka ndị a:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Usoro ígwè Antimony
Na 1954, TAPaybea nke bụbu Soviet Union kwadebere Sb(CH3COO)3 site na imeghachi omume na metalal antimony na peroxyacetyl na ngwọta benzene. Usoro mmeghachi omume bụ:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Usoro antimony trioxide
Na 1957, F. Nerdel nke West Germany jiri Sb2O3 meghachi omume na acetic anhydride iji mepụta Sb(CH3COO)3.
Sb2O3＋3（CH3CO）2O＝＝2Sb（CH3COO）3
Ihe na-adịghị mma nke usoro a bụ na kristal na-agbakọta n'ime nnukwu iberibe ma rapara nke ọma na mgbidi dị n'ime ihe nrụpụta ahụ, nke na-eme ka ngwaahịa ahụ ghara ịdị mma ma nwee agba dị mma.
4. Usoro ihe mgbaze antimony trioxide
Iji merie adịghị ike nke usoro a dị n'elu, a na-agbakwunye ihe mgbaze na-anọpụ iche n'oge mmeghachi omume nke Sb2O3 na acetic anhydride. Usoro nkwadebe kpọmkwem bụ dị ka ndị a:
(1) Na 1968, R. Thoms nke American Mosun Chemical Company bipụtara patent gbasara nkwadebe nke antimony acetate. Patent ahụ jiri 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 mepụtara ụzọ maka imepụta ezigbo antimony acetate site na iji toluene dị ka ihe mgbaze.
III. Ntụnyere nke ihe mkpali atọ dabere na antimony
| Antimony Trioxide | Acetate Antimony | Antimony Glycolate | |
| Njirimara Ndị Dị Mkpa | A maara ya nke ọma dị ka antimony white, molekul formula Sb2O3, molekul ibu 291.51, ntụ ọcha, ebe ịgbaze 656℃. Ọdịnaya antimony dị ihe dị ka 83.53%. Njupụta dị n'etiti 5.20g/ml. A na-agbaze na hydrochloric acid a chịkọtara, sulfuric acid a chịkọtara, nitric acid a chịkọtara, tartaric acid na alkali solution, anaghị agbaze na mmiri, mmanya, sulfuric acid a agwakọtara. | Usoro molekụla Sb(AC) 3, ibu molekụla 298.89, ọdịnaya antimony dị ihe dị ka 40.74%, ebe agbaze 126-131℃, njupụta 1.22g/ml (25℃), ntụ ọcha ma ọ bụ ntụ ọcha na-adịghị ọcha, a na-agbaze ngwa ngwa na ethylene glycol, toluene na xylene. | Usoro molekụla Sb2 (EG) 3, Ibu molekụla dị ihe dịka 423.68, ebe agbaze bụ ＞ 100℃ (dec.), ọdịnaya antimony nke echiche dị ihe dịka 57.47%, ọdịdị ya bụ kristal ọcha siri ike, ọ naghị egbu egbu ma na-enweghị ụtọ, ọ dị mfe ịmịkọrọ mmiri. Ọ na-agbaze ngwa ngwa na ethylene glycol. |
| Usoro na Teknụzụ Nhazi | A na-emepụta ya nke ọma site na usoro 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 3Rịba ama: Stibnite / Iron Ore / Limestone → Okpomọkụ na Ịfụ ọkụ → Nchịkọta | Ụlọ ọrụ a na-ejikarị usoro ihe mgbaze Sb 2O 3 eme ihe:Sb2O3 ＋ 3 (CH3CO) 2O → 2Sb(AC) 3Usoro: kpo oku reflux → nzacha ọkụ → kristalịzi → nkụ vacuum → ngwaahịaRịba ama: Sb(AC) 3 nwere ike ịdị mfe hydrolyzed, yabụ ihe mgbaze na-anọpụ iche toluene ma ọ bụ xylene ejiri ga-abụ anhydrous, Sb 2O 3 agaghị adị mmiri mmiri, akụrụngwa mmepụta ga-adịkwa akọrọ. | Ụlọ ọrụ a na-ejikarị usoro Sb 2 O 3 emepụta:Sb 2 O 3 +3EG→Sb 2 (EG) 3 +3H 2 O Usoro: Nri (Sb 2 O 3, ihe mgbakwunye na EG) → Mmeghachi omume ikpo ọkụ na nrụgide → iwepụ slag, ihe na-adịghị ọcha na mmiri → decolorization → nzacha ọkụ → oyi na kristal → nkewa na nkụ → ngwaahịa Rịba ama: A ghaghị ikewapụ usoro mmepụta ahụ na mmiri iji gbochie hydrolysis. Mmeghachi omume a bụ mmeghachi omume a na-agbanwe agbanwe, n'ozuzu ya, a na-akwalite mmeghachi omume ahụ site na iji oke ethylene glycol na iwepụ mmiri ngwaahịa ahụ. |
| Uru | Ọnụahịa ya dị ọnụ ala, ọ dị mfe iji, ọ nwere obere ọrụ mkpali na obere oge polycondensation. | Antimony acetate nwere ezigbo mgbaze na ethylene glycol ma gbasaa ya nke ọma na ethylene glycol, nke nwere ike ime ka arụmọrụ ojiji nke antimony ka mma; Antimony acetate nwere njirimara nke ọrụ catalytic dị elu, obere mmeghachi omume mmebi, ezigbo iguzogide okpomọkụ na nkwụsi ike nhazi; N'otu oge ahụ, iji antimony acetate dị ka ihe na-akpali akpali anaghị achọ mgbakwunye nke co-catalyst na ihe na-eme ka ọ kwụsie ike. Mmeghachi omume nke usoro antimony acetate catalytic dị obere, àgwà ngwaahịa ahụ dịkwa elu, ọkachasị agba, nke ka mma karịa nke sistemụ antimony trioxide (Sb2O3). | Ihe na-akpalite ihe ahụ nwere nnukwu mgbaze na ethylene glycol; a na-ewepụ antimony efu-valent, a na-ebelatakwa ihe ndị na-adịghị ọcha dịka molekul ígwè, chlorides na sulfates ndị na-emetụta polycondensation ruo n'ebe kachasị ala, na-ewepụ nsogbu nke nchara acetate ion na akụrụngwa;Sb 3+ na Sb 2 (EG) 3 dị elu, nke nwere ike ịbụ n'ihi na ọ na-agbaze na ethylene glycol na okpomọkụ mmeghachi omume karịrị nke Sb 2 O 3 Ma e jiri ya tụnyere Sb (AC) 3, ọnụọgụ Sb 3+ nke na-arụ ọrụ catalytic ka ukwuu. Agba nke ngwaahịa polyester nke Sb 2 (EG) 3 mepụtara ka mma karịa nke Sb 2 O 3. Ọ dị ntakịrị elu karịa nke mbụ, na-eme ka ngwaahịa ahụ dị ka nke na-enwu enwu ma na-acha ọcha karịa; |
| ọghọm | Ọgbara mmiri dị na ethylene glycol adịghị mma, naanị 4.04% na 150°C. N'ọrụ, ethylene glycol karịrị akarị ma ọ bụ na okpomọkụ nke ịgbaze na-amụba ruo 150°C. Agbanyeghị, mgbe Sb2O3 meghachiri omume na ethylene glycol ruo ogologo oge na okpomọkụ karịrị 120°C, mmiri ozuzo antimony nke ethylene glycol nwere ike ime, Sb2O3 nwekwara ike ibelata ka ọ bụrụ steepụ ígwè na mmeghachi omume polycondensation, nke nwere ike ibute "foogu isi awọ" na ibe polyester ma metụta mma ngwaahịa. Ihe na-eme na polyvalent antimony oxides na-eme n'oge nkwadebe nke Sb2O3, ịdị ọcha nke antimony na-emetụtakwa. | Ọdịnaya antimony nke ihe na-akpalite ihe dị obere; ihe ruru unyi acetic acid butere ngwa ọrụ na-emebi emebi, na-emerụ gburugburu ebe obibi, ọ dịghịkwa mma maka ọgwụgwọ mmiri mkpofu; usoro mmepụta ahụ dị mgbagwoju anya, ọnọdụ gburugburu ebe ọrụ adịghị mma, enwere mmetọ, ngwaahịa ahụ dịkwa mfe ịgbanwe agba. Ọ dị mfe ịgbari mgbe a na-ekpo ọkụ, ngwaahịa hydrolysis bụ Sb2O3 na CH3COOH. Oge obibi ihe onwunwe dị ogologo, karịsịa na ọkwa polycondensation ikpeazụ, nke dị elu karịa sistemụ Sb2O3. | Ojiji nke Sb 2 (EG) 3 na-eme ka ọnụ ahịa ihe na-akpalite ngwa ahụ dịkwuo elu (mmụba ọnụ ahịa ahụ nwere ike ịgbanwe naanị ma ọ bụrụ na ejiri 25% nke PET mee ihe maka ịtụgharị eriri onwe ya). Na mgbakwunye, uru b nke agba ngwaahịa ahụ na-abawanye ntakịrị. |