CN1116928C - Ti-series compound and/or carried catalyst and its preparing process - Google Patents
Ti-series compound and/or carried catalyst and its preparing process Download PDFInfo
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- CN1116928C CN1116928C CN 01115117 CN01115117A CN1116928C CN 1116928 C CN1116928 C CN 1116928C CN 01115117 CN01115117 CN 01115117 CN 01115117 A CN01115117 A CN 01115117A CN 1116928 C CN1116928 C CN 1116928C
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- titanium
- acid
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- supported catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 150000001875 compounds Chemical class 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- -1 titanium series compound Chemical class 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 23
- 150000002148 esters Chemical group 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 230000032050 esterification Effects 0.000 claims abstract description 8
- YTIITRMGDQULGC-UHFFFAOYSA-N [Ti+6] Chemical compound [Ti+6] YTIITRMGDQULGC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 69
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 47
- 239000010936 titanium Substances 0.000 claims description 40
- 229910052719 titanium Inorganic materials 0.000 claims description 36
- 150000001298 alcohols Chemical class 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- 229910021645 metal ion Inorganic materials 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 21
- 238000003828 vacuum filtration Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 230000000655 anti-hydrolysis Effects 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 241001502050 Acis Species 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 150000005672 tetraenes Chemical class 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- SMTNXTHHYPIVQU-UHFFFAOYSA-N butanoic acid;oxalic acid Chemical compound CCCC(O)=O.OC(=O)C(O)=O SMTNXTHHYPIVQU-UHFFFAOYSA-N 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 150000004703 alkoxides Chemical class 0.000 abstract 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical class [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 abstract 1
- 150000001462 antimony Chemical class 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 17
- 230000035484 reaction time Effects 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 13
- 239000008187 granular material Substances 0.000 description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- GUQHFNXMIJFYMU-UHFFFAOYSA-N ethane-1,2-diol;zinc Chemical compound [Zn].OCCO GUQHFNXMIJFYMU-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides an anti-hydrolyzation titanium series compound and/or supported catalyst and a preparation method thereof, and relates to a catalyst for esterification, ester exchange and polycondensation reactions, and a preparation method thereof. Titanium (IV) compounds easy to hydrolyze and at least one of inorganic acid, organic acid and metallic ion compounds with 1 to 4 valences react in dibasic alcohol to form compounds of oxides and alkoxide of the titanium (VI) or compounds of oxides and alkoxide of the titanium (VI) and alkoxide or inorganic salts of metallic ions. The nanometer anti-hydrolyzation titanium series compound or/and supported catalyst has the advantages of high activity and low cost, and is suitable for esterification reactions of catalytic acid and alcohol and macromolecule generating reactions through the ester condensation of dibasic acid and dibasic alcohol. The catalyst has the advantages of simple synthetic process, easy operation and low cost, and polyester synthesized by the catalyst can eliminate environmental pollution caused by using antimony series catalysts.
Description
Technical field
The present invention relates to the Catalysts and its preparation method of esterification, ester exchange and polycondensation reaction, it is compound or/and supported catalyst and preparation method thereof particularly to relate to the anti-hydrolysis high-activity titanium of nanoscale.
Background technology
As everyone knows, titanate esters is the important titanium sub-group compound of a class, and is used as the catalyst of esterification, ester exchange and polycondensation reaction, but because their facile hydrolysis, active unstable, there is turbid phenomenon etc. in the macromolecule that catalysis forms, and its application is very limited.
About the research of anti-hydrolysis Titanium series catalyst, according to Chem.Fiber Int.1999.49 (1) .27_29 (Eng), German Acordis company first this in the world develops the TiO that a kind of code name is C-64
2/ SiO
2Mixed oxide high activity PET catalyst, wherein the Ti/Si ratio is 9: 1, particle diameter is less than 10 microns, anti-hydrolysis, price is 120 German marks/kg, when the synthetic PET of catalysis, catalytic activity be antimony oxide 6_8 doubly, but the catalyst synthetic technology is not made reports.
Summary of the invention
It is compound or/and supported catalyst that purpose of the present invention just provides a kind of titanium, it is that the gang's anti-hydrolysis high-activity titanium of low-cost nanoscale that synthesizes is compound or/and supported catalyst, and make it be used for catalysis acid and pure esterification and binary acid binary alcohol esters condensation generation high molecular weight reactive, have high activity.
It is compound or/and the preparation method of supported catalyst that another object of the present invention just provides this titanium.
In order to reach purpose of the present invention, the present invention is by adopting facile hydrolysis titanium (IV) compound and inorganic acid, organic acid, at least a oxide and the compound of alcoholates or the oxide of titanium (VI) that consists of titanium (VI) that in dihydroxylic alcohols, react in the 1-4 valence metal ion compound, the compound of alcoholates and metal ion alcoholates or inorganic salts, form gel, and by adjusting the reaction system temperature, pressure or feeding inert gas etc. are discharged the low molecular compound that reaction generates gradually, make and in solution, generate a solid product, with this solid product through vacuum filtration or centrifugation, the washing decolouring, dry, promptly obtain can be used for the anti-hydrolysis high-activity titanium that the esterification and the condensation of binary acid binary alcohol esters of catalysis acid and alcohol generate high molecular weight reactive compound/supported catalyst, this catalyst is dispersed in the dihydroxylic alcohols through routine stirring or supersonic oscillations, and particle diameter is the 4-20 nanometer.
Introduce preparation method of the present invention below in detail:
Have stirring at one, in the reactor of distillation or rectifier unit, add facile hydrolysis titanium (IV) compound and inorganic acid, organic acid, at least a and dihydroxylic alcohols in the 1-4 valence metal ion compound, stir, heating, promote reactant reaction to form gel, by adjusting the reaction system temperature, pressure or feeding inert gas etc. are discharged the low molecular compound that reaction generates gradually, make and in solution, generate a granular solids product, when no longer including the distillate discharge in the question response system, stop heating and stir, leave standstill and be cooled to normal temperature, with product through vacuum filtration or centrifugation, the solution recycle and reuse, solids is through washing decolouring, drying, promptly obtain can be used for the anti-hydrolysis high-activity titanium that the esterification and the condensation of binary acid binary alcohol esters of catalysis acid and alcohol generate high molecular weight reactive compound/supported catalyst, this catalyst is dispersed in the dihydroxylic alcohols through routine stirring or supersonic oscillations, and particle diameter is the 4-25 nanometer.
Compound or/and the supported catalyst of the anti-hydrolysis high-activity titanium of nanoscale of the present invention, it consists of the compound of oxide, alcoholates and the metal ion alcoholates or the inorganic salts of the compound of the oxide of titanium (VI) and alcoholates or titanium (VI).
Wherein the compound of oxide of (1) titanium (VI) and alcoholates is to be synthesized by titanate esters and inorganic acid or organic acid direct reaction in dihydroxylic alcohols.(2) compound of the oxide of titanium (VI), alcoholates and metal ion alcoholates or inorganic salts is by titanate esters and at least a metal ions M n
+Compound in dihydroxylic alcohols, react synthetic; Wherein M represents Li
+, Na
+, K
+, Mg
2+, Ca
2+, Al
3+, Zn
2+, Sr
2+, Ba
2+, Mn
2+, Co
2+, Zr
4+, Si
4+, n represents the integer of 1-4. and metal ions M
N+Compound comprise oxide, hydroxide, carbonate, acetate, the alkoxide compound of M.
Facile hydrolysis titanium of the present invention (IV) compound is that metatitanic acid tetramethyl ester, metatitanic acid tetraene propyl ester and general formula are Ti (C
nH
2n+1O)
4The alkoxytitanium acid esters of (wherein n is 2-8).
Dihydroxylic alcohols of the present invention is that ethylene glycol and general formula are C
nH
2n(OH)
2Hydroxyl dihydroxylic alcohols between (wherein n is the integer of 3-6).These alcohol can form five-membered ring and six membered ring with chemical bond and coordinate bond by hydroxyl oxygen atom etc. and Ti atom, make the Ti atom generate anti-hydrolysis solid chemical compound, and be easy to form compound or/and supported catalyst with other solid chemical compound with 6 valency forms and this class alcoholic compound.Though 1.2-propane diols can form five-membered ring with the Ti atom, the Ti atom still exists with 4 valency forms in compound, can not get solid product in the 1.2-propane diols, and meet water and decompose immediately; 1.4-butanediol and carbon number more between the hydroxyl dihydroxylic alcohols because the influence of position or three-dimensional effect can not form anti-hydrolysis solid chemical compound with the Ti atom.
Inorganic acid of the present invention is boric acid, phosphoric acid and sulfuric acid.
Organic acid of the present invention is acetic acid, propionic acid, butyric acid, ethanedioic acid, malonic acid, succinic acid.
Metal ion compound of the present invention is oxide, hydroxide, carbonate, acetate, the alkoxide compound of 1-4 valence metal ion compound.Say so Li in more detail
+, Na
+, K
+, Mg
2+, Ca
2+, Al
3+, Zn
2+Oxide and hydroxide, Ba
2+Hydroxide, Li
+, Na
+, K
+, Mg
2+, Ca
2+, Al
3+, Zn
2+, Sr
2+, Ba
2+, Mn
2+, Co
2+Carbonate and acetate, Zr
4+, Si
4+Alkoxide compound such as esters of silicon acis, zirconate.
Facile hydrolysis titanium of the present invention (IV) compound (titanate esters) is respectively with boric acid, organic acid mol ratio: 1.0: 0.08-4.0.When sour consumption more after a little while, the reactions change of titanate esters in dihydroxylic alcohols is not obvious, and synthetic catalyst poor stability under daylight, flavescence easily; When sour consumption more for a long time, though can promote the conversion rate of titanate esters, the light stability that helps generating nano-scale particle and improve catalyst, but when sour consumption reaches certain value, increase consumption again, act on also not obvious, and the acid that adds also can be decomposed alcohol and the diol reaction generation ester that generates with titanate esters, particularly the ester of binary acid and dihydroxylic alcohols generation can bring difficulty to catalyst separation, also causes waste and cost to rise simultaneously.
Facile hydrolysis titanium of the present invention (IV) compound (titanate esters) with the mol ratio of various metal ion compounds is: titanate esters and metal ion acetate (comprising acetate, phosphate, sulfate that metal ion oxide, hydroxide and carbonate and acetic acid form) mol ratio is 1.0: 0.2-50.Facile hydrolysis titanium (IV) compound (titanate esters) is 1.0 with the mol ratio of esters of silicon acis, zirconate: 0.1-10.
Among the present invention, compound or the load on metal ion compound of titanate esters and metal ion compound has appreciable impact to catalytic performance, the stability of synthetic catalyst, when shared ratio in catalysis is formed such as the ethylene glycol zinc that generates in as reaction when metal ion compound, barium sulfate is higher, can make the titanium compound decentralization of load higher, improve the stable and catalytic performance of catalyst.
The mol ratio of titanate esters and dihydroxylic alcohols is among the present invention: 0.001-0.3: 1.0.
Be by reaction system being vacuumized or feeds inert gas or under normal pressure, directly deviating from the low molecular compound that generates in the system among the present invention, reaction temperature generally is controlled at 105 ℃ to the scope of the dihydroxylic alcohols boiling point left and right sides, when temperature be lower than 105 ℃ the reaction needed vacuum height (＜50Pa) and reaction speed slow, when temperature is higher than the two dihydroxylic alcohols boiling temperatures that participate in reaction, need to improve system pressure, this can make the complicated and increase energy consumption of operating condition.Reaction temperature remains in the 105 ℃-dihydroxylic alcohols boiling temperature scope, changes to the non-pressure process range at 50Pa with pressure, and makes reaction solution remain on fluidized state to react.The inert gas that uses in the reaction is N
2And He, generally adopt N
2, do not take dihydroxylic alcohols out of for guaranteeing to take low molecular compound out of, generally control flow and rise reactor at 0.01-1.0L/min.
Catalyst separation of the present invention is to adopt vacuum filtration or/and centrifugation.
Catalyst detergent decolouring of the present invention is to select low boiling point solvent washing catalysts such as ethanol, acetone for use.
Of the present invention compound/its composition of carrying catalyst in titanium series can be expressed as follows:
The diatomic alcohol compounds of binary titanium alkoxide/metal ion and binary titanium alkoxide/phosphate or barium sulfate.
Of the present invention compound/carrying catalyst in titanium series is applicable to the polycondensation reaction of esterification, ester exchange reaction and polyester.
Specific embodiments
Further specify the present invention below by embodiment:
Embodiment 1
Have agitator at one, in the reactor of distilling apparatus, add 25.5g butyl titanate, 9.3g boric acid and 124g ethylene glycol, wherein the mol ratio of butyl titanate and boric acid is 1.0: 2.0, with the mol ratio of ethylene glycol be 0.0375: 1.0, stir, the solution thickness is warming up to 130 ℃, feeds N
2And adjusting N
2Flow is that 0.5 liter/min rises reactor, continues to be warming up to 150-160 ℃, has distillate to discharge, temperature rise is during to 180-190 ℃, and the adularescent solids generates and continues to be heated to 197-198 ℃, when waiting to no longer include distillate and discharging, stop reaction, the reaction time needs 45min approximately, leaves standstill to be cooled to normal temperature, vacuum filtration, the filtrate recycle and reuse, solids decolours drying with the industrial alcohol washing, promptly obtain catalyst, the catalyst granules particle diameter is the 4-19 nanometer.
Embodiment 2
Have agitator at one, add 25.5g butyl titanate, 12g glacial acetic acid and 124g ethylene glycol in the reactor of distilling apparatus, wherein the mol ratio of butyl titanate and acetic acid is 1.0: 4.0, with the mol ratio of ethylene glycol be 0.0375: 1.0, stir, be warming up to 150 ℃, feed N
2And adjusting N
2Flow is that 1.0L/min rises reactor, continues to be warming up to 197-198 ℃, and constantly discharges the low molecular compound that reaction produces in temperature-rise period, when waiting to no longer include the distillate discharge, stop reaction, the reaction time needs 40min approximately, leaves standstill to be cooled to normal temperature, solids in the reactor is carried out vacuum filtration or centrifugation, the filtrate recycle and reuse, solids decolours drying with the industrial alcohol washing, promptly obtain catalyst, the catalyst granules particle diameter is the 4-19 nanometer.
Embodiment 3
Have agitator at one, in the reactor of distilling apparatus, add the 34.0g butyl titanate, 12.6g ethanedioic acid and 186g ethylene glycol, wherein the mol ratio of butyl titanate and ethanedioic acid is 1.0: 1.0, with the mol ratio of ethylene glycol be 0.033: 1.0, stir and heat up, directly be heated to 197-198 ℃, and in heating process, constantly discharge the low molecular compound that reaction produces, when waiting to no longer include the distillate discharge, stop reaction, reaction time needs 60min approximately, leave standstill and be cooled to normal temperature, solids in the reactor is carried out vacuum filtration or centrifugation, the filtrate recycle and reuse, solids decolours with the acetone washing, drying promptly obtains catalyst, and the catalyst granules particle diameter is the 4-19 nanometer.
Embodiment 4
Have agitator at one, in the reactor of distilling apparatus, add 51.6g metatitanic acid tetramethyl ester, 2.82g succinic acid and 90g1.3-butanediol, wherein the mol ratio of titanate esters and succinic acid is 1.0: 0.08, with the mol ratio of 1.3 butanediols be 0.3: 1.0, stir, be warming up to 150 ℃, feed N
2And adjusting N
2Flow is that 0.01L/min rises reactor, continues to be warming up to 204-206 ℃, and it is thick that solution is, this moment, the temperature rising and the distillate velocity of discharge were slow, stopped reaction, and the reaction time needs 90min approximately, leave standstill and be cooled to normal temperature, vacuum filtration, the filtrate recycle and reuse, solids decolours with the industrial alcohol washing, dry, promptly obtain catalyst, the catalyst granules particle diameter is the 4-12 nanometer, and this catalyst can partial hydrolysis in water.
Embodiment 5
Have agitator at one, in the reactor of distilling apparatus, add 14.1g metatitanic acid four monooctyl esters, 17g Sodium acetate trihydrate and 118g1.3-hexylene glycol, wherein the mol ratio of titanate esters and sodium acetate is 1.0: 5.0, with the mol ratio of 1.3-hexylene glycol be 0.025: 1.0, stir, be warming up to 180 ℃, vacuumize and be decompressed to 4.0 * 10
4Pa begins to have distillate to discharge, and continues to be warming up to 215-225 ℃, when no longer including the distillate discharge, stop heating, the reaction time needs 80min approximately, leaves standstill to be cooled to normal temperature, vacuum filtration, the filtrate recycle and reuse, solids decolours drying with the acetone washing, promptly obtain catalyst, the catalyst granules particle diameter is the 10-20 nanometer.
Embodiment 6
Have agitator at one, in the reactor of distilling apparatus, add the 28.4g tetraisopropyl titanate, 4.2g Acetic Acid Glacil magnesium and 152g1.3-propane diols, wherein the mol ratio of titanate esters and magnesium acetate is 1.0: 0.2, with the mol ratio of 1.3-propane diols be 0.05: 1.0, stir, directly be warming up to 210-212 ℃, and in heating process, constantly discharge the low molecular compound that generates in the reaction system by distilling apparatus, when no distillate is discharged, stop reaction, reaction time needs 60min approximately, leave standstill and be cooled to normal temperature, vacuum filtration, filtrate recycle and reuse, solids decolours with the industrial alcohol washing, drying promptly obtains catalyst, and the catalyst granules particle diameter is the 4-19 nanometer.
Embodiment 7
Have agitator at one, in the reactor of distilling apparatus, add the 0.6g butyl titanate, 19.37g Acetic Acid Glacil zinc and 100g ethylene glycol, wherein the mol ratio of titanate esters and zinc acetate is 1.0: 50, with the mol ratio of ethylene glycol be 0.001: 1.0, stir, directly be warming up to 196-198 ℃, and in heating process, constantly discharge the low molecular compound that generates in the reaction system by distilling apparatus, when no distillate is discharged, stop heating, reaction time needs 50min approximately, leave standstill and be cooled to normal temperature, vacuum filtration or centrifugation, filtrate recycle and reuse, solids decolours with the industrial alcohol washing, drying promptly obtains catalyst, and the catalyst granules particle diameter is the 10-20 nanometer.
Embodiment 8
Have agitator at one, in the reactor of rectifier unit, add 7.8gAI (OH)
3The phosphoric acid of 93g ethylene glycol and 10g95%, add hot reflux 60min, discharge the water that produces in the reaction system with the pH value of phosphoric acid regulator solution and by rectifier unit again, when treating anhydrous discharge, leave standstill and be cooled to below 60 ℃, add 1.38g metatitanic acid tetraene propyl ester, wherein the mol ratio of the aluminum phosphate of titanate esters and generation is 1.0: 20, with the mol ratio of ethylene glycol be 0.0067: 1.0, stir, directly be warming up to 195-198 ℃, and in heating process, constantly discharge the low molecular compound that generates in the reaction system by distilling apparatus, when no distillate is discharged, stop heating, reaction time needs 35min approximately, leave standstill and be cooled to normal temperature, vacuum filtration, filtrate recycle and reuse, solids decolours with the industrial alcohol washing, drying promptly obtains catalyst, and the catalyst granules particle diameter is the 10-25 nanometer.
Embodiment 9
Have agitator at one, in the reactor of rectifier unit, add 14.2gBa (OH)
2.8H
2O, 93g ethylene glycol and 10g water, the heating stirring and dissolving, the pH value that adds 98% sulfuric acid regulation solution gradually obtains white emulsion to 6-8.Heating and water by producing in the rectifier unit discharge reaction system, when treating anhydrous discharge, leave standstill and be cooled to below 60 ℃, add 1.7g metatitanic acid tetramethyl ester, wherein the mol ratio of the barium sulfate of titanate esters and generation is 1.0: 9.0, with the mol ratio of ethylene glycol be 0.0067: 1.0, stir, further be warming up to 196-198 ℃, and in heating process, constantly discharge the low molecular compound that generates in the reaction system by distilling apparatus, when no distillate is discharged, stop heating, the reaction time needs 30min approximately, leaves standstill to be cooled to normal temperature, vacuum filtration, the filtrate recycle and reuse, solids decolours drying with the industrial alcohol washing, promptly obtain catalyst, the catalyst granules particle diameter is the 8-20 nanometer.
Embodiment 10
Have agitator at one, in the reactor of rectifier unit, add the 4.16g silester, 124g ethylene glycol and 5g water, add hot reflux and make the silester complete hydrolysis, reaction time needs 50 minutes approximately, the low molecule product in the reaction system is discharged in rectifying then, leave standstill and be cooled to below 60 ℃, add 34.4g metatitanic acid tetramethyl ester, wherein the mol ratio of titanate esters and silester is 1.0: 0.1, with the mol ratio of ethylene glycol be 0.1: 1.0, stir, further be warming up to 194-196 ℃, and in heating process, constantly discharge the low molecular compound that generates in the reaction system by distilling apparatus, when no distillate is discharged, stop heating, the reaction time needs 45min approximately, leaves standstill to be cooled to normal temperature, vacuum filtration, the filtrate recycle and reuse, solids decolours drying with the industrial alcohol washing, promptly obtain catalyst, the catalyst granules particle diameter is the 4-20 nanometer.
Embodiment 11
Have agitator at one, in the reactor of rectifier unit, add 1.7g butyl titanate, 19.2g tetrabutyl zirconate, 124g ethylene glycol, wherein the mol ratio of titanate esters and tetrabutyl zirconate is 1.0: 10, with the mol ratio of ethylene glycol be 0.0025: 1.0, stir, heat temperature raising feeds N to 130-140 ℃
2And adjusting N
2Flow is that 0.5 liter/min rises reactor, continues to be warming up to 197-198 ℃, and constantly discharges the low molecular compound that generates in the reaction system by rectifier unit in heating process, when no distillate is discharged, stop heating, the reaction time needs 70min approximately, leaves standstill to be cooled to normal temperature, vacuum filtration, the filtrate recycle and reuse, solids decolours drying with the industrial alcohol washing, promptly obtain catalyst, the catalyst granules particle diameter is the 6-20 nanometer.
Embodiment 12
Have agitator at one, in the reactor of rectifier unit, add 11.9g butyl titanate, 5.75g tetrabutyl zirconate, 93g ethylene glycol, wherein the mol ratio of titanate esters and tetrabutyl zirconate is 7.0: 3.0, with the mol ratio of ethylene glycol be 0.023: 1.0, stir, heat temperature raising is to 130-140 ℃,, vacuumize and be decompressed to 8.0*10
4Pa begins to have distillate to discharge, and continues to be warming up to 189-192 ℃, and in heating process, constantly discharge the low molecular compound that generates in the reaction system by rectifier unit, when no distillate is discharged, stop heating, reaction time needs 55min approximately, leave standstill and be cooled to normal temperature, vacuum filtration, filtrate recycle and reuse, solids decolours with the industrial alcohol washing, drying promptly obtains catalyst, and the catalyst granules particle diameter is the 4-19 nanometer.
Embodiment 13
Have agitator at one, in the reactor of rectifier unit, add 23.65gBa (OH)
2.8H
2O, 124g ethylene glycol and 20g water, the heating stirring and dissolving, the pH value that adds 98% sulfuric acid regulation solution gradually is to 6-8, obtain white emulsion, further heating, and discharge the water that produces in the reaction system by rectifier unit, when treating anhydrous discharge, leave standstill and be cooled to below 60 ℃, add the 8.5g butyl titanate, wherein the mol ratio of the barium sulfate of titanate esters and generation is 1.0: 3.0, with the mol ratio of ethylene glycol be 0.0125: 1.0, stir, further be warming up to 90 ℃, vacuumize and be decompressed to 50-60Pa, continue to be warming up to 105-110 ℃, and in heating process, constantly discharge the low molecular compound that generates in the reaction system by distilling apparatus, when no distillate is discharged, stop heating, the reaction time needs 120min approximately, uses N
2Remove vacuum, leave standstill and be cooled to normal temperature, vacuum filtration, the filtrate recycle and reuse, solids decolours with the industrial alcohol washing, and drying promptly obtains catalyst, and the catalyst granules particle diameter is the 8-20 nanometer.
Use symbol: Pa among the present invention: handkerchief; L: rise; Min: minute; %: percentage by weight; G: gram.
Catalyst particle size assay method among the present invention is that catalyst is added in the ethylene glycol, disperses to make the dispersion liquid that contains catalyst 0.5-20% through routine stirring or supersonic oscillations, passes through transmissioning electric mirror determining.
Anti-hydrolysis described in the present invention is meant the solid catalyst moisture absorption or does not decompose when washing.
High activity described in the present invention is meant when adopting this catalyst to synthesize PET (abbreviation of PETG), with active ingredient TiO
2Meter, compare as catalyst with the employing antimony oxide, in the polycondensation time when identical, compound/supported catalyst consumption only is according to below 1/10 of antimony oxide consumption, and titanium perhaps of the present invention compound or/and supported catalyst consumption and the product of polycondensation time are less than antimony oxide consumption and below 1/10 of polycondensation time product.
The assay method of Ti content adopts AAS in the catalyst of the present invention.
From embodiment 1-13 as can be seen, the present invention has following characteristics:
1, synthesized the anti-hydrolysis high-activity titanium of gang's nanoscale compound/supported catalyst;
2, compound among the present invention/supported catalyst synthesis technique is simple, easy to operate, and cost is low;
3, adopt the present invention compound/the supported catalyst synthesizing polyester, can eliminate the environmental pollution of using antimony-based catalyst to exist;
4, providing a kind of anti-hydrolysis titanium is compound/load compound.
Claims (10)
1, a kind of titanium is compound or/and supported catalyst is characterized in that adopting boric acid or the acetic acid in phosphoric acid or sulfuric acid or the organic acid or propionic acid or butyric acid ethanedioic acid or malonic acid or succinic acid or metal ion Li in facile hydrolysis titanium (IV) compound and the inorganic acid
+, Na
+, K
+, Mg
2+, Ca
2+, Al
3+, Zn
2+Oxide or hydroxide or Ba
2+Hydroxide or metal ion Li
+, Na
+, K
+, Mg
2+, Ca
2+, Al
3+, Zn
2+, Sr
2+, Ba
2+, Mn
2+, Co
2+Carbonate or acetate or metal ion Zr
4+Or Si
4+Alkoxide compound at least aly in dihydroxylic alcohols, react, the compound of oxide, alcoholates and the metal ion alcoholates or the inorganic salts of the oxide of formation titanium (VI) and the compound of alcoholates or titanium (VI), and by further deviating from the low molecular compound that reaction produces, make gel be converted into the granular solids product, with solid product through vacuum filtration or centrifugation, the solution recycle and reuse, solids decolours, is drying to obtain through washing, and the particle diameter of this catalyst in dihydroxylic alcohols is the 4-25 nanometer.
2, titanium according to claim 1 is compound/supported catalyst, it is characterized in that said facile hydrolysis titanium (IV) compound is that metatitanic acid tetramethyl ester, metatitanic acid tetraene propyl ester or general formula are Ti (C
nH
2n+1O)
4The alkoxytitanium acid esters of (wherein n is 2-8).
3, titanium according to claim 1 is compound/supported catalyst, it is characterized in that described dihydroxylic alcohols is that ethylene glycol and general formula are C
nH
2n(OH)
2Hydroxyl dihydroxylic alcohols between (wherein n is the integer of 3-6).
4, be compound/supported catalyst according to claim 1, described titanium, it is characterized in that the titanium compound of described facile hydrolysis and the mol ratio of dihydroxylic alcohols are 0.001-0.3: 1.0, facile hydrolysis titanium (IV) compound (titanate esters) is respectively with boric acid, organic acid mol ratio: 1.0: 0.08-4.0; The mol ratio of the acetate of facile hydrolysis titanium compound and metal ion (comprising the metal ion oxide, the acetate that hydroxide and carbonate and acetic acid form), phosphate, sulfate is 1.0: 0.20-50; Facile hydrolysis titanium compound and Si
4+, Zr
4+The mol ratio of alkoxide compound be 1.0: 0.1-10.
5, be compound/supported catalyst according to claim 1, described titanium, it is characterized in that described Zr
4+, Si
4+Alkoxide compound be esters of silicon acis or zirconate.
6, titanium according to claim 1 is the preparation method of compound/supported catalyst, it is characterized in that having stirring at one, in the reactor of distillation or rectifier unit, add at least a and dihydroxylic alcohols in facile hydrolysis titanium (IV) compound and inorganic acid, organic acid, the 1-4 valence metal ion compound, stir, heating promotes reactant reaction to form gel; By the temperature of adjusting reaction system be 105 ℃ to the dihydroxylic alcohols boiling point, pressure is 50Pa to normal pressure and to feed flow be that 0.01-1.0L/min rises the low molecular compound that the reactor inert gas is discharged the reaction generation gradually, make and in solution, generate a granular solids product, when no longer including the distillate discharge in the question response system, stop heating and stirring, leave standstill and be cooled to normal temperature, with product through vacuum filtration or centrifugation, the solution recycle and reuse, solids is through the washing decolouring, drying, promptly obtain can be used for the anti-hydrolysis high-activity titanium that the esterification and the condensation of binary acid binary alcohol esters of catalysis acid and alcohol generate high molecular weight reactive compound/supported catalyst.
7, titanium according to claim 6 is the preparation method of compound/supported catalyst, it is characterized in that inert gas is N
2Or He.
8, titanium according to claim 6 is the preparation method of compound/supported catalyst, it is characterized in that catalyst separation is to adopt vacuum filtration or/and centrifugation.
9, titanium according to claim 6 is the preparation method of compound/supported catalyst, and the washing decolouring that it is characterized in that catalyst is with ethanol, acetone low boiling point solvent washing catalyst.
10, titanium according to claim 1 is compound/supported catalyst, it is characterized in that this catalyst needs to be dispersed in the dihydroxylic alcohols through routine stirring or supersonic oscillations.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01115117 CN1116928C (en) | 2001-07-05 | 2001-07-05 | Ti-series compound and/or carried catalyst and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01115117 CN1116928C (en) | 2001-07-05 | 2001-07-05 | Ti-series compound and/or carried catalyst and its preparing process |
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|---|---|
| CN1327879A CN1327879A (en) | 2001-12-26 |
| CN1116928C true CN1116928C (en) | 2003-08-06 |
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|---|---|---|---|
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1857483A4 (en) * | 2005-01-21 | 2015-01-21 | Mitsubishi Chem Corp | CATALYST FOR POLYCONDENSATION OF POLYESTERS AND METHOD OF SYNTHESIZING POLYESTER RESINS EMPLOYING SAID CATALYST |
| CN101148499B (en) * | 2006-09-20 | 2010-08-11 | 中国石油化工股份有限公司 | Titanium series catalyst |
| CN104558545B (en) * | 2013-10-15 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of catalyst system and the application in preparing aliphatic polyester reaction thereof |
| TWI738470B (en) * | 2019-10-30 | 2021-09-01 | 柏瑞克股份有限公司 | Catalyst for use in esterification reaction and synthesis method thereof |
| CN114479038B (en) * | 2020-10-23 | 2024-11-29 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method and application thereof |
| CN115772257B (en) * | 2021-09-08 | 2024-03-26 | 中国石油化工股份有限公司 | Modifier for high-heat-resistance polyester, preparation method of modifier, preparation method of polyester by using modifier and obtained polyester |
| US12303879B1 (en) | 2024-01-15 | 2025-05-20 | Jiangsu Guowang High-Technique Fiber Co., Ltd. | Nano-supported solid-phase titanium-based multi-metal catalyst, preparation method therefor and use thereof |
| CN117567730B (en) * | 2024-01-15 | 2024-04-30 | 江苏国望高科纤维有限公司 | Nano-supported solid-phase titanium-based multielement metal catalyst and preparation method and application thereof |
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