CN1327879A - 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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- CN1327879A CN1327879A CN 01115117 CN01115117A CN1327879A CN 1327879 A CN1327879 A CN 1327879A CN 01115117 CN01115117 CN 01115117 CN 01115117 A CN01115117 A CN 01115117A CN 1327879 A CN1327879 A CN 1327879A
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Abstract
A Ti-series composite and/or carried catalyst for the esterification reaction of acid and alcohol and the binary acid and biol ester condensation reaction to generate high-molecular resultant is prepared through the reaction of easily hydrolyzed Ti(IV) compound with at least one of inorganic acid, organic acid and 1-4 valence metallic ion compound in diol to generate said catalyst. Its advantages include high activity, simple preparing process, low cost and no environmental pollution.
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 1-4 valence metal ion compounds, 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 4-20 nanometers.
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 1-4 valence metal ion compounds, 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 4-25 nanometers.
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 1-4 integer. 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 3-6 integer).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 compounds.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: 0.1-10 with the mol ratio of esters of silicon acis, zirconate.
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 directly deviate from the low molecular compound that generates in the system under normal pressure 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 ℃ of needed vacuum height of reaction (＜50Pa) and reaction speed slow, when temperature is higher than the dihydroxylic alcohols boiling temperature that participates in reaction, need to improve system pressure, this can make operating condition complicated and increase energy consumption.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, during temperature rise to 180-190 ℃, 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 4-19 nanometers.
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 4-19 nanometers.
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 4-19 nanometers.
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 4-12 nanometers, 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 10-20 nanometers.
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 4-19 nanometers.
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 10-20 nanometers.
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 10-25 nanometers.
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 adds the pH value to 6-8 of 98% sulfuric acid regulation solution gradually, obtains white emulsion.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 8-20 nanometers.
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 4-20 nanometers.
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 to 130-140 ℃ feeds N
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 6-20 nanometers.
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 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 4-19 nanometers.
Embodiment 13
Have agitator at one, in the reactor of rectifier unit, add 23.65gBa (OH)
28H
2O, 124g ethylene glycol and 20g water, the heating stirring and dissolving, the pH value to 6-8 that adds 98% sulfuric acid regulation solution gradually, 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 8-20 nanometers.
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.
Can find out that from embodiment 1-13 the present invention has following characteristics:
1, synthesized gang's nanoscale resistant to hydrolysis high-activity titanium 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 and use antimony-based catalyst to exist Environmental pollution;
4, providing a kind of resistant to hydrolysis titanium is compound/load compound.
Claims (10)
1, a kind of titanium is compound or/and supported catalyst, it is characterized in that adopting and at least aly in facile hydrolysis titanium (IV) compound and inorganic acid, organic acid, 1-4 valence metal ion compounds in dihydroxylic alcohols, react, form 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).
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 inorganic acid is boric acid, phosphoric acid and sulfuric acid; Described organic acid is acetic acid, propionic acid, butyric acid, ethanedioic acid, malonic acid, succinic acid; Described metal ion compound is oxide, hydroxide, carbonate, acetate, the alkoxide compound of 1-4 valence metal ion compounds, promptly is Li
+, 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.
4, 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 3-6 integer).
5, be compound/supported catalyst according to claim 1,2,3 or 4 described titaniums, 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.
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, 1-4 valence metal ion compounds, stir, heating promotes reactant reaction to form gel; Discharge the low molecular compound that reaction generates gradually by temperature, pressure or the feeding inert gas of adjusting reaction system, 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 this catalyst is dispersed in the dihydroxylic alcohols through routine stirring or supersonic oscillations, and particle diameter is 4-25 nanometers.
8, titanium according to claim 6 is the preparation method of compound/supported catalyst, it is characterized in that reaction temperature be 105 ℃ to the dihydroxylic alcohols boiling point; Pressure is 50Pa-normal pressure; Inert gas is N
2And He, generally adopt N
2, its flow is that 0.01-1.0L/min rises reactor.
9, 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.
10, 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 low boiling point solvent washing catalysts such as ethanol, acetone.
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|---|---|---|---|
| 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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|---|---|---|---|
| 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 true CN1327879A (en) | 2001-12-26 |
| CN1116928C CN1116928C (en) | 2003-08-06 |
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| CN101148499B (en) * | 2006-09-20 | 2010-08-11 | 中国石油化工股份有限公司 | Titanium series catalyst |
| CN101107287B (en) * | 2005-01-21 | 2011-12-21 | 三菱化学株式会社 | Polyester polycondensation catalyst, and method for producing polyester resin using the polycondensation catalyst |
| CN104558545A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst system and application thereof in reaction for preparing aliphatic polyester |
| CN111944136A (en) * | 2019-10-30 | 2020-11-17 | 柏瑞克股份有限公司 | Catalyst for catalyzing esterification reaction and synthesis method thereof |
| CN114479038A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method and application thereof |
| CN115772257A (en) * | 2021-09-08 | 2023-03-10 | 中国石油化工股份有限公司 | Modifier for high-heat-resistance polyester, preparation method of modifier, polyester preparation method adopting modifier and polyester obtained by modifier |
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2001
- 2001-07-05 CN CN 01115117 patent/CN1116928C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101107287B (en) * | 2005-01-21 | 2011-12-21 | 三菱化学株式会社 | Polyester polycondensation catalyst, and method for producing polyester resin using the polycondensation catalyst |
| CN101148499B (en) * | 2006-09-20 | 2010-08-11 | 中国石油化工股份有限公司 | Titanium series catalyst |
| CN104558545A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst system and application thereof in reaction for preparing aliphatic polyester |
| 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 |
| CN111944136A (en) * | 2019-10-30 | 2020-11-17 | 柏瑞克股份有限公司 | Catalyst for catalyzing esterification reaction and synthesis method thereof |
| CN114479038A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method and application thereof |
| CN115772257A (en) * | 2021-09-08 | 2023-03-10 | 中国石油化工股份有限公司 | Modifier for high-heat-resistance polyester, preparation method of modifier, polyester preparation method adopting modifier and polyester obtained by modifier |
| 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 |
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