CN1162436C - Binary titanium alkoxide (VI) compound and its preparing process and application - Google Patents
Binary titanium alkoxide (VI) compound and its preparing process and application Download PDFInfo
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- CN1162436C CN1162436C CNB011151161A CN01115116A CN1162436C CN 1162436 C CN1162436 C CN 1162436C CN B011151161 A CNB011151161 A CN B011151161A CN 01115116 A CN01115116 A CN 01115116A CN 1162436 C CN1162436 C CN 1162436C
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Abstract
The present invention relates to a dibasic alcohol titanium (VI) compound, a preparation method and an application thereof. Easily hydrolytic titanium (IV) compounds or hydrolysis products of the easily hydrolytic titanium (IV) compounds directly react with dibasic alcohol or hydrous dibasic alcohol, which generates gel; low-molecular reaction products in a reaction system are gradually removed by regulating temperature and pressure of the reaction system or introducing inert gas, etc., the products are separated, decolorized and dried, and the hydrolysis-resisting dibasic alcohol titanium (VI) compound is obtained. The preparation method has the advantages of simple synthetic process, easy operation and low cost; the dibasic alcohol titanium compound can be used as high activated catalysts of an esterification reaction, an ester exchange reaction and a polycondensation reaction, and simultaneously, the dibasic alcohol titanium compound has optical catalytic performance. The synthetic dibasic alcohol titanium can reach the nano-grade, can resist hydrolysis, and has the obvious catalytic activity in catalytic esterification reaction and the polycondensation reaction; the dibasic alcohol titanium compound is used as polyester catalysts, the preparation process of antimony catalysts can be omitted, the production cost of polyester is reduced, and the environmental pollution in the process of polyester production and post processing is eliminated.
Description
Technical field
The invention belongs to the field of high activated catalyst, particularly relating to facile hydrolysis titanium (IV) compound and dibasic alcohol or moisture dibasic alcohol direct reaction, to prepare basic structural unit be C
nH
2n+1O
5Binary titanium alkoxide (VI) compound, its preparation method of Ti (wherein n is the even number of 4-12) and the catalyzer that is used as esterification, transesterify and polycondensation are used.
Background technology
As everyone knows, titanium (IV) acid esters is the important titanium sub-group compound of a class, and is used as the catalyzer of esterification, transesterify and polycondensation, but owing to their facile hydrolysis, active unstable, there is muddy phenomenon etc. in the polymer that catalysis forms, and its application is very limited.
Research about anti-hydrolysis Titanium series catalyst, according to Chem.Fibers Int.1999.49 (1) .27-29 (Eng), Germany Acordis company develops the titanium that a kind of code name is C-64/titanium-silicon mixed oxide compound high-activity PET (abbreviation of polyethylene terephthalate) catalyzer in the world first, wherein the ratio of Ti/Si is 9: 1, grain diameter is less than 10 μ m, anti-hydrolysis, price are 120 German Marks/kg.But the catalyzer synthetic technology is not made reports.
Summary of the invention
Purpose of the present invention has just provided a kind of high active anti-hydrolizable titanium compound that shows---binary titanium alkoxide (IV) compound in catalytic esterification, transesterify and polycondensation.
Another object of the present invention just provides the synthetic method of a kind of binary titanium alkoxide of the present invention (VI) compound.
A further object of the invention is with the application of binary titanium alkoxide of the present invention (VI) compound in catalytic esterification, transesterify and polycondensation.
In order to reach purpose of the present invention, adopt dibasic alcohol or moisture dibasic alcohol and facile hydrolysis titanium (IV) compound or their hydrolysate are carried out alcoholysis and form gel, and by adjusting temperature in the reactive system, pressure or feeding rare gas element etc. are deviate from the low molecular compound in the reactive system, by further promotion dibasic alcohol and titanic acid ester reaction, make the Sauerstoffatom of dibasic alcohol combine two 5 Yuans rings of formation intramolecularly or 6 Yuans rings with chemical bond and coordinate bond with titanium atom, make titanium atom with 6 valence states atom combination on every side together, fundamentally solve the hydrolysis problem of titanium compound, generate anti-hydrolysis binary titanium alkoxide (VI) compound, simultaneously because titanium atom strengthens in conjunction with electronic capability and binary titanium alkoxide (VI) disperses with nanoscale in dibasic alcohol and synthetic polyester, therefore at catalytic esterification, show high catalytic activity in transesterify and the polycondensation, and make the synthetic polyester have significant photochemical properties.
Introduce the present invention below in detail:
Have in the distillation or the reactor of rectifier unit at one, add titanic acid ester and dibasic alcohol or moisture dibasic alcohol and stir, reactant is the gel emulsus; Elevated temperature, under conditions such as normal pressure or decompression or feeding rare gas element, deviate from the low molecular compound that raises and generate with temperature in the reaction system gradually, make and in solution, generate a white product, solution colour presents by pale yellow to dark red variation with the variation that adds the titanium compound amount.Treat that temperature rises near the corresponding dibasic alcohol boiling point and when remaining unchanged, stopped reaction is reduced to normal temperature, reaction product is through vacuum filtration or centrifugation, the filtrate recycling use, solids promptly obtains anti-hydrolysis binary titanium alkoxide compound with low boiling point solvent washing decolouring, drying.
Facile hydrolysis titanium compound of the present invention is Ti (C
nH
2n+1O)
4The titanic acid ester of (wherein n is the integer of 1-8).
Dibasic alcohol of the present invention is that ethylene glycol or general formula are C
nH
2n(OH)
2Hydroxyl dibasic alcohol between (wherein n is the integer of 3-6).Ethylene glycol forms five-membered ring with titanium atom in reaction, general formula is C
nH
2n(OH)
2Between the hydroxyl dibasic alcohol then with Ti
6+Atom forms six membered ring, help forming anti-hydrolysis binary titanium alkoxide compound, other adjacent oxy-compound such as 1.2-propylene glycol, carbonatoms surpass 6 dibasic alcohol and non-hydroxyl dibasic alcohol such as 1.4-butyleneglycol etc. then can not or difficult and titanium atom formation six membered ring, and product facile hydrolysis.
With titanic acid ester and diol reaction the time, the mol ratio of titanic acid ester and dibasic alcohol is 0.0009-0.30: 1.0, when being lower than 0.0009: 1.0, can not get binary titanium alkoxide (VI) compound solid product in the reaction system; When being higher than 0.30: 1.0, the titanic acid ester transformation efficiency is low, and the binary titanium alkoxide compound thickness that obtains is not easy to separate decolouring, washing and dry, and part generation hydrolysis is arranged, and illustrates that reaction not exclusively.In reaction, introduce organic solvent, though can improve the mol ratio of titanic acid ester and dibasic alcohol, but technological operation complexity, it is high easily to produce pollution and cost, the mol ratio of titanic acid ester and dibasic alcohol is 0.0009-0.30: 1.0, be preferably in 0.005-0.25: in the time of in 1.0 scopes, the binary titanium alkoxide compound quality that obtains is stable and cost is lower.
In dibasic alcohol, add entry, can promote the decomposition of titanic acid ester, accelerate the conversion of titanate compound, improve the resultant color and luster, when the water yield is lower than 5% (weight ratio) of titanic acid ester amount, DeGrain; When moisture was higher than 60% (weight ratio) of titanic acid ester amount, because of raising with temperature in the reaction, titanic acid ester hydrolysis aggravation and very fast part were decomposed into metatitanic acid or metatitanic acid, therefore cause speed of response to reduce.
In the present invention, by reactive system being vacuumized or feeds rare gas element or under normal pressure, directly deviating from the low molecular compound that generates in the reactive system.Temperature of reaction generally should be controlled at 105 ℃ to the boiling point left and right sides scope of dibasic alcohol, when temperature of reaction is lower than 105 ℃, react required vacuum tightness height (＜50Pa) and long reaction time; When temperature is higher than the dibasic alcohol boiling temperature that participates in reaction, need to improve system pressure, this obviously can make the complicated and increase energy consumption of operational condition, temperature of reaction remains on 105 ℃ to the scope of the dibasic alcohol boiling point left and right sides, to the normal pressure scope, change at 50Pa with pressure, and make solution remain on boiling state to react, effect is better.The rare gas element that uses in the reaction is N
2And He, generally adopt nitrogen, do not take dibasic alcohol out of for guaranteeing to take low molecular compound out of, general dominant discharge rises reactor at 0.01-1.0L/min.
Anti-hydrolysis binary titanium alkoxide compound described in the present invention, its basic structural unit can be expressed as follows:
Wherein:---H represents hydrogen bond; R representative-CH
2CH
2-,-CH
2CH
2CH
2-the alkyl of hydroxyl butyleneglycol, a hydroxyl pentanediol, a hydroxyl hexylene glycol between reaching, they constitute five-membered ring and six membered ring together with Sauerstoffatom and titanium atom.
Binary titanium alkoxide compound among the present invention all has very high catalytic performance for esterification, transesterification reaction and polycondensation, and the generation of water does not influence catalytic performance in the esterification.Therefore, anti-hydrolysis binary titanium alkoxide (VI) compound can be used as the high activated catalyst of esterification, transesterify and polycondensation, has photocatalysis performance simultaneously.
The said esterification of the present invention is acid and alcohol reaction, and polycondensation refers to that the condensation of diprotic acid binary alcohol esters forms high molecular reaction.
Specific embodiments
Further specify the present invention below by embodiment.
Embodiment 1
In a reactor that has agitator, a water distilling apparatus, add the 25.5g tetrabutyl titanate, and 124g ethylene glycol, wherein the mol ratio of titanic acid ester and dibasic alcohol is 0.0375: 1.0.Stir, make its reaction form gel, be warming up to 130 ℃, feed N
2, and adjust N
2Flow is that 0.5L/min rises reactor, continue to be warming up to 197-198 ℃, when treating that temperature no longer changes, stopped reaction, reaction times needs 40min approximately, leave standstill and be cooled to normal temperature, vacuum filtration or centrifuging, the filtrate recycling use, solids is with the decolouring of industrial alcohol or washing with acetone, drying, promptly get titanium ethylene glycolate (VI) white solid, wherein Ti content is 25.9%, and after routine stirring or ultra-sonic oscillation dispersion, grain diameter is the 4-19 nanometer in dibasic alcohol for it, get 5.0g and add in the 100g deionized water, at least onely do not decompose round the clock.
Embodiment 2
In a reactor that has agitator and a water distilling apparatus, add the 25.5g tetrabutyl titanate, 124g ethylene glycol and 12.75g deionized water, wherein the mol ratio of titanic acid ester and dibasic alcohol is 0.0375: 1.0, stirs, and makes it reaction and forms gel, be warming up to 130 ℃, feed N
2And adjustment N
2Flow is that 1.0L/min rises reactor, begin to have overhead product to discharge, continue to be warming up to 197-198 ℃ of ethylene glycol boiling point, when treating that temperature no longer changes, stopped reaction, reaction times needs 45min approximately, leaves standstill to be cooled to normal temperature, vacuum filtration, the filtrate recycling use, solids decolours with washing with acetone, drying, and getting titanium ethylene glycolate white solid Ti content is 26.0%, it stirs or after ultra-sonic oscillation disperse through routine in dibasic alcohol, grain diameter is the 4-19 nanometer, gets 5.0g and adds in the 100g deionized water, at least one decomposition down round the clock.
Embodiment 3
In a reactor that has agitator and a rectifier unit, add 0.5g tetrabutyl titanate 99.5g ethylene glycol, wherein the mol ratio of titanic acid ester and dibasic alcohol is 0.0009: 1.0, stirs, make its reaction form gel, when being warming up to 50 ℃, solution is transparent, and is persistently overheating then to 197-198 ℃, it is transparent that solution keeps always, leave standstill the cooling diel, still do not have solids and produce, continue to add the 0.25g tetrabutyl titanate, stir, repeat aforesaid operations, then the adularescent solids produces, and solution colour is little yellow, vacuum filtration obtains solids, and use industrial washing with alcohol, and drying, getting titanium ethylene glycolate white solid Ti content is 26.1%, it stirs or after ultra-sonic oscillation disperse through routine in dibasic alcohol, grain diameter is the 4-19 nanometer, gets 5.0g and adds in the 100g deionized water, does not at least onely decompose round the clock.
Embodiment 4
In a reactor that has agitator and a rectifier unit, add the 8.5g tetrabutyl titanate, 124g ethylene glycol, wherein the mol ratio of titanic acid ester and dibasic alcohol is 0.0125: 1.0, stir, make its reaction form gel, when being warming up to 90 ℃, vacuumizing and be decompressed to 50-60Pa, continue to be warming up to 105-110 ℃, when overhead product not had is separated out, stop heating, use N
2Remove vacuum, reaction times needs 120min approximately, leave standstill and be cooled to the recovery of normal temperature vacuum filtration filtrate, solids washing with acetone drying, getting titanium ethylene glycolate (VI) white solid titanium content is 26.1%, and after routine stirring or ultra-sonic oscillation dispersion, grain diameter is the 4-19 nanometer in dibasic alcohol for it, get 5.0g and add in the 100g deionized water, at least onely do not decompose round the clock.
Embodiment 5
In a reactor that has agitator and a rectifier unit, add 51.6g metatitanic acid tetramethyl ester, 90g 1.3-butyleneglycol, wherein the mol ratio of titanic acid ester and dibasic alcohol is 0.30: 1.0, stirs, and makes its reaction form gel, when being warming up to 130 ℃, feeding N
2And adjusting N
2Flow is that 0.01L/min rises reactor, and beginning has overhead product, continues to be warming up to 204 ℃, solution is white in color thick, and temperature rises slowly, stops heating, reaction times needs 90min approximately, leaves standstill to be cooled to normal temperature, vacuum filtration, filtrate is reclaimed, and solids finds to have partial hydrolysis with industrial spirit washing decolouring, dry, 1.3-butyleneglycol titanium (VI) white solid, titanium content be 20.1%. its in dibasic alcohol, stir or after ultra-sonic oscillation disperseed, grain diameter was the 10-20 nanometer through routine.
Embodiment 6
In a reactor that has agitator and a water distilling apparatus, add 14.1g metatitanic acid four monooctyl esters, 118g 1.3-hexylene glycol, wherein the mol ratio of titanic acid ester and dibasic alcohol is 0.025: 1.0, stirs, and makes its reaction form gel, when being heated to 180 ℃, vacuumizing and be decompressed to 4.0 * 10
4Pa begins to have overhead product to discharge, and continues to be warming up to 215-225 ℃, when no longer including overhead product and separate out, stops heating, and the reaction times needs 70min approximately, uses N
2Remove vacuum, leave standstill and be cooled to normal temperature, centrifugation, solids decolours with washing with acetone, drying, get 1.3-hexylene glycol titanium (VI) white solid, titanium content is 16.5%, and after routine stirring or ultra-sonic oscillation dispersion, grain diameter is the 6-20 nanometer in dibasic alcohol for it, get 5.0g and add in the 100g deionized water, 3h does not decompose at least.
Embodiment 7
In a reactor that has agitator and a rectifier unit, add 34.4g metatitanic acid tetramethyl ester, the mol ratio of 93g titanium ethylene glycolate acid esters and dibasic alcohol is 0.10: 1.0, stir, make its reaction form gel, when being heated to 140-160 ℃, beginning has overhead product, continue to be warming up to 196-198 ℃, and constantly discharge overhead product, when no longer including the overhead product discharge, stop heating, leave standstill and be cooled to normal temperature, vacuum filtration, filtrate is reclaimed, and solids decolours with the industrial spirit washing, dry, titanium ethylene glycolate (VI) white solid, titanium content be 26.1% its in dibasic alcohol, stir or after ultra-sonic oscillation disperseed, grain diameter was the 4-19 nanometer through routine, get 5.0g and add in the 100g deionized water, at least onely do not decompose round the clock.
Embodiment 8
In 2.5 liters of stainless steel cauldrons, add the 996g terephthalic acid, 465g ethylene glycol and 0.041g titanium ethylene glycolate, wherein titanium content is 25.9-26.3% in the titanium ethylene glycolate, at 0.5-3.0kg/cm
2Carry out esterification under the G condition, and slough the water that reaction generates by rectifier unit, when temperature rise to 255 ℃, be depressurized to normal pressure, continue to be warming up to 260 ℃, until anhydrous discharge, reaction times needs 2 hours approximately, vacuumize and be decompressed to 20000Pa, and be decompressed to 300Pa in 45min, temperature is controlled at 260-285 ℃, further be decompressed to below the 50-60Pa gradually, temperature is 280-295 ℃, and when polymer viscosity reached 0.68dl/g, the poly-time of final minification was about 27 minutes, the synthetic polymkeric substance is light yellow transparence, places 10h and become colorless transparent under daylight.
Embodiment 9
In 2.5 liters of stainless steel cauldrons, add the 996g terephthalic acid, 465g ethylene glycol is at 0.5-3.0kg/cm
2Carry out esterification under the G condition, and slough the water that reaction generates by rectifier unit, when temperature rise to 255 ℃, be depressurized to normal pressure, continue to be warming up to 260 ℃, until anhydrous discharge, reaction times needs 2 hours 20 minutes approximately, gets the 0.041g titanium ethylene glycolate and adds in the 10g ethylene glycol, and this dispersion liquid is added in 2.5 liters of reactors, use the 10g ethylene glycol washing, vacuumize and be decompressed to 20000Pa, and be decompressed to 300Pa in 45min, temperature is controlled at 260-285 ℃, further be decompressed to below the 50-60Pa gradually, temperature is 280-295 ℃, and when polymer viscosity reached 0.68dl/g, the poly-time of final minification was about 25min, the synthetic polymkeric substance is light yellow transparence, places 10h and become colorless transparent under daylight; Titanium ethylene glycolate suspension is replaced by the ethylene glycol solution (annotate: heating for dissolving becomes homogeneous phase solution) of 10g trioxygen-containingization two antimony 0.36g, repeat embodiment 9, then the poly-time of final minification is 31min, and the synthetic polymkeric substance is light grey transparence, places the 10h nondiscoloration under daylight.
Symbol among the present invention: Pa is a handkerchief, and L rises, and min is minute, and h is hour, and % is a weight percent, and dl/g is a limiting viscosity, and g is a gram, and kg is a kilogram, cm
2Be square centimeter, G represents gauge pressure.
The particle size determination method of binary titanium alkoxide is that binary titanium alkoxide is added in the dibasic alcohol among the present invention, after making the dispersion liquid that contains binary titanium alkoxide 0.5-20% after routine stirring or the ultra-sonic oscillation dispersion, adopts transmissioning electric mirror determining.
Titanium content employing spectrophotometry in the binary titanium alkoxide compound among the present invention.
Among the present invention in the binary titanium alkoxide compound measuring method of C, H, O element be combustion method.
The resistance to hydrolysis of binary titanium alkoxide can be 5.0 gram binary titanium alkoxides to be added in the 100 gram water diel no change among the present invention.
Can find out that from embodiment 1-9 the present invention has following advantages:
1, the binary titanium alkoxide that synthesizes of the present invention reaches nanoscale, and resistant to hydrolysis, shows in catalytic esterification and polycondensation reaction Go out significant catalytic activity.
2, adopt synthesis of dibasic alcohol titanium of the present invention, technology is simple, and is easy to operate, and cost is low.
3, adopt binary titanium alkoxide that the present invention synthesizes as polyester catalyst, can save the modulation of using antimony-based catalyst Process reduces the production of polyester cost, eliminates the environmental pollution that exists in production of polyester and the rear process.
4, the polyester that adopts the present invention to synthesize has significant whitening effect.
5, compare with German C-64 and the disclosed prior art of TOHKEMY 2000-143789, polycondensation process catalysis is lived The property (with active ingredient Ti content meter) improved at least respectively 2-6 doubly.
Claims (9)
1, a kind of anti-hydrolysis binary titanium alkoxide (VI) compound, its chemical constitution or basic structural unit are C
nH
2n+1O
5Ti, wherein n is the even number of 4-12, by dibasic alcohol or moisture dibasic alcohol and the generation of facile hydrolysis titanium compound hybrid reaction, it is characterized in that dibasic alcohol or moisture dibasic alcohol and facile hydrolysis titanium compound hybrid reaction are in the reactor that has distillation or rectifier unit, under normal pressure or decompression or feeding inert gas conditions, deviate from the low molecular compound that raises and generate with temperature in the reaction system gradually, make and in solution, generate a white product, when treating that temperature rises to corresponding dibasic alcohol or moisture dibasic alcohol boiling point, cooling, separating solid substances promptly obtains anti-hydrolysis binary titanium alkoxide (VI) compound.
2, binary titanium alkoxide according to claim 1 (VI) compound is characterized in that said facile hydrolysis titanium compound is a titanic acid ester, and its general formula is Ti (C
nH
2n+1O)
4, wherein n is the integer of 1-8.
3, binary titanium alkoxide according to claim 1 (VI) compound is characterized in that said dibasic alcohol is that ethylene glycol or general formula are C
nH
2n(OH)
2Between the hydroxyl dibasic alcohol, n is the integer of 3-6 in the formula.
4, the preparation method of the described binary titanium alkoxide of a kind of claim 1 (VI) compound is characterized in that having in the distillation or the reactor of rectifier unit at one, adds titanic acid ester and dibasic alcohol or moisture dibasic alcohol and stirs, and reactant is the gel emulsus; Elevated temperature, under normal pressure or decompression or feeding inert gas conditions, deviate from the low molecular compound that raises and generate with temperature in the reaction system gradually, make and in solution, generate a white product, solution colour presents by pale yellow to dark red variation with the variation that adds the titanium compound amount; Treat that temperature rises near the corresponding dibasic alcohol boiling point and when remaining unchanged, stopped reaction is reduced to normal temperature, and reaction product is through vacuum filtration or centrifugation, filtrate recycling use, solids promptly obtain binary titanium alkoxide (VI) compound of anti-hydrolysis after with low boiling point solvent washing decolouring, drying.
5, the preparation method of binary titanium alkoxide according to claim 4 (VI) compound, the mol ratio that it is characterized in that titanic acid ester and dibasic alcohol is 0.0009-0.30: 1.0.
6, the preparation method of binary titanium alkoxide according to claim 4 (VI) compound is characterized in that temperature of reaction is 105 ℃ of boiling temperatures to dibasic alcohol, pressure be 50Pa to normal pressure, rare gas element is N
2Or He.
7, the preparation method of binary titanium alkoxide according to claim 4 (VI) compound, the mol ratio that it is characterized in that titanic acid ester and dibasic alcohol is 0.005-0.25: 1.0.
8, according to the preparation method of claim 4 or 6 described binary titanium alkoxide (VI) compounds, it is characterized in that feeding inert gas flow is that 0.01-1.0L/min rises reactor.
9, binary titanium alkoxide according to claim 1 (VI) compound is as the application of high activated catalyst in esterification, transesterify and polycondensation.
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|---|---|---|---|
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| CN102492120A (en) * | 2011-11-18 | 2012-06-13 | 上海华谊（集团）公司 | Nanometer catalyst for compounding polytrimethylene terephthalate and preparation method and application thereof |
| CN102875591B (en) * | 2012-09-25 | 2015-03-04 | 湖北新蓝天新材料股份有限公司 | Method for preparing tetra-tert-butyl orthotitanate composite |
| CN105085873A (en) * | 2014-05-13 | 2015-11-25 | 中国石油化工集团公司 | Continuous catalysis production method of PBT resin |
| CN105085889A (en) * | 2014-05-13 | 2015-11-25 | 中国石油化工集团公司 | Preparation method of catalyst for synthesis of PBT |
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