CN1328072A - High-activity catalyst and its application in synthesizing polyester - Google Patents
High-activity catalyst and its application in synthesizing polyester Download PDFInfo
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- CN1328072A CN1328072A CN 01115114 CN01115114A CN1328072A CN 1328072 A CN1328072 A CN 1328072A CN 01115114 CN01115114 CN 01115114 CN 01115114 A CN01115114 A CN 01115114A CN 1328072 A CN1328072 A CN 1328072A
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Abstract
A high-activity catalyst for both esterification and polycondensation contains anti-hydrolytic high-activity glycol titanium, the acetate, carbonate or oxalate of (1-4)-valence metal ions, and at least one of alkoxyl compound, organic acid and phosphorous compound. Its advantages are high activity, short reaction period, and no environmental pollution. Its resultant polyester has high photochemical performance and whiteness.
Description
Technical field
The present invention relates to polyester catalyst, relate to the high-activity titanium catalyst that adopts in the production of aromatic acid and aliphatic dihydroxy alcohol esterification condensation prepared in reaction polyester in more detail.
Background technology
In the polyester by diprotic acid and diol reaction, PET (abbreviation of polyethylene terephthalate) is a kind of polymkeric substance of high comprehensive performance, and Gross World Product surpasses 2,000 ten thousand tons at present, and still with annual speed increase more than 7%.PET is generally by terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol carries out direct esterification or transesterification reaction forms ethylene glycol terephthalate, and further polycondensation is synthetic in the presence of catalyzer again.As the PET polycondensation catalyst, generally adopt antimony compounds, germanium compound and facile hydrolysis titanium compound.Use germanium compound, as germanium dioxide, (general 1000 dollars/kg), can significantly improve the PET manufacturing cost of price height; And titanium compound can make the PET jaundice muddiness of preparation etc. owing to facile hydrolysis, and therefore the PET of the whole world more than 90% uses antimony compounds as Preparation of Catalyst at present, but the antimony compounds activity is low, makes PET be with grey easily, and causes environmental pollution.According to Chem.Fibers Int.1999.49 (1) .27-29 (Eng), German Acordis company develops the titanium that a kind of code name is C-64/silicon mixture compound high-activity PET catalyzer in the world first, and is used in the production of polyester.2000, the Japanese Patent spy opened the preparation process of polyester that 2000-143789 has also announced a kind of high activated catalyst based on titanic acid ester.
About the C-64 catalyzer of Germany, find no more detailed technology of preparing report, and cost is higher, every kg reaches 120 German Marks.
Ri Tekai 2000-143789 adopts facile hydrolysis titanic acid ester and magnesium acetate etc. to make catalyzer, improves than simple use titanic acid ester is active, still have titanic acid ester facile hydrolysis problem, and catalytic activity (in Ti) is still lower.
Summary of the invention
Purpose of the present invention just provides the synthetic middle anti-hydrolysis high activated catalyst that adopts of a kind of polyester, it is in the catalysis synthesizing polyester, improve esterification and polycondensation efficient, eliminate environmental pollution, and it is convenient that catalyzer is used because of using the antimony based compound to exist.
In order to reach above goal of the invention, the present invention adopts at least a in the acetate, carbonate, oxalate, malonate, succinate, alkoxy compound, organic acid, P contained compound of nano level anti-hydrolysis high reactivity titanium ethylene glycolate and 1-4 valence metal ions.
Introduce the present invention below in detail
Titanium ethylene glycolate of the present invention, its chemical formula are C
4H
9O
5Ti, particle diameter are 4-20 nanometers.
1-4 valence metal ions of the present invention are: Li
+, Na
+, K
+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Co
2+, Mn
2+, Zn
2+, Sn
2+, Al
3+, Si
4+, Zr
4+. its compound is Li
+, Na
+, K
+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Co
2+, Mn
2+, Zn
2+, Sn
2+, Al
3+, Si
4+, Zr
4+Acetate, carbonate, oxalate, malonate, succinate and alkoxy compound.
The phosphide that contains of the present invention is phosphoric acid salt, phosphite and phosphoric acid ester.
Organic acid of the present invention is oxalic acid, propanedioic acid, Succinic Acid.
Titanium ethylene glycolate consumption of the present invention is generally 0.001-0.1% (weight percent) of diprotic acid consumption, is preferably 0.001-0.03% (weight percent).
In the present invention, the consumption of described 1-4 valence metal ion compounds, organic acid and P contained compound is respectively 0.001-5.0% of diprotic acid consumption, is preferably 0.002-1.0% (weight percent).
The polyester of indication of the present invention, its raw material are aromatic acid and aliphatic dihydroxy alcohol, are terephthalic acid, phthalic acid, m-phthalic acid, ethylene glycol, 1.3-propylene glycol and 1.4-butyleneglycol or rather.
Preparation process of polyester of the present invention comprises two processes: esterification process and polycondensation process.Esterification process is the process that diprotic acid and dibasic alcohol direct reaction form the diprotic acid binary alcohol esters; Polycondensation process is the process that further condensation forms polyester macromolecule between the diprotic acid binary alcohol esters.In esterification process, general by discharging water yield judgement esterification terminal point, esterification yield at least will be more than 95%; In polycondensation phase, by vacuumizing or feed N
2Discharge the micromolecular compound that reaction generates, promote reaction to finish, and determine reaction end by power of agitator or rotating speed or limiting viscosity.For different polymkeric substance, condensation temperature generally is controlled at than high 20-60 centigradetemperatures of melting point polymer.
The present invention is example with PET, and the preparation method of other polyester such as PPT (abbreviation of poly terephthalic acid-1.3-propylene glycol ester), PBT (abbreviation of poly terephthalic acid-1.4-butanediol ester) and the preparation method of PET are same or similar.
Preparation process of polyester of the present invention is applicable to interrupter method, semi-continuous process and continuous processing.
Among the present invention, the mol ratio of diprotic acid and dibasic alcohol is: 1.0: 1.05-1.60, and interrupter method wherein, semi-continuous process generally is controlled at: 1.0: 1.1-1.60, continuous processing generally was controlled at: 1.0: 1.05-1.30.
When adopting interrupter method to prepare polyester, can adopt a reactor to be used for esterification and polycondensation process, also can adopt two reactors to be respectively applied for esterification and polycondensation process.For PET, esterification reaction pressure is 0.5-3.0kg/cm
2G, temperature is 185-275 ℃, the reaction times adds excessive dibasic alcohol and discharges the water that reaction generates rapidly generally at 1-5 hour in the reaction, can promote reaction to finish; The polycondensation temperature is: 260-300 ℃, pressure is: 0-20000Pa, the reaction times is generally at 1-4 hours.Polycondensation process also can adopt segmented mode, temperature and pressure is divided into two sections or three sections finishes.
When adopting semi-continuous process and continuous processing to prepare polyester, generally adopt two or more reactor segmentations to finish esterification and polycondensation process.First section esterification reaction temperature is 190-260 ℃, and pressure is 0.2-3.0kg/cm
2G, final esterification reaction temperature is 250-275 ℃, pressure is 0-1.0kg/cm
2G.Polycondensation process is divided into three phases, and precondensation, polycondensation and final minification are poly-, and wherein the precondensation temperature is 260-280 ℃, and pressure is 20000-2000Pa; Condensation temperature is 270-285 ℃, and pressure is 2000-300Pa; The poly-temperature of final minification is 275-300 ℃, and pressure is below 500-50Pa.
Catalyzer of the present invention adds mode, can add simultaneously with raw material diprotic acid and dibasic alcohol, also can be in esterification process or esterification process finish the back and add, but adding can improve esterification speed before esterification or in the esterification; Adding in form, with solid state or be dispersed in and be made into 0.5-20% suspension liquid in the dibasic alcohol and add and all can.
The present invention adopts limiting viscosity η to represent the extent of polymerization of polyester, and the unit of η is: dl/g (shorthand of deciliters/grams), the mensuration of η adopts phenol: the mixed solution dissolving of tetrachloroethane=1: 1 (weight ratio) is also passed through viscometer determining.
Specific embodiments
Further specify the present invention below by embodiment.
Embodiment 1
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 465 gram ethylene glycol and 0.04 gram titanium ethylene glycolate, wherein titanium content is that 26.1%. is at 2.0-3.0kg/cm in the titanium ethylene glycolate
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 133min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and in 60min, be depressurized to 300Pa, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is controlled in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 140min, and the synthetic polyester is little light yellow transparence, and it is transparent to become colorless in 10 hours under daylight.
Embodiment 2
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 465 gram ethylene glycol are at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 148min, reduce to normal pressure, .0.04 is restrained titanium ethylene glycolate (titanium content is 26.1%) to add in the 10g ethylene glycol, also spent glycol is clean in the reactor by adding after mechanical stirring or the ultrasonic dispersing, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and in 60min, be depressurized to 300Pa, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 134min, and the synthetic polyester is little light yellow transparence, and it is transparent to become colorless in 10 hours under daylight.
Embodiment 3
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%) and 0.1 gram Acetic Acid Glacil are received, at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 128min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and be depressurized to 300Pa in 60min, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 137min, and the synthetic polyester is the water white transparency shape.
Embodiment 4
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%) and 0.02 gram Acetic Acid Glacil cobalt are at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 130min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and be depressurized to 300Pa in 60min, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 140min, and the synthetic polyester is the water white transparency shape.
Embodiment 5
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.01 gram titanium ethylene glycolate (titanium content is 26.1%) and 50 gram Acetic Acid Glacil zinc are at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 143min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and be depressurized to 300Pa in 60min, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.62dl/g, total polycondensation time is about 130min, and the synthetic polyester is yellow opaque shape.
Embodiment 6
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%), 0.2g magnesiumcarbonate and 0.4g acetic acid are at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 130min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and be depressurized to 300Pa in 60min, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 136min, and the synthetic polyester is the water white transparency shape.
Embodiment 7
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%) and 0.02 gram tin oxalate are at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 135min, reduce to normal pressure, add 0.26 gram trimethyl phosphite 99, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumize and be decompressed to 20000Pa, and in 60min, be depressurized to 300Pa, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reached 0.68dl/g, total polycondensation time was about 125min, and the synthetic polyester is the water white transparency shape.
Embodiment 8
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%) and 0.01 gram tetrabutyl zirconate are at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 120min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and be depressurized to 300Pa in 60min, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 117min, and the synthetic polyester is little light yellow transparence.
Embodiment 9
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%) and 0.02 gram Acetic Acid Glacil manganese are at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 132min, reduce to normal pressure, add 0.05 gram trimethyl phosphite 99, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumize and be decompressed to 20000Pa, and in 60min, be depressurized to 300Pa, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reached 0.68dl/g, total polycondensation time was about 138min, and the synthetic polyester is the water white transparency shape.
Embodiment 10
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.3 gram titanium ethylene glycolate (titanium content is 26.1%) and 5.0 gram nanometer grade calcium carbonates, at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 125min, reduce to normal pressure, add 0.28 gram sodium phosphite, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumize and be decompressed to 20000Pa, and in 60min, be depressurized to 300Pa, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reached 0.68dl/g, total polycondensation time was about 145min, the synthetic polyester transparence that is white in color.
Embodiment 11
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 1.0 gram titanium ethylene glycolates (titanium content is 26.1%), at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 125min, reduce to normal pressure, add 1.0 gram Sodium phosphate dibasics, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumize and be decompressed to 20000Pa, and in 60min, be depressurized to 300Pa, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reached 0.68dl/g, total polycondensation time was about 135min, and it is transparent that the synthetic polyester is little yellow emulsus.
Embodiment 12
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%) and 7.70 gram ethylene glycol zinc, at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 130min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and be depressurized to 300Pa in 60min, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 135min, and the synthetic polyester is the water white transparency shape.
Embodiment 13
In 10 liters of stainless steel cauldrons, add 2490 gram terephthalic acids, 1395 gram ethylene glycol, 0.1 gram titanium ethylene glycolate (titanium content is 26.1%) and 0.07g crystal Cobaltous diacetate, at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates, when temperature rises to 260-270 ℃ by rectifier unit, reaction times is about 150min, reduce to normal pressure, continue to be warming up to 270 ℃, no longer include overhead product and discharge this moment, vacuumize and be decompressed to 20000Pa, and in 60min, be depressurized to 50-60Pa, with temperature increase to 280-287 ℃, when polymer viscosity reaches 0.65dl/g, total polycondensation time is about 90min, and the synthetic polyester is the water white transparency shape.
Embodiment 14
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%) and 0.03 gram ethylene glycol lithium, at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 130min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and be depressurized to 300Pa in 60min, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 125min, and the synthetic polyester is the water white transparency shape.
Embodiment 15
In 10 liters of stainless steel cauldrons, add 2490 gram terephthalic acids, 1395 gram ethylene glycol, 0.1 gram titanium ethylene glycolate (titanium content is 26.1%) and 0.1g crystal sodium oxalate, at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates, when temperature rises to 260-270 ℃ by rectifier unit, reaction times is about 150min, reduces to normal pressure, continues to be warming up to 270 ℃, no longer include overhead product and discharge this moment, add the 0.25g trimethyl phosphite 99, vacuumize and be decompressed to 20000Pa, and in 60min, be depressurized to 50-60Pa, temperature increase to 280-287 ℃, when polymer viscosity reached 0.65dl/g, total polycondensation time was about 87min, and the synthetic polyester is the water white transparency shape.
Embodiment 16
In 2.5 liters of stainless steel cauldrons, add 996g terephthalic acid, 30g m-phthalic acid, 498g ethylene glycol, 0.04 gram titanium ethylene glycolate (titanium content is 26.1%), 0.05g oxalic acid and 0.02 gram Lithium Acetate, at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 127min, reduce to normal pressure, add 0.01 gram trimethyl phosphite 99, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumize and be decompressed to 20000Pa, and in 60min, be depressurized to 300Pa, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reached 0.66dl/g, total polycondensation time was about 112min, and the synthetic polyester is the water white transparency shape.
Comparative Examples 1
In 2.5 liters of stainless steel cauldrons, add 996 gram terephthalic acids, 520 gram ethylene glycol, 0.36 gram antimonous oxide, at 2.0-3.0kg/cm
2Carry out esterification under the G pressure, and discharge the water that reaction generates by rectifier unit, when temperature rises to 255-260 ℃, reaction times is about 145min, reduce to normal pressure, continue to be warming up to 260 ℃, no longer include overhead product and discharge this moment, vacuumizes and be decompressed to 20000Pa, and in 60min, be depressurized to 300Pa, with temperature increase to 265-280 ℃, further be decompressed to below 50-60Pa, temperature is in 275-300 ℃, when polymer viscosity reaches 0.68dl/g, total polycondensation time is about 153min, and the synthetic polyester is transparence, little band Steel Gray.
The utilization symbol is as follows among the present invention, kg: kilogram, cm
2: square centimeter, l: rise min: minute, %: weight percent, g: gram, G: gauge pressure.
Catalyst particle size measuring method of the present invention is to adopt the solid titanium ethylene glycolate is added in the dibasic alcohol, stirs or after ultra-sonic oscillation disperse to make the dispersion liquid that contains titanium ethylene glycolate 0.5-20%, passes through transmissioning electric mirror determining through routine.
Catalyzer resistance to hydrolysis energy of the present invention is meant that getting 5.0 gram titanium ethylene glycolates adds in the 100 gram deionized waters, does not at least onely decompose round the clock.
Titanium ethylene glycolate Determination on content method among the present invention is the employing spectrophotometry.
Can find out that from embodiment 1-12 and Comparative Examples 1 the present invention has following advantages:
1, the titanium ethylene glycolate of the present invention's employing, its grain diameter reaches nanoscale and is not hydrolyzed, and has the catalysis ester The dual-use function of change and polycondensation reaction.
2, the present invention cooperates with 1-4 valence metal ion compounds or compound being suitable for by the employing titanium ethylene glycolate, Improved the polyester quality.
3, the present invention compares with German C-64 and TOHKEMY 2000-143789 technology, and catalyst is in polycondensation The catalytic activity of process (with active ingredient Ti content meter) has improved 2-6 times at least, with antimony-based catalyst (with The antimony meter) compares, then improved nearly 29 times.
4, the polyester that adopts the present invention to synthesize has significant photochemical properties, and polyester is shown brighten effect Really.
5, the present invention does not bring environmental pollution to polyester industrial.
6, the present invention provides foundation for production of polyester adopts heterogeneous catalyst.
Claims (9)
1, a kind of high activated catalyst, can make diprotic acid and dibasic alcohol carry out esterification, form diprotic acid binary alcohol esters monomer, and make the further polycondensation of these monomers prepare polyester, it is characterized in that it consists of at least a in the acetate of titanium ethylene glycolate and 1-4 valence metal ions, carbonate, oxalate, malonate, succinate, alkoxy compound, organic acid, the P contained compound.
2, catalyzer according to claim 1 is characterized in that said 1-4 valence metal ions are Li
+, Na
+, K
+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Co
2+, Mn
2+, Zn
2+, Sn
2+, Al
3+, Si
4+, Zr
4+In a kind of.
3, catalyzer according to claim 1 is characterized in that said organic acid is oxalic acid, propanedioic acid, Succinic Acid.
4, catalyzer according to claim 1 is characterized in that said P contained compound is phosphoric acid salt, phosphite or phosphoric acid ester.
5, catalyzer according to claim 1, the chemical formula that it is characterized in that titanium ethylene glycolate is C
4H
9O
5Ti.
6, the application of catalyzer in polyester is synthetic according to claim 1 or 5, the consumption that it is characterized in that titanium ethylene glycolate is 0.001-0.1% (weight percent) of diprotic acid consumption.
7, according to claim 1,2, the application of 3 or 4 described catalyzer in polyester is synthetic, it is characterized in that 1-4 valence metal ion compound, organic acid and P contained compound, its consumption is respectively the 0.001-5.0% (weight percent) of diprotic acid consumption.
8, the application of catalyzer according to claim 6 in polyester is synthetic is characterized in that the consumption of titanium ethylene glycolate is preferably 0.001-0.03% (weight percent) of diprotic acid consumption.
9, the application of catalyzer according to claim 7 in polyester is synthetic is characterized in that 1-4 valence metal ion compound, organic acid and phosphorus compound, and its consumption preferably is respectively 0.002-1.0% (weight percent) of diprotic acid consumption.
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2001
- 2001-07-05 CN CNB011151145A patent/CN1164641C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320026C (en) * | 2004-12-29 | 2007-06-06 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
| CN100386361C (en) * | 2005-12-06 | 2008-05-07 | 中国石油天然气股份有限公司 | Method for synthesizing non-fiber modified copolyester by catalysis of ethylene glycol titanium |
| CN102532561A (en) * | 2011-12-19 | 2012-07-04 | 四川达威科技股份有限公司 | Modified casein, leather finishing agent and preparation method thereof |
| CN102532561B (en) * | 2011-12-19 | 2013-12-04 | 四川达威科技股份有限公司 | Modified casein, leather finishing agent and preparation method thereof |
| CN103772673A (en) * | 2013-06-13 | 2014-05-07 | 淄博晓光化工材料有限公司 | Method for synthesizing PET polyester chips by using titanium catalyst |
| 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 |
| 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 |
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|---|---|
| CN1164641C (en) | 2004-09-01 |
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