CN104629033A - Production method of low acetaldehyde titanium system polyester - Google Patents
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Abstract
The invention relates to a production method of a low acetaldehyde titanium system polyester, and mainly solves the problems of low speed of solid-phase polymerization and high acetaldehyde residual of the polyester produced by the titanium system catalyst in the prior art. According to the invention, titanium system catalyst is used for the preparation of polyester; after esterification reaction, alkali metal carboxylate salt compound G and at least a metal compound H selected from the group consisting of IIA, IB, IIB, VIIB and VIII in the elements periodic table are added; and then melt phase polycondensation products are subjected to a solid-phase polymerization under appropriate temperature and pressure conditions, so as to further obtain polyester with high molecular weight and viscosity. The technical scheme well solves the above problems, and can be used in the industrial production of polyester.
Description
Technical field
The present invention relates to a kind of production method of low acetaldehyde titanium polyester.
Background technology
Polyethylene terephthalate is a kind of important industrial raw material, because it has excellent chemical property and physical properties, is widely used in the materials such as fiber, film, sheet, bottle.It has excellent physical strength, chemical stability, barrier properties for gases, fragrant retention, sanitation degree etc., and low price, lighter in weight, be particularly suitable for manufacturing the beverage container needing thermal sterilising filling.This container is by following manufacture technics, and first injection molding forming obtains a tubular precast billet with the end, then reheat make its soften, then carry out stretch-blow.Now, carry out heating to blow die and make bottle thermal-setting, and by stretching, molecular chain is aligned, crystallization is fixed, to improve the barrier properties for gases of bottle.
The polyester catalyst catalyzer that mainly antimony, germanium and titanium three is serial that current industrial production is more with research, wherein use most often antimony-based catalyst (comprising antimonous oxide, antimony acetate and antimony glycol etc.) in polyester industrial device, the polyester of more than 90% is produced by antimony-based catalyst in the world at present, and the polyester device of China also mainly adopts antimony-based catalyst.Metallic antimony belongs to heavy metal element, when the resin of this Catalyst Production is applied in beverage container field, there will be a problem: antimony-based catalyst can out, cause the antimony of trace to enter in in-built beverage by wash-out under the high temperature conditions from container.Germanium series catalysts has satisfactory stability, and the side reaction caused in reaction process is less, and made PET hue is good, but due to resource few, expensive.Titanium series polyester catalyst has high reactivity, but there is poor heat stability and goods yellowing, muddy problem in the polyester that titanium series polyester catalyst obtains, easily decompose under the high temperature conditions and produce acetaldehyde, cause acetaldehyde to enter in-built beverage, thus never used on a large scale.
CN1328072 and CN1327985 discloses and generates a kind of diatomic alcohol compounds of granular titanium as polyester catalyst using titanic acid ester and glycol reaction, this granular polyester catalyst is likely with and is served application problem in the industrial production of polyester, and the acetaldehyde adopting this catalyzer to obtain polyester of not reporting for work in patent.
EP1013692 points out, in polycondensation and melt molding process, acetaldehyde is as the generation of by product, titanium and some metallic compounds can be used to suppress as polycondensation catalyst, and titanium atom and atoms metal such as the Specific amounts of magnesium should be specific ratio.CN1457343 points out, can by adding the compound of titaniferous, magnesium, phosphorus, and order of addition is titanium after magnesium after first phosphorus, the method that titanium adds after esterification, prepare the polyester of low acetaldehyde content, according to the research of the present inventor, polyester prepared by this method truly has improvement in the generation of control acetaldehyde, but there is very large defect in polycondensation speed especially solid phase polycondensation speed.CN1863839 points out, titanium, zinc, phosphorus and lactic acid can be used as polycondensation catalyst, prepares the polyester of high solid phase polycondensation speed, but in literary composition, the acetaldehyde of not mentioned obtained polyester controls.
Summary of the invention
Technical problem to be solved by this invention is the problem that the polyester solid phase polymerization speed prepared of Titanium series catalyst is comparatively slow, acetaldehyde residual volume is higher in the past, provides a kind of production method of low acetaldehyde titanium polyester newly.The method has the polyester solid phase polymerization speed obtained, the advantage that the PET conglutination after solid state polymerization is good, acetaldehyde residual volume is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production method of low acetaldehyde titanium polyester, comprises the following steps:
A) with di-carboxylic acid and dibasic alcohol for raw material, it is 230 ~ 280 DEG C in temperature of reaction, reaction pressure is carry out esterification under normal pressure ~ 0.5MPa condition, obtain prepolymer, then be 250 ~ 320 DEG C in temperature of reaction, reaction pressure is carry out melt polycondensation reaction under the vacuum condition being less than 150Pa to obtain polyester product; The catalyzer used comprises following raw material in 0 ~ 200 DEG C of reaction reaction product of 0.5 ~ 10 hour:
(1) there is the titanium compound A of following general formula:
Ti(OR
1)
4
R
1for being selected from straight chain or the branched-alkyl of 1 ~ 10 carbon atom;
(2) the dibasic alcohol B with 2 ~ 10 carbon atoms is selected from;
(3) a kind of metallic compound C in periodic table of elements IA is selected from;
(4) at least one aliphatic organic acid D in organic acid is selected from;
(5) at least one phosphate compound E in phosphorus compound is selected from;
(6) at least one metallic compound F in the periodic table of elements in IIA, IB, IIB, VIIB, VIII is selected from;
Wherein, the mol ratio of dibasic alcohol B and titanium compound A is 1 ~ 8: 1; The mol ratio of metallic compound F and titanium compound A is 0.1 ~ 20: 1; The mol ratio of metallic compound C and titanium compound is >0 ~ 10: 1; The mol ratio of aliphatic organic acid D and titanium compound A is 1 ~ 20: 1; The mol ratio of phosphate compound E and titanium compound A is >0 ~ 10: 1;
At least one metallic compound H adding alkali metal carboxylate compound G after esterification and be selected from the periodic table of elements in IIA, IB, IIB, VIIB, VIII is as promotor, the weight of polyester product is obtained based on melt polycondensation reaction, the consumption of alkali metal carboxylate compound G is 1 ~ 200ppm, and the consumption of metallic compound H is 1 ~ 200ppm;
B) polyester product obtained by melt phase polycondensation, after pre-crystallized process, is 200 ~ 250 DEG C in temperature of reaction, and reaction pressure is carry out solid state polymerization to obtain the polyester of high viscosity (limiting viscosity dl/g is greater than 0.8) under the condition being less than 100Pa.
In technique scheme, titanium compound A is selected from least one compound in metatitanic acid four methyl esters, tetraethyl titanate, the own ester of metatitanic acid tetraethyl-, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate, the different monooctyl ester of metatitanic acid four.Dibasic alcohol B is selected from the one in 1,2-PD, 1,3-PD, BDO, ethylene glycol, Diethylene Glycol.The preferred version of IA race metallic compound C is selected from least one in lithium, sodium or the potassium compound in periodic table of elements IA, and more preferably scheme is selected from sodium hydroxide or potassium hydroxide.Aliphatic organic acid D is selected from least one in lactic acid, citric acid, oxysuccinic acid, tartrate, oxalic acid.Phosphate compound E is selected from least one phosphate compound in methyl-phosphoric acid, monoethyl-phosphate, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or triphenylphosphate.Metallic compound F is at least one metallic compound be selected from zinc, manganese, magnesium, calcium or cobalt element, comprises the organic salt of these elements and the hydrate of salt, as magnesium acetate, zinc acetate, Cobaltous diacetate etc.Alkali metal carboxylate compound G is selected from least one in Lithium Acetate, sodium-acetate, Potassium ethanoate, lithium oxalate, sodium oxalate, potassium oxalate.Metallic compound H is at least one metallic compound be selected from zinc, manganese, magnesium, calcium or cobalt element, comprises the organic salt of these elements and the hydrate of salt, as magnesium acetate, zinc acetate, Cobaltous diacetate etc.
In technique scheme, the mol ratio of dibasic alcohol B and titanium compound A is preferably 1 ~ 4: 1; The mol ratio of IA race metallic compound C is preferably 0.1 ~ 10: 1; The mol ratio of aliphatic organic acid D and titanium compound A is preferably 1 ~ 15: 1; The mol ratio of phosphoric acid ester phosphorus compound E and titanium compound A is preferably >0 ~ 6: 1; The mol ratio of metallic compound F and titanium compound A is preferably 0.1 ~ 10: 1.The weight preferable range that the consumption of the promotor alkali metal carboxylate compound G added after esterification obtains polyester product based on melt polycondensation reaction is 1 ~ 200ppm; The weight that the consumption of promoter metal compounds H obtains polyester product based on melt polycondensation reaction is 1 ~ 200ppm.
In technique scheme, di-carboxylic acid is selected from least one in terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid, preferred terephthalic acid; Dibasic alcohol is selected from least one in ethylene glycol, 1,3-PD, BDO, 1,6-hexylene glycol and 1,4 cyclohexane dimethanol, preferred ethylene glycol.
In technique scheme, the polyester product of the melt phase polycondensation for solid state polymerization obtained is solid-state.The temperature of reaction preferable range preparing polyester catalyst is 10 ~ 180 DEG C, and reaction times preferable range is 2 ~ 6 hours.Obtain the weight of polyester product based on melt polycondensation reaction, the addition of catalyzer counts 1 ~ 20ppm with titanium atom.Catalyzer is homogeneous phase liquid catalyst, can dissolve each other with ethylene glycol.
The preparation method of titanium series polyester catalyst of the present invention is as follows:
Titanium compound added the dibasic alcohol of aequum, be selected from least one metallic compound of IA in the periodic table of elements, the periodic table of elements and be selected from least one metallic compound, organic acid and phosphatization in IIA, IB, IIB, VIIB or VIII and close and be obtained by reacting homogeneous phase liquid titanium polyester catalyzer.
The preparation method of polyester is as follows:
Can adopt known preparation process of polyester, the first step carries out esterification by di-carboxylic acid and dibasic alcohol, obtains prepolymer, and temperature of reaction is 230 ~ 280 DEG C, and reaction pressure is normal pressure ~ 0.5MPa.Second step carries out polycondensation under a high vacuum, and temperature of reaction 250 ~ 320 DEG C, reaction pressure is for being less than 150Pa.Titanium series polyester catalyst joins in reaction system before esterification starts.Pelletizing preservation is carried out after reaction terminates.
After esterification terminates, alkali metal carboxylate compound G and metallic compound H is joined in system as promotor, the consumption of alkali metal carboxylate compound G is 1 ~ 200ppm, the consumption of metallic compound H be 1 ~ 200ppm(based on melt polycondensation reaction obtain polyester product weight).
Solid state polymerization (SSP) method of polyester:
The polyester prepared by aforesaid method carries out solid state polymerization further and improves viscosity.Before carrying out solid state polymerization, first should carry out pre-crystallized process to polyester.By polyester granulate prepared by above-mentioned preparation process of polyester, be placed in 80 ~ 130 DEG C, preferably under the vacuum environment of 90 ~ 120 DEG C, heating carries out drying in 1 minute ~ 3 hours.After drying terminates, under atmosphere of inert gases or vacuum environment, by temperature increase to 100 ~ 180 DEG C, preferably 140 ~ 170 DEG C are carried out pre-crystallized, and crystallization time is 1 ~ 10 hour, preferably 3 ~ 7 hours.
After pre-crystallized end, particle is sent in the rotary drum of DoubletaperedVacuumdrier, under the vacuum being less than 100Pa, continuous rotary drum is carried out to particle.Temperature of reaction is 200 ~ 250 DEG C, and preferably 210 ~ 230 DEG C, equipment was warming up to set(ting)value in 2 hours.Reaction times is 1 ~ 10 hour, preferably 3 ~ 8 hours.
In the present invention, the limiting viscosity of polyester and acetaldehyde (AA) etc. are tested by the following method:
(1) limiting viscosity: phenol tetrachloroethane mixes liquid and makes solvent, uses determination of ubbelohde viscometer at the temperature of 25 DEG C.
(2) acetaldehyde (AA): accurate weighing 0.5g loads in ml headspace bottle after the polyester sample of solid phase polycondensation is pulverized, seals with air in nitrogen replacement bottle.Setting head-space sampler furnace temperature 150 DEG C, starting time 60 minutes.The acetaldehyde of sample uses gas chromatograph (GC7890, Agilent) to carry out quantitative analysis by headspace sampling.
The present invention prepares polyester by adopting Titanium series catalyst, and carries out solid-phase polymerization to obtained polyester.The discovery that the present inventor is surprised, the polyester adopting the method to obtain has lower acetaldehyde after solid state polymerization, and contrast after solid state polymerization with the titanium polyester not adding alkali metal carboxylate G metallizing thing H, after solid state polymerization, acetaldehyde obviously reduces.Acetaldehyde cut into slices after requiring solid phase polycondensation in the national standard of Bottle grade Polyester Chips lower than 1.0, and conventional titanium polyester exceedes this standard usually, and the polyester slice acetaldehyde prepared by the present invention is far below 1.0, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The preparation of catalyst A
Ethylene glycol 12.4 grams (0.2 mole) is added in the reactor that agitator, condenser and thermometer are housed, slowly instillation titanium isopropylate 28.4 grams (0.1 mole) in reactor, separate out white depositions, react 2 hours at 70 DEG C, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 DEG C, obtain white powder material.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, add ethylene glycol 50 grams, aqueous sodium hydroxide solution (0.2 mole), lactic acid 18 grams (0.2 mole), the trimethyl phosphite 99 28 grams (0.2 mole) of 32 gram 25%, zinc acetate 73.2 grams (0.4 mole) reacts 2 hours under 150 DEG C of temperature of reaction, obtaining nearly colourless homogeneous liquid, is catalyst A.
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and catalyst A (based on the amount of the polyester generated, the weight of titanium atom is 3ppm), mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Be down to normal pressure after esterification terminates, add Potassium ethanoate 7.8 × 10
-3g(8 × 10
-5mole), zinc acetate 1.6 × 10
-2g(8 × 10
-5mole), vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 DEG C gradually, and stopped reaction after system reaction reaches 150min, extrudes with bar shaped bottom polymeric kettle continuously by reaction product afterwards, cooling, pelletizing.
The solid state polymerization of polyester
The polyester granulate obtained by liquid polycondensation carries out drying under vacuum environment, the condition of 100 DEG C, after drying, temperature increase to 160 DEG C is carried out pre-crystallized process 6 hours.Being positioned over by particle after process in revolution solid state polymerization device and under 0.1kpa, the condition of 230 DEG C, carrying out the solid state polycondensation of polyester, the reaction times is 10 hours.Take out for test after cooling.
Test result is in table 1.
[embodiment 2]
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and catalyst A (based on the amount of the polyester generated, the weight of titanium atom is 2.5ppm), mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Be down to normal pressure after esterification terminates, add Potassium ethanoate 6 × 10
-3g(6 × 10
-5mole), zinc acetate 1.6 × 10
-2g(8 × 10
-5mole), vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 DEG C gradually, and stopped reaction after system reaction reaches 150min, extrudes with bar shaped bottom polymeric kettle continuously by reaction product afterwards, cooling, pelletizing.
The solid state polymerization of polyester
By method similarly to Example 1 to polyester granulate solid state polymerization.
Test result is in table 1.
[embodiment 3]
The preparation of catalyst B
Ethylene glycol 12.4 grams (0.2 mole) is added in the reactor that agitator, condenser and thermometer are housed, slowly instillation titanium isopropylate 28.4 grams (0.1 mole) in reactor, separate out white depositions, react 2 hours at 70 DEG C, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 DEG C, obtain white powder material.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, add ethylene glycol 50 grams, aqueous sodium hydroxide solution (0.2 mole), Citric acid monohydrate Food grade 63 grams (0.3 mole), the trimethyl phosphite 99 28 grams (0.2 mole) of 32 gram 25%, magnesium acetate 42.6 grams (0.3 mole) reacts 2 hours under 150 DEG C of temperature of reaction, obtaining nearly colourless homogeneous liquid, is catalyst B.
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and catalyst B (based on the amount of the polyester generated, the weight of titanium atom is 2.5ppm), mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Be down to normal pressure after esterification terminates, add potassium oxalate 7.4 × 10
-3g(4 × 10
-5mole), magnesium acetate 1.1 × 10
-2g(8 × 10
-5mole), vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 DEG C gradually, and stopped reaction after system reaction reaches 150min, extrudes with bar shaped bottom polymeric kettle continuously by reaction product afterwards, cooling, pelletizing.
The solid state polymerization of polyester
By method similarly to Example 1 to polyester granulate solid state polymerization.
Test result is in table 1.
[embodiment 4]
Except in embodiment 1, change interpolation Potassium ethanoate into sodium-acetate 6.6 × 10
-3g(8 × 10
-5mole) outward, adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 5]
The preparation of catalyzer C
Ethylene glycol 12.4 grams (0.2 mole) is added in the reactor that agitator, condenser and thermometer are housed, slowly instillation titanium isopropylate 28.4 grams (0.1 mole) in reactor, separate out white depositions, react 2 hours at 70 DEG C, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 DEG C, obtain white powder material.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, add ethylene glycol 50 grams, aqueous sodium hydroxide solution (0.2 mole), Citric acid monohydrate Food grade 63 grams (0.3 mole), the trimethyl phosphite 99 28 grams (0.2 mole) of 32 gram 25%, zinc acetate 91.8 grams (0.5 mole) reacts 2 hours under 150 DEG C of temperature of reaction, obtaining nearly colourless homogeneous liquid, is catalyzer C.
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and the catalyzer C(amount based on the polyester generated, the weight of titanium atom is 2.5ppm), mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Be down to normal pressure after esterification terminates, add Potassium ethanoate 6 × 10
-3g(6 × 10
-5mole), zinc acetate 3.7 × 10
-3g(2 × 10
-5mole), vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 DEG C gradually, and stopped reaction after system reaction reaches 150min, extrudes with bar shaped bottom polymeric kettle continuously by reaction product afterwards, cooling, pelletizing.
The solid state polymerization of polyester
By method similarly to Example 1 to polyester granulate solid state polymerization.
Test result is in table 1.
[comparative example 1]
Except in embodiment 1, change interpolation Potassium ethanoate into tosic acid potassium 1.4 × 10
-2g(8 × 10
-5mole) outward, adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[comparative example 2]
Except in embodiment 1, change interpolation Potassium ethanoate into tosic acid potassium 1.0 × 10
-2g(6 × 10
-5mole) outward, adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[comparative example 3]
Except in embodiment 3, do not add outside potassium oxalate, adopt to use the same method with embodiment 3 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[comparative example 4]
Adopt antimony glycol as catalyzer (based on the amount of the polyester generated, the weight of antimony atoms is 180ppm).
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and glycol antimony catalyst (based on the amount of the polyester generated, the weight of antimony atoms is 180ppm), mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Be down to normal pressure after esterification terminates, vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 DEG C gradually, and stopped reaction after system reaction reaches 150min, extrudes with bar shaped bottom polymeric kettle continuously by reaction product afterwards, cooling, pelletizing.
Method similarly to Example 1 carries out the solid-phase polymerization of polyester.
Test result is in table 1.
[comparative example 5]
The preparation of catalyzer D
Ethylene glycol 12.4 grams (0.2 mole) is added in the reactor that agitator, condenser and thermometer are housed, slowly instillation titanium isopropylate 28.4 grams (0.1 mole) in reactor, separate out white depositions, react 2 hours at 70 DEG C, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 DEG C, obtain white powder material.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, add ethylene glycol 50 grams, the aqueous sodium hydroxide solution (0.2 mole) of 32 gram 25%, react 2 hours under 150 DEG C of temperature of reaction, obtaining nearly colourless homogeneous liquid, is catalyzer D.
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and the catalyzer D(amount based on the polyester generated, the weight of titanium atom is 2.5ppm), mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Be down to normal pressure after esterification terminates, vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 DEG C gradually, and stopped reaction after system reaction reaches 150min, extrudes with bar shaped bottom polymeric kettle continuously by reaction product afterwards, cooling, pelletizing.
The solid state polymerization of polyester
By method similarly to Example 1 to polyester granulate solid state polymerization.
Test result is in table 1.
[comparative example 6]
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and catalyst A (based on the amount of the polyester generated, the weight of titanium atom is 3ppm), mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Be down to normal pressure after esterification terminates, vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 DEG C gradually, and stopped reaction after system reaction reaches 150min, extrudes with bar shaped bottom polymeric kettle continuously by reaction product afterwards, cooling, pelletizing.
The solid state polymerization of polyester
By method similarly to Example 1 to polyester granulate solid state polymerization.
Test result is in table 1.
Table 1
Claims (10)
1. a production method for low acetaldehyde titanium polyester, comprises the following steps:
A) with di-carboxylic acid and dibasic alcohol for raw material, adopt titanium series polyester catalyst in temperature of reaction be 230 ~ 280 DEG C, reaction pressure is carry out esterification under normal pressure ~ 0.5MPa condition, obtain prepolymer, then be 250 ~ 320 DEG C in temperature of reaction, reaction pressure is carry out melt polycondensation reaction under the vacuum condition being less than 150Pa to obtain polyester product; Catalyzer used comprises following raw material in 0 ~ 200 DEG C of reaction reaction product of 0.5 ~ 10 hour:
(1) there is the titanium compound A of following general formula:
Ti(OR
1)
4
R
1for being selected from straight chain or the branched-alkyl of 1 ~ 10 carbon atom;
(2) the dibasic alcohol B with 2 ~ 10 carbon atoms is selected from;
(3) a kind of metallic compound C in periodic table of elements IA is selected from;
(4) at least one aliphatic organic acid D in organic acid is selected from;
(5) at least one phosphate compound E in phosphorus compound is selected from;
(6) at least one metallic compound F in the periodic table of elements in IIA, IB, IIB, VIIB, VIII is selected from;
Wherein, the mol ratio of dibasic alcohol B and titanium compound A is 1 ~ 8: 1; The mol ratio of metallic compound F and titanium compound A is 0.1 ~ 20: 1; The mol ratio of metallic compound C and titanium compound is >0 ~ 10: 1; The mol ratio of aliphatic organic acid D and titanium compound A is 1 ~ 20: 1; The mol ratio of phosphate compound E and titanium compound A is >0 ~ 10: 1;
At least one metallic compound H adding alkali metal carboxylate compound G after esterification and be selected from the periodic table of elements in IIA, IB, IIB, VIIB, VIII is as promotor, based on the weight of the polyester product that melt polycondensation reaction obtains, the consumption of alkali metal carboxylate compound G is 1 ~ 200ppm, and the consumption of metallic compound H is 1 ~ 200ppm;
B) polyester product obtained by melt phase polycondensation, after pre-crystallized process, is 200 ~ 250 DEG C in temperature of reaction, and reaction pressure is carry out solid state polymerization to obtain the polyester that limiting viscosity is greater than 0.8 deciliter/gram under the condition being less than 100Pa.
2. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that di-carboxylic acid is selected from least one in terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid; Dibasic alcohol is selected from least one in ethylene glycol, 1,3-PD, BDO, 1,6-hexylene glycol and 1,4 cyclohexane dimethanol.
3. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that titanium compound A is selected from least one in metatitanic acid four methyl esters, tetraethyl titanate, the own ester of metatitanic acid tetraethyl-, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate, the different monooctyl ester of metatitanic acid four; Dibasic alcohol B is selected from least one in 1,2-PD, 1,3-PD, BDO, ethylene glycol, Diethylene Glycol.
4. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that in metallic compound C, IA race metal is selected from least one in lithium, sodium or potassium.
5. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that aliphatic organic acid D is selected from least one in lactic acid, citric acid, oxysuccinic acid, tartrate or oxalic acid.
6. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that phosphate compound E is selected from least one in methyl-phosphoric acid, monoethyl-phosphate, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or triphenylphosphate.
7. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that metallic compound F is selected from least one in zinc, manganese, magnesium, calcium or cobalt compound.
8. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that alkali metal carboxylate compound G is selected from least one in Lithium Acetate, sodium-acetate, Potassium ethanoate, lithium oxalate, sodium oxalate, potassium oxalate.
9. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that metallic compound H is selected from least one in zinc, manganese, magnesium, calcium or cobalt compound.
10. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that the mol ratio of dibasic alcohol B and titanium compound A is 1 ~ 4: 1; The mol ratio of metallic compound C and titanium compound is 1 ~ 10: 1; The mol ratio of aliphatic organic acid D and titanium compound A is 1 ~ 15: 1; The mol ratio of phosphoric acid ester phosphorus compound E and titanium compound A is >0 ~ 6: 1; The mol ratio of metallic compound F and titanium compound A is 0.1 ~ 10: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106589340A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Method for producing low-acetaldehyde polyester product |
| CN108976398A (en) * | 2018-08-08 | 2018-12-11 | 济南朝晖科技有限公司 | The preparation method of polyester |
| CN108976403A (en) * | 2018-08-08 | 2018-12-11 | 济南朝晖科技有限公司 | The preparation method of polyester |
| CN110117356A (en) * | 2019-05-21 | 2019-08-13 | 中国石油化工股份有限公司 | A kind of preparation method and application of carboxy lower composition containing weight polyester and composition solution |
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