CN104629033B - The production method of low acetaldehyde titanium polyester - Google Patents
The production method of low acetaldehyde titanium polyester Download PDFInfo
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- CN104629033B CN104629033B CN201310544151.9A CN201310544151A CN104629033B CN 104629033 B CN104629033 B CN 104629033B CN 201310544151 A CN201310544151 A CN 201310544151A CN 104629033 B CN104629033 B CN 104629033B
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Abstract
The present invention relates to the production method of a kind of low acetaldehyde titanium polyester, mainly solve polyester solid phase polymerization speed prepared by conventional Titanium series catalyst relatively slow, the problem that acetaldehyde residual volume is higher.The present invention is first prepared polyester by Titanium series catalyst by using, add alkali metal carboxylate compound G and at least one metallic compound H being selected from the periodic table of elements in IIA, IB, IIB, VIIB, VIII the most after completion of the esterification reaction, product after being completed by melt polycondensation again carries out solid-phase polymerization under conditions of suitable temperature and pressure, obtain the technical scheme of the polyester product of high molecular and viscosity further, preferably resolve this problem, can be used in the commercial production of polyester.
Description
Technical field
The present invention relates to the production method of a kind of low acetaldehyde titanium polyester.
Background technology
Polyethylene terephthalate is a kind of important raw material of industry, the chemical property having excellence due to it and thing
Rationality matter, is widely used in the materials such as fiber, film, sheet, bottle.It has excellent mechanical strength, chemical stability, gas
Barrier, fragrance retention, sanitation degree etc., low price, lighter in weight, being particularly suitable for manufacture needs heat sterilization fill
Container for drink.This container can be manufactured by following technique, and first injection molding forming obtains a tubular prefabricated blank with the end, then
Reheat and make it soften, then carry out stretch-blow.Now, blow molding die is carried out heating and makes bottle heat setting, and by drawing
Stretching and make strand align, crystallization is fixing, to improve the barrier properties for gases of bottle.
Commercial production and the more polyester catalyst of research are mainly antimony, germanium and three serial catalyst of titanium at present, its
Most commonly used in middle polyester industrial device is that antimony-based catalyst (includes antimony oxide, antimony acetate and antimony glycol
Deng), the polyester of more than 90% is produced by antimony-based catalyst the most in the world, and the polyester device of China mainly uses
Antimony-based catalyst.Metallic antimony belongs to heavy metal element, when the resin of this Catalyst Production is applied in container for drink field, can go out
An existing problem: antimony-based catalyst can be eluted out under the high temperature conditions from container, causes the antimony of trace to enter built-in drink
In material.Germanium series catalysts has good stability, the PET hue that the side reaction of initiation is less, made in course of reaction
Good, but owing to resource is few, expensive.Titanium series polyester catalyst has a high activity, but what titanium series polyester catalyst prepared
There is poor heat stability and goods yellowing, muddy problem in polyester, easily decomposes under the high temperature conditions and produce acetaldehyde, cause acetaldehyde to enter
Enter built-in beverage, thus never obtain large-scale use.
CN1328072 and CN1327985 discloses and generates the two of a kind of granular titanium with titanate esters and glycol reaction
Unit's alcoholic compound is as polyester catalyst, and this granular polyester catalyst likely brings one in the commercial production of polyester
A little application problems, and the acetaldehyde using this catalyst to prepare polyester of not reporting for work in patent.
EP1013692 points out, during polycondensation and melt molding, acetaldehyde is as the generation of by-product, can use titanium and
A little metallic compounds suppress as polycondensation catalyst, and the Specific amounts of titanium atom and metallic atom such as magnesium should be specific than
Example.CN1457343 points out, can be by adding titaniferous, magnesium, the compound of phosphorus, and order of addition be titanium after magnesium after elder generation's phosphorus, titanium in
The method added after esterification, prepares the polyester of low acetaldehyde, and according to the research of the present inventor, polyester prepared by this method exists
Control acetaldehyde generation aspect and truly have improvement, but there is the biggest defect in polycondensation speed especially solid phase polycondensation speed.
CN1863839 points out, titanium, zinc, phosphorus and lactic acid can be used as polycondensation catalyst, prepare the polyester of high solid phase polycondensation speed, but
In literary composition, the acetaldehyde of not mentioned prepared polyester controls.
Summary of the invention
The technical problem to be solved is that the polyester solid phase polymerization speed prepared of conventional Titanium series catalyst is relatively slow, second
The problem that aldehyde residual volume is higher, it is provided that the production method of a kind of new low acetaldehyde titanium polyester.The method has the polyester obtained
Solid phase speed, the advantage that the PET conglutination after solid phase is good, acetaldehyde residual volume is low.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: the life of a kind of low acetaldehyde titanium polyester
Product method, comprises the following steps:
A) with dicarboxylic acids and dihydroxylic alcohols as raw material, be 230～280 DEG C in reaction temperature, reaction pressure be normal pressure～
Carrying out esterification under the conditions of 0.5MPa, obtain prepolymer, be then 250～320 DEG C in reaction temperature, reaction pressure is for being less than
Carry out melt polycondensation reaction under the vacuum condition of 150Pa and obtain polyester product；The catalyst used includes that following raw material is 0
～200 DEG C of reactions product of 0.5～10 hour:
(1) there is the titanium compound A of below general formula:
Ti(OR1)4
R1For selected from the straight chain of 1～10 carbon atom or branched-alkyl；
(2) selected from the dihydroxylic alcohols B with 2～10 carbon atoms；
(3) a kind of metallic compound C in periodic table of elements IA；
(4) at least one aliphatic organic acid D in organic acid；
(5) at least one phosphate compound E in phosphorus compound；
(6) at least one metallic compound F in IIA, IB, IIB, VIIB, VIII in the periodic table of elements；
Wherein, the mol ratio of dihydroxylic alcohols B and titanium compound A is 1～8: 1；Metallic compound F and titanium compound A mole
Ratio is 0.1～20: 1；Metallic compound C with the mol ratio of titanium compound is > 0～10: 1；Aliphatic organic acid D and titanium compound
The mol ratio of A is 1～20: 1；The mol ratio of phosphate compound E and titanium compound A is > 0～10: 1；
Add alkali metal carboxylate compound G after esterification and be selected from IIA, IB, IIB, VIIB in the periodic table of elements
, at least one metallic compound H in VIII as promoter, obtain the weight of polyester product 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 polycondensation is after pre-crystallized process, is 200～250 DEG C in reaction temperature, reaction
Pressure is for less than carrying out solid phase under conditions of 100Pa to obtain the polyester of high viscosity (intrinsic viscosity dl/g is more than 0.8).
In technique scheme, titanium compound A is selected from metatitanic acid four methyl ester, tetraethyl titanate, the own ester of metatitanic acid tetraethyl, metatitanic acid
At least one compound in orthocarbonate, tetraisopropyl titanate or butyl titanate, the different monooctyl ester of metatitanic acid four.Dihydroxylic alcohols B is selected from 1,
One in 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, ethylene glycol, diethylene glycol.IA race metallic compound C's is preferred
At least one in scheme lithium, sodium or potassium compound in the periodic table of elements IA, more preferably scheme selected from sodium hydroxide or
Potassium hydroxide.At least one in lactic acid, citric acid, malic acid, tartaric acid, oxalic acid of aliphatic organic acid D.Phosphation
Compound E is selected from methyl-phosphoric acid, etherophosphoric acid, trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl
At least one phosphate compound in ester, tributyl phosphate or triphenyl phosphate.Metallic compound F be selected from zinc, manganese, magnesium,
At least one metallic compound in calcium or cobalt element, including organic salt and the hydrate of salt of these elements, such as magnesium acetate, vinegar
Acid zinc, cobaltous acetate etc..Alkali metal carboxylate compound G is selected from lithium acetate, sodium acetate, potassium acetate, lithium oxalate, Disodium oxalate., oxalic acid
At least one in potassium.Metallic compound H is at least one metallic compound in zinc, manganese, magnesium, calcium or cobalt element, bag
Include the organic salt of these elements and the hydrate of salt, such as magnesium acetate, zinc acetate, cobaltous acetate etc..
In technique scheme, the mol ratio of dihydroxylic alcohols B and titanium compound A is preferably 1～4: 1；IA race metallic compound C
Mol ratio be preferably 0.1～10: 1；The mol ratio of aliphatic organic acid D and titanium compound A is preferably 1～15: 1；Phosphate ester
The mol ratio of phosphorus compound E and titanium compound A is preferably > 0～6: 1；Metallic compound F is preferred with the mol ratio of titanium compound A
It is 0.1～10: 1.The consumption of the promoter alkali metal carboxylate compound G added after esterification obtains based on melt polycondensation reaction
The preferred scope of weight of polyester product is 1～200ppm；The consumption of promoter metal compounds H obtains based on melt polycondensation reaction
Weight to polyester product is 1～200ppm.
In technique scheme, dicarboxylic acids selected from p-phthalic acid, phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid,
At least one in biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid, preferably p-phthalic acid；Dihydroxylic alcohols is selected from ethylene glycol, 1,3-the third two
Alcohol, BDO, 1, at least one in 6-hexanediol and 1,4-CHDM, preferably ethylene glycol.
In technique scheme, the polyester product of the melt polycondensation for solid phase obtained is solid-state.Prepare polyester
The preferred scope of reaction temperature of catalyst is 10～180 DEG C, and response time preferred scope is 2～6 hours.Anti-based on melt polycondensation
Should obtain the weight of polyester product, the addition of catalyst is calculated as 1～20ppm with titanium atom.Catalyst is the catalysis of homogeneous liquid
Agent, can dissolve each other with ethylene glycol.
The preparation method of titanium series polyester catalyst of the present invention is as follows:
Titanium compound is added the desired amount of dihydroxylic alcohols, in the periodic table of elements at least one metallic compound of IA,
In the periodic table of elements, at least one metallic compound in IIA, IB, IIB, VIIB or VIII, organic acid and phosphatization are closed anti-
Homogeneous liquid titanium polyester catalyst should be obtained.
The preparation method of polyester is as follows:
Can use known preparation process of polyester, the first step is carried out esterification by dicarboxylic acids and dihydroxylic alcohols, obtains
Prepolymer, reaction temperature is 230～280 DEG C, and reaction pressure is normal pressure～0.5MPa.It is anti-that second step carries out polycondensation under a high vacuum
Should, reaction temperature 250～320 DEG C, reaction pressure is less than 150Pa.Titanium series polyester catalyst adds before esterification starts
In reaction system.Reaction carries out pelletizing preservation after terminating.
Alkali metal carboxylate compound G and metallic compound H is joined body as promoter after terminating by esterification
In system, the consumption of alkali metal carboxylate compound G is 1～200ppm, and the consumption of metallic compound H is 1～200ppm(based on molten
Melt polycondensation reaction obtain polyester product weight).
Solid phase (SSP) method of polyester:
The polyester prepared by said method carries out solid phase further and improves viscosity.Before carrying out solid phase, Ying Xian
Polyester is carried out pre-crystallized process.The polyester granulate prepared by above-mentioned preparation process of polyester, is placed in 80～130 DEG C, preferably 90～
Under the vacuum environment of 120 DEG C, heating is dried for 1 minute～3 hours.It is dried after terminating, at atmosphere of inert gases or vacuum ring
Under border, temperature being promoted to 100～180 DEG C, preferably 140～170 DEG C carry out pre-crystallized, and crystallization time is 1～10 hour, preferably
3～7 hours.
After pre-crystallized end, granule is sent in the rotary drum of double conic rotary vacuum dryer, under the vacuum less than 100Pa
Granule is carried out continuous rotary drum.Reaction temperature is 200～250 DEG C, and preferably 210～230 DEG C, equipment was warming up in 2 hours
Setting value.Response time is 1～10 hour, preferably 3～8 hours.
In the present invention, the test by the following method such as the intrinsic viscosity of polyester and acetaldehyde (AA):
(1) intrinsic viscosity: phenol tetrachloroethane mixed liquor makees solvent, uses determination of ubbelohde viscometer at a 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,
With air sealing in nitrogen displacement bottle.Set head-space sampler furnace temperature 150 DEG C, equilibration time 60 minutes.The acetaldehyde of sample contains
Amount uses gas chromatograph (GC7890, Agilent) to carry out quantitative analysis by headspace sampling.
The present invention is by using Titanium series catalyst to prepare polyester, and prepared polyester is carried out solid-phase polymerization.This
A person of good sense has surprisingly found that, the polyester using the method to prepare has relatively low acetaldehyde after solid phase, and is not added with alkali
The titanium polyester of metal carboxylate G and metallic compound H contrasts after solid phase, and after solid phase, acetaldehyde substantially drops
Low.Acetaldehyde of cutting into slices after requiring solid phase polycondensation in the national standard of bottle-grade polyester chip is less than 1.0, and conventional titanium polyester is usual
Exceed this standard, and the polyester slice acetaldehyde prepared by the present invention is far below 1.0, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of catalyst A
Ethylene glycol 12.4 grams (0.2 mole) is added, toward reaction in the reactor equipped with agitator, condenser and thermometer
Device is slowly dropped into tetraisopropyl titanate 28.4 grams (0.1 mole), separates out white depositions, react 2 hours at 70 DEG C, will produce
Thing centrifugation, and with distilled water wash residue 3 times, product is vacuum dried at 70 DEG C, obtains white powder thing
Matter.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, adds
Ethylene glycol 50 grams, the sodium hydrate aqueous solution (0.2 mole) of 32 gram 25%, lactic acid 18 grams (0.2 mole), trimethyl phosphate 28 grams
(0.2 mole), zinc acetate 73.2 grams (0.4 mole) reacts 2 hours under 150 DEG C of reaction temperatures, obtains nearly colourless homogeneous liquid,
For catalyst A.
The preparation of polyester
By based on the polyester generated to 600 grams of p-phthalic acids and 316 grams of ethylene glycol and catalyst A(amount, the weight of titanium atom
Amount is 3ppm), mixing is made into slurry, joins in polymeric kettle, carries out esterification, and esterification temperature is 230～255 DEG C, pressure
For 0.25MPa, discharge, by rectifier unit, the water that reaction generates.Normal pressure is down in esterification after terminating, add potassium acetate 7.8 × 10-3g
(8 × 10-5Mole), zinc acetate 1.6 × 10-2G(8 × 10-5Mole), evacuation is decompressed to system pressure and is less than 130Pa, simultaneously
Reaction temperature is gradually increased to 280 DEG C, and stopped reaction after system reaction reaches 150min, afterwards by product from bottom of polymerizing pot
Portion extrudes continuously with bar shaped, cooling, pelletizing.
The solid phase of polyester
The polyester granulate obtained by liquid polycondensation is dried, after drying by temperature in vacuum environment, under conditions of 100 DEG C
It is promoted to 160 DEG C and carries out pre-crystallized process 6 hours.Will process after granule be positioned over revolution solid phase device in and
0.1kpa, carrying out the solid state polycondensation of polyester under conditions of 230 DEG C, the response time is 10 hours.Take out for test after cooling.
Test result is shown in Table 1.
[embodiment 2]
The preparation of polyester
By based on the polyester generated to 600 grams of p-phthalic acids and 316 grams of ethylene glycol and catalyst A(amount, the weight of titanium atom
Amount is 2.5ppm), mixing is made into slurry, joins in polymeric kettle, carries out esterification, and esterification temperature is 230～255 DEG C, pressure
Power is 0.25MPa, discharges, by rectifier unit, the water that reaction generates.Normal pressure is down in esterification after terminating, add potassium acetate 6 × 10-3g
(6 × 10-5Mole), zinc acetate 1.6 × 10-2G(8 × 10-5Mole), evacuation is decompressed to system pressure and is less than 130Pa, simultaneously
Reaction temperature is gradually increased to 280 DEG C, and stopped reaction after system reaction reaches 150min, afterwards by product from bottom of polymerizing pot
Portion extrudes continuously with bar shaped, cooling, pelletizing.
The solid phase of polyester
By method similarly to Example 1 to polyester granulate solid phase.
Test result is shown in Table 1.
[embodiment 3]
The preparation of catalyst B
Ethylene glycol 12.4 grams (0.2 mole) is added, toward reaction in the reactor equipped with agitator, condenser and thermometer
Device is slowly dropped into tetraisopropyl titanate 28.4 grams (0.1 mole), separates out white depositions, react 2 hours at 70 DEG C, will produce
Thing centrifugation, and with distilled water wash residue 3 times, product is vacuum dried at 70 DEG C, obtains white powder thing
Matter.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, adds
Ethylene glycol 50 grams, the sodium hydrate aqueous solution (0.2 mole) of 32 gram 25%, citric acid monohydrate 63 grams (0.3 mole), tripotassium phosphate
Ester 28 grams (0.2 mole), magnesium acetate 42.6 grams (0.3 mole) reacts 2 hours under 150 DEG C of reaction temperatures, obtain near colourless all
Phase liquid, for catalyst B.
The preparation of polyester
By based on the polyester generated to 600 grams of p-phthalic acids and 316 grams of ethylene glycol and catalyst B(amount, the weight of titanium atom
Amount is 2.5ppm), mixing is made into slurry, joins in polymeric kettle, carries out esterification, and esterification temperature is 230～255 DEG C, pressure
Power is 0.25MPa, discharges, by rectifier unit, the water that reaction generates.Esterification is down to normal pressure after terminating, add potassium oxalate 7.4 ×
10-3G(4 × 10-5Mole), magnesium acetate 1.1 × 10-2G(8 × 10-5Mole), evacuation is decompressed to system pressure and is less than 130Pa,
Simultaneous reactions temperature is gradually increased to 280 DEG C, and stopped reaction after system reaction reaches 150min, afterwards by product from polymerization
Bottom portion extrudes continuously with bar shaped, cooling, pelletizing.
The solid phase of polyester
By method similarly to Example 1 to polyester granulate solid phase.
Test result is shown in Table 1.
[embodiment 4]
Except in embodiment 1, changing interpolation potassium acetate into sodium acetate 6.6 × 10-3G(8 × 10-5Mole) outward, with enforcement
Example 1 uses same method to carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is shown in Table 1.
[embodiment 5]
The preparation of catalyst C
Ethylene glycol 12.4 grams (0.2 mole) is added, toward reaction in the reactor equipped with agitator, condenser and thermometer
Device is slowly dropped into tetraisopropyl titanate 28.4 grams (0.1 mole), separates out white depositions, react 2 hours at 70 DEG C, will produce
Thing centrifugation, and with distilled water wash residue 3 times, product is vacuum dried at 70 DEG C, obtains white powder thing
Matter.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, adds
Ethylene glycol 50 grams, the sodium hydrate aqueous solution (0.2 mole) of 32 gram 25%, citric acid monohydrate 63 grams (0.3 mole), tripotassium phosphate
Ester 28 grams (0.2 mole), zinc acetate 91.8 grams (0.5 mole) reacts 2 hours under 150 DEG C of reaction temperatures, obtain near colourless all
Phase liquid, for catalyst C.
The preparation of polyester
By based on the polyester generated to 600 grams of p-phthalic acids and 316 grams of ethylene glycol and catalyst C(amount, the weight of titanium atom
Amount is 2.5ppm), mixing is made into slurry, joins in polymeric kettle, carries out esterification, and esterification temperature is 230～255 DEG C, pressure
Power is 0.25MPa, discharges, by rectifier unit, the water that reaction generates.Normal pressure is down in esterification after terminating, add potassium acetate 6 × 10-3g
(6 × 10-5Mole), zinc acetate 3.7 × 10-3G(2 × 10-5Mole), evacuation is decompressed to system pressure and is less than 130Pa, simultaneously
Reaction temperature is gradually increased to 280 DEG C, and stopped reaction after system reaction reaches 150min, afterwards by product from bottom of polymerizing pot
Portion extrudes continuously with bar shaped, cooling, pelletizing.
The solid phase of polyester
By method similarly to Example 1 to polyester granulate solid phase.
Test result is shown in Table 1.
[comparative example 1]
Except in embodiment 1, changing interpolation potassium acetate into p-methyl benzenesulfonic acid potassium 1.4 × 10-2G(8 × 10-5Mole) outward,
Method as using with embodiment 1 carries out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is shown in Table 1.
[comparative example 2]
Except in embodiment 1, changing interpolation potassium acetate into p-methyl benzenesulfonic acid potassium 1.0 × 10-2G(6 × 10-5Mole) outward,
Method as using with embodiment 1 carries out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is shown in Table 1.
[comparative example 3]
Except in embodiment 3, without potassium oxalate outside, the method as using with embodiment 3 carries out the preparation of polyester
Solid-phase polymerization with polyester.
Test result is shown in Table 1.
[comparative example 4]
Use antimony glycol as catalyst (amount based on the polyester generated, the weight of antimony atoms is 180ppm).
By 600 grams of p-phthalic acids and 316 grams of ethylene glycol and glycol antimony catalyst (amount based on the polyester generated, antimony
The weight of atom is 180ppm), mixing be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature be 230～
255 DEG C, pressure is 0.25MPa, discharges, by rectifier unit, the water that reaction generates.Esterification is down to normal pressure after terminating, and evacuation subtracts
Being depressed into system pressure and be less than 130Pa, simultaneous reactions temperature is gradually increased to 280 DEG C, stops anti-after system reaction reaches 150min
Should, afterwards product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.
Method similarly to Example 1 carries out the solid-phase polymerization of polyester.
Test result is shown in Table 1.
[comparative example 5]
The preparation of catalyst D
Ethylene glycol 12.4 grams (0.2 mole) is added, toward reaction in the reactor equipped with agitator, condenser and thermometer
Device is slowly dropped into tetraisopropyl titanate 28.4 grams (0.1 mole), separates out white depositions, react 2 hours at 70 DEG C, will produce
Thing centrifugation, and with distilled water wash residue 3 times, product is vacuum dried at 70 DEG C, obtains white powder thing
Matter.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, adds
Ethylene glycol 50 grams, the sodium hydrate aqueous solution (0.2 mole) of 32 gram 25%, reacts 2 hours under 150 DEG C of reaction temperatures, obtains near
Colourless homogeneous liquid, for catalyst D.
The preparation of polyester
By based on the polyester generated to 600 grams of p-phthalic acids and 316 grams of ethylene glycol and catalyst D(amount, the weight of titanium atom
Amount is 2.5ppm), mixing is made into slurry, joins in polymeric kettle, carries out esterification, and esterification temperature is 230～255 DEG C, pressure
Power is 0.25MPa, discharges, by rectifier unit, the water that reaction generates.Esterification is down to normal pressure after terminating, and evacuation is decompressed to system
Pressure is less than 130Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C, stopped reaction after system reaction reaches 150min, afterwards will
Product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.
The solid phase of polyester
By method similarly to Example 1 to polyester granulate solid phase.
Test result is shown in Table 1.
[comparative example 6]
The preparation of polyester
By based on the polyester generated to 600 grams of p-phthalic acids and 316 grams of ethylene glycol and catalyst A(amount, the weight of titanium atom
Amount is 3ppm), mixing is made into slurry, joins in polymeric kettle, carries out esterification, and esterification temperature is 230～255 DEG C, pressure
For 0.25MPa, discharge, by rectifier unit, the water that reaction generates.Esterification is down to normal pressure after terminating, and evacuation is decompressed to system pressure
Power is less than 130Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C, stopped reaction after system reaction reaches 150min, afterwards will be anti-
Product is answered to extrude continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.
The solid phase of polyester
By method similarly to Example 1 to polyester granulate solid phase.
Test result is shown in Table 1.
Table 1
Claims (10)
1. a production method for low acetaldehyde titanium polyester, comprises the following steps:
A) with dicarboxylic acids and dihydroxylic alcohols as raw material, using titanium series polyester catalyst is 230～280 DEG C in reaction temperature, reaction
Pressure is to carry out esterification under the conditions of normal pressure～0.5MPa, obtains prepolymer, is then 250～320 DEG C in reaction temperature, instead
Answering pressure is to carry out melt polycondensation reaction under the vacuum condition less than 150Pa to obtain polyester product；Catalyst used include with
Lower raw material is in 0～200 DEG C of reaction product of 0.5～10 hour:
(1) there is the titanium compound A of below general formula:
Ti(OR1)4
R1For selected from the straight chain of 1～10 carbon atom or branched-alkyl；
(2) selected from the dihydroxylic alcohols B with 2～10 carbon atoms；
(3) a kind of metallic compound C in periodic table of elements IA；
(4) at least one aliphatic organic acid D in organic acid；
(5) at least one phosphate compound E in phosphorus compound；
(6) at least one metallic compound F in IIA, IB, IIB, VIIB, VIII in the periodic table of elements；
Wherein, the mol ratio of dihydroxylic alcohols 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；Metallic compound C with the mol ratio of titanium compound is > 0～10: 1；Aliphatic organic acid D and titanium compound A's
Mol ratio is 1～20: 1；The mol ratio of phosphate compound E and titanium compound A is > 0～10: 1；
Add after esterification alkali metal carboxylate compound G and in the periodic table of elements IIA, IB, IIB, VIIB,
At least one metallic compound H in VIII as promoter, weight based on 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 polycondensation is after pre-crystallized process, is 200～250 DEG C in reaction temperature, reaction pressure
For less than carrying out solid phase under conditions of 100Pa to obtain the intrinsic viscosity polyester more than 0.8 deciliter/gram.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that dicarboxylic acids is selected to benzene two
At least one in formic acid, phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid；Binary
At least one in ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-HD and 1,4 cyclohexane dimethanol of alcohol.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that titanium compound A is selected from metatitanic acid four
Methyl ester, tetraethyl titanate, the own ester of metatitanic acid tetraethyl, metatitanic acid orthocarbonate, tetraisopropyl titanate or butyl titanate, metatitanic acid four are different pungent
At least one in ester；Dihydroxylic alcohols B is selected from 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, ethylene glycol, diethylene glycol
In at least one.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that IA race gold in metallic compound C
Belong at least one in lithium, sodium or potassium.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that aliphatic organic acid D is selected from breast
At least one in acid, citric acid, malic acid, tartaric acid or oxalic acid.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that phosphate compound E is selected from phosphorus
Acid one methyl ester, etherophosphoric acid, trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate
Or at least one in triphenyl phosphate.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that metallic compound F selected from zinc,
At least one in manganese, magnesium, calcium or cobalt compound.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that alkali metal carboxylate compound G
At least one in lithium acetate, sodium acetate, potassium acetate, lithium oxalate, Disodium oxalate., potassium oxalate.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that metallic compound H selected from zinc,
At least one in manganese, magnesium, calcium or cobalt compound.
The production method of the lowest acetaldehyde titanium polyester, it is characterised in that dihydroxylic alcohols B and titanium compound A
Mol ratio be 1～4: 1；Metallic compound C is 1～10: 1 with the mol ratio of titanium compound；Aliphatic organic acid D closes with titanizing
The mol ratio of thing A is 1～15: 1；The mol ratio of phosphate ester phosphorus compound E and titanium compound A is > 0～6: 1；Metallic compound F
It is 0.1～10: 1 with the mol ratio of titanium compound A.
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| CN201310544151.9A CN104629033B (en) | 2013-11-06 | 2013-11-06 | The production method of low acetaldehyde titanium polyester |
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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 |
| CN108976403B (en) * | 2018-08-08 | 2021-01-12 | 济南朝晖科技有限公司 | Process for producing polyester |
| CN108976398B (en) * | 2018-08-08 | 2020-10-16 | 济南朝晖科技有限公司 | Process for producing 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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| CN1556127A (en) * | 2003-12-31 | 2004-12-22 | 浙江恒逸集团有限公司 | Dyeingable dalk coloured copolyester and its preparation method |
| CN101942078A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Titanium polyester catalyst for preparing polyester |
| CN102219894A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing semi-dulling titanium series polyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1556127A (en) * | 2003-12-31 | 2004-12-22 | 浙江恒逸集团有限公司 | Dyeingable dalk coloured copolyester and its preparation method |
| CN101942078A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Titanium polyester catalyst for preparing polyester |
| CN102219894A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing semi-dulling titanium series polyester |
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