CN109666135A - The preparation method of the polyester resin of low acetaldehyde - Google Patents
The preparation method of the polyester resin of low acetaldehyde Download PDFInfo
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- CN109666135A CN109666135A CN201710962753.4A CN201710962753A CN109666135A CN 109666135 A CN109666135 A CN 109666135A CN 201710962753 A CN201710962753 A CN 201710962753A CN 109666135 A CN109666135 A CN 109666135A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
Abstract
The present invention relates to a kind of preparation methods of the polyester resin of low acetaldehyde, mainly solve the problems, such as that polyester article especially bottle piece acetaldehyde residual volume after being molded of previous Titanium series catalyst preparation is high, by using the catalyst for the reaction product for including following raw material: 1) with the titanium compound A:Ti (OR) of following general formula4；2) selected from the dihydric alcohol B with 2~10 carbon atoms；3) selected from one of periodic table of elements IA metallic compound C；4) selected from least one of organic acid aliphatic organic acid D；5) selected from least one of phosphorus compound phosphate compound E；6) at least one of IIA, IB, IIB, VIIB, VIII metallic compound F in the periodic table of elements；7) technical solution of the nitrogenous compound G selected from organic amine or organic ammonium, preferably solves the problems, such as this, can be used in the industrial production of polyester with low content of acetaldehyde resin.
Description
Technical field
The present invention relates to a kind of preparation methods of the polyester resin of low acetaldehyde.
Background technique
Polyethylene terephthalate is a kind of important raw material of industry, since it is with excellent chemical property and object
Rationality matter is widely used in the materials such as fiber, film, piece, bottle.It is with excellent mechanical strength, chemical stability, gas
Barrier property, fragrant retention, sanitation degree etc., cheap, lighter in weight need heat sterilization filling particularly suitable for manufacture
Beverage container.
Industrial production and to study more polyester catalyst be mainly three antimony, germanium and titanium serial catalyst at present,
Most commonly used in middle polyester industrial device is antimony-based catalyst (including antimony oxide, antimony acetate and antimony glycol
Deng), 90% or more polyester is produced by antimony-based catalyst in the world at present, and the polyester device in China also mainly uses
Antimony-based catalyst.Metallic antimony belongs to heavy metal element, and the resin of catalyst production is in beverage container field in application, can go out
An existing problem: antimony-based catalyst can be eluted out from container under the high temperature conditions, and micro antimony is caused to enter built-in drink
In material.Germanium series catalysts are with good stability, and the side reaction caused during the reaction is less, made PET hue
It is good, but since resource is few, it is expensive.Titanium series polyester catalyst has high activity, but made from titanium series polyester catalyst
There is thermal stability difference and product yellowing, muddy in polyester, easily decompose generate acetaldehyde under the high temperature conditions, cause acetaldehyde into
Enter built-in beverage, thus never obtains large-scale use.
Special open 2000-143789 adds titanium compound and selected from magnesium compound, aluminium when disclosing a kind of progress polymerization reaction
At least one compound of compound, barium compound etc., but there are obtained polyester with poor for the method for above-mentioned disclosure
Tone.
CN1328072 and CN1327985 discloses generate a kind of granular titanium with titanate esters and glycol reaction two
As polyester catalyst, this granular polyester catalyst is possible to bring one in the industrial production of polyester first alcoholic compound
A little application problems, and do not register in patent and the acetaldehyde of polyester is made using this catalyst.
CN101687984 disclose it is a kind of addition hypophosphorous acid compound with improve organic titanate catalysis polyester solid phase
Polycondensation method, wherein polyester shows the generation of low acetaldehyde in melt-processed, but acetaldehyde after solid phase polycondensation is not directed in patent
The relevant report of content.
EP1013692 is pointed out, the acetaldehyde as by-product can be generated during polycondensation and melt molding, can be used titanium and
Some metallic compounds inhibit as polycondensation catalyst, and the Specific amounts of titanium and metallic atom such as magnesium should be specific ratio.
CN1457343 points out, can by addition titaniferous, magnesium, phosphorus compound, and order of addition is after first phosphorus after magnesium
The method added after titanium, titanium and esterification, prepares the polyester of low acetaldehyde, according to the present invention the research of people, this method preparation
Polyester improvement is truly had in terms of controlling acetaldehyde generation, but there is very big lack in polycondensation rate especially solid phase polycondensation rate
It falls into.
CN1863839 is pointed out, be can be used titanium, zinc, phosphorus and lactic acid as polycondensation catalyst, is prepared high solid phase polycondensation rate
Polyester, but Wen Zhongwei refers to the acetaldehyde control of obtained polyester.
CN102002214A is pointed out, can add phosphorous member by titaniferous element compound as polycondensation catalyst
Plain stabilizer and magnesium, while certain phosphorous and calcium compound is added, increase solid phase polycondensation speed, obtains lower bottle base second
Aldehyde.
CN101679620A is pointed out, can be used titanium, phosphorus as polycondensation catalyst, does not add acetaldehyde scavenger and using liquid phase
The mode of polycondensation obtains the polyester for being suitble to manufacture bottled water, and free aldehyde is low in polymer blend.
But generally existing color is partially yellow and hot after solid phase polycondensation using product made from the Titanium series catalyst of the above technology
The problem of stability difference causes the acetaldehyde of polyester article high.
Summary of the invention
The technical problem to be solved by the present invention is to previous Titanium series catalyst preparation polyester especially after being molded acetaldehyde
The high problem of residual volume, provides a kind of preparation method of the polyester resin of low acetaldehyde.This method has acetaldehyde residual volume low
The advantages of.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of polyester tree of low acetaldehyde
The preparation method of rouge, comprising the following steps:
A) using dicarboxylic acids and dihydric alcohol as raw material, use titanium series polyester catalyst in reaction temperature for 230~280 DEG C,
Reaction pressure carries out esterification under the conditions of being normal pressure~0.5MPa, obtains prepolymer, is then 250~320 in reaction temperature
DEG C, reaction pressure obtains polyester product to carry out melt polycondensation reaction under the vacuum condition less than 150Pa；Titanium polyester used
Catalyst includes the reaction product that following raw material reacts 0.5~10 hour at 0~200 DEG C:
(1) with the titanium compound A of following general formula:
Ti(OR)4
R is straight chain or branched-alkyl selected from 1~10 carbon atom；
(2) selected from the dihydric alcohol B with 2~10 carbon atoms；
(3) selected from one of periodic table of elements IA metallic compound C；
(4) selected from least one of organic acid aliphatic organic acid D；
(5) selected from least one of phosphorus compound phosphate compound E；
(6) at least one of IIA, IB, IIB, VIIB, VIII metallic compound F in the periodic table of elements；
(7) the nitrogenous compound G selected from organic amine or organic ammonium；
Wherein, the molar ratio of dihydric alcohol B and titanium compound A is (1~8): 1；Mole of metallic compound C and titanium compound
Than for (0~10): 1；The molar ratio of aliphatic organic acid D and titanium compound A is (1~20): 1；Phosphate compound E and titanizing
The molar ratio for closing object A is (0~10): 1；The molar ratio of metallic compound F and titanium compound A is (0.1~20): 1；Nitrogenous chemical combination
The molar ratio of object G and titanium compound A is (0.1~20): 1；
B) polyester product for obtaining melt polycondensation is 200~250 DEG C in reaction temperature, in nitrogen after pre-crystallized processing
Solid phase is carried out under gas circulation status to obtain the polyester that inherent viscosity is greater than 0.8 deciliter/gram.
Dicarboxylic acids described in above-mentioned technical proposal preferably is selected from terephthalic acid (TPA), phthalic acid, M-phthalic acid, naphthalene two
At least one of formic acid, biphenyl dicarboxylic acid or cyclohexane cyclohexanedimethanodibasic；The dihydric alcohol preferably be selected from ethylene glycol, 1,3- propylene glycol,
At least one of 1,4- butanediol, 1,6-HD and 1,4 cyclohexane dimethanol.
Titanium compound A described in above-mentioned technical proposal has general formula shown in formula (I):
Wherein, R1To R4It is independently selected from C1~C8Alkyl.As an example, the titanium compound A for example can be selected from titanium
Sour four methyl esters, tetraethyl titanate, the own ester of metatitanic acid tetraethyl, metatitanic acid orthocarbonate, tetraisopropyl titanate or butyl titanate, metatitanic acid four
At least one of different monooctyl ester.
Dihydric alcohol B described in above-mentioned technical proposal preferably is selected from 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediol, second
At least one of glycol, 1,6-HD, 1,4 cyclohexane dimethanol and diethylene glycol.
In above-mentioned technical proposal, IA race metal preferably is selected from least one of lithium, sodium or potassium in the metallic compound C.
The preferred hydroxide of the metallic compound C, carbonate, bicarbonate or C2~C4The salt of carboxylic acid.The metallic compound C is more
Preferred embodiment is selected from sodium hydroxide or potassium hydroxide.
In above-mentioned technical proposal, the aliphatic organic acid D preferably is selected from lactic acid, citric acid, malic acid, tartaric acid or oxalic acid
At least one of.
In above-mentioned technical proposal, the phosphate compound E preferably has general formula shown in formula (II):
Wherein R5、R6And R7H, C are independently selected from addition to it cannot be simultaneously H2~C6Alkyl.It as an example, such as can be with
Selected from methyl-phosphoric acid, etherophosphoric acid, trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, phosphoric acid
At least one of tributyl or triphenyl phosphate.
In above-mentioned technical proposal, the metallic compound F preferably is selected from least one in zinc, manganese, magnesium, calcium or cobalt compound
Kind；Such as at least one of magnesium acetate, zinc acetate, cobalt acetate.
In above-mentioned technical proposal, the nitrogenous compound G preferably is selected from ammonium acetate, triethylamine, Triammonium citrate and six first
At least one of urotropine.
In above-mentioned technical proposal, the molar ratio of dihydric alcohol B and titanium compound A are preferably (1~4): 1；Metallic compound C with
The molar ratio of titanium compound is preferably (1~10): 1；The molar ratio of aliphatic organic acid D and titanium compound A is preferably (1~15)
:1；The molar ratio of phosphate phosphorus compound E and titanium compound A is preferably (0~6): 1；Metallic compound F's and titanium compound A
Molar ratio is (0.1~20): 1；
In above-mentioned technical proposal, the molar ratio of nitrogenous compound G and titanium compound A are preferably (0.1~10): 1.
In above-mentioned technical proposal, the reaction temperature preferred scope for preparing titanium series polyester catalyst is 10~180 DEG C, when reaction
Between preferred scope be 2~6 hours.The weight of polyester product is obtained based on melt polycondensation reaction, the additive amount of catalyst is with titanium original
Son meter is preferably 1~20ppmw.
Titanium series polyester catalyst of the present invention the preparation method is as follows:
By titanium compound be added the desired amount of dihydric alcohol, in the periodic table of elements at least one metallic compound of IA,
It is closed instead in the periodic table of elements selected from least one of IIA, IB, IIB, VIIB or VIII metallic compound, organic acid and phosphatization
It should obtain homogeneous liquid titanium polyester catalyst.
Polyester the preparation method is as follows:
Known preparation process of polyester can be used, the first step carries out esterification by dicarboxylic acids and dihydric alcohol, obtains
Prepolymer, reaction temperature are 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
It answers, 250~320 DEG C of reaction temperature, reaction pressure is less than 150Pa.Titanium series polyester catalyst is added before esterification starts
Into reaction system.Extrusion pelletizing is carried out after reaction.
Solid phase (SSP) method of polyester:
The polyester further progress solid phase of above method preparation is improved into viscosity.Before carrying out solid phase, Ying Xian
Pre-crystallized processing is carried out to polyester.Polyester granulate prepared by above-mentioned preparation process of polyester, is placed in 80~130 DEG C, preferably 90~
1 minute~3 hours are heated under 120 DEG C of vacuum environment to be dried.After drying, in atmosphere of inert gases or vacuum ring
Under border, temperature is promoted to 100~180 DEG C, preferably 140~170 DEG C progress are pre-crystallized, and crystallization time is 1~10 hour, preferably
3~7 hours.
After pre-crystallized, particle is sent into solid-phase polymerization device, solid polycondensation is carried out to particle under nitrogen circulation
Close reaction.Reaction temperature is 200~250 DEG C, and preferably 210~230 DEG C, nitrogen flow rate is 0~10L/min, preferably 1~5L/
min.Equipment is warming up to setting value within 1 hour.Reaction time is 1~10 hour, preferably 3~8 hours.
In the present invention, the inherent viscosity, form and aspect of polyester and acetaldehyde (AA) etc. are tested by the following method:
(1) inherent viscosity: phenol -1,1,2,2- tetrachloroethanes mixed liquors (weight ratio 1:1) make solvent, at a temperature of 25 DEG C
Use determination of ubbelohde viscometer.
(2) form and aspect: pellet sample uses the automatic color difference of color-view of BYK Gardner company after handling 1 hour at 135 DEG C
Meter measures its Hunter L value (brightness), a value (red-green form and aspect) and b value (yellow-blue form and aspect).Wherein, L value is higher, brightness
It is bigger；Then polyester slice is partially yellow for b value height.For the present invention, it is desirable to pursue high L value, low b value.
(3) acetaldehyde (AA): accurate weighing 0.5g is fitted into ml headspace bottle after the polyester sample of solid phase polycondensation crushes, and is used
It air and is sealed in nitrogen displacement bottle.150 DEG C of head-space sampler furnace temperature, equilibration time 60 minutes of setting.The acetaldehyde of sample
Quantitative analysis is carried out by headspace sampling using gas chromatograph (GC7890, Agilent).
Present inventors have surprisingly found that after solid phase there is lower acetaldehyde to contain using polyester made from this method
Amount, acetaldehyde can be lower than 1ppmw, achieve preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
The preparation of catalyst A
12.4 grams of ethylene glycol (0.2 mole) is added in the reactor equipped with blender, condenser and thermometer, toward reaction
It is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions is precipitated, reacts 2 hours, will produce at 70 DEG C
Object centrifuge separation, and be washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder substance.
White powder substance after drying is placed in the reactor with blender, condenser and thermometer, is added
50 grams of ethylene glycol, the sodium hydrate aqueous solution (0.3 mole) of 48 grams of 25wt%, 42.8 grams of magnesium acetate (0.2 mole), a water lemon
Sour 42 grams (0.2 mole), 42 grams of trimethyl phosphate (0.3 mole), 15.4 grams of ammonium acetate (0.2 mole) is in 150 DEG C of reaction temperatures
Lower reaction 2 hours obtains nearly colourless homogeneous liquid, is catalyst A.
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst A (amount of the polyester based on generation, the weight of titanium atom
Amount is 5ppmw), mixing is made into slurry, is added in polymeric kettle, carries out esterification, and esterification temperature is 230~255 DEG C, pressure
For 0.25MPa, the water that reaction generates is discharged by rectifier unit.It is down to normal pressure after esterification, vacuumizes and is decompressed to system pressure
Power is lower than 100Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C, stops reaction after system reaction reaches 150min, later will be anti-
Product is answered continuously to squeeze out from polymeric kettle bottom with bar shaped, cooling, pelletizing.
The solid phase of polyester
The polyester granulate that liquid polycondensation obtains is dried under conditions of vacuum environment, 100 DEG C, by temperature after drying
It is promoted to 160 DEG C and carries out pre-crystallized processing 6 hours.By treated, particle is placed in solid-phase polymerization device and in nitrogen
Flow velocity 4L/min, the solid state polycondensation that polyester is carried out under conditions of 220 DEG C, reaction time are 10 hours.It is taken out after cooling.
It is 280 DEG C in cavity temperature, mould temperature temperature is 120 DEG C, injection molding by pellet in HAAKE MINI JET injection molding machine
Pressure is 500bar, dwell pressure 50bar, is molded under the conditions of this.
Test result is shown in Table 1.
[embodiment 2]
In addition to the amount of ammonium acetate to be changed to 38.5 grams (0.5 moles), polyester is carried out using same method with embodiment 1
The solid-phase polymerization of preparation and polyester.
Test result is shown in Table 1.
[embodiment 3]
In addition to the amount of ammonium acetate to be changed to 61.6 grams (0.8 moles), polyester is carried out using same method with embodiment 1
The solid-phase polymerization of preparation and polyester.
Test result is shown in Table 1.
[embodiment 4]
In addition to the amount of ammonium acetate to be changed to 77 grams (1 moles), the preparation of polyester is carried out using same method with embodiment 1
With the solid-phase polymerization of polyester.
Test result is shown in Table 1.
[embodiment 5]
The preparation of catalyst B
12.4 grams of ethylene glycol (0.2 mole) is added in the reactor equipped with blender, condenser and thermometer, toward reaction
It is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions is precipitated, reacts 2 hours, will produce at 70 DEG C
Object centrifuge separation, and be washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder substance.
White powder substance after drying is placed in the reactor with blender, condenser and thermometer, is added
50 grams of ethylene glycol, sodium hydrate aqueous solution (0.2 mole), 42.8 grams of the magnesium acetate (0.2 mole) of 32 grams of 25wt%, tripotassium phosphate
28 grams of ester (0.2 mole), 63 grams of Citric Acid Mono (0.3 mole), 20.2 grams of triethylamine (0.2 mole) are in 150 DEG C of reaction temperatures
Lower reaction 2 hours obtains nearly colourless homogeneous liquid, is catalyst B.
The preparation of polyester and the solid-phase polymerization of polyester are carried out using same method with embodiment 1.
Test result is shown in Table 1.
[embodiment 6]
The preparation of catalyst C
12.4 grams of ethylene glycol (0.2 mole) is added in the reactor equipped with blender, condenser and thermometer, toward reaction
It is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions is precipitated, reacts 2 hours, will produce at 70 DEG C
Object centrifuge separation, and be washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder substance.
White powder substance after drying is placed in the reactor with blender, condenser and thermometer, is added
50 grams of ethylene glycol, 48 grams of 35wt% potassium hydroxide aqueous solutions (0.2 mole), 42.8 grams of magnesium acetate (0.2 mole), trimethyl phosphate
28 grams (0.2 mole), 63 grams of Citric Acid Mono (0.3 mole), Triammonium citrate 48.6 (0.2 mole) are in 150 DEG C of reaction temperatures
Lower reaction 2 hours obtains nearly colourless homogeneous liquid, is catalyst C.
The preparation of polyester and the solid-phase polymerization of polyester are carried out using same method with embodiment 1.
Test result is shown in Table 1.
[embodiment 7]
The preparation of catalyst D
12.4 grams of ethylene glycol (0.2 mole) is added in the reactor equipped with blender, condenser and thermometer, toward reaction
It is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions is precipitated, reacts 2 hours, will produce at 70 DEG C
Object centrifuge separation, and be washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder substance.
White powder substance after drying is placed in the reactor with blender, condenser and thermometer, is added
50 grams of ethylene glycol, 48 grams of 35wt% potassium hydroxide aqueous solutions (0.2 mole), 42.8 grams of magnesium acetate (0.2 mole), trimethyl phosphate
28 grams (0.2 mole), 63 grams of Citric Acid Mono (0.3 mole), hexamethylenetetramine 28 (0.2 mole) are in 150 DEG C of reaction temperatures
Lower reaction 2 hours obtains nearly colourless homogeneous liquid, is catalyst C.
The preparation of polyester and the solid-phase polymerization of polyester are carried out using same method with embodiment 1.
Test result is shown in Table 1.
[embodiment 8]
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol, mixing is made into slurry, is added in polymeric kettle, be esterified anti-
It answers, esterification temperature is 230~255 DEG C, pressure 0.25MPa, and the water that reaction generates is discharged by rectifier unit.After esterification
It is down to normal pressure, catalyst C (amount of the polyester based on generation, the weight of titanium atom are 5ppmw) is added, after stirring 5min, takes out true
Sky is decompressed to system pressure lower than 100Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C, stops after system reaction reaches 150min
It only reacts, later continuously squeezes out reaction product with bar shaped from polymeric kettle bottom, cooling, pelletizing.
By method similarly to Example 1 to polyester granulate solid phase.
Test result is shown in Table 1.
[comparative example 1]
The preparation of catalyst E
12.4 grams of ethylene glycol (0.2 mole) is added in the reactor equipped with blender, condenser and thermometer, toward reaction
It is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions is precipitated, reacts 2 hours, will produce at 70 DEG C
Object centrifuge separation, and be washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder substance.
White powder substance after drying is placed in the reactor with blender, condenser and thermometer, is added
50 grams of ethylene glycol, the sodium hydrate aqueous solution (0.3 mole) of 48 grams of 25wt%, 42.8 grams of magnesium acetate (0.2 mole), a water lemon
Sour 42 grams (0.2 mole), 42 grams of trimethyl phosphate (0.3 mole) react 2 hours under 150 DEG C of reaction temperatures, obtain close colourless
Homogeneous liquid is catalyst E.
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst E (amount of the polyester based on generation, the weight of titanium atom
Amount is 5ppmw), mixing is made into slurry, is added in polymeric kettle, carries out esterification, and esterification temperature is 230~255 DEG C, pressure
For 0.25MPa, the water that reaction generates is discharged by rectifier unit.It is down to normal pressure after esterification, vacuumizes and is decompressed to system pressure
Power is lower than 100Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C, stops reaction after system reaction reaches 150min, later will be anti-
Product is answered continuously to squeeze out from polymeric kettle bottom with bar shaped, cooling, pelletizing.
The solid phase of polyester
The polyester granulate that liquid polycondensation obtains is dried under conditions of vacuum environment, 100 DEG C, by temperature after drying
It is promoted to 160 DEG C and carries out pre-crystallized processing 6 hours.By treated, particle is placed in solid-phase polymerization device and in nitrogen
Flow velocity 4L/min, the solid state polycondensation that polyester is carried out under conditions of 220 DEG C, reaction time are 10 hours.It is taken out after cooling.
It is 280 DEG C in cavity temperature, mould temperature temperature is 120 DEG C, injection molding by pellet in HAAKE MINI JET injection molding machine
Pressure is 500bar, dwell pressure 50bar, is molded under the conditions of this.
Test result is shown in Table 1.
[comparative example 2]
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst E (amount of the polyester based on generation, the weight of titanium atom
Amount is 5ppmw), ammonium acetate (mass number based on 2 times of titanium atom moles), and mixing is made into slurry, is added in polymeric kettle, into
Row esterification, esterification temperature are 230~255 DEG C, pressure 0.25MPa, and the water that reaction generates is discharged by rectifier unit.Ester
It is down to normal pressure after change, vacuumizes and is decompressed to system pressure lower than 100Pa, simultaneous reactions temperature is gradually increased to 280 DEG C, works as body
System's reaction stops reaction after reaching 150min, later continuously squeezes out reaction product with bar shaped from polymeric kettle bottom, and cooling is cut
Grain.
The solid phase of polyester
The polyester granulate that liquid polycondensation obtains is dried under conditions of vacuum environment, 100 DEG C, by temperature after drying
It is promoted to 160 DEG C and carries out pre-crystallized processing 6 hours.By treated, particle is placed in solid-phase polymerization device and in nitrogen
Flow velocity 4L/min, the solid state polycondensation that polyester is carried out under conditions of 220 DEG C, reaction time are 10 hours.It is taken out after cooling.
It is 280 DEG C in cavity temperature, mould temperature temperature is 120 DEG C, injection molding by pellet in HAAKE MINI JET injection molding machine
Pressure is 500bar, dwell pressure 50bar, is molded under the conditions of this.
Test result is shown in Table 1.
[comparative example 3]
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst E (amount of the polyester based on generation, the weight of titanium atom
Amount is 5ppmw), mixing is made into slurry, is added in polymeric kettle, carries out esterification, and esterification temperature is 230~255 DEG C, pressure
For 0.25MPa, the water that reaction generates is discharged by rectifier unit.It is down to normal pressure after esterification, vacuumizes and is decompressed to system pressure
Power is lower than 100Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C, stops reaction after system reaction reaches 150min, later will be anti-
Product is answered continuously to squeeze out from polymeric kettle bottom with bar shaped, cooling, pelletizing.
The solid phase of polyester
The polyester granulate that liquid polycondensation obtains is dried under conditions of vacuum environment, 100 DEG C, by temperature after drying
It is promoted to 160 DEG C and carries out pre-crystallized processing 6 hours.Will treated particle mixing ammonium acetate (based on 2 times of titanium atom moles
Mass number) after be placed in solid-phase polymerization device and carry out consolidating for polyester under conditions of nitrogen flow rate 4L/min, 220 DEG C
Phase polycondensation reaction, reaction time are 10 hours.It is taken out after cooling.
It is 280 DEG C in cavity temperature, mould temperature temperature is 120 DEG C, injection molding by pellet in HAAKE MINI JET injection molding machine
Pressure is 500bar, dwell pressure 50bar, is molded under the conditions of this.
Test result is shown in Table 1.
Table 1
Claims (10)
1. a kind of preparation method of the polyester resin of low acetaldehyde, comprising the following steps:
A) using dicarboxylic acids and dihydric alcohol as raw material, esterification is carried out using titanium series polyester catalyst, obtains prepolymer, then
It carries out melt polycondensation reaction and obtains polyester product；Titanium series polyester catalyst used includes that following raw material is anti-at 0~200 DEG C
Answer 0.5~10 hour reaction product:
(1) with the titanium compound A of following general formula:
Ti(OR)4
R is straight chain or branched-alkyl selected from 1~10 carbon atom；
(2) selected from the dihydric alcohol B with 2~10 carbon atoms；
(3) selected from one of periodic table of elements IA metallic compound C；
(4) selected from least one of organic acid aliphatic organic acid D；
(5) selected from least one of phosphorus compound phosphate compound E；
(6) at least one of IIA, IB, IIB, VIIB, VIII metallic compound F in the periodic table of elements；
(7) the nitrogenous compound G selected from organic amine or organic ammonium；
Wherein, the molar ratio of dihydric alcohol B and titanium compound A is (1~8): 1；The molar ratio of metallic compound C and titanium compound is
(0~10): 1；The molar ratio of aliphatic organic acid D and titanium compound A is (1~20): 1；Phosphate compound E and titanium compound
The molar ratio of A is (0~10): 1；The molar ratio of metallic compound F and titanium compound A is (0.1~20): 1；Nitrogenous compound G
Molar ratio with titanium compound A is (0.1~20): 1；
B) polyester product for obtaining melt polycondensation carries out solid phase after pre-crystallized processing, obtains inherent viscosity greater than 0.8
The polyester resin of the low acetaldehyde of deciliter/gram.
2. the preparation method of the polyester-injected parts of low acetaldehyde according to claim 1, it is characterised in that the esterification is anti-
The condition answered are as follows: reaction temperature is 230~280 DEG C, and reaction pressure is normal pressure~0.5MPa；The condition of the melt polycondensation reaction
Are as follows: reaction temperature is 250~320 DEG C, and reaction pressure is less than 150Pa；The condition of the solid phase are as follows: reaction temperature is
It 200~250 DEG C, is carried out under inert gas circulation.
3. the preparation method of the polyester resin of low acetaldehyde according to claim 1, it is characterised in that dicarboxylic acids is selected from
At least one in terephthalic acid (TPA), phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid, biphenyl dicarboxylic acid or cyclohexane cyclohexanedimethanodibasic
Kind；Dihydric alcohol in ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,6-HD and 1,4 cyclohexane dimethanol extremely
Few one kind.
4. the preparation method of the polyester resin of low acetaldehyde according to claim 1, it is characterised in that titanium compound A has
General formula shown in formula (I):
Wherein, R1To R4It is independently selected from C1~C8Alkyl.
5. the preparation method of the polyester resin of low acetaldehyde according to claim 1, it is characterised in that dihydric alcohol B is selected from
1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediol, ethylene glycol, 1,6-HD, 1,4 cyclohexane dimethanol and diethylene glycol
At least one of.
6. the preparation method of the polyester resin of low acetaldehyde according to claim 1, it is characterised in that in metallic compound C
IA race metal is selected from least one of lithium, sodium or potassium.
7. the preparation method of the polyester resin of low acetaldehyde according to claim 1, it is characterised in that aliphatic organic acid D
Selected from least one of lactic acid, citric acid, malic acid, tartaric acid or oxalic acid.
8. the preparation method of the polyester resin of low acetaldehyde according to claim 1, it is characterised in that phosphate compound E
With general formula shown in formula (II):
Wherein R5、R6And R7H, C are independently selected from addition to it cannot be simultaneously H2~C6Alkyl.
9. the preparation method of the polyester resin according to low acetaldehyde described in claim 1, it is characterised in that the metallic compound F
Selected from least one of zinc, manganese, magnesium, calcium or cobalt compound；The further preferred metallic compound F preferably be selected from magnesium acetate,
At least one of zinc acetate, cobalt acetate.
10. the preparation method of the polyester resin of any low acetaldehyde according to claim 1~9, it is characterised in that described
Nitrogenous compound G is selected from least one of ammonium acetate, triethylamine, Triammonium citrate and hexamethylenetetramine.
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| CN1344754A (en) * | 2000-09-15 | 2002-04-17 | 因文塔-费希尔股份有限两合公司 | Process for production polyester with low content of free aldehyde |
| CN1457343A (en) * | 2001-02-06 | 2003-11-19 | 三菱化学株式会社 | Polyester resin and method for prodution thereof |
| CN1640932A (en) * | 2004-01-15 | 2005-07-20 | 远东纺织股份有限公司 | Polyester composition with low aldehyde content and its preparation method |
| CN101263176A (en) * | 2005-09-16 | 2008-09-10 | 伊士曼化工公司 | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
| US20080260979A1 (en) * | 2004-11-30 | 2008-10-23 | Hiroshi Yokoyama | Polyester Resin, Molded Object Thereof, and Processes for Producing these |
| CN104558575A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of low-acetaldehyde titanium system polyester |
| 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 |
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2017
- 2017-10-17 CN CN201710962753.4A patent/CN109666135B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344754A (en) * | 2000-09-15 | 2002-04-17 | 因文塔-费希尔股份有限两合公司 | Process for production polyester with low content of free aldehyde |
| CN1457343A (en) * | 2001-02-06 | 2003-11-19 | 三菱化学株式会社 | Polyester resin and method for prodution thereof |
| CN1640932A (en) * | 2004-01-15 | 2005-07-20 | 远东纺织股份有限公司 | Polyester composition with low aldehyde content and its preparation method |
| US20080260979A1 (en) * | 2004-11-30 | 2008-10-23 | Hiroshi Yokoyama | Polyester Resin, Molded Object Thereof, and Processes for Producing these |
| CN101263176A (en) * | 2005-09-16 | 2008-09-10 | 伊士曼化工公司 | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
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