CN108774312A - Low adhesive aggregation ester and preparation method thereof - Google Patents
Low adhesive aggregation ester and preparation method thereof Download PDFInfo
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- CN108774312A CN108774312A CN201810693213.5A CN201810693213A CN108774312A CN 108774312 A CN108774312 A CN 108774312A CN 201810693213 A CN201810693213 A CN 201810693213A CN 108774312 A CN108774312 A CN 108774312A
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- low adhesive
- adhesive aggregation
- catalyst
- aggregation ester
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- 150000002148 esters Chemical class 0.000 title claims abstract description 91
- 239000000853 adhesive Substances 0.000 title claims abstract description 90
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 90
- 230000002776 aggregation Effects 0.000 title claims abstract description 90
- 238000004220 aggregation Methods 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 204
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 65
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 59
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 52
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 36
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 28
- 239000013067 intermediate product Substances 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 267
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 72
- 229920000728 polyester Polymers 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 230000032050 esterification Effects 0.000 claims description 28
- 238000005886 esterification reaction Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 21
- 239000007790 solid phase Substances 0.000 claims description 21
- 229920006351 engineering plastic Polymers 0.000 claims description 10
- 239000005022 packaging material Substances 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 11
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 15
- 238000010586 diagram Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- -1 antimony Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of low adhesive aggregation esters and preparation method thereof, and the low adhesive aggregation ester that inherent viscosity is 0.300-0.500dL/g is made in the opportunity that is added by controlling catalyst in building-up process；Wherein catalyst is added when the average degree of polymerization of the intermediate product of polycondensation reaction reaches 8-17；Polycondensation reaction temperature is 260-273 DEG C, and catalyst is antimony glycol, and the modulated process of antimony glycol is：Antimony glycol is uniformly mixed with ethylene glycol and is recycled in mixed process and is passed through nitrogen or inert gas that moisture content is less than 200ppm, the content of cyclic oligomer in low adhesive aggregation ester obtained<2wt%.A kind of low adhesive aggregation ester and preparation method thereof of the present invention, by the modulated process for controlling the antimony glycol being added in the addition opportunity of catalyst, polycondensation reaction temperature and building-up process in building-up process, reduce the content of oligomer in product, low adhesive aggregation ester quality obtained is high, there is fabulous promotional value.
Description
Technical field
The invention belongs to polyester preparation field, it is related to a kind of low adhesive aggregation ester and preparation method thereof.
Background technology
High viscosity polyester has preferable mechanical property and outstanding physicochemical property, is widely used in industrial yarn, packaging
The industrial circles such as material and engineering plastics, especially automobile, security protection and rope etc. need the industry neck of composite reinforcing material
Domain.In above-mentioned polyester application field, in order to ensure that the high-performance of product, people need to further decrease low in polyester slice
Copolymer content, when especially preparing the higher polyester of inherent viscosity, the content of oligomer has become measurement product property in polyester
One of key parameter.And content is at most cyclic oligomer in oligomer, thus how effectively to reduce cyclic oligomer and contain
Amount is the difficult point that current stated polyesters quality improves.
Currently, the preparation method of common stated polyesters is：First inherent viscosity is prepared on the left sides 0.65dL/g through melt polycondensation
Then stated polyesters are prepared by solid phase polycondensation thickening in right low adhesive aggregation ester.As people are to high viscosity polyester quality requirements
Continuous improvement, the quality requirements of low adhesive aggregation ester are also gradually increased in people, the ring-type in the low adhesive aggregation ester of above-mentioned inherent viscosity
Oligomer is more, cannot be satisfied quality requirements of the people to polyester, and the higher reason of oligomer is mainly such as in low adhesive aggregation ester
Under：
(1) the common preparation method of low adhesive aggregation ester (PET) is that progress polycondensation is anti-under 275-285 DEG C of temperature condition at present
It answers, the temperature of polycondensation reaction is higher, and higher reaction temperature can directly result in the generation of cyclic oligomer, therefore obtained low viscous
The content of oligomer necessarily also can accordingly increase in polyester；
(2) it prepares common catalyst when low adhesive aggregation ester and configures system diagram as shown in Figure 1, by the second two in fresh EG tank 8
Catalyst and ethylene glycol mixed in catalyst modulates tank 1 after alcohol input catalyst modulation tank 1 to configure catalyst, then general
Mixed solution in input catalyst charging-tank 4, is then directly inputted to catalyst confession again after the filtering of catalyst filter 6
In 7 should being pumped, the water imbibition of ethylene glycol is very strong, can absorb the moisture in air during transport and charging, and terephthalic acid (TPA)
It is antimony glycol with common catalyst in the reaction system of ethylene glycol, antimony glycol, which contacts to occur to hydrolyze with water, especially to exist
It is easily hydrolyzed under heating condition (in the case of such as catalyst refining temperature is higher), generates insoluble antimony oxide etc. and contain
Antimonial, this substance are easy to be aggregated agglomerating, formation precipitation.In addition, the antimony containing compounds such as antimony oxide are that polycondensation of polyester is anti-
The heterogeneous catalysis answered can cause to be catalyzed irregular so that part catalysis is excessively violent, causes the generation of side reaction, generates
Cyclic oligomer.
Therefore, studying a kind of low adhesive aggregation ester of oligomer and preparation method thereof that can effectively reduce in polyester has ten
Divide important meaning.
Invention content
The purpose of the invention is to overcome oligomer especially cyclic oligomer levels in the low adhesive aggregation ester of the prior art
Higher problem provides a kind of low adhesive aggregation ester and preparation method thereof that can effectively reduce oligomer in polyester.
In order to achieve the above object, the technical solution adopted by the present invention is：
The preparation method of low adhesive aggregation ester, the addition opportunity by controlling catalyst in building-up process are made inherent viscosity and are
The low adhesive aggregation ester of 0.300-0.500dL/g；The catalyst is to reach 8- in the average degree of polymerization of the intermediate product of polycondensation reaction
It is added when 17.Catalyst is added when synthesizing beginning in the prior art, and building-up process is divided into esterification and polycondensation is anti-
It answers, there is a transition stage between esterification and polycondensation reaction, fail to remove in the micromolecular water that the reaction of this stage esterification generates,
Catalyst is caused to hydrolyze, the present invention has found that catalyst hydrolysis is easy to cause oligomer and generates by research, thus the present invention
Addition opportunity by regulating and controlling catalyst avoids the contact for the micromolecular water that catalyst and esterification generate, and then avoids
Oligomer caused by being hydrolyzed due to catalyst is increased.Meanwhile the present invention has found production among regulation and control polycondensation reaction by studying
The uniform performance of object molecular chain length effectively inhibits oligomer to generate, and the present invention is added after polycondensation reaction carries out a period of time and urges
Agent, reaction speed is slower before catalyst is added, and the intermediate product uniformity of formation is higher, during the high uniformity of intermediate product is
Between the long and too short macromolecular chain that contains of product it is less, molecular chain length difference is small, the production that further polycondensation reaction is formed
The molecular chain length of object also can more uniformly, due to low molecule chain be difficult to continue increase formed linear oligomer and due to
The content that the macromolecular generation occlusion of long chain forms cyclic oligomer will significantly reduce.
As preferred technical solution：
The preparation method of low adhesive aggregation ester as described above, the building-up process is divided into esterification and polycondensation reaction, described
The temperature of polycondensation reaction is 260-273 DEG C, and the temperature of polycondensation reaction is conducive to that oligomer is inhibited to generate less than the prior art, with it
His technological means, which matches, can obtain better inhibition, and the catalyst is antimony glycol, the tune of the antimony glycol
Process processed is：Antimony glycol is uniformly mixed with ethylene glycol and cycle is passed through the nitrogen that moisture content is less than 200ppm in mixed process
Gas or inert gas.
The preparation method of low adhesive aggregation ester as described above, described be uniformly mixed carry out in catalyst modulates tank, urge
Agent modulation tank is internally provided with blender, and top and bottom connect with nitrogen treatment generator and gas circulation pump discharge respectively
Logical, nitrogen treatment generator is for generating nitrogen while processing, nitrogen treatment generator and gas circulation being dried to nitrogen
Pump intake is connected to.
The preparation method of low adhesive aggregation ester as described above, after the modulated process, antimony glycol enters with ethylene glycol
The bottom and top of catalyst charging-tank, the catalyst charging-tank are connected to the entrance and exit of liquid circulation pump respectively.
The preparation method of low adhesive aggregation ester as described above, the raw material of the esterification are terephthalic acid (TPA) and ethylene glycol,
The molar ratio of terephthalic acid (TPA) and ethylene glycol is 1:The temperature of 1.2-1.5, the esterification are 235-245 DEG C, time 2-
3h, pressure 0.1-0.2MPa；The pressure of the polycondensation reaction is 100-200Pa.
High viscosity polyester is made through solid-phase tack producing in the preparation method of low adhesive aggregation ester as described above, the low adhesive aggregation ester, and height is viscous
The inherent viscosity of polyester is 0.85-1.15dL/g, the content of cyclic oligomer<1.80wt%, in the high viscosity polyester of the prior art
The content of cyclic oligomer is generally 2~2.4wt%, and low adhesive aggregation ester of the invention is conducive to prepare the low height of oligomer viscous
Polyester achieves significant progress compared with the prior art；The oligomer total content of the high viscosity polyester<2.25wt%, it is special
Property viscosity deviation≤0.025dL/g, molecular weight distributing index<2.50 diethylene glycol content<0.90wt%；The high viscosity polyester is answered
For industrial yarn, packaging material or engineering plastics field.
The preparation method of low adhesive aggregation ester as described above, is dried before the solid-phase tack producing pre-crystallized, and the drying is pre-
Crystallization carries out in pre-crystallizer, and the pre-crystallized temperature of the drying is 150-170 DEG C, time 10-20min, atmosphere
For nitrogen.
The preparation method of low adhesive aggregation ester as described above, the solid-phase tack producing are divided into pre-reaction and end reaction；It is described pre- anti-
Should be carried out in pre-reactor, in pre-reactor from top to bottom the temperature in 4th area be respectively 211-223 DEG C, 217-229 DEG C,
217-229 DEG C and 210-222 DEG C, the time of the pre-reaction is 8-10h；The end reaction carries out in end reaction device,
The temperature of the end reaction is 215-225 DEG C, time 18-20h.
The present invention also provides low adhesive aggregation ester made from the preparation method using low adhesive aggregation ester as described above, in low adhesive aggregation ester
The content of cyclic oligomer<2wt%.The content of cyclic oligomer is generally 2.4% or more in the low adhesive aggregation ester of the prior art, this
Invention product achieves significant progress compared with the prior art.
As preferred technical solution：
Low adhesive aggregation ester as described above, the oligomer total content of the low adhesive aggregation ester<3wt%, oligomer as by-product,
Processing difficulties can be caused in subsequent spinning and post-processing because of heated precipitation surface, product defect, while to product lastness
Can have an adverse effect, oligomer is low, superior product quality；Inherent viscosity deviation≤0.02dL/g, inherent viscosity deviation are
One of molecular weight of polyesters macroeconomic stability index is embodied, inherent viscosity deviation is low, and the uniformity and stability of polyester are good；Molecular weight point
Cloth index<2.9, molecular weight distributing index embodies the width of molecular weight distribution, and numerical value is smaller, and molecular weight distribution width is smaller, right
Fiberizing and performance especially Effect on Mechanical Properties are larger；Diethylene glycol content<0.8wt%, diethylene glycol (DEG) (DEG) content is low, gathers
The spinning workability of ester can be good.
Invention mechanism：
The building-up process of low adhesive aggregation ester is broadly divided into esterification and polycondensation reaction, and catalyst is anti-in polycondensation in the application
The average degree of polymerization of intermediate product, which reaches, after should starting is added when 8-17, on the one hand, has between esterification and polycondensation reaction
A transition stage fails to remove, be easy to cause catalyst and hydrolyze in the micromolecular water that the reaction of this stage esterification generates, this hair
It is bright that the contact for the micromolecular water that catalyst can effectively avoid catalyst and esterification from generating is added in specific time, and then avoid
Oligomer caused by being hydrolyzed due to catalyst is increased；On the other hand, the addition opportunity that the present invention passes through control catalyst
Polycondensation reaction is divided into two stages：It is preceding from polycondensation phase and catalyzed polycondensation stage, wherein before from polycondensation phase be not add and urge
The stage of agent, the preceding reaction from polycondensation phase extremely mitigate, and the reaction that can not show a candle to the generation of catalyzed polycondensation stage is violent, in this rank
The strand entirety uniformity that section is formed is far above the catalyzed polycondensation stage.The present invention by it is preceding from polycondensation phase obtain centre
Catalyst is added when the uniformity of product is higher makes polycondensation reaction enter the catalyzed polycondensation stage, and the high uniformity of intermediate product is
The long and too short macromolecular chain that intermediate product contains is less, and molecular chain length difference is small, therefore in subsequent catalyzed polycondensation
The molecular chain length for the product that stage is formed also can more uniformly to reduce since molecular chain length difference is excessive, contract
The macromolecular generation occlusion formation for being difficult to continue growth and forming linear oligomer and long chain of low molecule chain in collecting process
The phenomenon that cyclic oligomer, will be reduced, and occlusion is less likely to occur and forms cyclic oligomer for catalyzed polycondensation stage PET macromolecular chains,
To significantly reduce the content of oligomer in final product.
Meanwhile catalyst modulation tank of the invention is internally provided with blender, top and bottom occur with nitrogen treatment respectively
Device is connected to gas circulation pump discharge, and nitrogen treatment generator is connected to gas circulation pump intake, so that by nitrogen treatment
Nitrogen after generator is generated and is dried enters catalyst modulation pot bottom after gas circulation pump circulation, then passes through second
It emerges, takes out of in antimony glycol and ethylene glycol modulation system from catalyst modulation tank top after the mixed liquor of glycol antimony and ethylene glycol
Moisture, the nitrogen for finally carrying moisture are again introduced into cycle after the drying process of nitrogen treatment generator.The present invention passes through above-mentioned
It is arranged and significantly reduces antimony glycol and the moisture in ethylene glycol modulation system, effectively reduces antimony glycol in modulated process
Hydrolysis phenomena so that catalyst is uniform when subsequently preparing polyester, reduces the generation of side reaction, reduces oligomeric in polyester
The content of object especially cyclic oligomer, while again since antimony glycol a small amount of when modulating still can hydrolyze three oxidation two of generation
The antimony containing compounds such as antimony, therefore the bottom and top of subsequent catalyst charging-tank connect with the entrance and exit of liquid circulation pump respectively
Logical, liquid circulation pump can make the mixed liquor of antimony glycol and ethylene glycol form dynamic flow circuit, prevent generate three oxidations two
The further agglutination of the compounds such as antimony, prevents antimony glycol to be precipitated from solution.
Advantageous effect：
(1) a kind of low adhesive aggregation ester of the invention, inherent viscosity is low, and oligomer is low in low adhesive aggregation ester, and polyester quality is high；
(2) preparation method of a kind of low adhesive aggregation ester of the invention, effectively reduces the hydrolysis phenomena of antimony glycol, effectively keeps away
Antimony glycol precipitation is exempted from, catalysis is uniform, significantly reduces the content of oligomer in product；
(3) preparation method of a kind of low adhesive aggregation ester of the invention, polycondensation reaction temperature is low, effectively reduces obtained low viscous
The content of oligomer in polyester；
(4) preparation method of a kind of low adhesive aggregation ester of the invention, by the preceding intermediate product obtained from polycondensation phase
Catalyst is added when uniformity is higher makes polycondensation reaction enter the catalyzed polycondensation stage, reduces catalyzed polycondensation stage PET molecules
The chance that occlusion forms cyclic oligomer occurs for chain, to significantly reduce the content of the finally oligomer of polyester obtained.
Description of the drawings
Fig. 1 is that prior art custom catalysts configure system diagram；
Fig. 2 is that catalyst of the present invention configures system diagram；
Fig. 3 is the PET molecular weight distribution curve comparison diagrams that the embodiment of the present invention 1 is prepared with comparative example 1；
Fig. 4 is the PET molecular weight distribution curve comparison diagrams that the embodiment of the present invention 1 is prepared with comparative example 2；
Wherein, 1 tank is modulated for catalyst, 2 be nitrogen treatment generator, and 3 be gas circulator, and 4 be catalyst charging-tank,
5 be liquid circulation pump, and 6 be catalyst filter, and 7 be catalyst transfer pump, and 8 be fresh EG tank, 9 being prepared into for comparative example 1
The PET molecular weight distribution curves arrived, the 10 PET molecular weight distribution curves being prepared for embodiment 1,11 be the system of comparative example 2
Standby obtained PET molecular weight distribution curves.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the appended claims of the present invention and limited
Fixed range.
Embodiment 1
The preparation method of low adhesive aggregation ester, is as follows：
(1) modulation of antimony glycol；
It will be uniformly mixed in catalyst modulates tank 1 with ethylene glycol, cycle is passed through moisture content and is in mixed process
The nitrogen of 155ppm；Catalyst configures system diagram as shown in Fig. 2, catalyst configuration system includes catalyst modulation tank 1 and catalysis
Agent charging-tank 4, catalyst modulation tank 1 are internally provided with blender, top and bottom respectively with nitrogen treatment generator 2 and gas
Processing, nitrogen treatment hair is dried to nitrogen simultaneously for generating nitrogen in 3 outlet of circulating pump, nitrogen treatment generator 2
Raw device 2 is connected to 3 entrance of gas circulator；After modulated process, antimony glycol is laggard through catalyst filter 6 with ethylene glycol
Enter catalyst charging-tank 4, the bottom and top of catalyst charging-tank 4 are connected to the entrance and exit of liquid circulation pump 5 respectively；
(2) it is 1 by molar ratio:1.2 terephthalic acid (TPA) carries out esterification and polycondensation reaction with ethylene glycol, when polycondensation is anti-
Antimony glycol is added in the average degree of polymerization for the intermediate product answered when reaching 11, low adhesive aggregation ester, wherein esterification is finally made
Temperature is 240 DEG C, time 2.5h, pressure 0.1MPa；The temperature of polycondensation reaction is 263 DEG C, pressure 150Pa, ethylene glycol
The addition of antimony is the 250ppm of terephthalic acid (TPA) addition.
Low viscous polyester inherent viscosity obtained is 0.300dL/g, and the content of cyclic oligomer is in low adhesive aggregation ester
1.3wt%.Oligomer total content is 2.2wt%, and inherent viscosity deviation is 0.02dL/g, molecular weight distributing index 2.5, DEG
Content is 0.77wt%.
High viscosity polyester is prepared using low adhesive aggregation ester obtained above：
(1) low adhesive aggregation ester obtained is dried in pre-crystallizer pre-crystallized, dry pre-crystallized temperature is 150
DEG C, time 10min, atmosphere is nitrogen；
(2) solid-phase tack producing pre-reaction is carried out in pre-reactor, the temperature in 4th area is respectively from top to bottom in pre-reactor
219 DEG C, 220 DEG C, 229 DEG C and 210 DEG C, the time of pre-reaction is 8.5h；
(3) solid-phase tack producing end reaction is carried out in end reaction device, and high viscosity polyester is made, the temperature of end reaction is 215 DEG C, when
Between be 18h.
The number-average molecular weight Mn of high viscosity polyester obtained is 41500, and inherent viscosity 0.85dL/g, cyclic oligomer contains
Amount is 1.2wt%, and oligomer total content is 1.85wt%, and inherent viscosity deviation is 0.025dL/g, and molecular weight distributing index is
2.45, DEG content 0.88wt%；High viscosity polyester obtained is applied to industrial yarn, packaging material or engineering plastics field.
Comparative example 1
A kind of preparation method of PET, specific steps and embodiment 1 are almost the same, the difference is that in step (2), work as polycondensation
Antimony glycol is added when being 3 in the average degree of polymerization of the intermediate product of reaction, and oligomer is higher in final PET obtained, PET
Mn be 41000, wherein the content of cyclic oligomer be 1.9wt%.Oligomer total content is 3.2wt%, inherent viscosity deviation
For 0.026dL/g, molecular weight distributing index 2.91, DEG content 0.93wt%.Low viscous PET produced by the present invention and comparison
The molecular weight distribution curve comparison diagram of PET made from example 1 is as shown in figure 3, it is seen that preparation method using the present invention
The molecular weight distribution relative narrower of obtained polyester, molecular weight distribution curve can illustrate that oligomer, molecular weight distribution are got over
It is narrow, illustrate that oligomer is lower, thus the present invention by control polymerization process in antimony glycol addition opportunity, significantly
Reduce the content of the oligomer and cyclic oligomer etc. in prepared polyester.
Comparative example 2
A kind of preparation method of PET, specific steps and embodiment 1 are almost the same, the difference is that in step (2), work as polycondensation
Antimony glycol is added when being 20 in the average degree of polymerization of the intermediate product of reaction, and oligomer is higher in final PET obtained,
The Mn of PET is 41000, and wherein the content of cyclic oligomer is 2.05wt%.Oligomer total content is 3.3wt%, inherent viscosity
Deviation is 0.027dL/g, molecular weight distributing index 2.99, DEG content 0.96%.Low viscous PET produced by the present invention with it is right
The molecular weight distribution curve comparison diagram of PET made from ratio 1 is as shown in figure 4, it is seen that preparation side using the present invention
The molecular weight distribution relative narrower for the polyester that method obtains, molecular weight distribution curve can illustrate oligomer, molecular weight distribution
It is narrower, illustrate that oligomer is lower, thus the present invention is shown by the addition opportunity of antimony glycol in control polymerization process
Writing reduces the content of oligomer and cyclic oligomer etc. in prepared polyester.
Embodiment 2
The preparation method of low adhesive aggregation ester, is as follows：
(1) modulation of antimony glycol；
Antimony glycol is uniformly mixed with ethylene glycol in catalyst modulates tank, wherein recycled in mixed process
Be passed through moisture content be 190ppm helium, the configuration system of catalyst substantially with embodiment 1, the difference is that, for generating
Gas is simultaneously that helium handles generator to the withering device of gas；
(2) it is 1 by molar ratio:1.3 terephthalic acid (TPA) carries out esterification and polycondensation reaction with ethylene glycol, when polycondensation is anti-
Antimony glycol is added in the average degree of polymerization for the intermediate product answered when reaching 8, low adhesive aggregation ester, the wherein temperature of esterification is finally made
Degree is 238 DEG C, time 2h, pressure 0.MPa；The temperature of polycondensation reaction is 273 DEG C, pressure 130Pa, and antimony glycol adds
Enter the 200ppm that amount is terephthalic acid (TPA) addition.
Low viscous polyester inherent viscosity obtained is 0.360dL/g, and the content of cyclic oligomer is in low adhesive aggregation ester
1.9wt%.Oligomer total content is 2.8wt%, and inherent viscosity deviation is 0.01dL/g, and molecular weight distributing index 2, DEG contains
Amount is 0.74wt%.
High viscosity polyester is prepared using low adhesive aggregation ester obtained above：
(1) low adhesive aggregation ester obtained is dried in pre-crystallizer pre-crystallized, dry pre-crystallized temperature is 155
DEG C, time 13min, atmosphere is nitrogen；
(2) solid-phase tack producing pre-reaction is carried out in pre-reactor, the temperature in 4th area is respectively from top to bottom in pre-reactor
211 DEG C, 217 DEG C, 220 DEG C and 214 DEG C, the time of pre-reaction is 8h；
(3) solid-phase tack producing end reaction is carried out in end reaction device, and high viscosity polyester is made, the temperature of end reaction is 225 DEG C, when
Between be 18h.
The inherent viscosity of high viscosity polyester obtained is 0.85dL/g, and the content of cyclic oligomer is 1.55wt%, oligomer
Total content is 2.0wt%, and inherent viscosity deviation is 0.022dL/g, molecular weight distributing index 2.28, and DEG content is
0.88wt%；High viscosity polyester obtained is applied to industrial yarn, packaging material or engineering plastics field.
Embodiment 3
The preparation method of low adhesive aggregation ester, is as follows：
(1) modulation of antimony glycol；
Antimony glycol is uniformly mixed with ethylene glycol in catalyst modulates tank, wherein recycled in mixed process
Be passed through moisture content be 185ppm neon, the configuration system of catalyst substantially with embodiment 1, the difference is that, for generating
Gas is simultaneously that neon handles generator to the withering device of gas；
(2) it is 1 by molar ratio:1.4 terephthalic acid (TPA) carries out esterification and polycondensation reaction with ethylene glycol, when polycondensation is anti-
Antimony glycol is added in the average degree of polymerization for the intermediate product answered when reaching 13, low adhesive aggregation ester, wherein esterification is finally made
Temperature is 235 DEG C, time 3h, pressure 0.2MPa；The temperature of polycondensation reaction is 269 DEG C, pressure 170Pa, antimony glycol
Addition be terephthalic acid (TPA) addition 220ppm.
Low viscous polyester inherent viscosity obtained is 0.450dL/g, and the content of cyclic oligomer is in low adhesive aggregation ester
1.5wt%.Oligomer total content is 2.3wt%, and inherent viscosity deviation is 0.015dL/g, molecular weight distributing index 2.2, DEG
Content is 0.66wt%.
High viscosity polyester is prepared using low adhesive aggregation ester obtained above：
(1) low adhesive aggregation ester obtained is dried in pre-crystallizer it is pre-crystallized, dry pre-crystallized temperature be 150 DEG C,
Time is 15min, and atmosphere is nitrogen；
(2) solid-phase tack producing pre-reaction is carried out in pre-reactor, the temperature in 4th area is respectively from top to bottom in pre-reactor
212 DEG C, 219 DEG C, 223 DEG C and 210 DEG C, the time of pre-reaction is 9.5h；
(3) solid-phase tack producing end reaction is carried out in end reaction device, and high viscosity polyester is made, the temperature of end reaction is 225 DEG C, when
Between be 19h.
The inherent viscosity of high viscosity polyester obtained is 1.1dL/g, and the content of cyclic oligomer is 1.77wt%, and oligomer is total
Content is 2.22wt%, and inherent viscosity deviation is 0.025dL/g, molecular weight distributing index 2.3, DEG content 0.83wt%；
High viscosity polyester obtained is applied to industrial yarn, packaging material or engineering plastics field.
Embodiment 4
The preparation method of low adhesive aggregation ester, is as follows：
(1) modulation of antimony glycol；
Antimony glycol is uniformly mixed with ethylene glycol in catalyst modulates tank, wherein recycled in mixed process
Be passed through moisture content be 180ppm argon gas, the configuration system of catalyst substantially with embodiment 1, the difference is that, for generating
Gas is simultaneously that argon gas handles generator to the withering device of gas；
(2) it is 1 by molar ratio:1.5 terephthalic acid (TPA) carries out esterification and polycondensation reaction with ethylene glycol, when polycondensation is anti-
Antimony glycol is added in the average degree of polymerization for the intermediate product answered when reaching 17, low adhesive aggregation ester, wherein esterification is finally made
Temperature is 241 DEG C, time 2.5h, pressure 0.18MPa；The temperature of polycondensation reaction is 270 DEG C, pressure 200Pa, ethylene glycol
The addition of antimony is the 250ppm of terephthalic acid (TPA) addition.
Low viscous polyester inherent viscosity obtained is 0.400dL/g, and the content of cyclic oligomer is in low adhesive aggregation ester
1.7wt%.Oligomer total content is 2.8wt%, and inherent viscosity deviation is 0.014dL/g, molecular weight distributing index 2.8, DEG
Content is 0.5wt%.
High viscosity polyester is prepared using low adhesive aggregation ester obtained above：
(1) low adhesive aggregation ester obtained is dried in pre-crystallizer pre-crystallized, dry pre-crystallized temperature is 160
DEG C, time 18min, atmosphere is nitrogen；
(2) solid-phase tack producing pre-reaction is carried out in pre-reactor, the temperature in 4th area is respectively from top to bottom in pre-reactor
220 DEG C, 219 DEG C, 228 DEG C and 215 DEG C, the time of pre-reaction is 9h；
(3) solid-phase tack producing end reaction is carried out in end reaction device, and high viscosity polyester is made, the temperature of end reaction is 220 DEG C, when
Between be 18.5h.
The inherent viscosity of high viscosity polyester obtained is 0.9dL/g, and the content of cyclic oligomer is 1.2wt%, and oligomer is total
Content is 1.9wt%, and inherent viscosity deviation is 0.017dL/g, molecular weight distributing index 2.15, DEG content 0.8wt%；
High viscosity polyester obtained is applied to industrial yarn, packaging material or engineering plastics field.
Embodiment 5
The preparation method of low adhesive aggregation ester, is as follows：
(1) modulation of antimony glycol；
Antimony glycol is uniformly mixed with ethylene glycol in catalyst modulates tank, wherein recycled in mixed process
Be passed through moisture content be 160ppm Krypton, the configuration system of catalyst substantially with embodiment 1, the difference is that, for generating
Gas is simultaneously that Krypton handles generator to the withering device of gas；
(2) it is 1 by molar ratio:1.2 terephthalic acid (TPA) carries out esterification and polycondensation reaction with ethylene glycol, when polycondensation is anti-
Antimony glycol is added in the average degree of polymerization for the intermediate product answered when reaching 11, low adhesive aggregation ester, wherein esterification is finally made
Temperature is 245 DEG C, time 2.5h, pressure 0.12MPa；The temperature of polycondensation reaction is 262 DEG C, pressure 150Pa, ethylene glycol
The addition of antimony is the 280ppm of terephthalic acid (TPA) addition.
Low viscous polyester inherent viscosity obtained is 0.500dL/g, and the content of cyclic oligomer is in low adhesive aggregation ester
1.5wt%.Oligomer total content is 2.9wt%, and inherent viscosity deviation is 0.01dL/g, molecular weight distributing index 2.3, DEG
Content is 0.74wt%.
High viscosity polyester is prepared using low adhesive aggregation ester obtained above：
(1) low adhesive aggregation ester obtained is dried in pre-crystallizer pre-crystallized, dry pre-crystallized temperature is 165
DEG C, time 20min,；
(2) solid-phase tack producing pre-reaction is carried out in pre-reactor, the temperature in 4th area is respectively from top to bottom in pre-reactor
223 DEG C, 225 DEG C, 229 DEG C and 218 DEG C, the time of pre-reaction is 10h；
(3) solid-phase tack producing end reaction is carried out in end reaction device, and high viscosity polyester is made, the temperature of end reaction is 215 DEG C, when
Between be 20h.
The inherent viscosity of high viscosity polyester obtained is 1.15dL/g, and the content of cyclic oligomer is 1.58wt%, oligomer
Total content is 1.95wt%, and inherent viscosity deviation is 0.016dL/g, molecular weight distributing index 2.3, and DEG content is
0.82wt%；High viscosity polyester obtained is applied to industrial yarn, packaging material or engineering plastics field.
Embodiment 6
The preparation method of low adhesive aggregation ester, is as follows：
(1) modulation of antimony glycol；
Antimony glycol is uniformly mixed with ethylene glycol in catalyst modulates tank, wherein recycled in mixed process
It is passed through the nitrogen that moisture content is 195ppm；Catalyst configures system with embodiment 1；
(2) it is 1 by molar ratio:1.5 terephthalic acid (TPA) carries out esterification and polycondensation reaction with ethylene glycol, when polycondensation is anti-
Antimony glycol is added in the average degree of polymerization for the intermediate product answered when reaching 15, low adhesive aggregation ester, wherein esterification is finally made
Temperature is 235 DEG C, time 2h, pressure 0.1MPa；The temperature of polycondensation reaction is 273 DEG C, pressure 190Pa, antimony glycol
Addition be terephthalic acid (TPA) addition 270ppm.
Low viscous polyester inherent viscosity obtained is 0.440dL/g, and the content of cyclic oligomer is in low adhesive aggregation ester
1.8wt%.Oligomer total content is 2.2wt%, and inherent viscosity deviation is 0.017dL/g, molecular weight distributing index 2.5, DEG
Content is 0.78wt%.
High viscosity polyester is prepared using low adhesive aggregation ester obtained above：
(1) low adhesive aggregation ester obtained is dried in pre-crystallizer pre-crystallized, dry pre-crystallized temperature is 170
DEG C, time 10min, atmosphere is nitrogen；
(2) solid-phase tack producing pre-reaction is carried out in pre-reactor, the temperature in 4th area is respectively from top to bottom in pre-reactor
211 DEG C, 219 DEG C, 229 DEG C and 212 DEG C, the time of pre-reaction is 8h；
(3) solid-phase tack producing end reaction is carried out in end reaction device, and high viscosity polyester is made, the temperature of end reaction is 223 DEG C, when
Between be 18h.
The inherent viscosity of high viscosity polyester obtained is 0.85dL/g, and the content of cyclic oligomer is 1.45wt%, oligomer
Total content is 1.95wt%, and inherent viscosity deviation is 0.015dL/g, molecular weight distributing index 1.9, and DEG content is
0.79wt%；High viscosity polyester obtained is applied to industrial yarn, packaging material or engineering plastics field.
Embodiment 7
The preparation method of low adhesive aggregation ester, is as follows：
(1) modulation of antimony glycol；
Antimony glycol is uniformly mixed with ethylene glycol in catalyst modulates tank, wherein recycled in mixed process
It is passed through the nitrogen that moisture content is 150ppm；Catalyst configures system with embodiment 1；
(2) it is 1 by molar ratio:1.4 terephthalic acid (TPA) carries out esterification and polycondensation reaction with ethylene glycol, when polycondensation is anti-
Antimony glycol is added in the average degree of polymerization for the intermediate product answered when reaching 10, low adhesive aggregation ester, wherein esterification is finally made
Temperature is 244 DEG C, time 3h, pressure 0.16MPa；The temperature of polycondensation reaction is 260 DEG C, pressure 100Pa, antimony glycol
Addition be terephthalic acid (TPA) addition 280ppm.
Low viscous polyester inherent viscosity obtained is 0.500dL/g, and the content of cyclic oligomer is in low adhesive aggregation ester
1.6wt%.Oligomer total content is 2wt%, and inherent viscosity deviation is 0.016dL/g, and molecular weight distributing index 2.5, DEG contains
Amount is 0.6wt%.
High viscosity polyester is prepared using low adhesive aggregation ester obtained above：
(1) low adhesive aggregation ester obtained is dried in pre-crystallizer pre-crystallized, dry pre-crystallized temperature is 170
DEG C, time 11min, atmosphere is nitrogen；
(2) solid-phase tack producing pre-reaction is carried out in pre-reactor, the temperature in 4th area is respectively from top to bottom in pre-reactor
213 DEG C, 226 DEG C, 217 DEG C and 222 DEG C, the time of pre-reaction is 8.5h；
(3) solid-phase tack producing end reaction is carried out in end reaction device, and high viscosity polyester is made, the temperature of end reaction is 225 DEG C, when
Between be 20h.
The inherent viscosity of high viscosity polyester obtained is 1.06dL/g, and the content of cyclic oligomer is 1.5wt%, and oligomer is total
Content is 1.95wt%, and inherent viscosity deviation is 0.015dL/g, molecular weight distributing index 1.7, DEG content 0.85wt%；
High viscosity polyester obtained is applied to industrial yarn, packaging material or engineering plastics field.
Claims (10)
1. the preparation method of low adhesive aggregation ester, it is characterized in that：Characteristic is made in addition opportunity by controlling catalyst in building-up process
Viscosity is the low adhesive aggregation ester of 0.300-0.500dL/g；The catalyst is the average degree of polymerization in the intermediate product of polycondensation reaction
Reach and is added when 8-17.
2. the preparation method of low adhesive aggregation ester according to claim 1, which is characterized in that it is anti-that the building-up process is divided into esterification
Should and polycondensation reaction, the temperature of the polycondensation reaction be 260-273 DEG C, the catalyst is antimony glycol, the antimony glycol
Modulated process be：Antimony glycol is uniformly mixed with ethylene glycol and cycle is passed through moisture content less than 200ppm in mixed process
Nitrogen or inert gas.
3. the preparation method of low adhesive aggregation ester according to claim 2, which is characterized in that described be uniformly mixed is in catalyst
Carried out in modulation tank, catalyst modulation tank is internally provided with blender, top and bottom respectively with nitrogen treatment generator and
Gas circulator outlet, nitrogen treatment generator is for generating nitrogen while processing, nitrogen treatment being dried to nitrogen
Generator is connected to gas circulation pump intake.
4. the preparation method of low adhesive aggregation ester according to claim 3, which is characterized in that after the modulated process, second
Glycol antimony and ethylene glycol enter catalyst charging-tank, the bottom and top of the catalyst charging-tank respectively with liquid circulation pump
Entrance and exit is connected to.
5. the preparation method of low adhesive aggregation ester according to claim 4, which is characterized in that the raw material of the esterification is pair
The molar ratio of phthalic acid and ethylene glycol, terephthalic acid (TPA) and ethylene glycol is 1:The temperature of 1.2-1.5, the esterification is
235-245 DEG C, time 2-3h, pressure 0.1-0.2MPa；The pressure of the polycondensation reaction is 100-200Pa.
6. the preparation method of low adhesive aggregation ester according to claim 5, which is characterized in that the low adhesive aggregation ester is through solid-phase tack producing
High viscosity polyester is made, the inherent viscosity of high viscosity polyester is 0.85-1.15dL/g, the content of cyclic oligomer<1.80wt%, it is described
The oligomer total content of high viscosity polyester<2.25wt%, inherent viscosity deviation≤0.025dL/g, molecular weight distributing index<2.50
Diethylene glycol content<0.90wt%；The high viscosity polyester is applied to industrial yarn, packaging material or engineering plastics field.
7. the preparation method of low adhesive aggregation ester according to claim 6, which is characterized in that be dried before the solid-phase tack producing
Pre-crystallized, the drying is pre-crystallized to be carried out in pre-crystallizer, and the pre-crystallized temperature of the drying is 150-170 DEG C, when
Between be 10-20min, atmosphere is nitrogen.
8. the preparation method of low adhesive aggregation ester according to claim 7, which is characterized in that the solid-phase tack producing is divided into pre-reaction
And end reaction；The pre-reaction carries out in pre-reactor, and the temperature in 4th area is respectively from top to bottom in pre-reactor
211-223 DEG C, 217-229 DEG C, 217-229 DEG C and 210-222 DEG C, the time of the pre-reaction is 8-10h；The end reaction is
It is carried out in end reaction device, the temperature of the end reaction is 215-225 DEG C, time 18-20h.
9. using low adhesive aggregation ester, feature as made from the preparation method of the low adhesive aggregation ester of claim 1~8 any one of them
It is：The content of cyclic oligomer in low adhesive aggregation ester<2wt%.
10. low adhesive aggregation ester according to claim 9, which is characterized in that the oligomer total content of the low adhesive aggregation ester<
3wt%, inherent viscosity deviation≤0.02dL/g, molecular weight distributing index<2.9, diethylene glycol content<0.8wt%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097353A (en) * | 2000-09-25 | 2002-04-02 | Teijin Ltd | Resin composition and method of producing the same |
| US20040254330A1 (en) * | 2003-06-11 | 2004-12-16 | Duan Jiwen F. | Polyester process |
| CN106188510A (en) * | 2016-07-12 | 2016-12-07 | 上海众挚化工科技有限公司 | A kind of low viscosity unsaturated polyester (UP) and preparation method thereof |
| CN107118339A (en) * | 2016-02-25 | 2017-09-01 | 中国纺织科学研究院 | A kind of continuous method for preparing modified poly ester |
| CN107723831A (en) * | 2016-08-10 | 2018-02-23 | 中国纺织科学研究院 | A kind of original liquid coloring polyester fiber and preparation method thereof |
-
2018
- 2018-06-29 CN CN201810693213.5A patent/CN108774312B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097353A (en) * | 2000-09-25 | 2002-04-02 | Teijin Ltd | Resin composition and method of producing the same |
| US20040254330A1 (en) * | 2003-06-11 | 2004-12-16 | Duan Jiwen F. | Polyester process |
| CN107118339A (en) * | 2016-02-25 | 2017-09-01 | 中国纺织科学研究院 | A kind of continuous method for preparing modified poly ester |
| CN106188510A (en) * | 2016-07-12 | 2016-12-07 | 上海众挚化工科技有限公司 | A kind of low viscosity unsaturated polyester (UP) and preparation method thereof |
| CN107723831A (en) * | 2016-08-10 | 2018-02-23 | 中国纺织科学研究院 | A kind of original liquid coloring polyester fiber and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023226834A1 (en) * | 2022-05-24 | 2023-11-30 | 珠海金发生物材料有限公司 | Semi-aromatic polyester, preparation method therefor, and application thereof |
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