CN104710602B - The preparation method of copolymerized polymer - Google Patents
The preparation method of copolymerized polymer Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of copolymerized polymer, including first stage esterification, second stage esterification, phase III prepolymerization reaction and fourth stage polycondensation reaction at end, wherein, in first stage esterification, various ingredients is individually allocated and is esterified.Compared with prior art, the present invention uses various ingredients to be individually esterified, and further mixes the mode of copolymerization, it is therefore an objective to make each component to be esterified uniformly, it is to avoid to cause certain component not uniformly to be esterified because of the difference of esterifying efficiency.The component of more difficult esterification can be made to carry out ester exchange more fully, it is easier to be embedded in the macromolecular chain of polycondensation, end product quality improves simultaneously.Component is changed convenient and swift simultaneously, is unlikely to produce a large amount of Transition Materials and increase production cost, and conversion efficiency is also greatly improved.
Description
Technical field
The present invention relates to the preparation method of a kind of copolymerized polymer.Belong to technical field of polymer materials.
Background technology
In recent years, polyethylene terephthalate (PET polyester) material is widely used in daily life, such as plastics
Bottle, fiber product, thin film etc., the life with people is closely bound up, but the glass transition temperature of PET polyester material
Only 70 DEG C, limit PET application in the slightly higher environment of temperature.In recent years the polyester material of thermostability is developed successively
Material, such as PETG, Yi Shiman Tritan etc., glass transition temperature at 80～100 DEG C, but owing to being come by raw material
The restriction in source, is not widely applied.Glass transition temperature, transparency, oxygen-barrier property need to promote.
Separately, in existing polyester production process, needing to use multiple additives component, every kind of additive has specific merit
Energy or effect, current way is to add to various ingredients in a making beating tank to pull an oar, when certain component needs
During replacing, can produce substantial amounts of Transition Materials, the time of conversion is long, and some component also influences each other, and accordingly, there exist material
Waste, the problem that conversion efficiency is low and end product quality declines.In recent years, the process units of polyester material is increasing,
For enterprise, production cost is greatly improved.It is thus desirable to a kind of new solution is to change existing conventional conversion mould
Formula.
Summary of the invention
The technical problem to be solved is to provide a kind of vitrification point height, color and luster for the above-mentioned state of the art
The preparation method of good copolymerized polymer.
The technical problem to be solved is to provide a kind of component to change convenient, conversion for the above-mentioned state of the art
The preparation method of the copolymerized polymer that the time is short and then production efficiency is high.
The present invention solves the technical scheme that above-mentioned technical problem used: the preparation method of a kind of copolymerized polymer, and it is special
Levy and be to comprise the steps:
First stage esterification:
With catalyst, binary acid, dihydroxylic alcohols are first modulated into slurry, and in this slurry, the mol ratio of alcohol and acid is between 1.1～1.25:
1；Again slurry pipeline steel is carried out first stage esterification to the first esterifying kettle, under nitrogen atmosphere, reaction temperature between
240～265 DEG C, reaction absolute pressure pressure is between 0～0.5MPa, and the response time was between 3～6 hours；First esterifying kettle outlet
Conversion rate of esterification is between 75～85%；
Another group binary acid, dihydroxylic alcohols are modulated into slurry with catalyst, antioxidant, stabilizer, alcohol and acid in this slurry
Mol ratio between 1.1～1.25:1；Again slurry pipeline steel is carried out first stage esterification to the first esterifying kettle；Blanket of nitrogen
Under enclosing, reaction temperature, between 200～245 DEG C, reacts absolute pressure pressure between 0～0.4MPa response time between 3～6 hours；
The conversion rate of esterification of second esterification kettle outlet is between 75～85%；
Second stage esterification:
The monomer that the monomer made by first esterifying kettle and second esterification kettle are made all is delivered in the 3rd esterifying kettle；Blanket of nitrogen
Under enclosing, reaction temperature is between 240～265 DEG C, and esterification absolute pressure pressure is between 0～0.4MPa, and reaction time of esterification is between 0.5～2
Hour；The conversion rate of esterification of the 3rd esterifying kettle outlet is more than 92%；Add dye additive at the 3rd esterifying kettle to mix colours；
Phase III prepolymerization reaction:
The monomer made by 3rd esterifying kettle, is delivered to precondensation still and carries out prepolymerization reaction, obtain low polymer；Reaction
Temperature is between 255～270 DEG C；Absolute pressure pressure is between 1～30kPa, and the time was between 0.5～1.5 hour；
Fourth stage polycondensation reaction at end:
Low polymer after above-mentioned prepolymerization reaction, is delivered to whole polycondensation vessel and carries out polycondensation reaction, whole polycondensation reaction further
Temperature between 270～285 DEG C；Glycol steam ejector pump vacuum mechanism is utilized to make the vacuum absolute pressure pressure of whole polycondensation vessel low
In 160Pa, the time of reaction between 0.5～2 hour, final improve intrinsic viscosity to 0.65dl/g.
This preparation method completes in a co-polyester production combination unit, and aforesaid co-polyester production combination unit includes
First esterifying kettle, connect have first ethylene glycol backflow mechanism；
First slurry preparation, is connected by the feed end of one first dosing pump with aforementioned first esterifying kettle；
Oneth PTA storage tank, is connected by the feed end of one first metering valve with aforementioned first slurry preparation；
First additive preparing tank, is connected by the feed end of one second dosing pump with aforementioned first slurry preparation；
First catalyst preparation tank, is connected with the feed end of aforementioned first slurry preparation by one the 3rd dosing pump；
Second esterification kettle, connect have second ethylene glycol backflow mechanism；
Second slurry preparation, is connected with the feed end of aforementioned second esterification kettle by one the 4th dosing pump；
2nd PTA storage tank, is connected by the feed end of one second metering valve with aforementioned second slurry preparation；
Second addition preparing tank, is connected with the feed end of aforementioned second slurry preparation by one the 5th dosing pump；
Second catalyst preparation tank, is connected with the feed end of aforementioned second slurry preparation by one the 6th dosing pump；
3rd esterifying kettle, connects and has triethylene glycol to reflux mechanism, feed end and aforementioned first esterifying kettle and second esterification kettle
Connect；
3rd additive preparing tank, is connected with the feed end of aforementioned 3rd esterifying kettle by one the 7th dosing pump；
Precondensation still, connects and has precondensation vacuum mechanism feed end to be connected with aforementioned 3rd esterifying kettle；And
Whole polycondensation vessel, connects and has ethylene glycol steam vacuum mechanism feed end to be connected with aforementioned precondensation still, and discharge end connects
There is fondant filter；
Aforesaid the first described esterifying kettle, second esterification kettle, the 3rd esterifying kettle, precondensation still and whole polycondensation vessel are all provided with
There is agitator；The discharging opening of aforesaid precondensation still and whole polycondensation vessel is equipped with rear pump.
Further, it is simple to batch mixing is abundant, the feed end of described 3rd esterifying kettle include the first charging aperture, the second charging aperture and
3rd charging aperture, aforesaid first charging aperture and the first esterifying kettle connect, and aforesaid second charging aperture is with second esterification kettle even
Connecing, aforesaid 3rd charging aperture and the 3rd additive preparing tank connect, and, the first charging aperture is positioned on the second charging aperture
Side.
As preferably, described binary acid be p-phthalic acid, M-phthalic acid, to naphthalenedicarboxylic acid, 2,5-furan diformazan
At least one in acid；Described dihydroxylic alcohols bag is ethylene glycol, isosorbide, propylene glycol, butanediol, 1,4-hexamethylene
At least one in dimethanol.
As preferably, the binary acid in described first esterifying kettle is p-phthalic acid and M-phthalic acid mixing, described first
Dihydroxylic alcohols in esterifying kettle is ethylene glycol, and the binary acid in described second esterification kettle is p-phthalic acid, described second esterification
Dihydroxylic alcohols in still is isosorbide, and, the mol ratio of described ethylene glycol and isosorbide is 10:1～1:1.
As preferably, described stabilizer is at least one in phosphoric acid, phosphate ester or phosphite ester, and addition is binary
1ppm～10ppm of acid.
As preferably, described antioxidant is at least one in Irgafos-168, Irganox-1010, Irgamod-195,
Addition is the 0.1%～0.3% of binary acid.
As preferably, the catalyst in described first esterifying kettle is acetate or other alkanoate, the Sb (III) of Sb (III)
And the oxide of Ge (IV) and Ti (OR) 4, wherein R be carbon number be the alkyl group of 2～12.
As preferably, the catalyst in described second esterification kettle is oxide and the Ti (OR) 4 of Ge (IV), and wherein R is carbon
Atomic number is the alkyl group of 2～12.
Sb (III) addition be 180ppm～300ppm of binary acid, Ge (IV) addition be binary acid
60ppm～100ppm, Ti (IV) addition is 1ppm～10ppm of binary acid.
As preferably, described dye additive includes red pigment and blue pigment, and, aforementioned red pigment addition
0.1ppm～0.5ppm for binary acid weight；Aforementioned blue pigment addition be binary acid weight 0.5ppm～
1.5ppm.For improving the colour that the copolyester of the present invention is cut into slices, need to add blue dyes and adjust with Hunter color
The color and luster b value of the polyester slice measured.The blue dyes added, such as, select " the PRT of Jia Luosi (ColorMatrix)
Whole world blue dispersions-2 " (285-10135-2).It addition, for avoiding the color and luster of polyester slice measured with Hunter color
The lowest outward appearance of a value is the greenest, can add a small amount of orchil, such as, select " the PRT of Jia Luosi (ColorMatrix)
The red dispersant-2 in the whole world " (283-10068-2).
Compared with prior art, it is an advantage of the current invention that: the present invention uses various ingredients to be individually esterified, and further mixes
Amount to the mode gathered, it is therefore an objective to make each component to be esterified uniformly, it is to avoid to cause certain because of the difference of esterifying efficiency
Plant component can not uniformly be esterified.The component of more difficult esterification can be made to carry out ester exchange more fully, it is easier to be embedded into contracting simultaneously
In poly-macromolecular chain, end product quality improves.Component is changed convenient and swift simultaneously, is unlikely to produce a large amount of Transition Materials and increase
Adding production cost, conversion efficiency is also greatly improved.
Accompanying drawing explanation
Fig. 1 is that in embodiment 1, schematic diagram arranged by co-polyester production combination unit.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
First stage esterification:
Weigh p-phthalic acid (PTA) 13.954Kg, M-phthalic acid (IPA) 0.285Kg, ethylene glycol (EG) 6.65Kg,
Antimony glycol 6g.Under nitrogen atmosphere, PTA, IPA, EG are first modulated into slurry, at 50L the first ester with catalyst
Change still and carry out first stage esterification.Reaction temperature is between 240～245 DEG C, and reaction pressure is between 0.25～0.3MPa
(absolute pressure), in 3 hours response time, the conversion rate of esterification of the first esterifying kettle is between 80～85%.
Weigh PTA 0.749Kg, isosorbide 0.824Kg, Li-Ti catalyst 1g (solution of 0.3% Ti content),
Irganox-1010 0.2g, phosphoric acid 0.121g (solution of 85% weight).Under nitrogen atmosphere, at temperature in the kettle 65～70 DEG C,
PTA, isosorbide are modulated into slurry with catalyst, antioxidant, stabilizer, carry out first at 3L second esterification kettle
Stage esterification reacts.Reaction temperature is between 215～220 DEG C, and reaction pressure is between 0.15～0.2MPa (absolute pressure), reaction
4 hours time, the conversion rate of esterification of second esterification kettle is between 80～85%.
Second stage esterification:
Under nitrogen atmosphere, the monomer that above-mentioned first esterifying kettle is made, utilize pressure differential to be delivered in the 3rd esterifying kettle；Above-mentioned
The monomer that second esterification kettle is made, utilizes rear pump to be delivered in the 3rd esterifying kettle and is esterified further.Reaction temperature between
250～255 DEG C, esterification pressures is between 0.2～0.25MPa (absolute pressure), and 0.5 hour response time, subsequently at 20min
Interior pressure reduces to normal pressure 0.1MPa (absolute pressure), and the 3rd esterifying kettle conversion rate of esterification is more than 92%.
Phase III prepolymerization reaction:
The monomer above-mentioned esterification made, utilizes pressure differential to be delivered to precondensation still and carries out prepolymerization reaction；Reaction temperature
Degree is between 265～270 DEG C, and pressure is slowly dropped to 1KPa (absolute pressure) by normal pressure in 1h, and reaction terminates.
Fourth stage polycondensation reaction at end:
Low polymer after above-mentioned prepolymerization reaction, the whole polycondensation vessel being delivered to high vacuum carries out polycondensation reaction further；
The temperature of whole polycondensation reaction is between 270～275 DEG C, and vacuum pressure is less than 160Pa (absolute pressure), the 1 hour time of reaction.
Above-mentioned whole polycondensation reaction complete after polymer, be cut into amorphous state ground sections through discharging chilling, to made base
Plinth section is dried, and carries out every detection, and it is the results detailed in Table shown in 1.
As it is shown in figure 1, co-polyester production combination unit includes first esterifying kettle the 11, first slurry preparation in embodiment 1
Tank the 81, the oneth PTA storage tank the 31, first additive preparing tank the 33, first catalyst preparation tank 35, second esterification kettle
12, the second slurry preparation the 82, the 2nd PTA storage tank 32, Second addition preparing tank the 34, second catalyst preparation tank
36, the 3rd esterifying kettle the 13, the 3rd additive preparing tank 37, precondensation still 14 and whole polycondensation vessel 15.
First esterifying kettle 11 connects has ethylene glycol to reflux mechanism, the first slurry preparation 81 by the first dosing pump 21 with
The feed end of the first esterifying kettle 11 connects, and a PTA storage tank 31 is by the first metering valve 28 and the first slurry preparation
The feed end of 81 connects, and the first additive preparing tank 33 is entered by the second dosing pump 22 and the first slurry preparation 81
Material end connects, and the first catalyst preparation tank 35 is by the feed end of the 3rd dosing pump 23 and the first slurry preparation 81 even
Connect.
Second esterification kettle 12 connects has ethylene glycol to reflux mechanism, the second slurry preparation 82 by the 4th dosing pump 24 with
The feed end of second esterification kettle 12 connects, and the 2nd PTA storage tank 32 is by the second metering valve 29 and the second slurry preparation
The feed end of 82 connects, and Second addition preparing tank 34 is entered by the 5th dosing pump 25 and the second slurry preparation 82
Material end connects, and the second catalyst preparation tank 36 is by the feed end of the 6th dosing pump 25 and the second slurry preparation 82 even
Connect.
3rd esterifying kettle 13 connect have ethylene glycol reflux mechanism, feed end and the first esterifying kettle 11 and second esterification kettle 12
Connecting, the 3rd additive preparing tank 37 is connected with the feed end of the 3rd esterifying kettle 13 by the 7th dosing pump 27, preshrunk
Poly-still 14 connects has precondensation vacuum mechanism 70 feed end and the 3rd esterifying kettle 13 to connect, precondensation vacuum mechanism 70
Connect a vacuum pump 71.Whole polycondensation vessel 15 connects ethylene glycol steam vacuum mechanism 6 feed end and precondensation still 14
Connecting, discharge end connects fondant filter 10.
In first esterifying kettle 11, second esterification kettle the 12, the 3rd esterifying kettle 13, precondensation still 14 and whole polycondensation vessel 15 all
It is provided with agitator (without display in figure).The discharging opening of second esterification kettle 12, precondensation still 14 and whole polycondensation vessel 15 is equipped with
Rear pump 5.
The feed end of the 3rd esterifying kettle 13 includes the first charging aperture, the second charging aperture and the 3rd charging aperture, the first charging aperture
Being connected with the first esterifying kettle 11, the second charging aperture is connected with second esterification kettle 12, and the 3rd charging aperture and the 3rd additive are joined
Tank 37 processed connects, and, the first charging aperture is positioned at above the second charging aperture.So lack the leading portion carboxylate of component from the
The bottom of three esterifying kettles 13 enters, and multi-component leading portion carboxylate enters from the middle part of the 3rd esterifying kettle 13, and stirring uses
The mode that material upwards rolls, each component uniformly mixes, and in few component substantial amounts of embedding multicomponent, forms uniform oligomerisation
Thing.
Ethylene glycol steam vacuum mechanism in the present embodiment includes three grades of steam mechanisms, condenser 69, vaporizer 67, true
Empty pump 68 and ethylene glycol collecting tank 60, three grades of steam mechanisms include first injector 61, the first-stage condenser being sequentially connected with
62, second injector 63,64, three grades of ejectors 65 of secondary condenser and three grades of condensers 66；Condenser 69 one end
It is connected the other end with whole polycondensation vessel 15 to be connected with first injector 61；Vaporizer 67 respectively with first injector 61, two
Level ejector 63 and three grades of ejectors 65 connect；Vacuum pump 68 is connected with three grades of condensers 66；Ethylene glycol collecting tank 60
Liquid feeding end is connected with first-stage condenser 62, secondary condenser 64 and three grades of condensers 66 respectively.
In the present embodiment ethylene glycol backflow mechanism include process tower 42, reflux condenser 41 and reflux pump 43, returned cold
The liquid feeding end of condenser 41 and inlet end are connected with the outlet side of process tower 42 and backflow end respectively, reflux pump 43 then with work
The liquid outlet of skill tower 42 connects.The ethylene glycol formed in esterification reaction process and water etc. are via generating tube (without display in figure)
Entering process tower 42 to separate, the ethylene glycol of process tower 42 bottom collection is back to reaction kettle of the esterification, process tower 42 again
Waste water is gone to process after the water vapour of collected overhead is condensed.
Embodiment 2
Such as the practice of embodiment 1,50L reactor 2 weighs p-phthalic acid (PTA) 13.490Kg, isophthalic two
Formic acid (IPA) 0.270Kg, ethylene glycol (EG) 6.300Kg, antimony glycol 5.4g.PTA is weighed in 3L reactor 1
1.499Kg, isosorbide 1.648Kg, Li-Ti catalyst 2g, Irganox-1010 0.2g, phosphoric acid 0.121g.
Drying made ground sections, carry out every detection, it is the results detailed in Table shown in 1.
Embodiment 3
Such as the practice of embodiment 1,50L reactor 2 weighs p-phthalic acid (PTA) 11.991Kg, isophthalic two
Formic acid (IPA) 0.240Kg, ethylene glycol (EG) 5.600Kg, antimony glycol 4.8g.PTA is weighed in 3L reactor 1
2.998Kg, isosorbide 3.296Kg, Li-Ti catalyst 4g, Irganox-1010 0.2g, phosphoric acid 0.121g.
For improving the colour of copolyester section, add blue dyes and select " the PRT whole world of Jia Luosi (ColorMatrix)
Blue dispersions-2 " (285-10135-2) 0.093g；Add orchil and select " the PRT of Jia Luosi (ColorMatrix)
The red dispersant-2 in the whole world " (283-10068-2) 0.023g.
Drying made ground sections, carry out every detection, it is the results detailed in Table shown in 1.
Result
Through the PEIT copolyester section of embodiment 1 to 3 preparation, the index recorded such as table 1.By using individually
Esterification, the mode further mixing copolymerization prepares copolyester.The component that can make more difficult esterification carries out ester friendship more fully
Change, it is easier to be embedded in the macromolecular chain of polycondensation.Along with the increase of isosorbide addition, can effectively improve copolymerization
The vitrification point of polyester slice.
Table 1 PEIT cuts into slices Testing index
1) using Hunter color measurement amount, L-value is the highest, and color and luster is whiter, and transparency is the best；B value is the lowest, and color and luster is the most blue,
B value is the highest, and color and luster is the most yellow.
Claims (7)
1. the preparation method of a copolymerized polymer, it is characterised in that comprise the steps:
First stage esterification:
With catalyst, binary acid, dihydroxylic alcohols are first modulated into slurry, and in this slurry, the mol ratio of alcohol and acid is between 1.1～1.25:
1；Again slurry pipeline steel is carried out first stage esterification to the first esterifying kettle, under nitrogen atmosphere, reaction temperature between
240～265 DEG C, reaction absolute pressure pressure is between 0～0.5MPa, and the response time was between 3～6 hours；First esterifying kettle outlet
Conversion rate of esterification is between 75～85%；
Another group binary acid, dihydroxylic alcohols are modulated into slurry with catalyst, antioxidant, stabilizer, alcohol and acid in this slurry
Mol ratio between 1.1～1.25:1；Again slurry pipeline steel to second esterification kettle is carried out first stage esterification；Blanket of nitrogen
Under enclosing, reaction temperature, between 200～245 DEG C, reacts absolute pressure pressure between 0～0.4MPa response time between 3～6 hours；
The conversion rate of esterification of second esterification kettle outlet is between 75～85%；
Second stage esterification:
The monomer that the monomer made by first esterifying kettle and second esterification kettle are made all is delivered in the 3rd esterifying kettle；Blanket of nitrogen
Under enclosing, reaction temperature is between 240～265 DEG C, and esterification absolute pressure pressure is between 0～0.4MPa, and reaction time of esterification is between 0.5～2
Hour；The conversion rate of esterification of the 3rd esterifying kettle outlet is more than 92%；Add dye additive at the 3rd esterifying kettle to mix colours；
Phase III prepolymerization reaction:
The monomer made by 3rd esterifying kettle, is delivered to precondensation still and carries out prepolymerization reaction, obtain low polymer；Reaction
Temperature is between 255～270 DEG C；Absolute pressure pressure is between 1～30kPa, and the time was between 0.5～1.5 hour；
Fourth stage polycondensation reaction at end:
Low polymer after above-mentioned prepolymerization reaction, is delivered to whole polycondensation vessel and carries out polycondensation reaction, whole polycondensation reaction further
Temperature between 270～285 DEG C；Glycol steam ejector pump vacuum mechanism is utilized to make the vacuum absolute pressure pressure of whole polycondensation vessel low
In 160Pa, the time of reaction, between 0.5～2 hour, final improves intrinsic viscosity to 0.65dl/g；
This preparation method completes in a co-polyester production combination unit, and aforesaid co-polyester production combination unit includes
First esterifying kettle, connect have first ethylene glycol backflow mechanism；
First slurry preparation, is connected by the feed end of one first dosing pump with aforementioned first esterifying kettle；
Oneth PTA storage tank, is connected by the feed end of one first metering valve with aforementioned first slurry preparation；
First additive preparing tank, is connected by the feed end of one second dosing pump with aforementioned first slurry preparation；
First catalyst preparation tank, is connected with the feed end of aforementioned first slurry preparation by one the 3rd dosing pump；
Second esterification kettle, connect have second ethylene glycol backflow mechanism；
Second slurry preparation, is connected with the feed end of aforementioned second esterification kettle by one the 4th dosing pump；
2nd PTA storage tank, is connected by the feed end of one second metering valve with aforementioned second slurry preparation；
Second addition preparing tank, is connected with the feed end of aforementioned second slurry preparation by one the 5th dosing pump；
Second catalyst preparation tank, is connected with the feed end of aforementioned second slurry preparation by one the 6th dosing pump；
3rd esterifying kettle, connects and has triethylene glycol to reflux mechanism, feed end and aforementioned first esterifying kettle and second esterification kettle
Connect；
3rd additive preparing tank, is connected with the feed end of aforementioned 3rd esterifying kettle by one the 7th dosing pump；
Precondensation still, connects and has precondensation vacuum mechanism feed end to be connected with aforementioned 3rd esterifying kettle；And
Whole polycondensation vessel, connects and has ethylene glycol steam vacuum mechanism feed end to be connected with aforementioned precondensation still, and discharge end connects
There is fondant filter；
Aforesaid the first described esterifying kettle, second esterification kettle, the 3rd esterifying kettle, precondensation still and whole polycondensation vessel are all provided with
There is agitator；The discharging opening of aforesaid precondensation still and whole polycondensation vessel is equipped with rear pump；
Binary acid in described first esterifying kettle is p-phthalic acid and M-phthalic acid mixing, in described first esterifying kettle
Dihydroxylic alcohols is ethylene glycol, and the binary acid in described second esterification kettle is p-phthalic acid, the binary in described second esterification kettle
Alcohol is isosorbide, and, the mol ratio of described ethylene glycol and isosorbide is 10:1～1:1.
The preparation method of copolymerized polymer the most according to claim 1, it is characterised in that described 3rd esterifying kettle
Feed end includes that the first charging aperture, the second charging aperture and the 3rd charging aperture, aforesaid first charging aperture and the first esterifying kettle are even
Connecing, aforesaid second charging aperture is connected with second esterification kettle, and aforesaid 3rd charging aperture and the 3rd additive preparing tank connect,
Further, the first charging aperture is positioned at above the second charging aperture.
The preparation method of copolymerized polymer the most according to claim 1, it is characterised in that described stabilizer is phosphorus
At least one in acid, phosphate ester or phosphite ester, addition is 1ppm～10ppm of binary acid.
The preparation method of copolymerized polymer the most according to claim 1, it is characterised in that described antioxidant is
At least one in Irgafos-168, Irganox-1010, Irgamod-195, addition is the 0.1%～0.3% of binary acid.
The preparation method of copolymerized polymer the most according to claim 1, it is characterised in that in described first esterifying kettle
The acetate that catalyst is Sb (III) or other alkanoate, Sb (III) and the oxide of Ge (IV) and Ti (OR) 4, its
Middle R be carbon number be the alkyl group of 2～12.
The preparation method of copolymerized polymer the most according to claim 1, it is characterised in that in described second esterification kettle
The oxide that catalyst is Ge (IV) and Ti (OR) 4, wherein R be carbon number be the alkyl group of 2～12.
The preparation method of copolymerized polymer the most according to claim 1, it is characterised in that described dye additive bag
Include red pigment and blue pigment, and, aforementioned red pigment addition is 0.1ppm～0.5ppm of binary acid weight；
Aforementioned blue pigment addition is 0.5ppm～1.5ppm of binary acid weight.
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| CN110078903A (en) * | 2019-05-17 | 2019-08-02 | 北京壹鼎壹管理咨询有限公司 | A method of continuously preparing Biodegradable resin side by side |
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| CN111269405B (en) * | 2020-02-27 | 2022-04-01 | 浙江恒澜科技有限公司 | Preparation method of bio-based polyester for inhibiting discoloration |
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| CN102443149A (en) * | 2011-10-28 | 2012-05-09 | 金发科技股份有限公司 | Continuous production method for biodegradable aliphatic-aromatic copolyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078903A (en) * | 2019-05-17 | 2019-08-02 | 北京壹鼎壹管理咨询有限公司 | A method of continuously preparing Biodegradable resin side by side |
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