CN104710602A - Preparation method of copolymerization polymer - Google Patents
Preparation method of copolymerization polymer Download PDFInfo
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Abstract
The invention discloses a preparation method of a copolymerization polymer. The preparation method comprises a first-stage esterification reaction, a second-stage esterification reaction, a third-stage prepolymerization reaction and a fourth-stage prepolymerization reaction, wherein various components in the first-stage esterification reaction are individually blended and esterified. Compared with the prior art, the preparation method has the advantages that the manner of various components are independently esterified and then further subjected to mixed copolymerization, so that the purpose that all components are uniformly esterified respectively is achieved, and the fact that certain component cannot be uniformly esterified due to the difference of esterifying efficiency is avoided. Besides, the components which are relatively difficult to esterify can be subjected to ester exchange more sufficiently and embedded in a condensed macromolecular chain more easily, so that the finished product quality is improved. Moreover, the components are convenient and quick to replace, the fact that the production cost is increased due to the generation of plenty of transition materials is avoided, and the conversion efficiency is also greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method 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, as Plastic Bottle, fiber product, film etc., closely bound up with the life of people, but the second-order transition temperature of PET polyester material only has 70 DEG C, limits the application of PET in the slightly high environment of temperature.In recent years develop the polyester material of thermotolerance successively, as PETG, Yi Shiman Tritan etc., second-order transition temperature at 80 ~ 100 DEG C, but owing to being subject to the restriction of raw material sources, is not applied widely.Second-order transition temperature, transparency, oxygen-barrier property need to promote.
Separately, in existing polyester production process, need to use multiple additives component, often kind of additive has specific function or effect, current way various ingredients is added in a making beating tank to pull an oar, when certain component needs to change, can produce a large amount of Transition Materials, the time of conversion is long, some component also influences each other, therefore, there is waste of material, the problem that the low and final product quality of efficiency of conversion declines.In recent years, the production equipment of polyester material is increasing, greatly improves production cost enterprise.Therefore need a kind of new solution to change existing conventional conversion pattern.
Summary of the invention
Technical problem to be solved by this invention is the preparation method providing the copolymerized polymer that a kind of second-order transition temperature is high, color and luster is good for the above-mentioned state of the art.
Technical problem to be solved by this invention is the preparation method providing a kind of component to change the copolymerized polymer convenient, switching time is short and then production efficiency is high for the above-mentioned state of the art.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of copolymerized polymer, it is characterized in that comprising the steps:
First stage esterification:
Diprotic acid, dibasic alcohol and catalyzer 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 to the first esterifying kettle is carried out first stage esterification, under nitrogen atmosphere, temperature of reaction is between 240 ~ 265 DEG C, and reaction absolute pressure pressure is between 0 ~ 0.5MPa, and the reaction times was between 3 ~ 6 hours; The conversion rate of esterification of the first esterifying kettle outlet is between 75 ~ 85%;
Another group diprotic acid, dibasic alcohol and catalyzer, oxidation inhibitor, stablizer are 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 to the first esterifying kettle is carried out first stage esterification; Under nitrogen atmosphere, temperature of reaction, between 200 ~ 245 DEG C, reacts absolute pressure pressure between 0 ~ 0.4MPa reaction times between 3 ~ 6 hours; The conversion rate of esterification of second esterification kettle outlet is between 75 ~ 85%;
Subordinate phase esterification:
The monomer that the monomer make the first esterifying kettle and second esterification kettle are made all is delivered in the 3rd esterifying kettle; Under nitrogen atmosphere, temperature of reaction is between 240 ~ 265 DEG C, and esterification absolute pressure pressure is between 0 ~ 0.4MPa, and reaction time of esterification was between 0.5 ~ 2 hour; The conversion rate of esterification of the 3rd esterifying kettle outlet is greater than 92%; Add dye additive at the 3rd esterifying kettle to mix colours;
Phase III prepolymerization reaction:
By the monomer that the 3rd esterifying kettle is made, be delivered to precondensation still and carry out prepolymerization reaction, obtain low-grade polymer; Temperature of reaction is between 255 ~ 270 DEG C; Absolute pressure pressure is between 1 ~ 30kPa, and the time was between 0.5 ~ 1.5 hour;
The whole polycondensation of fourth stage:
Low-grade polymer after above-mentioned prepolymerization reaction, is delivered to whole polycondensation vessel and carries out polycondensation further, and the temperature of whole polycondensation is between 270 ~ 285 DEG C; Utilize glycol steam squirt pump vacuum mechanism to make the vacuum absolute pressure pressure of whole polycondensation vessel lower than 160Pa, the time of reaction between 0.5 ~ 2 hour, the final limiting viscosity that improves is to 0.65dl/g.
This preparation method completes in a co-polyester production combination unit, and aforesaid co-polyester production combination unit comprises
First esterifying kettle, is connected with the first ethylene glycol backflow mechanism;
First slurry preparation, is connected by the feed end of one first volume pump with aforementioned first esterifying kettle;
One 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 volume 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 volume pump;
Second esterification kettle, is connected with the second ethylene glycol backflow mechanism;
Second slurry preparation, is connected with the feed end of aforementioned second esterification kettle by one the 4th volume 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 volume pump;
Second catalyst preparation tank, is connected with the feed end of aforementioned second slurry preparation by one the 6th volume pump;
3rd esterifying kettle, be connected with triethylene glycol backflow mechanism, feed end is connected with aforementioned first esterifying kettle and second esterification kettle;
3rd additive preparing tank, is connected by the feed end of one the 7th volume pump with aforementioned 3rd esterifying kettle;
Precondensation still, is connected with precondensation vacuum mechanism and feed end is connected with aforementioned 3rd esterifying kettle; And
Whole polycondensation vessel, is connected with ethylene glycol steam vacuum mechanism and feed end is connected with aforementioned precondensation still, and discharge end is connected with fondant filter;
Agitator is equipped with in aforesaid described the first esterifying kettle, second esterification kettle, the 3rd esterifying kettle, precondensation still and whole polycondensation vessel; The discharge port of aforesaid precondensation still and whole polycondensation vessel is equipped with Send out pump.
Further, be convenient to batch mixing abundant, the feed end of described 3rd esterifying kettle comprises the first opening for feed, the second opening for feed and the 3rd opening for feed, aforesaid first opening for feed is connected with the first esterifying kettle, aforesaid second opening for feed is connected with second esterification kettle, aforesaid 3rd opening for feed is connected with the 3rd additive preparing tank, and the first opening for feed is positioned at above the second opening for feed.
As preferably, described diprotic acid be terephthalic acid, m-phthalic acid, at least one in naphthalic acid, FDCA; Described dibasic alcohol bag is at least one in ethylene glycol, Isosorbide, propylene glycol, butyleneglycol, 1,4 cyclohexane dimethanol.
As preferably, diprotic acid in described first esterifying kettle is terephthalic acid and m-phthalic acid mixing, dibasic alcohol in described first esterifying kettle is ethylene glycol, diprotic acid in described second esterification kettle is terephthalic acid, dibasic alcohol in described second esterification kettle is Isosorbide, further, the mol ratio of described ethylene glycol and Isosorbide is 10:1 ~ 1:1.
As preferably, described stablizer is at least one in phosphoric acid, phosphoric acid ester or phosphorous acid ester, and addition is the 1ppm ~ 10ppm of diprotic acid.
As preferably, described oxidation inhibitor is at least one in Irgafos-168, Irganox-1010, Irgamod-195, and addition is 0.1% ~ 0.3% of diprotic acid.
As preferably, catalyzer in described first esterifying kettle is the acetate of Sb (III) or the oxide compound of other alkanoate, Sb (III) and Ge (IV) and Ti (OR) 4, wherein R to be carbonatoms be 2 ~ 12 alkyl group.
As preferably, the catalyzer in described second esterification kettle is oxide compound and the Ti (OR) 4 of Ge (IV), wherein R to be carbonatoms be 2 ~ 12 alkyl group.
Sb (III) addition is the 180ppm ~ 300ppm of diprotic acid, Ge (IV) addition be the 60ppm ~ 100ppm of diprotic acid, Ti (IV) addition is the 1ppm ~ 10ppm of diprotic acid.
As preferably, described dye additive comprises red pigment and blue pigments, and aforementioned red pigment addition is the 0.1ppm ~ 0.5ppm of diprotic acid weight; Aforementioned blue pigment addition is the 0.5ppm ~ 1.5ppm of diprotic acid weight.For improving the colour of copolyester of the present invention section, need to add the color and luster b value that blue dyes adjusts the polyester slice measured with Hunter look.The blue dyes added, such as, select " PRT whole world blue dispersions-2 " (285-10135-2) of Jia Luosi (ColorMatrix).In addition, for avoiding the too low outward appearance of color and luster a value of the polyester slice measured with Hunter look partially green, a small amount of orchil can be added, such as, select " the red dispersion agent-2 in the PRT whole world " (283-10068-2) of Jia Luosi (ColorMatrix).
Compared with prior art, the invention has the advantages that: the present invention adopts the independent esterification of various ingredients, mix the mode of copolymerization more further, object is that each component can be completed in esterification uniformly, avoids causing because of the difference of esterifying efficiency certain component can not evenly esterification.The component of more difficult esterification can be made to carry out transesterify more fully simultaneously, more easily be embedded in the macromolecular chain of polycondensation, final product quality improves.Component is changed convenient and swift simultaneously, and be unlikely to produce a large amount of Transition Materials and increase production cost, efficiency of conversion also improves greatly.
Accompanying drawing explanation
Fig. 1 is that in embodiment 1, schematic diagram arranged by co-polyester production combination unit.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
First stage esterification:
Take pure terephthalic acid (PTA) 13.954Kg, m-phthalic acid (IPA) 0.285Kg, ethylene glycol (EG) 6.65Kg, antimony glycol 6g.Under nitrogen atmosphere, PTA, IPA, EG and catalyzer are first modulated into slurry, carry out first stage esterification at 50L first esterifying kettle.Temperature of reaction is between 240 ~ 245 DEG C, and reaction pressure is between 0.25 ~ 0.3MPa (absolute pressure), and in 3 hours reaction times, the conversion rate of esterification of the first esterifying kettle is between 80 ~ 85%.
Take PTA 0.749Kg, Isosorbide 0.824Kg, Li-Ti catalyzer 1g (solution of 0.3% titanium content), Irganox-10100.2g, phosphoric acid 0.121g (solution of 85% weight).Under nitrogen atmosphere, at temperature in the kettle 65 ~ 70 DEG C, PTA, Isosorbide and catalyzer, oxidation inhibitor, stablizer are modulated into slurry, carry out first stage esterification at 3L second esterification kettle.Temperature of reaction is between 215 ~ 220 DEG C, and reaction pressure is between 0.15 ~ 0.2MPa (absolute pressure), and in 4 hours reaction times, the conversion rate of esterification of second esterification kettle is between 80 ~ 85%.
Subordinate phase esterification:
Under nitrogen atmosphere, the monomer that above-mentioned first esterifying kettle is made, utilizes pressure difference to be delivered in the 3rd esterifying kettle; The monomer that above-mentioned second esterification kettle is made, utilizes Send out pump to be delivered to further esterification in the 3rd esterifying kettle.Temperature of reaction is between 250 ~ 255 DEG C, and esterification pressures is between 0.2 ~ 0.25MPa (absolute pressure), and in 0.5 hour reaction times, reduce to normal pressure 0.1MPa (absolute pressure) subsequently in 20min internal pressure, the 3rd esterifying kettle conversion rate of esterification is greater than 92%.
Phase III prepolymerization reaction:
By the monomer that above-mentioned esterification is made, utilize pressure difference to be delivered to precondensation still and carry out prepolymerization reaction; Temperature of reaction is between 265 ~ 270 DEG C, and pressure is slowly down to 1KPa (absolute pressure) by normal pressure in 1h, and reaction terminates.
The whole polycondensation of fourth stage:
Low-grade polymer after above-mentioned prepolymerization reaction, the whole polycondensation vessel being delivered to high vacuum carries out polycondensation further; The temperature of whole polycondensation between 270 ~ 275 DEG C, vacuum pressure lower than 160Pa (absolute pressure), the 1 hour time of reaction.
Polymer after above-mentioned whole polycondensation completes, is cut into non-crystalline state ground sections through discharging chilling, and dry made ground sections, carry out every detection, it is the results detailed in Table shown in 1.
As shown in Figure 1, in embodiment 1, co-polyester production combination unit comprises the first esterifying kettle 11, first slurry preparation 81, PTA storage tank 31, first additive preparing tank 33, a first catalyst preparation tank 35, second esterification kettle 12, second slurry preparation 82, the 2nd PTA storage tank 32, Second addition preparing tank 34, second catalyst preparation tank 36, the 3rd esterifying kettle 13, the 3rd additive preparing tank 37, precondensation still 14 and whole polycondensation vessel 15.
First esterifying kettle 11 is connected with ethylene glycol backflow mechanism, first slurry preparation 81 is connected with the feed end of the first esterifying kettle 11 by the first volume pump 21, one PTA storage tank 31 is connected with the feed end of the first slurry preparation 81 by the first metering valve 28, first additive preparing tank 33 is connected with the feed end of the first slurry preparation 81 by the second volume pump 22, and the first catalyst preparation tank 35 is connected with the feed end of the first slurry preparation 81 by the 3rd volume pump 23.
Second esterification kettle 12 is connected with ethylene glycol backflow mechanism, second slurry preparation 82 is connected with the feed end of second esterification kettle 12 by the 4th volume pump 24,2nd PTA storage tank 32 is connected with the feed end of the second slurry preparation 82 by the second metering valve 29, Second addition preparing tank 34 is connected with the feed end of the second slurry preparation 82 by the 5th volume pump 25, and the second catalyst preparation tank 36 is connected with the feed end of the second slurry preparation 82 by the 6th volume pump 25.
3rd esterifying kettle 13 is connected with ethylene glycol backflow mechanism, feed end is connected with the first esterifying kettle 11 and second esterification kettle 12,3rd additive preparing tank 37 is connected with the feed end of the 3rd esterifying kettle 13 by the 7th volume pump 27, precondensation still 14 is connected with precondensation vacuum mechanism 70 and feed end is connected with the 3rd esterifying kettle 13, and precondensation vacuum mechanism 70 connects a vacuum pump 71.Whole polycondensation vessel 15 is connected with ethylene glycol steam vacuum mechanism 6 and feed end is connected with precondensation still 14, and discharge end is connected with fondant filter 10.
Agitator (without display in figure) is equipped with in first esterifying kettle 11, second esterification kettle 12, the 3rd esterifying kettle 13, precondensation still 14 and whole polycondensation vessel 15.The discharge port of second esterification kettle 12, precondensation still 14 and whole polycondensation vessel 15 is equipped with Send out pump 5.
The feed end of the 3rd esterifying kettle 13 comprises the first opening for feed, the second opening for feed and the 3rd opening for feed, first opening for feed is connected with the first esterifying kettle 11, second opening for feed is connected with second esterification kettle 12,3rd opening for feed is connected with the 3rd additive preparing tank 37, further, the first opening for feed is positioned at above the second opening for feed.The leading portion carboxylate of component enters from the bottom of the 3rd esterifying kettle 13 so less, multi-component leading portion carboxylate enters from the middle part of the 3rd esterifying kettle 13, stirs the mode adopting material upwards to roll, each component Homogeneous phase mixing, in the embedding polycomponent that few component is a large amount of, form uniform oligopolymer.
Ethylene glycol steam vacuum mechanism in the present embodiment comprises three grades of steam mechanisms, condenser 69, vaporizer 67, vacuum pump 68 and ethylene glycol receiving tank 60, three grades of steam mechanisms and comprises the first injector 61, first-stage condenser 62, second injector 63, secondary condenser 64, three grades of injectors 65 and the three grades of condensers 66 that connect successively; Condenser 69 one end is connected the other end with whole polycondensation vessel 15 and is connected with first injector 61; Vaporizer 67 is connected with first injector 61, second injector 63 and three grades of injectors 65 respectively; Vacuum pump 68 is connected with three grades of condensers 66; Ethylene glycol receiving tank 60 liquid feeding end is connected with first-stage condenser 62, secondary condenser 64 and three grades of condensers 66 respectively.
Ethylene glycol backflow mechanism in the present embodiment comprises process tower 42, reflux exchanger 41 and reflux pump 43, the liquid feeding end of reflux exchanger 41 is connected with refluxing to hold with the outlet side of process tower 42 respectively with inlet end, and reflux pump 43 is connected with the outlet end of process tower 42.The ethylene glycol formed in esterification reaction process and water etc. enter process tower 42 via vaporizing tube (without display in figure) and are separated, the ethylene glycol of process tower 42 bottom collection is back to reaction kettle of the esterification again, and the water vapor of process tower 42 collected overhead goes wastewater treatment after condensation.
Embodiment 2
As the practice of embodiment 1, in 50L reactor 2, take pure terephthalic acid (PTA) 13.490Kg, m-phthalic acid (IPA) 0.270Kg, ethylene glycol (EG) 6.300Kg, antimony glycol 5.4g.PTA1.499Kg, Isosorbide 1.648Kg, Li-Ti catalyzer 2g, Irganox-10100.2g, phosphoric acid 0.121g is taken in 3L reactor 1.
Dry made ground sections, carry out every detection, it is the results detailed in Table shown in 1.
Embodiment 3
As the practice of embodiment 1, in 50L reactor 2, take pure terephthalic acid (PTA) 11.991Kg, m-phthalic acid (IPA) 0.240Kg, ethylene glycol (EG) 5.600Kg, antimony glycol 4.8g.PTA2.998Kg, Isosorbide 3.296Kg, Li-Ti catalyzer 4g, Irganox-10100.2g, phosphoric acid 0.121g is taken in 3L reactor 1.
For improving the colour of copolyester section, add " PRT whole world blue dispersions-2 " (285-10135-2) 0.093g that blue dyes selects Jia Luosi (ColorMatrix); Add " the red dispersion agent-2 in the PRT whole world " (283-10068-2) 0.023g that orchil selects Jia Luosi (ColorMatrix).
Dry made ground sections, carry out every detection, it is the results detailed in Table shown in 1.
Result
Through PEIT copolyester section prepared by embodiment 1 to 3, the index recorded is as table 1.By adopting independent esterification, then the mode mixing copolymerization further prepares copolyester.The component of more difficult esterification can be made to carry out transesterify more fully, be more easily embedded in the macromolecular chain of polycondensation.Along with the increase of Isosorbide addition, the second-order transition temperature of copolyester section effectively can be improved.
Table 1PEIT section Testing index
1) use Hunter look measurement amount, L value is higher, and color and luster is whiter, and transparency is better; B value is lower, and color and luster is blue, and b value is higher, and color and luster is yellow.
Claims (10)
1. a preparation method for copolymerized polymer, is characterized in that comprising the steps:
First stage esterification:
Diprotic acid, dibasic alcohol and catalyzer 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 to the first esterifying kettle is carried out first stage esterification, under nitrogen atmosphere, temperature of reaction is between 240 ~ 265 DEG C, and reaction absolute pressure pressure is between 0 ~ 0.5MPa, and the reaction times was between 3 ~ 6 hours; The conversion rate of esterification of the first esterifying kettle outlet is between 75 ~ 85%;
Another group diprotic acid, dibasic alcohol and catalyzer, oxidation inhibitor, stablizer are 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 to the first esterifying kettle is carried out first stage esterification; Under nitrogen atmosphere, temperature of reaction, between 200 ~ 245 DEG C, reacts absolute pressure pressure between 0 ~ 0.4MPa reaction times between 3 ~ 6 hours; The conversion rate of esterification of second esterification kettle outlet is between 75 ~ 85%;
Subordinate phase esterification:
The monomer that the monomer make the first esterifying kettle and second esterification kettle are made all is delivered in the 3rd esterifying kettle; Under nitrogen atmosphere, temperature of reaction is between 240 ~ 265 DEG C, and esterification absolute pressure pressure is between 0 ~ 0.4MPa, and reaction time of esterification was between 0.5 ~ 2 hour; The conversion rate of esterification of the 3rd esterifying kettle outlet is greater than 92%; Add dye additive at the 3rd esterifying kettle to mix colours;
Phase III prepolymerization reaction:
By the monomer that the 3rd esterifying kettle is made, be delivered to precondensation still and carry out prepolymerization reaction, obtain low-grade polymer; Temperature of reaction is between 255 ~ 270 DEG C; Absolute pressure pressure is between 1 ~ 30kPa, and the time was between 0.5 ~ 1.5 hour;
The whole polycondensation of fourth stage:
Low-grade polymer after above-mentioned prepolymerization reaction, is delivered to whole polycondensation vessel and carries out polycondensation further, and the temperature of whole polycondensation is between 270 ~ 285 DEG C; Utilize glycol steam squirt pump vacuum mechanism to make the vacuum absolute pressure pressure of whole polycondensation vessel lower than 160Pa, the time of reaction between 0.5 ~ 2 hour, the final limiting viscosity that improves is to 0.65dl/g.
2. the preparation method of copolymerized polymer according to claim 1, it is characterized in that this preparation method completes in a co-polyester production combination unit, aforesaid co-polyester production combination unit comprises
First esterifying kettle, is connected with the first ethylene glycol backflow mechanism;
First slurry preparation, is connected by the feed end of one first volume pump with aforementioned first esterifying kettle;
One 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 volume 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 volume pump;
Second esterification kettle, is connected with the second ethylene glycol backflow mechanism;
Second slurry preparation, is connected with the feed end of aforementioned second esterification kettle by one the 4th volume 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 volume pump;
Second catalyst preparation tank, is connected with the feed end of aforementioned second slurry preparation by one the 6th volume pump;
3rd esterifying kettle, be connected with triethylene glycol backflow mechanism, feed end is connected with aforementioned first esterifying kettle and second esterification kettle;
3rd additive preparing tank, is connected by the feed end of one the 7th volume pump with aforementioned 3rd esterifying kettle;
Precondensation still, is connected with precondensation vacuum mechanism and feed end is connected with aforementioned 3rd esterifying kettle; And
Whole polycondensation vessel, is connected with ethylene glycol steam vacuum mechanism and feed end is connected with aforementioned precondensation still, and discharge end is connected with fondant filter;
Agitator is equipped with in aforesaid described the first esterifying kettle, second esterification kettle, the 3rd esterifying kettle, precondensation still and whole polycondensation vessel; The discharge port of aforesaid precondensation still and whole polycondensation vessel is equipped with Send out pump.
3. the preparation method of copolymerized polymer according to claim 2, it is characterized in that the feed end of described 3rd esterifying kettle comprises the first opening for feed, the second opening for feed and the 3rd opening for feed, aforesaid first opening for feed is connected with the first esterifying kettle, aforesaid second opening for feed is connected with second esterification kettle, aforesaid 3rd opening for feed is connected with the 3rd additive preparing tank, further, the first opening for feed is positioned at above the second opening for feed.
4. the preparation method of copolymerized polymer according to claim 1, it is characterized in that described diprotic acid be terephthalic acid, m-phthalic acid, at least one in naphthalic acid, FDCA; Described dibasic alcohol bag is at least one in ethylene glycol, Isosorbide, propylene glycol, butyleneglycol, 1,4 cyclohexane dimethanol.
5. the preparation method of copolymerized polymer according to claim 4, it is characterized in that the diprotic acid in described first esterifying kettle is terephthalic acid and m-phthalic acid mixing, dibasic alcohol in described first esterifying kettle is ethylene glycol, diprotic acid in described second esterification kettle is terephthalic acid, dibasic alcohol in described second esterification kettle is Isosorbide, further, the mol ratio of described ethylene glycol and Isosorbide is 10:1 ~ 1:1.
6. the preparation method of copolymerized polymer according to claim 1, it is characterized in that described stablizer is at least one in phosphoric acid, phosphoric acid ester or phosphorous acid ester, addition is the 1ppm ~ 10ppm of diprotic acid.
7. the preparation method of copolymerized polymer according to claim 1, it is characterized in that described oxidation inhibitor is at least one in Irgafos-168, Irganox-1010, Irgamod-195, addition is 0.1% ~ 0.3% of diprotic acid.
8. the preparation method of copolymerized polymer according to claim 1, the catalyzer that it is characterized in that in described first esterifying kettle is the acetate of Sb (III) or the oxide compound of other alkanoate, Sb (III) and Ge (IV) and Ti (OR) 4, wherein R to be carbonatoms be 2 ~ 12 alkyl group.
9. the preparation method of copolymerized polymer according to claim 1, the catalyzer that it is characterized in that in described second esterification kettle is oxide compound and the Ti (OR) 4 of Ge (IV), wherein R to be carbonatoms be 2 ~ 12 alkyl group.
10. the preparation method of copolymerized polymer according to claim 1, is characterized in that described dye additive comprises red pigment and blue pigments, and aforementioned red pigment addition is the 0.1ppm ~ 0.5ppm of diprotic acid weight; Aforementioned blue pigment addition is the 0.5ppm ~ 1.5ppm of diprotic acid weight.
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| CN110790907A (en) * | 2019-11-18 | 2020-02-14 | 扬州普立特科技发展有限公司 | Production equipment and process flow of full-continuous PETG |
| CN111269405A (en) * | 2020-02-27 | 2020-06-12 | 浙江恒澜科技有限公司 | Preparation method of bio-based polyester for inhibiting discoloration |
| CN111378104A (en) * | 2020-04-21 | 2020-07-07 | 浙江古纤道绿色纤维有限公司 | Six cauldron polymerization facility |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110790907A (en) * | 2019-11-18 | 2020-02-14 | 扬州普立特科技发展有限公司 | Production equipment and process flow of full-continuous PETG |
| CN111269405A (en) * | 2020-02-27 | 2020-06-12 | 浙江恒澜科技有限公司 | Preparation method of bio-based polyester for inhibiting discoloration |
| 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 |
| CN111378104A (en) * | 2020-04-21 | 2020-07-07 | 浙江古纤道绿色纤维有限公司 | Six cauldron polymerization facility |
| CN114380988A (en) * | 2022-01-21 | 2022-04-22 | 无锡奥克特包装材料有限公司 | Preparation method of anti-electromagnetic radiation APET film |
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