CN111100280A - Method for adding catalyst in industrial production of optical film grade polyester chips - Google Patents
Method for adding catalyst in industrial production of optical film grade polyester chips Download PDFInfo
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- CN111100280A CN111100280A CN201811249027.9A CN201811249027A CN111100280A CN 111100280 A CN111100280 A CN 111100280A CN 201811249027 A CN201811249027 A CN 201811249027A CN 111100280 A CN111100280 A CN 111100280A
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- polyester
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- 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 invention discloses a method for adding a catalyst in the industrial production of optical film grade polyester chips. The method comprises the following specific steps: adding a part of titanium catalyst according to a conventional method, uniformly stirring an ethylene glycol solution containing the other part of titanium catalyst, a certain amount of a chroma agent, an optical brightener and a heat stabilizer, reacting on a final polymerization kettle feeding pipeline of a continuous polyester device through an injector injection system, and carrying out final polycondensation reaction to obtain the optical film grade polyester chip. The polyester chip obtained by the invention has high transparency, stable color and excellent performance.
Description
Technical Field
The invention belongs to the technical field of polyester production, and particularly relates to a method for adding a catalyst in industrial production of optical film grade polyester chips.
Background
The polyester film (PET) is a film material which is prepared by using polyethylene glycol terephthalate as a raw material, preparing a thick sheet by an extrusion method, and performing biaxial stretching.
The optical polyester film has good high transparency, excellent mechanical properties and chemical resistance, and is widely applied to protective films and reflective films of liquid crystal displays, touch screens and the like with high requirements on optical properties. However, the polyester chips in the current market have defects in transparency, glossiness and other properties, so that the subsequently produced polyester optical film has the defects of yellow color, gray color and the like, and the application of the polyester film in the fields of electronic products and the like is restricted. Additives are usually added during the production of optical film grade chips to improve the properties of subsequent polyester films, but this affects the optical properties such as transparency of the films, and limits further applications.
Chinese patent CN102585181A discloses a polyester chip for optical film and an optical-grade polyester film. Mixing ethylene glycol, terephthalic acid and isophthalic acid in a pulping kettle to prepare slurry; adding ethylene glycol and antimony acetate or ethylene glycol antimony into a catalyst preparation kettle, and uniformly stirring to prepare a catalyst solution; adding the nano-scale additive, the micron-scale additive and ethylene glycol into an additive preparation kettle, and uniformly stirring to prepare an additive solution; adding the slurry and the catalyst liquid into an esterification kettle, and heating for reaction to obtain an esterified substance; after the reaction, pressing the esterified substance into a pre-polycondensation kettle, pressing an additive liquid into the pre-polycondensation kettle, vacuumizing the pre-polycondensation reaction process, and discharging excessive glycol; pressing the pre-polycondensation product into a final polycondensation kettle to obtain a melt; and cooling the melt, pelletizing, discharging and packaging. The invention requires that nano-scale and micron-scale additives are added in the preparation process, and three raw materials of ethylene glycol, terephthalic acid and isophthalic acid are adopted. Chinese patent CN104086756A discloses a method for producing optical transparent film-grade polyester, which comprises stirring PTA, EG and IPA to prepare uniform slurry, and esterifying; then carrying out di-esterification, and simultaneously adding 50-200 ppm of pentaerythritol into the di-esterification; then carrying out a first pre-polycondensation reaction on the di-esterification product, and further carrying out a second pre-polycondensation reaction to finally obtain a pre-melt; and finally polycondensing the pre-melted body to obtain the optical transparent film grade polyester. But the invention requires that pentaerythritol is added in the preparation process, and three raw materials of ethylene glycol, terephthalic acid and isophthalic acid are adopted at the same time. Chinese patent CN102516509A discloses a polyester chip for an optical film and a preparation method of the optical film, in the method, ethylene glycol and dimethyl terephthalate are mixed in a pulping kettle to prepare slurry, and the ethylene glycol and a catalyst are put into a catalyst preparation kettle to be mixed to prepare catalyst liquid; adding the nano-scale additive and glycol into an additive preparation kettle, and mixing to prepare an additive solution; adding the slurry and the catalyst liquid into an esterification kettle, and heating to perform an ester exchange reaction to obtain an esterified substance; the esterified substance and the additive are hydraulically pressed into a pre-polycondensation kettle, the pre-polycondensation reaction process is vacuumized, and the excessive glycol is discharged; and pressing the product of the pre-polycondensation into a final polymerization kettle to improve the viscosity of the melt, and cooling and dicing the melt to obtain the polyester chip for the optical film. The invention requires that a nano-scale additive is added in the preparation process, and ethylene glycol and dimethyl terephthalate are taken as raw materials.
In summary, in the prior art, a catalyst and an auxiliary additive need to be added into an oligomer pipeline in the production process of an optical film grade polyester chip, which may cause the technical problems of too long retention time of a prepolymerization reactor, and nonuniform gas-liquid phase mixing, and further influence on optical properties such as transparency of the chip.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a method for adding a catalyst in the industrial production of optical film grade polyester chips. In the invention, part of the titanium catalyst, the chroma agent, the whitening agent and the heat stabilizer are injected from the original oligomer pipeline and are changed into the final polymerization kettle feeding pipeline. The post-injection includes: the titanium catalyst, the chroma agent, the optical brightener and the heat stabilizer realize the control of parameters such as product color, intrinsic viscosity, agglomerated particles and the like, and produce the polyester chip with good light transmission and excellent performance. The manufacturing method can effectively realize industrialized large-scale continuous production, and simultaneously, the obtained polyester chip has stable color, excellent performance and good film drawing property, and the film optical product produced subsequently has more transparent color and more stable quality.
The invention provides a method for adding a catalyst in industrial production of optical film grade polyester chips, which comprises the following steps:
(1) adding before a catalyst: injecting part of the titanium catalyst (namely, the titanium catalyst is added before) from an oligomer pipeline in the conventional method;
(2) post-addition of catalyst: mixing the ethylene glycol solution containing the other part of titanium catalyst (called as post-added titanium catalyst) with a certain amount of chroma agent, optical brightener and heat stabilizer, and stirring;
(3) and injecting the mixed solvent into a final polymerization kettle feeding pipeline of a continuous polyester device through an injector, carrying out final polycondensation reaction in a final polymerization kettle under certain process conditions, and obtaining the optical film grade polyester chip after the final polycondensation reaction.
Further, the titanium catalyst is any one of tetrabutyl titanate, tetraisopropyl titanate or titanium glycol or any combination thereof.
Furthermore, the addition amount of the titanium ions added before is 0.8-1.5 ppm based on the theoretical weight of the polyester.
Furthermore, the addition amount of the post-added titanium ions is 0.15-0.20 ppm based on the theoretical weight of the polyester.
Further, the molecular formula of the chroma agent is C32H30N2O2The amount of the polyester is 0.0025 to 0.0032ppm based on the theoretical weight of the polyester.
Further, the molecular formula of the optical brightening agent is C28H18N2O2The amount of the polyester is 0.30 to 0.40ppm based on the theoretical weight of the polyester.
Further, the heat stabilizer is trimethyl phosphate, and the molecular formula is C3H9O4P is added in an amount of 0.25 to 0.35ppm based on the theoretical weight of the polyester.
Further, in the step (3), a back pressure valve is arranged on the pipeline where the catalyst is located. Because the feeding pipeline of the final polymerization reactor is a vacuum pipeline, in order to avoid the fluctuation of the catalyst flow caused by the vacuum fluctuation, a back pressure valve is added on the catalyst pipeline, and the stability of the catalyst injection amount is ensured.
Further, in the step (3), vacuumizing is needed in the final polycondensation reaction process, and excessive small molecules such as ethylene glycol and water are discharged; the reaction conditions can be optimized according to actual needs, and the preferable final polycondensation reaction conditions are as follows: the absolute pressure is 10-800 Pa, the temperature is 270-300 ℃, the reaction residence time is 1.8-2.5 h, and the esterification rate is 99-99.5%.
Further, in the step (3), the final polycondensation reaction kettle is a horizontal type squirrel-cage stirring final polycondensation reaction kettle.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the low-temperature short-flow plug flow tower type three-kettle continuous reaction flow, the viscosity of materials in the pre-polycondensation kettle is reduced to a certain extent by adding part of titanium catalysts and additives later, so that gas-liquid exchange in the pre-polycondensation kettle is more uniform, the obtained polyester product is cleaner, and the transparency is higher;
(2) the post-adding method of part of the titanium catalyst can sensitively adjust the proportion of the titanium catalyst according to the quality condition of the raw material Pure Terephthalic Acid (PTA), so that the reaction system has stronger adaptability to the raw materials PTA with different qualities and the product quality is more stable;
(3) the use of the optical brightening agent further improves the color of the polyester product, so that the polyester product is clearer and brighter, and the optical properties such as transparency of subsequent film products are better;
(4) the use of the heat stabilizer enables the reaction conditions of the final polymerization kettle to be more stable, and the quality control of the obtained polyester product to be more stable.
Under the action of the beneficial effects, the control on parameters such as product color, intrinsic viscosity and agglomerated particles is finally realized, and the optical film grade polyester chip meeting the market demand is produced. Compared with the prior art, the manufacturing method realizes industrial large-scale continuous production, the obtained polyester chip has stable color, excellent performance and high transparency, and the subsequently produced film optical product has more transparent color and more stable quality, and is suitable for the production of high-grade optical films.
Drawings
FIG. 1: the equipment structure schematic diagram that the catalyst after-addition technology used, wherein, in the dotted line frame is catalyst syringe and back pressure valve that the invention compares the addition of prior art.
Detailed Description
The essence of the present invention can be better understood by combining with the specific embodiments, and the adjustment or modification made by those skilled in the relevant art based on the actual needs, such as adjusting the reaction pressure, the reaction temperature, the mixture ratio of each material and additive, etc., still belong to the protection scope of the present invention. These examples are listed for illustrative purposes only and do not limit the invention in any way.
The performance test method comprises the following steps: the performance such as intrinsic viscosity, melting point, carboxyl end group content, hue, DEG content and the like is tested according to the national standard GB/T14190-2008 fiber grade polyester chip (PET) test method.
The starting materials in the following examples are all commercially available unless otherwise specified.
Examples 1 to 9:
a method for adding a catalyst in industrial production of optical film grade polyester chips comprises the following specific steps:
(1) preparing 50Kg of titanium catalyst with titanium content of 0.4 percent and 1250L of ethylene glycol into solution, and uniformly stirring the solution and a certain amount of chroma agent, optical brightener and heat stabilizer;
(2) the mixed solvent is injected into a feeding pipeline of a final polymerization kettle through an injector, and the reaction is carried out in the final polymerization kettle under the process conditions that the absolute pressure is 10-800 Pa, the temperature is 270-300 ℃ and the reaction residence time is 1.8-2.5 h. The titanium adding amount added in the front of the reaction materials is 0.8-1.5 ppm, the titanium adding amount added in the back is 0.15-0.20 ppm, the adding amount of a colorimeter is 0.0025-0.0032 ppm, the adding amount of a whitening agent is 0.30-0.40 ppm, and the adding amount of a heat stabilizer is 0.25-0.35 ppm based on the theoretical amount of polyester.
(3) Cooling and dicing the melt after reaction in a final polycondensation reaction kettle to obtain optical film grade polyester chips
The optical film grade polyester produced by the method is easy to stretch, has good optical performance, better hue, high transparency and no graying and yellowing phenomena.
The contents of the catalyst, colorimeter, optical brightener and thermal stabilizer used in each example were controlled, the reaction conditions and the main quality indexes of the polyester product are shown in tables 1, 2 and 3 below, respectively, and the amounts of all the additives were calculated based on the theoretical yield of the polyester. (examples 4 to 9 are post-addition)
The analytical data of examples 1-9 are shown in table 3, and the data show that the B value is lower and the L value is higher when the post-added three example products are adopted, which shows that the post-added three examples have more excellent hue performance and can effectively improve the yellowing and graying phenomena of the polyester chips.
TABLE 1 Process recipes for examples 1-9
TABLE 2 reaction conditions of examples 1-9
TABLE 3 Main quality index for examples 1 to 9
Claims (10)
1. A method for adding a catalyst in the industrial production of optical film grade polyester chips is characterized by comprising the following steps:
(1) adding before a catalyst: injecting part of the titanium catalyst from an oligomer pipeline according to a conventional method;
(2) post-addition of catalyst: stirring the ethylene glycol solution containing the other part of the titanium catalyst and a certain amount of the chroma agent, the optical brightener and the heat stabilizer uniformly;
(3) and injecting the mixed solvent into a final polymerization kettle feeding pipeline of a continuous polyester device through an injector, carrying out final polycondensation reaction in a final polymerization kettle under certain process conditions, and obtaining the optical film grade polyester chip after the final polycondensation reaction.
2. The method of adding a catalyst according to claim 1, characterized in that: the titanium catalyst is any one or any combination of tetrabutyl titanate, tetraisopropyl titanate or titanium glycol.
3. The method of adding a catalyst according to claim 1, characterized in that: in the former adding step, the adding amount of the titanium ions is 0.8-1.5 ppm based on the theoretical weight of the polyester.
4. The method of adding a catalyst according to claim 1, characterized in that: in the post-addition step, the addition amount of the titanium ions is 0.15-0.20 ppm based on the theoretical weight of the polyester.
5. The method of adding a catalyst according to claim 1, characterized in that: the molecular formula of the chroma agent is C32H30N2O2The amount of the polyester is 0.0025 to 0.0032ppm based on the theoretical weight of the polyester.
6. The method of adding a catalyst according to claim 1, characterized in that: the molecular formula of the optical brightening agent is C28H18N2O2The amount of the polyester is 0.30 to 0.40ppm based on the theoretical weight of the polyester.
7. The method of adding a catalyst according to claim 1, characterized in that: the heat stabilizer is trimethyl phosphate with the molecular formula of C3H9O4P is added in an amount of 0.25 to 0.35ppm based on the theoretical weight of the polyester.
8. The method of adding a catalyst according to claim 1, characterized in that: in the step (3), a back pressure valve is arranged on a pipeline where the catalyst is located.
9. The method of adding a catalyst according to claim 1, characterized in that: in the step (3), the final polycondensation reaction conditions are as follows: the absolute pressure is 10-800 Pa, the temperature is 270-300 ℃, the reaction residence time is 1.8-2.5 h, and the esterification rate is 99-99.5%.
10. The method of adding a catalyst according to claim 1, characterized in that: in the step (3), the final polycondensation reaction kettle is a horizontal final polycondensation reaction kettle with squirrel-cage stirring.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811249027.9A CN111100280A (en) | 2018-10-25 | 2018-10-25 | Method for adding catalyst in industrial production of optical film grade polyester chips |
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| CN201811249027.9A CN111100280A (en) | 2018-10-25 | 2018-10-25 | Method for adding catalyst in industrial production of optical film grade polyester chips |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368547A (en) * | 2022-07-29 | 2022-11-22 | 浙江恒创先进功能纤维创新中心有限公司 | Industrialized application of titanium catalyst in three-kettle polyester device |
| WO2023103333A1 (en) * | 2021-12-10 | 2023-06-15 | 江苏新视界先进功能纤维创新中心有限公司 | Method for preparing environment-friendly pet polyester having good hue quality on continuous polymerization device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5898058A (en) * | 1996-05-20 | 1999-04-27 | Wellman, Inc. | Method of post-polymerization stabilization of high activity catalysts in continuous polyethylene terephthalate production |
| CN107880255A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of manufacture method of optical film grade polyester chip |
-
2018
- 2018-10-25 CN CN201811249027.9A patent/CN111100280A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5898058A (en) * | 1996-05-20 | 1999-04-27 | Wellman, Inc. | Method of post-polymerization stabilization of high activity catalysts in continuous polyethylene terephthalate production |
| CN107880255A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of manufacture method of optical film grade polyester chip |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023103333A1 (en) * | 2021-12-10 | 2023-06-15 | 江苏新视界先进功能纤维创新中心有限公司 | Method for preparing environment-friendly pet polyester having good hue quality on continuous polymerization device |
| CN115368547A (en) * | 2022-07-29 | 2022-11-22 | 浙江恒创先进功能纤维创新中心有限公司 | Industrialized application of titanium catalyst in three-kettle polyester device |
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Application publication date: 20200505 |