CN110669211A - Barrier polyester and preparation method thereof - Google Patents
Barrier polyester and preparation method thereof Download PDFInfo
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- CN110669211A CN110669211A CN201810709758.0A CN201810709758A CN110669211A CN 110669211 A CN110669211 A CN 110669211A CN 201810709758 A CN201810709758 A CN 201810709758A CN 110669211 A CN110669211 A CN 110669211A
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- polyester
- monomer
- barrier
- pta
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
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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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
Abstract
The invention relates to barrier polyester and a preparation method thereof, belonging to the field of polyester. The method takes terephthalic acid, hydroxyethylated bisphenol A, polyalcohol or polybasic acid and anhydride thereof as well as ethylene glycol as main raw materials, adds auxiliary agents such as polymerization catalyst, ether inhibitor and the like, directly increases the intrinsic viscosity of a polyester melt to be within the range of (0.55-0.70) dL/g through direct esterification and polycondensation reaction, and then cools and granulates the melt to obtain the polyester granules. Compared with the conventional polyester product, the high-barrier polyester prepared by the invention has the advantages that the modified monomer with low cost is added in the formula, the production process is simple, and the oxygen transmission rate is 30% lower than that of the conventional product.
Description
Technical Field
The invention belongs to the field of polyester, and particularly relates to barrier polyester and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is a semi-crystalline thermoplastic polyester which has many advantages, such as CO barrier2、O2And water vapor, high strength, impact resistance, chemical resistance, pressure resistance, good transparency, good glossiness and the like, and is widely applied to fibers, films and packaging materials of various foods, beverages and medicines. However, in some special packages, the requirement for the barrier property of the packaging material is high, such as beer bottles, the storage period of beer is usually 120 days, which requires that the permeability of the beer bottle body to external oxygen during the storage period can not be more than 1X10-6g, for internal CO2The loss rate of the PET is not more than 15%, and the barrier property is required to be 2-5 times that of common PET. In addition, the medical polyester vacuum blood collection tube is required to be stored for 10 months under the condition of normal temperature (26 ℃), the negative pressure loss is less than 10%, and the barrier property is required to be 2-5 times of that of common PET.
At present, the methods for preparing the high-barrier polyester mainly comprise copolymerization modification, blending modification, multilayer composite modification, surface coating modification, nano composite modification and the like. The most reported copolymerization modification is the modification of 2,6-DNC monomer, but the monomer is high in price and the raw materials are difficult to purchase. Other methods also have the disadvantages of high cost, complex production flow and the like.
Therefore, development of a polyester which is low in cost and can improve PET by a copolymerization method is an important research direction for high-barrier PET.
Chinese patent 201110320992.2 discloses a barrier polyester and a preparation method thereof. A barrier polyester comprises terephthalic acid, ethylene glycol and a barrier comonomer, wherein the comonomer is a hydroxycarboxylic acid compound or benzoic acid derivative with at least two substituents, and the substituents are selected from hydroxyl or carboxyl, but not simultaneously carboxyl. Unlike this patent, this patent relates to monomers that are both homocarboxyl or hydroxyl compounds.
The article: preparation research of the high-resistance water vapor-proof PET copolyester film. Adopts the process of firstly carrying out esterification reaction on terephthalic acid, isophthalic acid and polyhydric alcohol and then adding cis-9, 12-octadecadienol for copolymerization to synthesize the PET copolyester resinThen mixing with polyester master batch (containing TiO)2、SiO2) Blending, melting and stretching to prepare the high-resistance water vapor-proof PET copolyester.
Chinese patent 201010508024.X is a polyester film prepared by biaxially stretching a polyester film, the polyester including a modified polyester containing intercalated montmorillonite.
Chinese patent 201110352203.3 discloses a high-barrier polyester composite material and a preparation method thereof, which is characterized by comprising the following components in parts by weight: 60-95 parts of polyester, 1-20 parts of PVDCI and 0.1-1 part of antioxidant.
The modified monomer and the modification method for improving the barrier property of the polyester in the prior patents are different from the prior patents.
Disclosure of Invention
The first purpose of the present invention is to provide a barrier polyester, which is synthesized by adding a third monomer and a fourth monomer to a barrier copolyester, wherein the third monomer is hydroxyethylated bisphenol a, and the fourth monomer is polyol or polybasic acid and anhydride thereof, and through copolymerization, the molecular chain structure density is improved, the molecular chain spin steric hindrance is improved, the intermolecular hole is reduced, the solubility of gas in the material is reduced, and the purpose of reducing the oxygen permeability is achieved.
It is a further object of the present invention to provide a process for preparing the above barrier polyester.
The purpose of the invention can be realized by the following technical scheme:
a barrier polyester prepared by the method comprising: taking terephthalic acid, ethylene glycol, hydroxyethylated bisphenol A and a fourth monomer as raw materials, adding a polymerization catalyst and an ether inhibitor, improving the intrinsic viscosity of a polyester melt to 0.55-0.70dL/g after esterification and polycondensation reaction, and then cooling and granulating the melt to obtain polyester particles; wherein the fourth monomer is selected from at least one of a polyol, a polyacid and a polyanhydride.
The technical scheme of the invention is as follows: the fourth monomer is at least one of pyromellitic anhydride, trimellitic anhydride, citric acid, glycerol and pentaerythritol.
The technical scheme of the invention is as follows: the addition amount of the hydroxyethylated bisphenol A accounts for 1-30% of the total mass of the PTA; the addition amount of the fourth monomer accounts for 0.001-1% of the total mass of the PTA.
The technical scheme of the invention is as follows: the addition amount of the hydroxyethylated bisphenol A accounts for 1-20% of the total mass of the PTA; the addition amount of the fourth monomer accounts for 0.001-0.5% of the total mass of the PTA.
A preparation method of the barrier polyester takes terephthalic acid, ethylene glycol, hydroxyethylated bisphenol A and a fourth monomer as raw materials, a polymerization catalyst and an ether inhibitor are added, the intrinsic viscosity of a polyester melt is improved to 0.55-0.70dL/g after esterification and polycondensation, and then the melt is cooled and granulated to obtain polyester particles; wherein the fourth monomer is selected from at least one of a polyol, a polyacid and a polyanhydride.
The preparation method comprises the following steps: the fourth monomer is at least one of pyromellitic anhydride, trimellitic anhydride, citric acid, glycerol and pentaerythritol.
The preparation method comprises the following steps: the addition amount of the hydroxyethylated bisphenol A accounts for 1 to 30 percent of the total mass of the PTA; the addition amount of the fourth monomer accounts for 0.001-1% of the total mass of the PTA.
The preparation method comprises the following steps: the addition amount of the hydroxyethylated bisphenol A accounts for 1 to 20 percent of the total mass of the PTA; the addition amount of the fourth monomer accounts for 0.001-0.5% of the total mass of the PTA.
The invention has the beneficial effects that:
compared with the conventional polyester product, the high-barrier polyester prepared by the invention has the advantages that the modified monomer with low cost is added in the formula, the production process is simple, and the oxygen transmission rate is 30% lower than that of the conventional product.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1. Using a 20L polymerization apparatus, terephthalic acid: 5Kg, ethylene glycol: 3Kg, hydroxyethylated bisphenol A: 50g, pyromellitic anhydride: and 25g, adding a polymerization catalyst and an ether inhibitor, performing esterification and polycondensation reaction, and cooling and granulating the melt when the stirring current reaches a preset target. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.55dL/g, carboxyl end group: 32mol/t, diethylene glycol: 1.2 percent.
Example 2. using a 20L polymerization apparatus, terephthalic acid: 5Kg, ethylene glycol: 3Kg, hydroxyethylated bisphenol A: 1Kg, trimellitic anhydride: 0.05g, adding a polymerization catalyst and an ether inhibitor, carrying out esterification and polycondensation reaction, and cooling and granulating the melt when the stirring current reaches a preset target. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.70dL/g, carboxyl end group: 26mol/t, diethylene glycol: 1.0 percent.
Example 3. Using a 20L polymerization apparatus, terephthalic acid: 5Kg, ethylene glycol: 3Kg, hydroxyethylated bisphenol A: 250g, citric acid: 2.5g, adding a polymerization catalyst and an ether inhibitor, carrying out esterification and polycondensation reaction, and cooling and granulating the melt when the stirring current reaches a preset target. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.62dL/g, carboxyl end group: 29mol/t, diethylene glycol: 1.3 percent.
Example 4. Using a 20L polymerization apparatus, terephthalic acid: 5Kg, ethylene glycol: 3Kg, hydroxyethylated bisphenol A: 500g, glycerin: 5g, adding a polymerization catalyst and an ether inhibitor, carrying out esterification and polycondensation reaction, and cooling and granulating the melt when the stirring current reaches a preset target. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.60dL/g, carboxyl end group: 28mol/t, diethylene glycol: 1.4 percent.
Example 5. Using a 20L polymerization apparatus, terephthalic acid: 5Kg, ethylene glycol: 3Kg, hydroxyethylated bisphenol A: 500g, pentaerythritol: 10g, adding a polymerization catalyst and an ether inhibitor, carrying out esterification and polycondensation reaction, and cooling and granulating the melt when the stirring current reaches a preset target. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.60dL/g, carboxyl end group: 28mol/t, diethylene glycol: 1.4 percent.
Comparative example 1: a 20L polymerization apparatus was used, and terephthalic acid: 5Kg, ethylene glycol: 3Kg, adding polymerization catalyst and ether inhibitor, and carrying out esterification and polycondensation reaction, cooling and granulating the melt when the stirring current reaches the preset target. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.65dL/g, carboxyl end group: 32mol/t, diethylene glycol: 1.1 percent.
Comparative example 2: a 20L polymerization apparatus was used, and terephthalic acid: 5Kg, ethylene glycol: 3Kg, hydroxyethylated bisphenol A: 500g, adding a polymerization catalyst and an ether inhibitor, carrying out esterification and polycondensation reaction, and cooling and granulating the melt when the stirring current reaches a preset target. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.65dL/g, carboxyl end group: 32mol/t, diethylene glycol: 1.1 percent.
Comparative example 3: a 20L polymerization apparatus was used, and terephthalic acid: 5Kg, ethylene glycol: 3Kg, trimellitic anhydride: 0.05g, adding a polymerization catalyst and an ether inhibitor, carrying out esterification and polycondensation reaction, and cooling and granulating the melt when the stirring current reaches a preset target. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.65dL/g, carboxyl end group: 32mol/t, diethylene glycol: 1.1 percent.
Comparative example 4: a 20L polymerization apparatus was used, and terephthalic acid: 5Kg, ethylene glycol: 3Kg, hydroxyethylated bisphenol A: 1.5Kg, then adding polymerization catalyst and ether inhibitor, through esterification and polycondensation reaction, when the stirring current reaches the preset target, cooling and granulating the melt. The conventional quality indexes of the polyester chips are as follows: intrinsic viscosity of 0.65dL/g, carboxyl end group: 32mol/t, diethylene glycol: 1.1 percent.
The copolyester prepared by the method is prepared into a test sample with the thickness of 1mm by an injection molding machine, the oxygen transmission rate of the sample is tested by adopting an equal-pressure oxygen transmission rate tester, and the test results are as follows:
Claims (8)
1. a barrier polyester characterized by: the polyester is prepared by the following method: taking terephthalic acid, ethylene glycol, hydroxyethylated bisphenol A and a fourth monomer as raw materials, adding a polymerization catalyst and an ether inhibitor, improving the intrinsic viscosity of a polyester melt to 0.55-0.70dL/g after esterification and polycondensation reaction, and then cooling and granulating the melt to obtain polyester particles; wherein the fourth monomer is selected from at least one of a polyol, a polyacid and a polyanhydride.
2. The barrier polyester of claim 1, wherein: the fourth monomer is at least one of pyromellitic anhydride, trimellitic anhydride, citric acid, glycerol and pentaerythritol.
3. The barrier polyester of claim 1, wherein: the addition amount of the hydroxyethylated bisphenol A accounts for 1-30% of the total mass of the PTA; the addition amount of the fourth monomer accounts for 0.001-1% of the total mass of the PTA.
4. The barrier polyester of claim 3, wherein: the addition amount of the hydroxyethylated bisphenol A accounts for 1-20% of the total mass of the PTA; the addition amount of the fourth monomer accounts for 0.001-0.5% of the total mass of the PTA.
5. A method of making the barrier polyester of claim 1, wherein: the method takes terephthalic acid, ethylene glycol, hydroxyethylated bisphenol A and a fourth monomer as raw materials, adds a polymerization catalyst and an ether inhibitor, improves the intrinsic viscosity of a polyester melt to 0.55-0.70dL/g after esterification and polycondensation, and then cools and granulates the melt to obtain polyester particles; wherein the fourth monomer is selected from at least one of a polyol, a polyacid and a polyanhydride.
6. The method of making a barrier polyester of claim 5, wherein: the fourth monomer is at least one of pyromellitic anhydride, trimellitic anhydride, citric acid, glycerol and pentaerythritol.
7. The method of making a barrier polyester of claim 5, wherein: the addition amount of the hydroxyethylated bisphenol A accounts for 1 to 30 percent of the total mass of the PTA; the addition amount of the fourth monomer accounts for 0.001-1% of the total mass of the PTA.
8. The method of making a barrier polyester of claim 5, wherein: the addition amount of the hydroxyethylated bisphenol A accounts for 1 to 20 percent of the total mass of the PTA; the addition amount of the fourth monomer accounts for 0.001-0.5% of the total mass of the PTA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810709758.0A CN110669211A (en) | 2018-07-02 | 2018-07-02 | Barrier polyester and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810709758.0A CN110669211A (en) | 2018-07-02 | 2018-07-02 | Barrier polyester and preparation method thereof |
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| CN110669211A true CN110669211A (en) | 2020-01-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028817A (en) * | 2022-04-26 | 2022-09-09 | 华润化学材料科技股份有限公司 | Barrier polyester material and preparation method and application thereof |
| CN117599526A (en) * | 2024-01-19 | 2024-02-27 | 江苏兴达净化科技发展有限公司 | Self-cleaning type industrial dust removal filter cylinder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09314783A (en) * | 1996-05-30 | 1997-12-09 | Kuraray Co Ltd | Multilayer structure |
| CN103059276A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Barrier polyester and preparation method thereof |
| CN104181785A (en) * | 2013-05-22 | 2014-12-03 | 佳能株式会社 | Toner for electrostatic image development |
-
2018
- 2018-07-02 CN CN201810709758.0A patent/CN110669211A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09314783A (en) * | 1996-05-30 | 1997-12-09 | Kuraray Co Ltd | Multilayer structure |
| CN103059276A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Barrier polyester and preparation method thereof |
| CN104181785A (en) * | 2013-05-22 | 2014-12-03 | 佳能株式会社 | Toner for electrostatic image development |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028817A (en) * | 2022-04-26 | 2022-09-09 | 华润化学材料科技股份有限公司 | Barrier polyester material and preparation method and application thereof |
| CN115028817B (en) * | 2022-04-26 | 2024-02-02 | 华润化学材料科技股份有限公司 | Barrier polyester material and preparation method and application thereof |
| CN117599526A (en) * | 2024-01-19 | 2024-02-27 | 江苏兴达净化科技发展有限公司 | Self-cleaning type industrial dust removal filter cylinder |
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Application publication date: 20200110 |
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