CN117402335A - Transparent PET material, method for producing same, and PET product - Google Patents
Transparent PET material, method for producing same, and PET product Download PDFInfo
- Publication number
- CN117402335A CN117402335A CN202210933511.3A CN202210933511A CN117402335A CN 117402335 A CN117402335 A CN 117402335A CN 202210933511 A CN202210933511 A CN 202210933511A CN 117402335 A CN117402335 A CN 117402335A
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- China
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- pet material
- pet
- cyclohexanedimethanol
- producing
- isophthalic acid
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 84
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 19
- SLGGJMDAZSEJNG-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;terephthalic acid Chemical compound OCCOCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 SLGGJMDAZSEJNG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 abstract description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 49
- 239000005020 polyethylene terephthalate Substances 0.000 description 49
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 7
- 230000002087 whitening effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 235000008766 Murraya exotica Nutrition 0.000 description 2
- 240000001899 Murraya exotica Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000011141 cosmetic packaging material Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—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
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a transparent PET material, a manufacturing method thereof and a PET product. Terephthalic Acid (PTA) and Ethylene Glycol (EG) are subjected to transesterification to form diethylene glycol terephthalate (BHET). Thereafter, diethylene glycol terephthalate (BHET) was copolymerized with isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) to form a transparent PET material.
Description
Technical Field
The present invention relates to a transparent PET material, a method for producing the same, and a PET product, and more particularly, to a highly transparent non-crystalline transparent PET material, a method for producing the same, and a PET product.
Background
Unmodified polyethylene terephthalate (PET) materials have a melting point of 245 ℃ to 255 ℃, and undergo whitening and white haze phenomena after crystallization, so that they cannot be applied to products with high thickness and high transparency requirements, and also cannot be applied to transparent products with thermal bonding requirements and vacuum molding packaging materials due to their high melting point characteristics.
If the crystallization and melting point of the PET material are to be lowered, isophthalic acid (IPA) and adipic acid may be introduced to adjust the melting point and crystallization of the material. However, although this method helps to reduce the crystallization rate and melting point of PET, it does not completely eliminate its crystallization characteristics, and therefore, whitening phenomenon still exists when it is applied to the injection of high-thickness products. Alternatively, 1, 4-Cyclohexanedimethanol (CHDM) may be introduced into the PET material to provide an amorphous transparent material PETG. However, 1, 4-Cyclohexanedimethanol (CHDM) requires a high introduction ratio and high material cost, and thus has a limit in use.
Based on the above, a PET material which can be applied to products with high thickness, high transparency and thermal adhesion requirement is developed, the phenomena of whitening and white fog are effectively solved, and the material cost is reduced, which is an important subject of the current required research.
Disclosure of Invention
The invention provides a transparent PET material, a manufacturing method thereof and a PET product, which can effectively solve the phenomena of whitening and white fog, reduce the material cost and can be applied to products with high thickness, high transparency and heat bonding requirements.
The method for manufacturing the transparent PET material comprises the following steps. Terephthalic Acid (PTA) and Ethylene Glycol (EG) are subjected to transesterification to form diethylene glycol terephthalate (BHET). Thereafter, diethylene glycol terephthalate (BHET) was copolymerized with isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) to form a transparent PET material.
In one embodiment of the present invention, the copolymerization is carried out under vacuum, and the copolymerization is carried out at a reaction temperature of 240 ℃ to 300 ℃ and a vacuum of 0.05kPa to 0.1kPa using a catalyst (catalyst) comprising a titanium catalyst (titanium isopropoxide, sodium titanate, titania-silica composite, tetrabutoxytitanium, titania-hydrotalcite composite), an antimony catalyst (antimony trioxide, sodium antimonate), a germanium catalyst (germanium oxide) or a combination thereof.
In one embodiment of the present invention, the transesterification reaction is carried out at a temperature of 240 ℃ to 250 ℃ and the ratio of terephthalic acid (PTA) to Ethylene Glycol (EG) is 1:1.15 to 1:1.3.
In one embodiment of the present invention, isophthalic acid (IPA) is added in an amount of 10 to 20mol% and 1, 4-Cyclohexanedimethanol (CHDM) is added in an amount of 10 to 18mol% based on 100mol% of the transparent PET material.
The transparent PET material is prepared by the method for preparing the transparent PET material.
In one embodiment of the present invention, the content of isophthalic acid (IPA) is 10 to 20mol% and the content of 1, 4-Cyclohexanedimethanol (CHDM) is 10 to 18mol% based on 100mol% of the transparent PET material.
The PET product of the invention is made of the transparent PET material.
In one embodiment of the invention, the thickness of the PET product is from 1mm to 10mm.
Based on the above, the present invention provides a method for producing a transparent PET material, in which diethylene glycol terephthalate (BHET) is copolymerized with isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) to form the transparent PET material. By introducing isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) simultaneously, the crystallization characteristics of PET are destroyed, the impact resistance of the material is improved by 1, 4-Cyclohexanedimethanol (CHDM), and the addition amount of 1, 4-Cyclohexanedimethanol (CHDM) is reduced by introducing isophthalic acid (IPA), so that the overall cost is reduced.
Drawings
Without any means for
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are illustrative, and the present disclosure is not limited thereto.
In this document, a range from "one value to another value" is a shorthand way of referring individually to all the values in the range, which are avoided in the specification. Thus, recitation of a particular numerical range includes any numerical value within that range, as well as the smaller numerical range bounded by any numerical value within that range, as if the any numerical value and the smaller numerical range were written in the specification.
The method for manufacturing the transparent PET material comprises the following steps. Terephthalic Acid (PTA) and Ethylene Glycol (EG) are subjected to transesterification to form diethylene glycol terephthalate (BHET). Thereafter, diethylene glycol terephthalate (BHET) was copolymerized with isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) to form a transparent PET material.
In this embodiment, the copolymerization is carried out, for example, in a vacuum state having a vacuum of 0.05kPa to 0.1kPa, and the reaction temperature is, for example, 240 ℃ to 300 ℃, and the catalyst (catalyst) used for the copolymerization may comprise a titanium catalyst (titanium isopropoxide, sodium titanate, titania-silica composite, tetrabutoxytitanium, titania-hydrotalcite composite), an antimony catalyst (antimony trioxide, sodium antimonate), a germanium catalyst (germanium oxide), or a combination thereof. The transesterification reaction is carried out at a reaction temperature of, for example, 240℃to 250℃and a terephthalic acid (PTA) and Ethylene Glycol (EG) ratio of, for example, 1:1.15 to 1:1.3. The amount of isophthalic acid (IPA) added is, for example, 10 to 20mol% and the amount of 1, 4-Cyclohexanedimethanol (CHDM) added is, for example, 10 to 18mol% based on 100mol% of the transparent PET material, and the amount of 1, 4-Cyclohexanedimethanol (CHDM) added can be reduced by introducing isophthalic acid (IPA), thereby reducing the overall cost.
The invention also provides a transparent PET material, which is prepared by the manufacturing method of the transparent PET material. In this example, the content of isophthalic acid (IPA) is, for example, 10mol% to 20mol% and the content of 1, 4-Cyclohexanedimethanol (CHDM) is, for example, 10mol% to 18mol%, based on 100mol% of the transparent PET material.
The invention also provides a transparent PET product which is made of the transparent PET material. In this embodiment, the thickness of the PET product is, for example, 1mm to 10mm.
The method for manufacturing the transparent PET material can effectively solve the phenomena of whitening and white fog by simultaneously introducing isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) to destroy the crystallization property of PET, and the 1, 4-Cyclohexanedimethanol (CHDM) can further improve the impact resistance property of the material. The transparent PET material of the invention can be applied to products with high thickness (10 mm), high transparency and heat bonding requirement, such as cosmetic packaging materials (cosmetic boxes, cosmetic bottles), transparent carrier trays, transparent packaging materials and the like. In addition, the transparent PET material of the invention has no melting point and high impact resistance, and can replace PETG to be applied to the surface layer of a PETG-APET-PETG (GAG) three-layer co-extrusion structure sheet material as an adhesive material of a vacuum forming packaging material.
Hereinafter, the transparent PET material, the method for producing the same, and the PET product according to the present invention will be described in detail with reference to experimental examples. However, the following experimental examples are not intended to limit the present invention.
Experimental example
In order to demonstrate that the manufacturing method according to the present invention can produce transparent PET materials having no melting point and high impact resistance, this experimental example is given below.
The types and proportions of the modified monomers and the physical properties of the modified monomers in examples 1 and 2 and comparative examples 1 to 3 are shown in Table 1 below. Melting point test is a test analysis using Differential Scanning Calorimetry (DSC) at a rate of 10℃per minute. GAG film impact resistance test: the total thickness was 400. Mu.m (G: 40. Mu.m, A: 320. Mu.m, G:40 μm).
As can be seen from Table 1, in examples 1 and 2 of the production method of the present invention, the copolymerization reaction was carried out with isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) simultaneously, and the obtained PET material had a better crystallization inhibiting effect than that of the PET obtained by comparative examples 2 and 3, in which IPA was used alone for the modification, and the introduction of 1, 4-Cyclohexanedimethanol (CHDM) was advantageous for improving the impact resistance. In addition, in comparison with the PETG modified by CHDM alone in comparative example 1, in examples 1 and 2 of the production method of the present invention, the copolymerization reaction is carried out by isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) at the same time, which can achieve the equivalent effect to the PETG in comparative example 1 in terms of transparency and impact resistance, and in examples 1 and 2, the addition amount of 1, 4-Cyclohexanedimethanol (CHDM) can be reduced by introducing isophthalic acid (IPA), thus, the cost can be effectively reduced, and the product competitiveness can be improved.
TABLE 1
In summary, the present invention provides a method for producing a transparent PET material, wherein diethylene glycol terephthalate (BHET) is copolymerized with isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM) to form the transparent PET material. By simultaneously introducing isophthalic acid (IPA) and 1, 4-Cyclohexanedimethanol (CHDM), the crystallization property of PET is destroyed, the phenomena of whitening and white fog are effectively solved, the impact resistance property of the material can be improved by 1, 4-Cyclohexanedimethanol (CHDM), and the addition amount of 1, 4-Cyclohexanedimethanol (CHDM) can be reduced by introducing isophthalic acid (IPA), so that the overall cost is reduced. The transparent PET material of the invention can be applied to products with high thickness (10 mm), high transparency and heat bonding requirement, such as cosmetic packaging materials (cosmetic boxes, cosmetic bottles), transparent carrier trays, transparent packaging materials and the like. In addition, the transparent PET material of the invention has no melting point and high impact resistance, and can replace PETG to be applied to the surface layer of a PETG-APET-PETG (GAG) three-layer co-extrusion structure sheet material as an adhesive material of a vacuum forming packaging material.
Claims (8)
1. A method for producing a PET material, comprising:
transesterification of terephthalic acid and ethylene glycol to form diethylene glycol terephthalate; and
diethylene glycol terephthalate is copolymerized with isophthalic acid and 1, 4-cyclohexanedimethanol to form a PET material.
2. The method for producing PET material according to claim 1, wherein the copolymerization is performed in a vacuum state, the reaction temperature is 240 ℃ to 300 ℃, the vacuum degree is 0.05kPa to 0.1kPa, the catalyst used comprises a titanium catalyst comprising titanium isopropoxide, sodium titanate, a titania-silica composite, titanium tetrabutoxide, a titania-hydrotalcite composite, the antimony catalyst comprises antimony trioxide, sodium antimonate, and the germanium catalyst comprises germanium oxide, or a combination thereof.
3. The method for producing a PET material according to claim 1, wherein the reaction temperature of the transesterification reaction is 240 ℃ to 250 ℃, and the ratio of terephthalic acid to ethylene glycol is 1:1.15 to 1:1.3.
4. The method for producing a PET material according to claim 1, wherein the content of isophthalic acid is 10mol% to 20mol% and the content of 1, 4-cyclohexanedimethanol is 10mol% to 18mol%, based on 100mol% of the PET material.
5. A PET material characterized by being produced by the method for producing a PET material according to any one of claims 1 to 4.
6. The PET material according to claim 5, wherein the content of isophthalic acid is 10 to 20mol% and the content of 1, 4-cyclohexanedimethanol is 10 to 18mol%, based on 100mol% of the PET material.
7. A PET product, characterized in that it is made of the PET material of claim 5 or 6.
8. The PET product of claim 7, wherein the PET product has a thickness of 1mm to 10mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW111125710A TWI803384B (en) | 2022-07-08 | 2022-07-08 | Transparent pet material, manufacturing method thereof, and pet product |
| TW111125710 | 2022-07-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117402335A true CN117402335A (en) | 2024-01-16 |
Family
ID=87424662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210933511.3A Pending CN117402335A (en) | 2022-07-08 | 2022-08-04 | Transparent PET material, method for producing same, and PET product |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN117402335A (en) |
| TW (1) | TWI803384B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7199210B2 (en) * | 2003-11-28 | 2007-04-03 | Futura Polymers, A Division Of Futura Polyesters Limited | Process for the preparation of polyethylene terephthalate (PET) |
| US7799836B2 (en) * | 2006-03-01 | 2010-09-21 | Sabic Innovative Plastics Ip B.V. | Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET) |
| US7211634B1 (en) * | 2006-04-28 | 2007-05-01 | Eastman Chemical Company | Process for the preparation of polyesters containing 1,4-cyclohexanedimethanol |
| CN101525422B (en) * | 2008-03-04 | 2012-06-06 | 东丽纤维研究所（中国）有限公司 | Polyethylene terephthalate-1,4-cyclohexandiol ester for optical thin film |
-
2022
- 2022-07-08 TW TW111125710A patent/TWI803384B/en active
- 2022-08-04 CN CN202210933511.3A patent/CN117402335A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TWI803384B (en) | 2023-05-21 |
| TW202402874A (en) | 2024-01-16 |
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