Modified PETG material and application thereof in preparation of heat-resistant container

Abstract

The invention discloses a modified PETG material and application thereof in preparation of a heat-resistant container, and the modified PETG material comprises the following raw materials by mass: 80-97% of PETG, 0.5-5% of a phthalazinone diphenol monomer, 0.5-5% of a styrene-maleic anhydride copolymer, 1-3% of a compatilizer, and 1-2% of nano-silica. Wherein acid anhydride in the styrene-maleic anhydride copolymer can be subjected to a ring-opening esterification reaction with phenolic hydroxyl groups of the phthalazinone diphenol monomer, and the formed cross-linked polymer can endow the modified PETG material with excellent high-temperature resistance (the thermal deformation temperature reaches 130 DEG C or above) and a rigid characteristic (the Young modulus reaches 3 GPa or above); and the nano silicon dioxide is beneficial to improving the good surface hardness (the surface hardness reaches 2H) of the modified PETG material.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a modified PETG material and its application in the preparation of heat-resistant containers. Background Technology

[0002] PETG is a new type of polyester material, officially known as polyethylene terephthalate-1,4-cyclohexanediethanol ester. PETG possesses excellent transparency (light transmittance exceeding 90%) and gloss; superior toughness and impact resistance (primarily due to the inclusion of the 1,4-cyclohexanediethanol comonomer in its molecular structure), allowing it to maintain its integrity well under impact; good processability; and good chemical resistance (not easily corroded by acids, alkalis, or other chemicals). These characteristics make PETG a promising candidate for widespread application in packaging products such as food, pharmaceuticals, and cosmetics.

[0003] However, PETG also has some drawbacks, such as relatively low hardness and rigidity, making the products made from it prone to deformation when subjected to greater pressure or weight; and relatively low heat resistance, generally around 70-80℃, which limits its application in high-temperature environments.

[0004] Therefore, modifying PETG to improve its high-temperature resistance, rigidity, and hardness is an urgent problem to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide a modified PETG material and its application in the preparation of heat-resistant containers. This modified PETG material has good high-temperature resistance, rigidity, and hardness.

[0006] To achieve the above-mentioned objectives, the technical solution of the present invention is as follows: This invention first provides a modified PETG material, which, by mass percentage, comprises the following raw materials: PETG 80-97%； diaza-naphthyl ketone biphenol monomer 0.5-5%； Styrene-maleic anhydride copolymer 0.5-5%； compatibilizer 1-3%； Nano silica 1-2%。 The modified PETG material of this invention uses PETG as a base material and adds diazanaphthol biphenyl monomer, styrene-maleic anhydride copolymer and nano-silica. Among them, the anhydride in the styrene-maleic anhydride copolymer can undergo a ring-opening esterification reaction with the phenolic hydroxyl group of the diazanaphthol biphenyl monomer. The resulting cross-linked polymer can endow the modified PETG material with excellent high-temperature resistance (heat distortion temperature of over 130°C) and rigidity characteristics (Young's modulus of over 3 GPa). Nano-silica is beneficial to improving the good hardness of the modified PETG material (Shore hardness of D90).

[0007] Preferably, in the modified PETG material described above, the proportion of 1,4-cyclohexanediethanol monomer in the PETG is 30-40%. An appropriate proportion of 1,4-cyclohexanediethanol monomer helps ensure that the modified PETG material maintains high transparency, suitable toughness, and impact strength.

[0008] Preferably, in the modified PETG material described above, the structural formula of the diazanaphthone biphenol monomer is: ; In the formula, R1, R2, R3, and R4 are independently selected from hydrogen, halogen, alkyl, or phenyl.

[0009] As a further preferred embodiment, in the above-mentioned modified PETG material, the diazanaphthone biphenol monomer is 4-(4-hydroxy)phenyl-2,3-diazanaphth-1-one, with the following structural formula: .

[0010] Preferably, in the modified PETG material described above, the styrene-maleic anhydride copolymer contains 20-30% maleic anhydride by mass. The weight-average molecular weight of the styrene-maleic anhydride copolymer is between 2000 and 8000 Da.

[0011] Controlling the maleic anhydride content in the styrene-maleic anhydride copolymer within a suitable range is beneficial for its full reaction with the diazanaphthone biphenol monomer.

[0012] Preferably, in the modified PETG material described above, the compatibilizer includes EVA or SEBS.

[0013] As a further preferred option, the modified PETG material described above, by weight percentage, comprises the following raw materials: PETG 91.5%； diaza-naphthyl ketone biphenol monomer 1.5%； Styrene-maleic anhydride copolymer 3%； compatibilizer 2%； Nano silica 2%。 The present invention also provides a method for preparing the above-mentioned modified PETG material, the method comprising the following steps: (1) Under an inert atmosphere, diazanaphthone biphenol monomer, styrene-maleic anhydride copolymer, catalyst and solvent are mixed in a predetermined mass ratio and reacted at 120-180℃ to obtain cross-linked polymer; The catalyst can be a tertiary amine (such as triethylamine, tributylamine, N,N-dimethylbenzylamine, 4-dimethylaminopyridine, etc.) or a metal carboxylate (such as zinc acetate, sodium acetate, etc.); the solvent can be N-methylpyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, etc. (2) The crosslinked polymer, PETG, compatibilizer and nano silica are mixed in a preset mass ratio and melt-extruded to obtain the modified PETG material.

[0014] The present invention also provides the application of the above-mentioned modified PETG material in the preparation of heat-resistant containers.

[0015] Compared with the prior art, the beneficial effects of the present invention are reflected in: The modified PETG material of this invention uses PETG as a base material and adds diazanaphthol biphenyl monomer, styrene-maleic anhydride copolymer and nano-silica. Among them, the anhydride in the styrene-maleic anhydride copolymer can undergo a ring-opening esterification reaction with the phenolic hydroxyl group of the diazanaphthol biphenyl monomer. The resulting cross-linked polymer can endow the modified PETG material with excellent high-temperature resistance (heat distortion temperature of over 130°C) and rigidity characteristics (Young's modulus of over 3 GPa). Nano-silica is beneficial to improving the good hardness of the modified PETG material (Shore hardness of D90). Attached Figure Description

[0016] Figure 1 This is a test report on the dinner plates made using the modified PETG material of this invention. Detailed Implementation

[0017] The following examples illustrate the technical solution of the present invention in a more detailed manner.

[0018] Example 1 This embodiment describes a modified PETG material, comprising the following raw materials: PETG (30% of 1,4-cyclohexanediethanol) 91.5%； 4-(4-hydroxy)phenyl-2,3-diazanaphth-1-one 1.5%； Styrene-maleic anhydride copolymer (number average molecular weight 6000 Da, maleic anhydride mass percentage 30%) 3%； SEBS 2%； Nano silica 2%。 The preparation method of this modified PETG material includes the following steps: (1) Under an inert atmosphere, diazanaphthone biphenol monomer, styrene-maleic anhydride copolymer, catalyst and solvent are mixed in a predetermined mass ratio and reacted at 160°C to obtain cross-linked polymer; Specifically, under a nitrogen protective atmosphere, 1.5 g of dried 4-(4-hydroxy)phenyl-2,3-diazanaphth-1-one, 3 g of styrene-maleic anhydride copolymer (number average molecular weight 6000 Da, maleic anhydride mass percentage 30%), 0.09 g of triethylamine, and 250 mL of N,N-dimethylacetamide were added to a reaction vessel equipped with a stirrer. After stirring evenly, the temperature was raised to 160℃ and the reaction was carried out for 20 h. After the reaction was completed, the product was washed and dried at 80℃ to obtain the crosslinked polymer. (2) The crosslinked polymer, PETG, SEBS and nano silica are mixed in a preset mass ratio, melt extruded and granulated to obtain the modified PETG material of this embodiment.

[0019] Example 2 This embodiment describes a modified PETG material, comprising the following raw materials: PETG (30% of 1,4-cyclohexanediethanol) 96.5%； 4-(4-hydroxy)phenyl-2,3-diazanaphth-1-one 0.5%； Styrene-maleic anhydride copolymer (number average molecular weight 6000 Da, maleic anhydride mass percentage 30%) 1%； SEBS 1%； Nano silica 1%。 The preparation method of this modified PETG material is the same as that in Example 1.

[0020] Example 3 This embodiment describes a modified PETG material, comprising the following raw materials: PETG (30% of 1,4-cyclohexanediethanol) 88.5%； 4-(4-hydroxy)phenyl-2,3-diazanaphth-1-one 2.5%； Styrene-maleic anhydride copolymer (number average molecular weight 6000 Da, maleic anhydride mass percentage 30%) 5%； SEBS 3%； Nano silica 1%。 The preparation method of this modified PETG material is the same as that in Example 1.

[0021] Comparative Example 1 This comparative example describes a modified PETG material, comprising the following raw materials: PETG (30% of 1,4-cyclohexanediethanol) 93.5%； Styrene-maleic anhydride copolymer (number average molecular weight 6000 Da, maleic anhydride mass percentage 30%) 4.5%； SEBS 2%。 The modified PETG material is prepared by mixing PETG, styrene-maleic anhydride copolymer (number average molecular weight 6000 Da, maleic anhydride mass percentage 30%) and SEBS in a preset mass ratio, followed by melt extrusion and granulation to obtain the modified PETG material of this comparative example.

[0022] The modified PETG materials from Examples 1-3 and Comparative Example 1 were used to test various properties of the materials, and the results are shown in Table 1. A plate made from the modified PETG material of Example 1 was submitted for testing; the test report is available here. Figure 1 .

[0023] Table 1 Test Project Standard Method Example 1 Example 2 Example 3 Comparative Example 1 Heat distortion temperature (HDT) ISO 75-2 180℃ 160℃ 170℃ 100℃ Long-term operating temperature (1000h) ISO 2578 150℃ 120℃ 130℃ 70℃ Young's modulus ISO 527-2 3.5 GPa 3 GPa 3.2 GPa 2.8 GPa Shore hardness ASTM D2240 D90 D90 D90 D80 Wear rate ASTM G99 0.06 mm³ / N·m 0.05 mm³ / N·m 0.06 mm³ / N·m 0.08 mm³ / N·m Light transmittance ASTM D1003 90% 90% 89% 90% Impact resistance ASTM D256-24 <![CDATA[11 KJ / m 2 ]]> <![CDATA[12 KJ / m 2 ]]> <![CDATA[10 KJ / m 2 ]]> <![CDATA[14 KJ / m 2 ]]> Yellowing index (ΔE) ASTM D1925 1.5 1.6 1.6 2.0 From the test results in Table 1 and Figure 1 The test report shows that the modified PETG material of this invention not only has excellent high temperature resistance, deformation resistance, hardness, and yellowing resistance, but also retains the excellent light transmittance and impact resistance of PETG.

Claims

1. A modified PETG material, characterized in that, By weight percentage, it includes the following raw materials: PETG 80-97%; 0.5-5% of diazanaphthol biphenol monomer; 0.5-5% styrene-maleic anhydride copolymer; Compatibilizer 1-3%; Nano-silica 1-2%.

2. The modified PETG material as described in claim 1, characterized in that, The 1,4-cyclohexanediethanol monomer in the PETG contains 30-40%.

3. The modified PETG material as described in claim 1, characterized in that, The structural formula of the diazanaphthone biphenol monomer is as follows: ； In the formula, R1, R2, R3, and R4 are independently selected from hydrogen, halogen, alkyl, or phenyl.

4. The modified PETG material as described in claim 1, characterized in that, The diazanaphthone biphenol monomer is 4-(4-hydroxy)phenyl-2,3-diazanaphth-1-one.

5. The modified PETG material as described in claim 1, characterized in that, In the styrene-maleic anhydride copolymer, the mass percentage of maleic anhydride is 20-30%.

6. The modified PETG material as described in claim 1, characterized in that, The weight-average molecular weight of the styrene-maleic anhydride copolymer is between 2000 and 8000 Da.

7. The modified PETG material as described in claim 1, characterized in that, The compatibilizers mentioned include EVA or SEBS.

8. The modified PETG material as described in claim 1, characterized in that, By weight percentage, it includes the following raw materials: PETG 91.5%; 1.5% diazanaphthone biphenol monomer; 3% styrene-maleic anhydride copolymer; Compatibilizer 2%; 2% nano-silica.

9. The method for preparing the modified PETG material according to any one of claims 1-8, characterized in that, Includes the following steps: (1) Under an inert atmosphere, diazanaphthone biphenol monomer, styrene-maleic anhydride copolymer, catalyst and solvent are mixed in a predetermined mass ratio and reacted at 120-180℃ to obtain cross-linked polymer; (2) The crosslinked polymer, PETG, compatibilizer and nano silica are mixed in a preset mass ratio and melt-extruded to obtain the modified PETG material.

10. The use of the modified PETG material as described in any one of claims 1-8 in the preparation of heat-resistant containers.

Images