PET (Polyethylene Terephthalate) material as well as preparation method and application thereof

Abstract

The invention relates to a PET material as well as a preparation method and application thereof. The PET material is prepared from the following components in parts by weight: 75 to 95 parts of PET resin, 2 to 10 parts of PCTG, 3 to 8 parts of flexibilizer, 2 to 5 parts of glass flake and 0.2 to 1 part of poly alkyl glycol dibenzoate. The toughening agent comprises an ethylene-methacrylic acid copolymer and / or ethylene-butyl acrylate. According to the PET material provided by the invention, the PET resin and the PCTG are taken as base materials, the ethylene-methacrylic acid copolymer and / or ethylene-butyl acrylate are / is taken as a toughening unit, the glass flakes are taken as a reinforcing framework, and the poly alkyl glycol dibenzoate is taken as a crystallization inhibitor, so that the PET material has good transparency through the design of all the components; meanwhile, the PET material has good strength and rigidity and can well meet the high-performance requirements of the fields of low-temperature food packaging industry and the like on the PET material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a PET material and a preparation method and application thereof. BACKGROUND

[0002] Polyethylene terephthalate (PET) has many advantages such as high strength, good color and low price. In addition, unlike amorphous materials such as polycarbonate, PET has a relatively soft molecular chain and good solvent resistance, and is not prone to cracking due to solvent induction during use, and is a high polymer polyester resin widely used. However, it is prone to crystallization and fogging during processing, resulting in reduced transparency, and the product has poor toughness and is prone to brittle fracture at low temperature.

[0003] CN107841097A discloses a halogen-free flame-retardant PET composite material for transparent film and a preparation method. The halogen-free flame-retardant PET composite material comprises the following formula components in percentage by weight: PET resin 75-85%, organic flame retardant 10-20%, thermal stabilizer 0.1-0.4%, glass fiber 0.7-1.5%, nano-montmorillonite 1.5-3%, antimony trioxide 2-4%, antioxidant 0.1-0.4%, compatibilizer 0.5-1.5%, dispersant 0.1-0.5%. CN102367326A discloses an anti-fog transparent PET color master batch and a preparation method thereof. The color master batch is prepared from the following components in percentage by weight: carrier 65~85%, color powder 0.1~10%, dispersant 0.1~3%, processing aid 0.1~2%, nucleating agent 12~20%, the dispersant being polar wax, the processing aid being turpentine oil, and the nucleating agent being salin resin. However, it is difficult to obtain high transparency of the existing PET material under the condition of adding a large amount of flame retardant, compatibilizer or nucleating agent.

[0004] Therefore, there is an urgent need to provide a PET material with good transparency, high strength and good rigidity. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a PET material and a preparation method and application thereof. Through the design of various components and the mutual cooperation between the components, the PET material has excellent transparency, excellent strength and excellent rigidity.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a PET material, which comprises the following components in parts by weight:

[0008] PET resin 75~95 parts by weight

[0009] PCTG 2~10 parts by weight

[0010] Toughening agent 3~8 parts by weight

[0011] Glass flake 2~5 parts by weight

[0012] Polyalkylene glycol dibenzoate 0.2~1 parts by weight

[0013] The toughening agent includes ethylene-methacrylic acid copolymer (EMA) and / or ethylene-butyl acrylate (EBA).

[0014] The present application designs a high-transparency toughened and reinforced PET material through a large number of researches, which takes PET resin and PCTG as base materials, ethylene-methacrylic acid copolymer and / or ethylene-butyl acrylate as toughening units, glass flake as a reinforcing framework, and polyalkylene glycol dibenzoate as a crystallization inhibitor. The PET material has good transparency, good strength and rigidity, and can well meet the requirements of the low-temperature food packaging industry on the material.

[0015] The PET resin is 75~95 parts by weight, for example, can be 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight, 89 parts by weight, 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, etc.

[0016] In the present application, the mass percentage content of PET resin in the PET material is ≥75%.

[0017] The PCTG is 2~10 parts by weight, for example, can be 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, etc.

[0018] The toughening agent is 3~8 parts by weight, for example, can be 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, etc.

[0019] The glass flake is 2~5 parts by weight, for example, can be 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.8 parts by weight, etc.

[0020] The polyalkylene glycol dibenzoate is 0.2 to 1 parts by weight, for example, it can be 0.22 parts by weight, 0.25 parts by weight, 0.28 parts by weight, 0.3 parts by weight, 0.32 parts by weight, 0.35 parts by weight, 0.38 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.48 parts by weight, 0.5 parts by weight, 0.52 parts by weight, 0.55 parts by weight, 0.58 parts by weight, 0.6 parts by weight, 0.62 parts by weight, 0.65 parts by weight, 0.68 parts by weight, 0.7 parts by weight, 0.72 parts by weight, 0.75 parts by weight, 0.78 parts by weight, 0.8 parts by weight, 0.82 parts by weight, 0.85 parts by weight, 0.88 parts by weight, 0.9 parts by weight, 0.92 parts by weight, 0.95 parts by weight, 0.98 parts by weight, etc.

[0021] The following is a preferred technical solution of the present application, but not as a restriction on the technical solutions provided by the present application, through the following preferred technical solution, the purpose and beneficial effects of the present application can be better achieved and realized.

[0022] As a preferred technical solution, the intrinsic viscosity of the PET resin is 0.78 to 0.90 dL / g, for example, it can be 0.79 dL / g, 0.8 dL / g, 0.81 dL / g, 0.82 dL / g, 0.83 dL / g, 0.84 dL / g, 0.85 dL / g, 0.86 dL / g, 0.87 dL / g, 0.88 dL / g, 0.89 dL / g, etc.

[0023] In the present application, the intrinsic viscosity of the PET resin is measured according to the method A in GB / T 14190-2008 standard; the specific method is: the outflow time of the solvent (phenol and tetrachloroethane are prepared according to the mass ratio of 1:1) at 25℃ and the concentration of 0.005g / mL of PET solution is measured, and the intrinsic viscosity is calculated according to the measured outflow time and the concentration of the sample solution.

[0024] Preferably, the melting point of the PET resin is 241-255℃, for example, it can be 242℃, 243℃, 244℃, 245℃, 246℃, 247℃, 248℃, 248.5℃, 249℃, 249.5℃, 250℃, 250.5℃, 251℃, 251.5℃, 252℃, 252.5℃, 253℃, 253.5℃, 254℃, 255℃, etc., further preferably 249-253℃.

[0025] In the present application, the melting point of the PET resin is measured by DSC once heating curve according to GB / T 19466.3-2004 standard.

[0026] Preferably, the PCTG has a Charpy notched impact strength at -30°C of 9-30 kJ / m 2 , for example 9.1 kJ / m 2 , 9.5 kJ / m 2 , 10 kJ / m 2 , 10.5 kJ / m 2 , 11 kJ / m 2 , 11.5 kJ / m 2 , 12 kJ / m 2 , 12.5 kJ / m 2 , 13 kJ / m 2 , 13.5 kJ / m 2 , 14 kJ / m 2 , 14.5 kJ / m 2 , 15 kJ / m 2 , 16 kJ / m 2 , 18 kJ / m 2 , 20 kJ / m 2 , 22 kJ / m 2 , 24 kJ / m 2 , 26 kJ / m 2 , 28 kJ / m 2 , etc.

[0027] In the present application, the Charpy notched impact strength of the PCTG is obtained according to the ASTM D256-2010 standard test.

[0028] Preferably, the PCTG has a melt index at 250°C under a load of 2.16 kg of 10-50 g / 10 min, for example 12 g / 10 min, 15 g / 10 min, 20 g / 10 min, 22 g / 10 min, 25 g / 10 min, 30 g / 10 min, 32 g / 10 min, 35 g / 10 min, 40 g / 10 min, 42 g / 10 min, 45 g / 10 min, etc.

[0029] The melt index of the PCTG is obtained according to the ISO 1133-1:2022 test.

[0030] In the present invention, the glass flake means a glass fragment with an average thickness of 0.35-7 μm, such as 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, etc.; preferably, the average thickness of the glass flake is 1-7 μm; and / or, the average particle size of the glass flake is 12-800 μm, such as 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, etc.; preferably, the average particle size of the glass flake is 100-600 μm.

[0031] In the present invention, the average thickness of the glass flake is tested by an electron microscope (FE-1050, JEOL Ltd.); and the average particle size of the glass flake is tested by a laser particle size analyzer (Bettersize 2000, Bettersize Instruments Co., Ltd.).

[0032] Preferably, the polyalkylene glycol dibenzoate has a structure as shown in Formula I:

[0033] Formula I.

[0034] wherein R is selected from any one of C2-C4 (such as C2, C3, C4) linear or branched alkylene.

[0035] n is an integer selected from 2-4, such as 2, 3 or 4.

[0036] Preferably, the polyalkylene glycol dibenzoate includes any one of dipropylene glycol dibenzoate, diethylene glycol dibenzoate or triethylene glycol dibenzoate or a combination of at least two thereof.

[0037] Preferably, the PET material further includes a color stabilizer.

[0038] Preferably, the color stabilizer includes any one of a phosphite stabilizer, a hindered phenol stabilizer or an amide stabilizer or a combination of at least two thereof.

[0039] Preferably, the phosphite stabilizer includes tris(2,4-di-tert-butylphenyl) phosphite and / or bis(2,4-dicumylphenyl) pentaerythrityl-diphosphite.

[0040] Preferably, the hindered phenolic stabilizer includes tetrakis [β-(3,5-di-tert-butyl-4- hydroxyphenyl) propionic acid] pentaerythritol ester and / or β-(3,5-di-tert-butyl-4- hydroxyphenyl) propionic acid n-octadecyl ester.

[0041] Preferably, the amide stabilizer includes any one of o-aminobenzamide, allantoin or N,N'-1,6-hexanediylbis(2-amino-benzamide), or a combination of at least two thereof.

[0042] Preferably, the color stabilizer in the PET material is 0.02-0.1 parts by weight, for example, can be 0.025 parts by weight, 0.03 parts by weight, 0.035 parts by weight, 0.04 parts by weight, 0.045 parts by weight, 0.05 parts by weight, 0.055 parts by weight, 0.06 parts by weight, 0.065 parts by weight, 0.07 parts by weight, 0.075 parts by weight, 0.08 parts by weight, 0.085 parts by weight, 0.09 parts by weight, 0.095 parts by weight, etc.

[0043] In a second aspect, the present application provides a preparation method of the PET material according to the first aspect, the preparation method comprising:

[0044] The components are melt blended according to the parts by weight and then extruded to obtain the PET material.

[0045] Preferably, the preparation method specifically comprises the following steps:

[0046] (1) mixing the components other than the glass flake according to the parts by weight to obtain a first mixture;

[0047] (2) melt blending the first mixture and the glass flake and then extruding to obtain the PET material.

[0048] Preferably, the melt extrusion is performed in a twin-screw extruder.

[0049] Preferably, the temperature of the first zone of the twin-screw extruder is 30-200°C, the temperature of the second zone is 220-260°C, the temperature of the third zone is 220-260°C, the temperature of the fourth zone is 200-240°C, the temperature of the fifth zone is 170-240°C, the temperature of the sixth zone is 170-230°C, the temperature of the seventh zone is 170-230°C, the temperature of the eighth zone is 170-230°C, the temperature of the ninth zone is 170-240°C, the temperature of the die is 210-250°C, the residence time is 1-3 min, and the rotation speed of the main machine is 300-500 rpm.

[0050] Preferably, the extrusion is further followed by a step of granulation.

[0051] In a third aspect, the present application provides a use of the PET material according to the first aspect in a food packaging box or a food and beverage bottle.

[0052] The numerical ranges recited herein are inclusive of the endpoints and of any point or range of points within the aforementioned ranges. In this disclosure, the use of "or" means "and" in the absence of contradictory context. In this disclosure, the use of "an" means "one or more". In this disclosure, the use of "at least one of X, Y and Z" means X or Y or Z or any combination thereof. In this disclosure, the use of "one or more of X, Y and Z" means that one or more X or one or more Y or one or more Z or any combination thereof. In this disclosure, the use of "one or more of X, Y, or Z" means that one or more X or one or more Y or one or more Z or any combination thereof. In this disclosure, the use of "X, Y and / or Z" means X or Y or Z or any combination thereof.

[0053] Compared with the prior art, the present application has the following beneficial effects:

[0054] The present application provides a high-transparency toughened and reinforced PET material, which takes PET resin and PCTG as base material, EMA and / or EBA as toughening unit, glass flake as reinforcing framework, and polyalkylene glycol dibenzoate as crystallization inhibitor. Through the design of various components, the high-performance requirements of PET material in the field of low-temperature food packaging industry and the like can be well met. DETAILED DESCRIPTION

[0055] In order to facilitate the understanding of the present application, the present application lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0056] In the following examples and comparative examples, some components are from the following sources:

[0057] (1) PET resin

[0058] PET resin-1, PET BG801, 0.80 dL / g, melting point 253℃, Sinopec Yizheng Chemical Fibre Co., Ltd.;

[0059] PET resin-2, PET BG85, 0.87 dL / g, melting point 249℃, Sinopec Yizheng Chemical Fibre Co., Ltd.;

[0060] PET resin-3, PET CR-8818, 0.81 dL / g, melting point 241℃, Huarun Chemical Material Technology Co., Ltd.;

[0061] The intrinsic viscosity of the above PET resin is measured according to the method A in the standard GB / T 14190-2008. The specific method is as follows: the outflow time of the PET solution with a concentration of 0.005 g / mL in a solvent (phenol and tetrachloroethane are prepared according to a mass ratio of 1:1) at 25℃ is measured, and the intrinsic viscosity is calculated according to the measured outflow time and the concentration of the sample solution.

[0062] The melting point of the above PET resin is measured by DSC one-time heating curve according to the standard GB / T 19466.3-2004;

[0063] (2) PCTG

[0064] PCTG-1, DN011, Eastman, Charpy notched impact strength of 10 kJ / m at -30°C 2 ;

[0065] PCTG-2, Eastar® GN007, Eastman, Charpy notched impact strength of 30 kJ / m at -30°C 2 ;

[0066] The Charpy notched impact strength of the above PCTG was obtained according to the standard test of ASTM D256-2010;

[0067] (3) Toughener

[0068] EMA, Elvaloy AC 1125, Dow Chemical, USA;

[0069] EBA, Elvaloy AC 34035, Dow Chemical, USA;

[0070] POE-GMA type toughener, SOG-03, Jia Yirong Polymer (Shanghai) Co., Ltd.;

[0071] (4) Glass flake

[0072] Glass flake-1, REFG-101, Nippon Sheet Glass Co., Ltd., average thickness of 5 pm, average particle size of 600 pm;

[0073] Glass flake-2, REFG-301, Nippon Sheet Glass Co., Ltd., average thickness of 5 pm, average particle size of 160 pm;

[0074] Glass flake-3, MEG160FY-M01, Nippon Sheet Glass Co., Ltd., average thickness of 0.7 pm, average particle size of 160 pm;

[0075] Glass flake-4, MEC140FY-01, Nippon Sheet Glass Co., Ltd., average thickness of 0.35 pm, average particle size of 160 pm;

[0076] Glass flake-5, REFG-015, Nippon Sheet Glass Co., Ltd., average thickness of 5 pm, average particle size of 12 pm;

[0077] The average thickness of the above glass flake was obtained by electron microscope (Jianrenak Detection Technology Co., Ltd., FE-1050); the average particle size of the glass flake was obtained by laser particle size analyzer (Dandong Better Instrument Co., Ltd., Bettersize 2000);

[0078] (5) Polyalkylene glycol dibenzoate

[0079] Dipropylene glycol dibenzoate, Wuhan Yikede Fine Chemical Co., Ltd.;

[0080] Diethylene glycol dibenzoate, Wuhan Yikede Fine Chemical Co., Ltd.;

[0081] Triethylene glycol dibenzoate, Wuhan Yikede Fine Chemical Co., Ltd.;

[0082] (6) Neopentyl glycol dibenzoate, Wuhan Yikede Fine Chemical Co., Ltd.;

[0083] (7) Color stabilizer, antioxidant 168, BASF, Germany.

[0084] Example 1

[0085] A PET material, its raw material components and their amounts are shown in Table 1; the preparation method of the PET material comprises:

[0086] (1) The PET resin, PCTG, toughening agent, polyalkylene glycol dibenzoate and color stabilizer are first mixed to obtain a first mixture;

[0087] (2) The first mixture is added to a twin-screw extruder, and glass flake is added in the form of side feeding; the temperature of the first zone of the twin-screw extruder is 50°C, the temperature of the second zone is 240°C, the temperature of the third zone is 260°C, the temperature of the fourth zone is 220°C, the temperature of the fifth zone is 200°C, the temperature of the sixth zone is 200°C, the temperature of the seventh zone is 200°C, the temperature of the eighth zone is 200°C, the temperature of the ninth zone is 220°C, the temperature of the die head is 240°C, the residence time is 2 min, and the main machine speed is 450 rpm; the above components are melt blended and then extruded and pelletized to obtain the PET material.

[0088] Examples 2-9 and Comparative Examples 1-5

[0089] A PET material, which is different from Example 1 only in the type and / or amount (parts by weight) of the components, is shown in Table 1 and Table 2, wherein " / " represents that the substance is not used; the preparation method of the PET material provided in Examples 2-9 and Comparative Examples 1-5 is referred to Example 1.

[0090] Table 1

[0091]

[0092]

[0093] Table 2

[0094]

[0095] Performance test

[0096] (1) Low temperature impact strength: tested according to ISO 180:2023 standard, sample thickness is 4mm, test temperature is -30℃;

[0097] (2) Bending modulus: tested according to ISO 178:2019 standard A method;

[0098] (3) Visible light transmittance: measured according to ISO 13468-1:2019 standard under 2mm thickness.

[0099] The PET material provided by the above examples and comparative examples is tested according to the above method, and the test results are shown in Table 3:

[0100] Table 3

[0101]

[0102] From the data in Table 3, it can be seen that by designing various components and mutual cooperation between components, the PET material has excellent transparency, and at the same time has excellent strength and rigidity, wherein the low temperature impact strength is ≥5kJ / m 2 , the bending modulus is ≥2300MPa, and the visible light transmittance is ≥89%.

[0103] From Comparative Example 1, it can be seen that using neopentyl glycol dibenzoate to replace polyalkylene glycol dibenzoate as a crystallization inhibitor, the light transmittance of the PET material is significantly reduced.

[0104] In Comparative Example 2, the amount of PCTG is too much, which causes the bending modulus of the PET material to decrease significantly, and the material becomes soft.

[0105] In Comparative Example 3, the amount of polyalkylene glycol dibenzoate is too much, which causes the bending modulus of the PET material to decrease.

[0106] In Comparative Example 4, polyalkylene glycol dibenzoate is not used, which causes the light transmittance of the PET material to decrease.

[0107] In Comparative Example 5, POE-GMA type toughening agent is selected as the toughening agent, and compared with ethylene-methacrylic acid copolymer and ethylene-butyl acrylate, the POE-GMA type toughening agent as the toughening agent causes the light transmittance of the PET material to decrease significantly.

[0108] The applicant states that the PET material, the preparation method and the application of the present application are illustrated by the above-mentioned examples, but the present application is not limited to the above-mentioned examples, that is, it does not mean that the present application must rely on the above-mentioned examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A PET material, characterized in that, The PET material comprises the following components by weight parts: PET resin 75-95 weight parts PCTG 2-10 weight parts Toughening agent 3-8 weight parts Glass flake 2-5 weight parts Polyalkylene glycol dibenzoate 0.2-1 weight parts The toughening agent comprises ethylene-methacrylic acid copolymer and / or ethylene-butyl acrylate.

2. The PET material according to claim 1, characterized in that, The PET resin has an intrinsic viscosity of 0.78-0.90 dL / g.

3. The PET material according to claim 1, characterized in that, The PET resin has a melting point of 241-255℃, further preferably 249-253℃.

4. The PET material according to claim 1, characterized in that, The PCTG has a notched Izod impact strength at -30°C of 9 to 30 kJ / m 2 .

5. The PET material according to claim 1, characterized in that, The glass flake has an average thickness of 0.35-7 μm; preferably, the glass flake has an average thickness of 1-7 μm; and / or, the glass flake has an average particle size of 12-800 μm; preferably, the glass flake has an average particle size of 100-600 μm.

6. The PET material according to claim 1, characterized in that, The polyalkylene glycol dibenzoate has a structure as shown in Formula I: Formula I; wherein, R is selected from any one of C2-C4 linear or branched alkylene; n is an integer selected from 2-4; Preferably, the polyalkylene glycol dibenzoate comprises any one or a combination of at least two of dipropylene glycol dibenzoate, diethylene glycol dibenzoate or triethylene glycol dibenzoate.

7. The PET material according to claim 1, characterized in that, The PET material further comprises a color stabilizer; Preferably, the color stabilizer comprises any one or a combination of at least two of phosphite stabilizer, hindered phenol stabilizer or amide stabilizer; Preferably, the color stabilizer in the PET material is 0.02-0.1 weight parts.

8. A process for the preparation of a PET material according to any one of claims 1 to 7, characterized in that, The preparation method comprises: The components are melt-blended according to weight parts and then extruded to obtain the PET material.

9. The production method according to claim 8, characterized by, The preparation method specifically comprises the following steps: (1) mixing the components other than the glass flake according to weight parts to obtain a first mixture; (2) melt-blending the first mixture and the glass flake and then extruding to obtain the PET material; Preferably, the extruding further comprises a step of granulation.

10. Use of the PET material according to any one of claims 1-7 in food packaging boxes or food and beverage bottles.

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