High gas barrier composite PET material and preparation method and application thereof

Abstract

The application discloses a kind of high gas barrier composite PET materials and preparation method and application thereof, it is related to high polymer material technical field, high gas barrier composite PET material includes: PET resin, PA-MXD6, glass flake, alkyl polyol.The high gas barrier composite PET material of the application, with PET resin as matrix, add PA-MXD6 fill the intermolecular gap of PET resin, form more dense composite material structure, reduce the penetration channel of gas molecule, to improve the overall gas barrier property.Add specific amount of alkyl polyol as third monomer simultaneously, form gas barrier micro network in material, compound thin-walled structure glass flake as gas barrier medium, to improve the gas barrier property and mechanical strength of material, and reduce the loss of light transmittance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular material, more particularly, to a high gas barrier composite PET material, a preparation method and application thereof. BACKGROUND

[0002] Polyethylene terephthalate (PET) resin has many advantages such as high strength, high transparency and low price, and is a high molecular polyester resin widely used, especially in the field of film and beverage bottles. However, compared with inorganic materials such as glass, the gas barrier property of pure PET material is slightly insufficient, and it is difficult to meet the requirements of beer, yogurt and other organic beverages on gas barrier property.

[0003] The existing methods for improving the gas barrier property of PET include multilayer composite method, surface spraying method and single-layer blending modification method. Although the PET bottle developed by the multilayer composite method can meet the requirements of beverages such as beer on barrier property, the multilayer structure is prone to delamination between layers, and the technical requirements for production equipment are also high, which requires additional equipment investment. Moreover, regardless of which barrier material is used for the interlayer, there is a problem of difficult material recycling due to the coexistence of multiple layers of materials. The PET bottle produced by the surface spraying method has good transparency and is easy to recycle. However, since the coating is very thin, the coating is prone to cracking and delamination when the bottle is subjected to external impact, which affects its barrier property. Moreover, this technology requires additional surface coating equipment, resulting in high product cost. When the PET bottle prepared by the single-layer blending modification method improves the gas barrier property, the light transmittance and mechanical strength of the bottle are significantly reduced. SUMMARY

[0004] The purpose of the present application is to overcome the defects and deficiencies of the existing PET material, and to provide a composite PET material that can simultaneously have light transmittance and gas barrier property.

[0005] Another purpose of the present application is to provide a preparation method of a high gas barrier composite PET material.

[0006] Another purpose of the present application is to provide the application of a high gas barrier composite PET material in the preparation of packaging film or beverage bottle.

[0007] The above-mentioned purposes of the present application are achieved by the following technical solutions:

[0008] The present application protects a high gas barrier composite PET material, which comprises the following components by mass:

[0009]

[0010]

[0011] Preferably, the PET accounts for a minimum mass fraction of 88% of the composite PET material.

[0012] The high gas barrier composite PET material of the present application, with PET resin as the matrix, the addition of PA-MXD6 can fill the interstitial structure of PET resin microcrystalline, form a more dense composite material structure, reduce the penetration channel of gas molecules, thereby improving the overall gas barrier properties. At the same time, add a specific amount of alkyl polyol as the third monomer, form a gas barrier micro-network in the material, and compound thin-walled glass flake structure as a gas barrier medium, thereby improving the gas barrier property and mechanical strength of the material, and reducing the loss of light transmission.

[0013] In some embodiments, the PET resin content that can achieve the purpose of the present application can be 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts.

[0014] In some embodiments, the intrinsic viscosity of the PET resin is 0.5-1 dl / g; preferably, the intrinsic viscosity is 0.7-0.9 dl / g.

[0015] Preferably, the melting point of the PET resin determined by DSC first heating curve is ≥ 248℃.

[0016] In some embodiments, the PA-MXD6 content that can achieve the purpose of the present application can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts.

[0017] In some embodiments, the relative viscosity of the PA-MXD6 is 2.0-2.8, which is measured by Ubbelohde viscometer with 96% concentrated sulfuric acid, and the test standard is ISO 307:2007. Preferably, the relative viscosity is 2.0-2.5.

[0018] In some embodiments, the alkyl polyol is a C3-C10 alkyl polyol; preferably a C3-C5 alkyl polyol,

[0019] In some embodiments, the alkyl polyol is one or more of dihydric alcohol or trihydric alcohol.

[0020] In some embodiments, the alkyl polyol is one or more of glycerol, 1,2,3-butanetriol, 1,2,5-pentanetriol or 1,2-propanediol.

[0021] In some embodiments, the glass flake content that can achieve the purpose of the present application can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts.

[0022] In some embodiments, the glass flake has an average thickness of ≤ 6 μm and an average particle size of ≥ 100 μm; and 45-300 μm particle size accounts for 80% or more, specifically 85% or more, 90% or more. Preferably, the glass flake has an average thickness of 0.3-6 μm and an average particle size of 100-300 μm; more preferably, the glass flake has an average thickness of 0.5-1 μm and an average particle size of 140-200 μm; the thickness is determined by electron microscopy and the average particle size is determined by a laser particle size analyzer.

[0023] In some embodiments, the color stabilizer is further included in an amount of 0.02-0.1 parts.

[0024] In some embodiments, the color stabilizer is at least one of a phosphite stabilizer, a hindered phenol stabilizer, and an amide stabilizer.

[0025] Preferably, the amide stabilizer is at least one of an anthranilic acid, 1,8-diaminonaphthalene, allantoin, and N,N'-1,6-hexanediylbis(2-amino-benzamide).

[0026] The PET material can further include conventional additives in the art, including but not limited to antioxidants, lubricants, and processing aids; preferably, the additives are included in an amount of ≤ 5 wt.%.

[0027] The present application protects a method for preparing a high gas barrier composite PET material, comprising the following steps: uniformly mixing raw material components in a formula amount, melt-extruding and granulating, vacuum solid phase reaction (SSP), to obtain the composite PET material.

[0028] In some embodiments, the melt-extruding and granulating is performed by a twin-screw extruder, wherein 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 minutes, and the main machine rotation speed is 300-500 rpm.

[0029] In some embodiments, the vacuum solid phase reaction is performed at a temperature of 200-240 °C.

[0030] In some embodiments, the vacuum solid phase reaction is performed for a time of 4-6 h.

[0031] In some embodiments, the high gas barrier composite PET material has an intrinsic viscosity of 0.78-0.90 dl / g.

[0032] The application protects the use of a high gas barrier composite PET material in the preparation of packaging film or beverage bottles.

[0033] Compared with the prior art, the application has the following beneficial effects:

[0034] The application provides a high gas barrier composite PET material, which takes PET resin as a base, adds PA-MXD6 to fill the intermolecular gaps of the PET resin, forms a more compact composite material structure, reduces the penetration channels of gas molecules, and thus improves the overall gas barrier performance. A specific amount of alkyl polyol is added as a third monomer to form a gas barrier micro-network in the material, and a glass flake with a thin wall structure is compounded as a gas barrier medium, so as to improve the gas barrier property and mechanical strength of the material and reduce the loss of light transmittance. DETAILED DESCRIPTION

[0035] The application will be further described below in combination with the specific embodiments, but the embodiments do not limit the application in any form. Unless otherwise specified, the raw materials used in the embodiments of the application are commonly purchased raw materials.

[0036] The raw materials used in the following examples and comparative examples are as follows:

[0037] PET resin (A):

[0038] PET 1#: PET BG801, SINOPEC Yizheng Chemical Fibre Co., Ltd.; intrinsic viscosity 0.80 dL / g;

[0039] PET 2#: PET BG85, SINOPEC Yizheng Chemical Fibre Co., Ltd.; intrinsic viscosity 0.87 dL / g.

[0040] PA-MXD6 resin (B):

[0041] PA-MXD6 1#: Nylon-MXD6 CM001, Anshan Qicai Chemical Co., Ltd.; relative viscosity 2.1.

[0042] PA-MXD6 2#: ING00-MXD6-24, Shanghai Yinggu Chemical Co., Ltd.; relative viscosity 2.4.

[0043] PA-MXD6 3#: Nylon-MXD6 CM007, Anshan Qicai Chemical Co., Ltd.; relative viscosity 2.7.

[0044] PA66: PA66 U4800 NC01 SS, Inventa Nylon Chemical (China) Co., Ltd.; relative viscosity is 2.7;

[0045] PA612: A120, Shanghai Yinggu Chemical Co., Ltd.; relative viscosity is 2.4;

[0046] The relative viscosity is measured by 96% concentrated sulfuric acid by Ubbelohde viscometer, and the test standard is ISO 307:2007.

[0047] Glass flake (C):

[0048] Glass flake 1#: MEG160FY-M01, Japan Glass Co., Ltd.; average thickness is 0.7 microns, average particle size is 160 microns, and 45-300 microns account for 90% using laser particle size instrument.

[0049] Glass flake 2#: REF-160, Japan Glass Co., Ltd.; average thickness is 5 microns, average particle size is 165 microns, and 45-300 microns account for 92% using laser particle size instrument.

[0050] Montmorillonite: MDH-6, Shanghai Zhuangjing Chemical Co., Ltd.

[0051] Alkyl polyol (D):

[0052] D1: Glycerol, Suzhou Minghua Glycerol Co., Ltd.;

[0053] D2: 1,2,3-Butanetriol, Shanghai Aladdin Biochem Technology Co., Ltd.;

[0054] D3: 1,2,5-Pentanetriol, Shanghai Aladdin Biochem Technology Co., Ltd.;

[0055] D4: 1,2-Propanediol, Henan Dingchi Chemical Co., Ltd.;

[0056] 1-Propanol, Jinan Qichen Chemical Co., Ltd.

[0057] Polyester polyol, molecular weight is 300; CAPA 3031, Perstorp Group Co., Ltd.

[0058] Color stabilizer (E):

[0059] Color stabilizer 1#: 168, commercially available;

[0060] Color stabilizer 2#: N,N'-1,6-hexanediyl bis(2-amino-benzamide), commercially available.

[0061] The following examples and comparative examples of a high gas barrier composite PET material preparation method, including the following steps:

[0062] (1) Mix the formula amount of raw material components uniformly, melt-extrude and granulate through a twin-screw extruder to obtain the high gas barrier composite PET material.

[0063] The temperature of the first zone of the twin-screw extruder is 115°C, the temperature of the second zone is 240°C, the temperature of the third zone is 240°C, the temperature of the fourth zone is 220°C, the temperature of the fifth zone is 205°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 205°C, the temperature of the die head is 230°C, the residence time is 2 minutes, and the main machine rotation speed is 400 rpm.

[0064] (2) Vacuum solid phase reaction (SSP) of the high gas barrier composite PET material at 220°C for 5 hours to obtain the high gas barrier composite PET material.

[0065] Examples 1-13

[0066] This example provides a high gas barrier composite PET material, and the raw material components are shown in Table 1.

[0067] Table 1 Raw material components (parts by weight) of Examples 1-13

[0068]

[0069]

[0070] Comparative Examples 1-10

[0071] This comparative example provides a high gas barrier composite PET material, and the raw material components are shown in Table 2.

[0072] Table 2 Raw material components (parts by weight) of Comparative Examples 1-10

[0073]

[0074] Performance test

[0075] A high gas barrier composite PET material of Examples 1-13 and Comparative Examples 1-10 is subjected to the following tests:

[0076] 1. Oxygen transmission rate test: tested according to GB / T 1038-2000 standard, sample thickness is 0.25 mm, and test temperature is 23°C.

[0077] 2. Visible light transmittance: tested according to ISO 13468-1 standard, sample thickness is 2 mm;

[0078] 3. Burst pressure test: the sample thickness is blow molded into a beverage bottle, and the internal pressure resistance value is tested according to the QB-T 1868-2004 standard.

[0079] The results are shown in Tables 3-4.

[0080] Table 3

[0081]

[0082] Table 4

[0083]

[0084] As can be seen from Tables 3-4, the high gas barrier composite PET material of the present application has higher light transmittance, gas barrier property and internal pressure resistance value performance. The visible light transmittance is more than 64%, and the oxygen transmission amount is less than 3.3 cm 3 / (m 2 ·d·MPa), and the burst pressure is more than 5.8 MPa.

[0085] Compared with Example 1, Comparative Example 1 does not add PA-MXD6 and glass flake, the oxygen transmission amount is too high, the burst pressure decreases, and the gas barrier property and mechanical strength are poor.

[0086] Compared with Example 1, when polyamide PA66 or PA612 is used instead of PA-MXD6 in Comparative Examples 2-3, the oxygen transmission amount is too high, and the gas barrier property is poor.

[0087] When the glycerol is excessive in Comparative Example 4, it will cause partial degradation of PET, the burst pressure decreases significantly, and the transparency and gas barrier property decrease. When the content of PA-MXD6 or glass flake is too large in Comparative Examples 5-6, the gas barrier property does not improve significantly, but the visible light transmittance decreases significantly. In Comparative Example 7, PA-MXD6 is used to replace glass flake and glycerol, at this time, the light transmittance of the material is poor, and the gas barrier property decreases. In Comparative Example 8, montmorillonite is used to replace glass flake, not only the visible light transmittance of the material is greatly reduced, the gas barrier property is reduced, but also the burst pressure is greatly reduced. In Comparative Examples 9-10, polyester polyol and propanol are used to replace glycerol, the gas barrier property of the material decreases.

[0088] The above examples of the present application are merely examples for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, it is not necessary and impossible to exhaust all the embodiments. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. A composite PET material, characterized in that, The composite PET material comprises the following components by mass fraction: PET resin 88-95 parts, PA-MXD6 3-7 parts, Glass flake 2-5 parts, Alkyl polyol 0.03-1.05 parts; The alkyl polyol is a C3-C10 alkyl polyol. The average thickness of the glass flake is 0.3-6 μm, and the average particle size is 100-300 μm.

2. The composite PET material of claim 1, wherein, The intrinsic viscosity of the PET resin is 0.5-1 dl / g.

3. The composite PET material of claim 1, wherein, The relative viscosity of the PA-MXD6 is 2.0-2.

5.

4. The composite PET material of claim 1, wherein, The alkyl polyol is a C3-C5 alkyl polyol.

5. The composite PET material of claim 1, wherein, The alkyl polyol is a dihydric alcohol and / or a trihydric alcohol.

6. The composite PET material of claim 1, 4, or 5, wherein, The alkyl polyol is one or two or more of glycerol, 1,2,3-butanetriol, 1,2,5-pentanetriol or 1,2-propanediol.

7. The composite PET material of claim 1, wherein, The average thickness of the glass flake is 0.5-1 μm, and the average particle size is 140-200 μm.

8. A method of producing the composite PET material according to any one of claims 1 to 7, characterized in that, The composite PET material comprises the following steps: uniformly mixing the raw material components in a formula amount, melt-extruding and granulating, and vacuum solid-phase reaction to obtain the composite PET material.

9. The method for preparing the composite PET material according to claim 8, characterized in that, The temperature of the vacuum solid-phase reaction is 200-240 °C.

10. Use of the composite PET material according to any one of claims 1-7 in the preparation of a packaging film or a beverage bottle.

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