Preparation method of organic-inorganic composite water vapor barrier material and water vapor barrier master batch

Abstract

The invention discloses an organic-inorganic composite water vapor barrier functional master batch, the master batch is prepared by compounding a polyethylene glycol terephthalate plastic slice base material and an organic-inorganic composite water vapor barrier material through a plastic granulator, and the addition amount of the water vapor barrier material is 1-20wt% of the master batch. In addition, the invention also discloses a preparation method of the organic-inorganic composite water vapor barrier material. The organic-inorganic composite water vapor barrier functional master batch can be used for a water vapor barrier functional film, has outstanding water vapor barrier performance, and can play an important role in the related fields of OLED screens and illumination, photovoltaic cells, solar backboards and the like.

Description

Technical Field

[0001] The invention relates to a water vapor barrier masterbatch and a preparation method of an organic-inorganic composite water vapor barrier material. Background Art

[0002] With the rapid development of the packaging industry, some fields with special requirements, such as precision electronics, solar cells, displays, food and medicine, have gradually increased their requirements for the barrier properties of packaging materials. Packaging film materials with better water vapor barrier function have received more attention.

[0003] Compared with more complex and high-cost methods such as multi-layer composite and surface plasma treatment (such as magnetron sputtering, electron evaporation, vapor deposition, etc.), the addition and improvement of water vapor barrier masterbatch as a simpler and more effective method has become a major direction of applied research and has developed rapidly.

[0004] Chinese patent CN106905671A discloses a PET water vapor barrier masterbatch, which is a functional masterbatch obtained by compounding nano-inorganic fillers, nano-montmorillonite, nano-silicon dioxide, mica flakes, nano-titanium nitride and a resin matrix. The masterbatch has a certain water vapor barrier function, but there is much room for improvement in the dispersion and uniformity of the nano-inorganic filler in the matrix and the water vapor barrier functionality.

[0005] Chinese patent CN108456351A discloses a water vapor barrier film, which is prepared using polyolefin, polyester, elastomer and compatibility as raw materials. It not only has water vapor barrier properties, but also has good thermal stability and mechanical properties. In terms of water vapor barrier properties, a film with a thickness of 500 μm can achieve 0.1 g / (m 2 day) water vapor transmission rate.

[0006] How to achieve better water vapor barrier properties at a smaller thickness through better material selection, compounding and preparation is an issue that urgently needs to be solved in practical applications. Summary of the invention

[0007] In view of the above-mentioned deficiencies of the existing methods and technologies, according to an embodiment of the present invention, it is hoped to provide a water vapor barrier masterbatch, which can achieve outstanding water vapor barrier function through relatively simple and efficient preparation; in addition, the present invention also hopes to propose a method for preparing an organic-inorganic composite water vapor barrier material.

[0008] According to an embodiment, the present invention provides a method for preparing an organic-inorganic composite water vapor barrier material, comprising the following steps:

[0009] (1) According to the mass ratio, 50 parts of terephthalic acid, 100 parts of isophthalic acid, 100 parts of neopentyl glycol, 20 parts of ethylene glycol, and 1 part of p-toluenesulfonic acid were uniformly mixed under nitrogen atmosphere, and the temperature was raised to 180° C. for reaction for 2-4 hours;

[0010] (2) adding 5 parts of trimellitic anhydride and 30-50 parts of hydroxylated flaky nano-silica, heating to 220° C., and stirring under a nitrogen atmosphere for reaction for 5-8 hours;

[0011] (3) reacting in vacuum for 3 hours, returning to normal temperature and pressure, washing with ethanol and acetone three times respectively, and drying in vacuum at 50° C. for 24-48 hours to obtain an organic-inorganic composite water vapor barrier material.

[0012] According to one embodiment, in the method for preparing the aforementioned organic-inorganic composite water vapor barrier material of the present invention, the particle size of the hydroxylated flaky nano-silicon dioxide is preferably 0.5-2 μm, and the thickness is preferably 30-50 nm.

[0013] According to an embodiment, the present invention provides a water vapor barrier masterbatch, which is compounded by a polyethylene terephthalate plastic chip substrate and the aforementioned organic-inorganic composite water vapor barrier material and prepared by a plastic granulator, wherein the addition amount of the organic-inorganic composite water vapor barrier material is 1-20wt% of the masterbatch.

[0014] The water vapor barrier masterbatch prepared by the present invention obtains an organic-inorganic composite water vapor barrier material by a simple method, which makes up for the problem that the general functional materials have poor dispersion, easy migration, and unevenness, resulting in poor water vapor barrier performance, improves functionality, and meets the needs of relevant market and social development. The following examples and test examples will prove that, compared with the prior art, the plastic film prepared by the water vapor barrier masterbatch has outstanding water vapor barrier performance. DETAILED DESCRIPTION

[0015] The present invention will be further described below in conjunction with specific embodiments. These embodiments should be understood to be only used to illustrate the present invention and not to limit the scope of protection of the present invention. After reading the content of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent changes and modifications also fall within the scope defined by the claims of the present invention.

[0016] In the following examples of the present invention, hydroxylated flaky nano-silica is prepared by the following method:

[0017] (1) 500 g of silica nanosheets were dispersed in 5 L of water and ultrasonically stirred for 6 h;

[0018] (2) Add 2.5 L of 5 mol / L sodium hydroxide solution, heat to 80 °C, and stir for 4 h;

[0019] (3) After natural cooling, the mixture was filtered and separated, and dried in a vacuum oven at 40° C. for 48 h to obtain hydroxylated flaky nano-silica with a particle size of 0.5-2 μm and a thickness of 30-50 nm.

[0020] In the following examples of the present invention, the raw materials used are commercially available products unless otherwise specified.

[0021] Example 1

[0022] The organic-inorganic composite water vapor barrier material is prepared by the following method:

[0023] (1) Under nitrogen atmosphere, 500 g of terephthalic acid, 1000 g of isophthalic acid, 1000 g of neopentyl glycol, 200 g of ethylene glycol, and 10 g of p-toluenesulfonic acid were uniformly mixed, heated to 180° C., and stirred for reaction for 4 h;

[0024] (2) Add 50 g of trimellitic anhydride and 350 g of hydroxylated flaky nano-silica, raise the temperature to 220° C., and stir the mixture under a nitrogen atmosphere for 6 h.

[0025] (3) adjusting the reaction to vacuum for 3 hours, returning to normal temperature and pressure, washing with ethanol and acetone three times respectively, and vacuum drying at 50° C. for 48 hours to obtain an organic-inorganic composite water vapor barrier material.

[0026] The water vapor barrier masterbatch is prepared by compounding a polyethylene terephthalate plastic chip substrate and an organic-inorganic composite water vapor barrier material in a mass ratio of 80:20 through a plastic granulator.

[0027] Example 2

[0028] The organic-inorganic composite water vapor barrier material is prepared by the following method:

[0029] (1) Under nitrogen atmosphere, 500 g of terephthalic acid, 1000 g of isophthalic acid, 1000 g of neopentyl glycol, 200 g of ethylene glycol, and 10 g of p-toluenesulfonic acid were uniformly mixed, heated to 180° C., and stirred for reaction for 3 h;

[0030] (2) Add 50 g of trimellitic anhydride and 400 g of hydroxylated flaky nano-silica, raise the temperature to 220° C., and stir the mixture under a nitrogen atmosphere for 6 h.

[0031] (3) adjusting the reaction to vacuum for 3 hours, returning to normal temperature and pressure, washing with ethanol and acetone three times respectively, and vacuum drying at 50° C. for 48 hours to obtain an organic-inorganic composite water vapor barrier material.

[0032] The water vapor barrier masterbatch is prepared by compounding a polyethylene terephthalate plastic chip substrate and an organic-inorganic composite water vapor barrier material in a mass ratio of 80:20 through a plastic granulator.

[0033] Example 3

[0034] The organic-inorganic composite water vapor barrier material is prepared by the following method:

[0035] (1) Under nitrogen atmosphere, 500 g of terephthalic acid, 1000 g of isophthalic acid, 1000 g of neopentyl glycol, 200 g of ethylene glycol, and 10 g of p-toluenesulfonic acid were uniformly mixed, heated to 180° C., and stirred for reaction for 4 h;

[0036] (2) Add 50 g of trimellitic anhydride and 500 g of hydroxylated flaky nano-silica, raise the temperature to 220° C., and stir the mixture under a nitrogen atmosphere for 8 h.

[0037] (3) adjusting the reaction to vacuum for 3 hours, returning to normal temperature and pressure, washing with ethanol and acetone three times respectively, and vacuum drying at 50° C. for 48 hours to obtain an organic-inorganic composite water vapor barrier material.

[0038] The water vapor barrier masterbatch is prepared by compounding a polyethylene terephthalate plastic chip substrate and an organic-inorganic composite water vapor barrier material in a mass ratio of 80:20 through a plastic granulator.

[0039] Test example

[0040] The water vapor barrier masterbatch prepared in each embodiment was blended and extruded with ordinary PET plastic chips at a mass ratio of 5%, and a 50 μm thick film was prepared by a biaxial stretching process, and the water vapor permeability performance of each sample was tested. The test results are shown in Table 1. The samples prepared in each embodiment have good water vapor barrier properties, and the sample of Example 3 has a relatively better water vapor barrier effect. This is because the amount of flaky nano-silicon dioxide is increased, which improves its barrier performance.

[0041] Table 1. Water vapor barrier performance test of each embodiment

[0042]

[0043] The water vapor barrier masterbatch prepared by the present invention can achieve an outstanding water vapor barrier effect with a lower thickness, and has a good application prospect in packaging and encapsulation materials.

Claims

1. A method for preparing an organic-inorganic composite water vapor barrier material, characterized in that: The steps include: (1) According to the mass ratio, 50 parts of terephthalic acid, 100 parts of isophthalic acid, 100 parts of neopentyl glycol, 20 parts of ethylene glycol, and 1 part of p-toluenesulfonic acid were uniformly mixed under nitrogen atmosphere, and the temperature was raised to 180° C. for reaction for 2-4 hours; (2) adding 5 parts of trimellitic anhydride and 30-50 parts of hydroxylated flaky nano-silica, heating to 220° C., and stirring under a nitrogen atmosphere for reaction for 5-8 hours; (3) reacting in vacuum for 3 hours, returning to normal temperature and pressure, washing with ethanol and acetone three times respectively, and drying in vacuum at 50° C. for 24-48 hours to obtain an organic-inorganic composite water vapor barrier material.

2. The method for preparing the organic-inorganic composite water vapor barrier material according to claim 1, characterized in that: In step (2), the particle size of the hydroxylated flaky nano-silicon dioxide is 0.5-2 μm and the thickness is 30-50 nm.

3. An organic-inorganic composite water vapor barrier functional masterbatch, characterized in that: The masterbatch is compounded by a polyethylene terephthalate plastic chip substrate and an organic-inorganic composite water vapor barrier material prepared by the preparation method of claim 1 or 2, and is prepared by a plastic granulator, wherein the addition amount of the water vapor barrier material is 1-20wt% of the masterbatch.

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