CN106750438A - A kind of water/oxygen barrier polymer based composites and its preparation method and application - Google Patents

Abstract

The invention discloses a water/oxygen barrier polymer-based composite material, which is composed of an inorganic layered filler dispersed in a polymer matrix material after reacting with a surface modifier and an intercalation agent, and the polymer matrix material is Organic polymers containing amide linkages or hydroxyl or carboxyl groups. The invention has the advantages of: the structure of the water/oxygen barrier layer is simple and effective; the preparation method is a solution state process, and the preparation process does not need to involve a vacuum process, and the preparation method is simple; the preparation cost of the water/oxygen barrier polymer-based composite material is low , and has a wide range of applications.

Description

A kind of water/oxygen barrier polymer-based composite material and its preparation method and application

technical field

The invention relates to the fields of flexible electronics and display devices.

Background technique

With the rapid development of science and technology, the application of packaging materials with barrier properties has rapidly expanded from the traditional food and pharmaceutical packaging fields to the packaging of electronic products. Various high-tech electronic products have increasingly strict requirements on the barrier properties of packaging materials. The requirements for water and oxygen barrier properties in different fields are shown in Table 1:

Table 1. Range of requirements for barrier properties of packaging materials in different fields

In the field of organic electroluminescent devices (OLEDs), the barrier performance requirements for encapsulation materials are particularly stringent. Organic Light-Emitting Diode (OLED), also known as Organic Light-Emitting Diode (OLED), was discovered in the laboratory by Chinese-American professor Deng Qingyun, and the research on OLED was launched. OLED has the characteristics of low production cost, all solid state, active light emission, high brightness, high contrast, low voltage DC drive, low power consumption, wide viewing angle, fast response, thin thickness, wide operating temperature range, and flexible display. Traditional liquid crystal display (LCD) packaging requires water vapor transmission rate (WVTR) and oxygen transmission rate (OTR) to be less than 0.1g/m ² /day and 0.1cm ³ /m ² /day respectively. However, organic light-emitting materials and cathodes in OLEDs are particularly sensitive to water vapor and oxygen. In order to obtain effective electron injection in OLED devices, metals with low work function (such as Ca, Li) are often used as materials for the cathode layer. The chemical properties of this kind of metal materials are relatively active, and they are easily corroded by water vapor and oxygen in the environment. If the water vapor and oxygen in the environment oxidize the cathode metal layer and affect the interface between the metal layer and the oxide layer, electrons cannot be emitted effectively, resulting in pixel shrinkage and seriously shortening the life of the OLED device. If the OLED device is not properly packaged after it is produced, it will lose its light-emitting performance in a short time, causing it to fail to work. Therefore, in order to block the influence of water and oxygen on the device, we need to add a waterproof and oxygen barrier structure between the device and the substrate. If the lifetime of an OLED is calculated as 10,000 hours, and the minimum water and oxygen required for OLED low work function cathode failure are used to estimate the permeability of water and oxygen to the OLED package, the WVTR and OTR of the OLED package are required to be less than 10 ^-6 g /m ² /day and 10 ^-5 ~ 10 ^-3 cm ³ /m ² /day. In order to reduce the gas permeability of the packaging material,

Compared with inorganic barrier materials, polymer barrier materials have many advantages such as small specific gravity, flexibility, multi-layer composite, low dielectric, excellent insulation performance, and functionalization, and occupy a very important position in barrier materials. . However, the shortcomings of using polymers as barrier materials are also very obvious. The air permeability of most polymer materials is higher than that of inorganic materials, and there is still a long way to go to achieve high barriers, especially in the field of OLED packaging. Therefore, the development of a polymer film material with high barrier properties, high mechanical properties, high heat resistance, and transparency has a very huge market application prospect.

Polyimide (PI) is an excellent high temperature resistant material with excellent mechanical properties, dielectric properties, radiation resistance and solvent resistance. The new PI material has the characteristics of high barrier properties, high mechanical properties, high heat resistance, high glass transition temperature, low cost and easy preparation, etc. It can be widely used in high-tech fields such as electronic packaging, and its significance is self-evident. As a polymer material with high heat resistance, high T _g , high mechanical properties and certain transparency, polyimide has an oxygen transmission rate of about 30cm ³ /m ² /day and a water transmission rate of 50g/m ² /day, compared with other polymer materials, the barrier performance is good, and it has a good advantage in research and application as a high barrier material. The barrier properties of polyimide resin can be effectively reduced and its properties can be improved by methods such as blending modification, multi-component copolymerization, nanoparticle hybridization, and adding fillers.

In recent years, the main preparation methods of barrier polymer composites can be divided into surface treatment method, multilayer composite method, layered blending method and nanomaterial blending method according to their different processing techniques. Scholars at home and abroad have researched and produced a series of materials with high barrier properties to water vapor and oxygen, such as silicon nitride film, photopolymerized polyacrylamide film, and Barix film. However, such a technology is complicated and expensive, and it is difficult to realize large-scale application. Therefore, it is quite important to realize the encapsulation technology of an efficient flexible waterproof oxygen barrier layer with simple process and low cost.

This patent uses the principle that the inorganic sheet material greatly prolongs the diffusion path of gas molecules inside the material to improve the barrier properties of the polymer substrate. At the same time, it uses the special "amide bond", "hydroxyl" and "carboxyl" in the polymer structure Equipolar groups, while prolonging the diffusion path of gas molecules, greatly increase the probability of contact between the diffusing water molecules and the polar functional groups in the polymer chain segment, so that the effect of "water locking" and water blocking can be maximized , to maximize the water/oxygen barrier properties of the material.

Contents of the invention

The purpose of the present invention is to provide a water/oxygen barrier polymer-based composite material and its manufacturing method for flexible electronics and display devices, so as to ensure that the produced water/oxygen barrier polymer-based composite material has good water and oxygen barrier performance.

Another object of the present invention is to provide a water/oxygen barrier polymer-based composite film applied to flexible electronics and display devices.

In order to achieve the purpose of the above invention, the present invention adopts the following technical scheme: a water/oxygen barrier polymer-based composite material, which is dispersed in the polymer matrix material after the inorganic layered filler is reacted with a surface modifier and an intercalation agent Constituted, the polymer matrix material is an organic polymer containing amide bonds or hydroxyl or carboxyl groups.

The organic polymer is a polyimide material synthesized by polymerizing dianhydride monomers and diamine monomers containing amide bonds or hydroxyl or carboxyl groups.

The inorganic layered filler has various aspect ratios and lamellar spacings, and the inorganic layered filler can be montmorillonite, or quartz, or mica, or graphene, or boron nitride inorganic filler. Interlamellar spacing here refers to the spacing between the lamellar layers of the inorganic material itself due to stacking before being dispersed into the polymer matrix.

The surface modifier is a silane coupling agent or a diamine monomer having an amino group that can participate in a polymerization reaction; the intercalation agent includes cetyltrimethylammonium chloride, or cetyltrimethylammonium Methyl ammonium bromide, or octadecyltrimethylammonium chloride, or an organic quaternary ammonium salt of a diamine monomer having an amino group that can participate in a polymerization reaction of octadecyltrimethylammonium bromide. The advantage of using the diamine monomer as an intercalation agent is that on the one hand, the diamine monomer can enter the interior of the montmorillonite sheet and expand the distance between the sheets. On the other hand, during the polymerization reaction, the diamine monomer between the layers can also participate in the polymerization, the principle is similar to the in-situ reaction, so the compatibility between the polyimide matrix and the montmorillonite material will also be to a certain extent It is enhanced, which helps to improve the performance of thin film materials. It is precisely because of the use of diamine monomers as intercalation agents that the interfacial interaction between montmorillonite and polyimide will be greatly reduced. The polymer matrix material is a polyimide material prepared by participating in a polymerization reaction of a diamine monomer of the following formula (I).

Note: R, R" represent alkyl segments; Ar, Ar' represent aromatic segments.

In the above system, diamine monomers containing amide bonds or hydroxyl or carboxyl groups are used for synthesis. Amide bonds, hydroxyl groups, and carboxyl groups are structures with hydrogen bonds. The existence of hydrogen bonds in the movement of polymer chain segments can enhance the interaction force between segments, and the high temperature annealing process can restore the movement of PI molecular segments, and the interaction of hydrogen bonds can make the polymer chains more tightly packed, thereby reducing the free volume of the polymer. The space that gas molecules can pass through in the polymer is reduced, so as to achieve the purpose of improving the barrier performance. The hydrogen bond between the amide bond or the hydroxyl or carboxyl structure and the water molecule can hinder the diffusion of the water molecule inside the material, so as to achieve the purpose of improving the barrier performance of the material. After the amide bond or hydroxyl or carboxyl structure forms hydrogen bonds with water molecules, the water molecules tend to condense. The diffusion of this form of water molecules in the material is much smaller than that of non-condensed free water in the polymer material. Diffusion speed, using the water-locking effect of amide bonds or hydroxyl or carboxyl groups to reduce the water vapor transmission rate of PI film materials.

A method of manufacturing a water/oxygen barrier polymer-based composite material, comprising the steps of:

(1) Stir the inorganic layered filler with water to make a suspension, and after standing, take the upper layer of the suspension and centrifuge to obtain the small particle size inorganic layered filler;

(2) Intercalation treatment: disperse the small particle size inorganic layered filler into the intercalation agent, take the reaction precipitate after fully reacting, wash and dry at 100°C for 24 hours to obtain the intercalated inorganic layered filler;

(3) adding the intercalated inorganic layered filler into the organic modifier, fully stirring, filtering to take the precipitate, drying and grinding to obtain the organically modified intercalated inorganic layered filler;

(4) Preparation of the prepolymer of the polymer matrix material: take the prepolymer monomer of the polymer matrix material, fully mix to form a sol;

(5) Adding the organically modified intercalation inorganic layered filler obtained in step (3) to the sol in step (4), and ultrasonically mechanically stirring for 5 hours to obtain a mixed sol;

(6) Coating the mixed sol obtained in step (5) on the surface of the material to be prepared to obtain a water/oxygen barrier layer.

A water/oxygen barrier polymer-based composite film, which is composed of upper, middle and lower layers, the middle layer is the water/oxygen barrier layer described above, and the upper and lower layers do not contain amide bonds, hydroxyl groups, A polymer surface layer composed of carboxyl organic polymers.

The preparation method of the water/oxygen barrier polymer-based composite film comprises the following steps:

S1. Prepare the polymer surface layer solution and apply or melt to form a thin film, and obtain the lower polymer surface layer after solidification;

S2. Prepare the mixed sol of the water/oxygen barrier layer, apply the mixed sol on the surface of the lower surface layer of the polymer prepared in S1, and form a water/oxygen barrier layer on the surface of the lower polymer surface layer after curing;

S3. Prepare a polymer surface layer solution and apply it on the surface of the water/oxygen barrier layer prepared in S2, and form an upper polymer surface layer on the surface of the water/oxygen barrier layer after curing;

S4. heat-treating the composite film obtained in S3.

An application of the water/oxygen barrier polymer-based composite material described above in a multilayer encapsulation structure.

An application of the water/oxygen barrier polymer-based composite material in flexible electronics or flexible display devices, the flexible electronics or flexible display devices are preferably electronic paper, flexible TFT devices, flexible OLED devices, sensors or printing electronic devices.

The advantages of the present invention are:

1. The structure of the water/oxygen barrier layer is simple and effective;

2. The preparation method is a solution-state process, and no vacuum process is involved in the preparation process, and the preparation method is simple;

3. The preparation cost of the water/oxygen barrier polymer-based composite material is low, and it has a wide range of applications.

Description of drawings

Fig. 1 is a schematic structural view of the composite film material of the present invention.

Among them, polymer upper surface layer 1, water/oxygen barrier layer 2, polymer lower surface layer 3

detailed description

Example 1

This example is a preparation example of a water/oxygen barrier polymer-based composite film material.

The water/oxygen barrier polymer-based composite film material is prepared according to the following steps:

1. Prepare the prepolymer of the upper and lower polymer surface layers: take 0.8049g (4.02mmol) of diamine monomer diaminodiphenyl ether ODA and add it to 10mL of DMF solution, and continue stirring for a period of time to fully mix the system; add to the above system 0.8943g (4.10mmol) of the dianhydride monomer 1,2,4,5-pyromellitic dianhydride PMDA was added and stirred at a medium speed for 6 hours until the system formed a sol.

2. Modification and intercalation of inorganic layered fillers: take 10g of sodium montmorillonite and 100mL of ultrapure water to make a 5%-10% suspension under ultrasonic stirring conditions, and after standing at room temperature for 24h to settle, take Centrifuge the upper suspension to obtain montmorillonite with smaller particle size; disperse 1 g of montmorillonite with small particle size into 50 mL of 1 mol/L cetyltrimethylammonium bromide aqueous solution, stir and reflux at 90 ° C for 24 h, The reaction precipitate was taken, washed several times with ultrapure water, and dried at 100° C. for 24 hours to obtain an intercalated montmorillonite material.

Prepare a solution according to the mass ratio of silane coupling agent (KH-550) 20% + ethanol 72% + water 8%, add 1g of intercalated montmorillonite material into 50mL solution and stir for 1h, filter with suction, and oven dry at 120°C , to obtain organically modified intercalated montmorillonite materials.

3. Preparation of the polymer layer prepolymer in the middle layer:

Take 1.0504g (4.62mmol) diamine monomer diaminobenzoanilide DABA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; add 1.0284g (4.71mmol) dianhydride monomer 1 to the above system , 2,4,5-Pyromellitic dianhydride PMDA, after adding, stir at a medium speed for 1 hour until the system forms a sol; add 1% of the monomer weight (total weight of diamine + dianhydride) to the sol system. 0.0208g of intercalation montmorillonite material, ultrasonic mechanical stirring for 5h, to obtain a waterproof oxygen barrier layer mixed sol.

4. Use the sol in step 1 to coat on a glass plate with a dry and clean surface, and dry it in an oven at 150°C for 30 minutes to remove the solvent to obtain a dry PAA film, which is the polymer lower surface layer 1;

Coat the mixed sol of the waterproof oxygen barrier layer in step 3 on the surface of the above-mentioned dry PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry double-layer PAA film;

Use the sol in step 1 to coat the surface of the above-mentioned dry double-layer PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry three-layer PAA film;

Put the above three layers of PAA film into an oven at 150°C, raise the temperature to 250°C for 1 hour, and raise the temperature to 350°C for 1 hour; after natural cooling to room temperature, soak the composite film in hot water to peel off the composite film from the glass plate to obtain a multilayer Water/oxygen barrier polymer based composite film.

The water vapor barrier test was carried out on the obtained water/oxygen barrier composite film samples, and the results are shown in Table 2 to Table 5 below.

Example 2

This example is a preparation example of a water/oxygen barrier polymer-based composite film material.

The water/oxygen barrier polymer-based composite film material is prepared according to the following steps:

1. Prepare the prepolymer of the upper and lower polymer surface layers: take 1.0248g (4.74mmol) diamine monomer 4,4'-diaminodiphenyl sulfide SDA and add it to 10mL DMF solution, and keep stirring for a period of time to make the system fully Mixing; add 1.0540 g (4.83 mmol) of dianhydride monomer 1,2,4,5-pyromellitic dianhydride PMDA to the above system, and stir at a medium speed for 6 hours after the addition until the system forms a sol.

2. Modification and intercalation of inorganic layered fillers: take 10g of sodium montmorillonite and 100mL of ultrapure water to make a 5%-10% suspension under ultrasonic stirring conditions, and after standing at room temperature for 24h to settle, take Centrifuge the upper suspension to obtain montmorillonite with smaller particle size; disperse 1 g of montmorillonite with small particle size into 50 mL of 1 mol/L cetyltrimethylammonium bromide aqueous solution, stir and reflux at 90 ° C for 24 h, The reaction precipitate was taken, washed several times with ultrapure water, and dried at 100° C. for 24 hours to obtain an intercalated montmorillonite material.

Prepare a solution according to the mass ratio of silane coupling agent (KH-550) 20% + ethanol 72% + water 8%, add 1g of intercalated montmorillonite material into 50mL solution and stir for 1h, filter with suction, and oven dry at 120°C , to obtain organically modified intercalated montmorillonite materials.

3. Preparation of the polymer layer prepolymer in the middle layer:

Take 1.0504g (4.62mmol) diamine monomer diaminobenzoanilide DABA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; add 1.0284g (4.71mmol) dianhydride monomer 1 to the above system , 2,4,5-Pyromellitic dianhydride PMDA, after adding, stir at a medium speed for 1 hour until the system forms a sol; add 1% of the monomer weight (total weight of diamine + dianhydride) to the sol system. 0.0208g of intercalation montmorillonite material, ultrasonic mechanical stirring for 5h, to obtain a waterproof oxygen barrier layer mixed sol.

4. Use the sol in step 1 to coat on a glass plate with a dry and clean surface, and dry it in an oven at 150°C for 30 minutes to remove the solvent to obtain a dry PAA film, which is the polymer lower surface layer 1;

Coat the mixed sol of the waterproof oxygen barrier layer in step 3 on the surface of the above-mentioned dry PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry double-layer PAA film;

Use the sol in step 1 to coat the surface of the above-mentioned dry double-layer PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry three-layer PAA film;

Put the above three layers of PAA film into an oven at 150°C, raise the temperature to 250°C for 1 hour, and raise the temperature to 350°C for 1 hour; after natural cooling to room temperature, soak the composite film in hot water to peel off the composite film from the glass plate to obtain a multilayer Water/oxygen barrier polymer based composite film.

A water vapor barrier test was performed on the obtained water/oxygen barrier polymer-based composite film samples, and the results are shown in Tables 2 to 5 below.

Example 3

This example is a preparation example of a water/oxygen barrier polymer-based composite film material.

The water/oxygen barrier polymer-based composite film material is prepared according to the following steps:

1. Prepare the prepolymer of the upper and lower polymer surface layers: take 1.3841g (3.28mmol) diamine monomer 2,2'-bis(4-aminophenoxyphenyl)propane BAPP and add it to 10mL DMF solution, and continue Stir for a period of time to fully mix the system; add 0.7307g (3.35mmol) of dianhydride monomer 1,2,4,5-pyromellitic dianhydride PMDA to the above system, and stir at a medium speed for 6 hours until the system is formed Sol.

2. Modification and intercalation of inorganic layered fillers: take 10g of sodium montmorillonite and 100mL of ultrapure water to make a 5%-10% suspension under ultrasonic stirring conditions, and after standing at room temperature for 24h to settle, take Centrifuge the upper suspension to obtain montmorillonite with smaller particle size; disperse 1 g of montmorillonite with small particle size into 50 mL of 1 mol/L cetyltrimethylammonium bromide aqueous solution, stir and reflux at 90 ° C for 24 h, take The reaction precipitate was washed several times with ultrapure water, and dried at 100° C. for 24 hours to obtain an intercalated montmorillonite material.

Prepare a solution according to the mass ratio of silane coupling agent (KH-550) 20% + ethanol 72% + water 8%, add 1g of intercalated montmorillonite material into 50mL solution and stir for 1h, filter with suction, and oven dry at 120°C , to obtain organically modified intercalated montmorillonite materials.

3. Preparation of the polymer layer prepolymer in the middle layer:

Take 1.0504g (4.62mmol) diamine monomer diaminobenzoanilide DABA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; add 1.0284g (4.71mmol) dianhydride monomer 1 to the above system , 2,4,5-Pyromellitic dianhydride PMDA, after adding, stir at a medium speed for 1 hour until the system forms a sol; add 1% of the monomer weight (total weight of diamine + dianhydride) to the sol system. 0.0208g of intercalation montmorillonite material, ultrasonic mechanical stirring for 5h, to obtain a waterproof oxygen barrier layer mixed sol.

4. Use the sol in step 1 to coat on a glass plate with a dry and clean surface, and dry it in an oven at 150°C for 30 minutes to remove the solvent to obtain a dry PAA film, which is the polymer lower surface layer 1;

Coat the mixed sol of the waterproof oxygen barrier layer in step 3 on the surface of the above-mentioned dry PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry double-layer PAA film;

Use the sol in step 1 to coat the surface of the above-mentioned dry double-layer PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry three-layer PAA film;

Put the above three layers of PAA film into an oven at 150°C, raise the temperature to 250°C for 1 hour, and raise the temperature to 350°C for 1 hour; after natural cooling to room temperature, soak the composite film in hot water to peel off the composite film from the glass plate to obtain a multilayer Waterproof oxygen composite film.

Example 4

This example is a preparation example of a water/oxygen barrier polymer-based composite film material.

The water/oxygen barrier polymer-based composite film material is prepared according to the following steps:

1. Prepare the prepolymer of the upper and lower polymer surface layers: Take 0.8319g (4.15mmol) diamine monomer diaminodiphenyl ether ODA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; Add 1.2469g (4.23mmol) of dianhydride monomer 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA, and stir at a medium speed for 6 hours after the addition until the system forms a sol.

2. Modification and intercalation of inorganic layered fillers: take 10g of sodium montmorillonite and 100mL of ultrapure water to make a 5%-10% suspension under ultrasonic stirring conditions, and after standing at room temperature for 24h to settle, take Centrifuge the upper suspension to obtain montmorillonite with smaller particle size; disperse 1 g of montmorillonite with small particle size into 50 mL of 1 mol/L cetyltrimethylammonium bromide aqueous solution, stir and reflux at 90 ° C for 24 h, The reaction precipitate was taken, washed several times with ultrapure water, and dried at 100° C. for 24 hours to obtain an intercalated montmorillonite material.

Prepare a solution according to the mass ratio of silane coupling agent (KH-550) 20% + ethanol 72% + water 8%, add 1g of intercalated montmorillonite material into 50mL solution and stir for 1h, filter with suction, and oven dry at 120°C , to obtain organically modified intercalated montmorillonite materials.

3. Preparation of the middle layer polymer layer prepolymer:

Take 0.8958g (3.94mmol) diamine monomer diaminobenzoanilide DABA and add it to 10mL DMF solution, and keep stirring for a period of time to make the system fully mixed; add 1.1830g (4.02mmol) dianhydride monomer 3 to the above system , 3',4,4'-biphenyltetracarboxylic dianhydride BPDA, after adding, stir at a medium speed for 1 hour until the system forms a sol; add 1% of monomer weight (total weight of diamine + dianhydride) to the sol system 0.0208 g of the organically modified intercalation montmorillonite material was stirred ultrasonically for 5 hours to obtain a mixed sol of the water/oxygen barrier layer.

4. Use the sol in step 1 to coat on a glass plate with a dry and clean surface, and dry it in an oven at 150°C for 30 minutes to remove the solvent to obtain a dry PAA film, which is the polymer lower surface layer 1;

Coat the mixed sol of the waterproof oxygen barrier layer in step 3 on the surface of the above-mentioned dry PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry double-layer PAA film;

Use the sol in step 1 to coat the surface of the above-mentioned dry double-layer PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry three-layer PAA film;

Put the above three layers of PAA film into an oven at 150°C, raise the temperature to 250°C for 1 hour, and raise the temperature to 350°C for 1 hour; after natural cooling to room temperature, soak the composite film in hot water to peel off the composite film from the glass plate to obtain a multilayer Water/oxygen barrier composite film. The water vapor barrier test was carried out on the obtained water/oxygen barrier composite film samples, and the results are shown in Table 2 to Table 5 below.

Example 5

This example is a preparation example of a water/oxygen barrier polymer-based composite film material.

The water/oxygen barrier polymer-based composite film material is prepared according to the following steps:

1. Prepare the prepolymer of the upper and lower polymer surface layers: Take 0.7870g (3.93mmol) diamine monomer diaminodiphenyl ether ODA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; Add 1.2918 g (4.01 mmol) of dianhydride monomer 3,3',4,4'-benzophenonetetraacid dianhydride BTDA, and stir at a medium speed for 6 hours after the addition until the system forms a sol.

2. Modification and intercalation of inorganic layered fillers: take 10g of sodium montmorillonite and 100mL of ultrapure water to make a 5%-10% suspension under ultrasonic stirring conditions, and after standing at room temperature for 24h to settle, take Centrifuge the upper suspension to obtain montmorillonite with smaller particle size; disperse 1 g of montmorillonite with small particle size into 50 mL of 1 mol/L cetyltrimethylammonium bromide aqueous solution, stir and reflux at 90 ° C for 24 h, The reaction precipitate was taken, washed several times with ultrapure water, and dried at 100° C. for 24 hours to obtain an intercalated montmorillonite material.

Prepare a solution according to the mass ratio of silane coupling agent (KH-550) 20% + ethanol 72% + water 8%, add 1g of intercalated montmorillonite material into 50mL solution and stir for 1h, filter with suction, and oven dry at 120°C , to obtain organically modified intercalated montmorillonite materials.

3. Preparation of the middle layer polymer layer prepolymer:

Take 0.8498g (3.74mmol) diamine monomer diaminobenzoanilide DABA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; add 1.2290g (3.81mmol) dianhydride monomer 3 to the above system , 3',4,4'-Benzophenonetetraacid dianhydride BTDA, after adding, stir at a medium speed for 1 hour until the system forms a sol; add 1% of monomer weight (total weight of diamine + dianhydride) to the sol system 0.0208 g of the organically modified intercalated montmorillonite material was stirred ultrasonically for 5 hours to obtain a water/oxygen barrier layer mixed sol.

4. Use the sol in step 1 to coat on a glass plate with a dry and clean surface, and dry it in an oven at 150°C for 30 minutes to remove the solvent to obtain a dry PAA film, which is the polymer lower surface layer 1;

Coat the mixed sol of the waterproof oxygen barrier layer in step 3 on the surface of the above-mentioned dry PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry double-layer PAA film;

Use the sol in step 1 to coat the surface of the above-mentioned dry double-layer PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry three-layer PAA film;

Put the above three layers of PAA film into an oven at 150°C, raise the temperature to 250°C for 1 hour, and raise the temperature to 350°C for 1 hour; after natural cooling to room temperature, soak the composite film in hot water to peel off the composite film from the glass plate to obtain a multilayer Water/oxygen barrier composite film.

Example 6

This example is a preparation example of a water/oxygen barrier polymer-based composite film material.

The water/oxygen barrier polymer-based composite film material is prepared according to the following steps:

1. Prepare the prepolymer of the upper and lower polymer surface layers: Take 0.8049g (4.02mmol) diamine monomer diaminodiphenyl ether ODA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; Add 0.8943g (4.10mmol) of the dianhydride monomer 1,2,4,5-pyromellitic dianhydride PMDA, and stir at a medium speed for 6 hours after the addition until the system forms a sol.

2. Modification and intercalation of inorganic layered fillers: take 10g of sodium montmorillonite and 100mL of ultrapure water to make a 5%-10% suspension under ultrasonic stirring conditions, and after standing at room temperature for 24h to settle, take Centrifuge the upper suspension to obtain montmorillonite with smaller particle size; disperse 1 g of montmorillonite with small particle size into 50 mL of 0.1 mol/L diaminodiphenyl ether ODA hydrochloric acid aqueous solution, stir and reflux at 60 ° C for 24 h, take The reaction precipitate was washed several times with ultrapure water, and dried at 60° C. for 24 hours to obtain a diamine-intercalated montmorillonite material.

Prepare a solution according to the mass ratio of silane coupling agent (KH-550) 20% + ethanol 72% + water 8%, add 1g of intercalated montmorillonite material into 50mL solution and stir for 1h, filter with suction, and dry in an oven at 60°C , to obtain organically modified intercalated montmorillonite materials.

3. Preparation of the polymer layer prepolymer in the middle layer:

Take 1.0504g (4.62mmol) diamine monomer diaminobenzoanilide DABA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; add 1.0284g (4.71mmol) dianhydride monomer 1 to the above system , 2,4,5-Pyromellitic dianhydride PMDA, after adding, stir at a medium speed for 1 hour until the system forms a sol; add 1% of the monomer weight (total weight of diamine + dianhydride) to the sol system. 0.0208g of intercalation montmorillonite material, ultrasonic mechanical stirring for 5h, to obtain a waterproof oxygen barrier layer mixed sol.

4. Use the sol in step 1 to coat on a glass plate with a dry and clean surface, and dry it in an oven at 150°C for 30 minutes to remove the solvent to obtain a dry PAA film, which is the polymer lower surface layer 1;

Coat the mixed sol of the water/oxygen barrier layer in step 3 on the surface of the above-mentioned dry PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry double-layer PAA film;

Use the sol in step 1 to coat the surface of the above-mentioned dry double-layer PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry three-layer PAA film;

Put the above three layers of PAA film into an oven at 150°C, raise the temperature to 250°C for 1 hour, and raise the temperature to 350°C for 1 hour; after natural cooling to room temperature, soak the composite film in hot water to peel off the composite film from the glass plate to obtain a multilayer Water/oxygen barrier composite film.

Example 7

This example is a preparation example of a water/oxygen barrier polymer-based composite film material.

The water/oxygen barrier polymer-based composite film material is prepared according to the following steps:

1. Prepare the prepolymer of the upper and lower polymer surface layers: Take 0.8049g (4.02mmol) of diamine monomer diaminodiphenyl ether ODA and add it to 10mL of DMF solution, and keep stirring for a period of time to fully mix the system; Add 0.8943g (4.10mmol) of the dianhydride monomer 1,2,4,5-pyromellitic dianhydride PMDA, and stir at a medium speed for 6 hours after the addition until the system forms a sol.

2. Modification and intercalation of inorganic layered fillers: 100g of sericite powder was incubated at 800°C in a muffle furnace for 1 hour to obtain thermally activated sericite; 10g of thermally activated sericite was dissolved in 100mL5mol/L nitric acid solution in Stir and react at 95°C for 4h, filter with suction and dry at 60°C to obtain acidified sericite; take 1g of acidified sericite in 50mL6mol/L NaCl solution and stir for 1h at 95°C, repeat 3 times and use ultrapure water Wash once, filter with suction and dry at 60°C to obtain sodium sericite; disperse 1g of sodium sericite into 50mL of 1mol/L cetyltrimethylammonium bromide aqueous solution, stir and reflux at 90°C for 24h, take The reaction precipitate was washed several times with ultrapure water, and dried at 100° C. for 24 hours to obtain an intercalated sericite material.

Prepare a solution according to the mass ratio of silane coupling agent (KH-550) 20% + ethanol 72% + water 8%, add 1g of intercalated sericite material into 50mL solution and stir for 1h, filter with suction, and dry in an oven at 120°C. An organically modified intercalation sericite material is obtained.

3. Preparation of the polymer layer prepolymer in the middle layer:

Take 1.0504g (4.62mmol) diamine monomer diaminobenzoanilide DABA and add it to 10mL DMF solution, and keep stirring for a period of time to fully mix the system; add 1.0284g (4.71mmol) dianhydride monomer 1 to the above system , 2,4,5-Pyromellitic dianhydride PMDA, after adding, stir at a medium speed for 1 hour until the system forms a sol; add 1% of the monomer weight (total weight of diamine + dianhydride) to the sol system. 0.0208g of intercalation sericite material, ultrasonic mechanical stirring for 5h, to obtain a mixed sol of water/oxygen barrier layer.

4. Use the sol in step 1 to coat on a glass plate with a dry and clean surface, and dry it in an oven at 150°C for 30 minutes to remove the solvent to obtain a dry PAA film, which is the polymer lower surface layer 1;

Coat the mixed sol of the waterproof oxygen barrier layer in step 3 on the surface of the above-mentioned dry PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry double-layer PAA film;

Use the sol in step 1 to coat the surface of the above-mentioned dry double-layer PAA film, dry in an oven at 150°C for 30 minutes to remove the solvent, and obtain a dry three-layer PAA film;

Put the above three layers of PAA film into an oven at 150°C, raise the temperature to 250°C for 1 hour, and raise the temperature to 350°C for 1 hour; after natural cooling to room temperature, soak the composite film in hot water to peel off the composite film from the glass plate to obtain a multilayer Water/oxygen barrier composite film.

Water vapor transmission tests were performed on the upper and lower polymer surface layers and the middle layer after polymerization using different diamines and dianhydride monomers, and the results are shown in Tables 2 to 5 below.

Table 2. Film Water Vapor Transmission Test

Note:

WVTR is the actual measured water vapor transmission rate of the film, and the actual thickness t of the film is in brackets;

WVTR' is the water vapor transmission rate calculated by the formula WVTR'=WVTR*t/t', t'=50μm, which means the water vapor transmission rate when the film thickness is uniformly converted to 50μm.

The diamine monomer not containing an amide bond used in Table 2 is ODA, the diamine monomer containing an amide bond is DABA, and the dianhydride monomer is PMDA. 8ODA-2DABA in the table represents the polyimide material synthesized by mixing ODA and DABA at a mass content of 8:2 and then polymerizing with PMDA. Similarly, 7ODA-3DABA means that ODA and DABA are mixed at a mass content of 7:3.

Table 3. Film Water Vapor Transmission Test

Note:

WVTR is the actual measured water vapor transmission rate of the film, and the actual thickness t of the film is in brackets;

WVTR' is the water vapor transmission rate calculated by the formula WVTR'=WVTR*t/t', t'=50μm, which means the water vapor transmission rate when the film thickness is uniformly converted to 50μm.

The diamine monomer not containing an amide bond used in Table 3 is SDA, the diamine monomer containing an amide bond is DABA, and the dianhydride monomer is PMDA.

Table 4. Film Water Vapor Transmission Test

Note:

WVTR is the actual measured water vapor transmission rate of the film, and the actual thickness t of the film is in brackets;

WVTR' is the water vapor transmission rate calculated by the formula WVTR'=WVTR*t/t', t'=50μm, which means the water vapor transmission rate when the film thickness is uniformly converted to 50μm.

The diamine monomer not containing an amide bond used in Table 4 is BAPP, the diamine monomer containing an amide bond is DABA, and the dianhydride monomer is BPDA.

Table 5 Film Water Vapor Transmission Test

Note:

WVTR is the actual measured water vapor transmission rate of the film, and the actual thickness t of the film is in brackets;

WVTR' is the water vapor transmission rate calculated by the formula WVTR'=WVTR*t/t', t'=50μm, which means the water vapor transmission rate when the film thickness is uniformly converted to 50μm.

The diamine monomer not containing an amide bond used in Table 5 is ODA, the diamine monomer containing an amide bond is DABA, and the dianhydride monomer is BPDA.

The data in Table 2 to Table 5 shows that with the increase of the relative proportion of DABA in the diamine monomer, the WVTR (water vapor transmission rate) of the obtained polyimide material is in a downward trend, which proves that the amide bond structure in the monomer DABA can Effectively reduce the penetration of water and help to improve the water vapor barrier performance of the material. The experimental results are consistent with the results deduced in the experimental principle, that is, the mechanism of "water-locking" of the amide bond in DABA and the amide bond in DABA contribute to the improvement of the interaction between polyimide molecular segments.

Claims (10)

1. A water/oxygen barrier polymer-based composite material, characterized in that it is composed of an inorganic layered filler dispersed in a polymer matrix material after reacting with a surface modifier and an intercalation agent, and the polymer matrix material It is an organic polymer containing amide bonds or hydroxyl or carboxyl groups. 2. The water/oxygen barrier polymer-based composite material according to claim 1, wherein the organic polymer is synthesized by a polymerization reaction between a dianhydride monomer and a diamine monomer containing an amide bond or a hydroxyl or carboxyl group polyimide material. 3. The water/oxygen barrier polymer-based composite material according to claim 1, characterized in that, the inorganic layered filler has multiple different aspect ratios and lamellar spacings, and the inorganic layered filler can be Mongolian Desoil, or quartz, or mica, or graphene, or boron nitride inorganic filler. 4. The water/oxygen barrier polymer-based composite material according to claim 1, wherein the surface modifier is a silane coupling agent or a diamine monomer having an amino group that can participate in a polymerization reaction; The intercalation agent is to include cetyl trimethyl ammonium chloride, or cetyl trimethyl ammonium bromide, or octadecyl trimethyl ammonium chloride, or octadecyl trimethyl ammonium bromide Ammonium chloride is an organic quaternary ammonium salt of a diamine monomer with an amino group that can participate in a polymerization reaction. 5. The water/oxygen barrier polymer-based composite material according to claim 1, characterized in that, the polymer matrix material is polyimide prepared by participating in the polymerization reaction of the diamine monomer of the following formula (I) Amine material. Note: R, R" represent alkyl segments; Ar, Ar' represent aromatic segments. 6. A method for manufacturing a water/oxygen barrier polymer-based composite material, comprising the following steps: (1) Stir the inorganic layered filler with water to make a suspension, and after standing, take the upper layer of the suspension and centrifuge to obtain the small particle size inorganic layered filler; (2) Intercalation treatment: disperse the small particle size inorganic layered filler into the intercalation agent, take the reaction precipitate after fully reacting, wash and dry at 100°C for 24 hours to obtain the intercalated inorganic layered filler; (3) adding the intercalated inorganic layered filler into the organic modifier, fully stirring, filtering to take the precipitate, and drying to obtain the organically modified intercalated inorganic layered filler; (4) Preparation of the prepolymer of the polymer matrix material: take the prepolymer monomer of the polymer matrix material, fully mix to form a sol; (5) Add the organically modified intercalated inorganic layered filler obtained in step (3) to the sol in step (4), and stir it ultrasonically for 5 hours to obtain a mixed sol; (6) Coating the mixed sol obtained in step (5) on the surface of the material to be prepared to obtain a water/oxygen barrier layer. 7. A water/oxygen barrier polymer-based composite film, characterized in that: it is composed of upper, middle and lower layers, and the middle layer is the water/oxygen barrier polymer-based composite film according to any one of claims 1 to 6. Materials, the upper and lower layers are polyimides formed by the polymerization reaction of dianhydride monomers and diamine monomers that do not contain amide bonds, hydroxyl groups, or carboxyl groups. Among them, the dianhydride monomers are PMDA, BPDA, One of BTDA, the diamine monomer without amide bond, no hydroxyl group, and no carboxyl group is one of ODA, SDA, and BAPP. 8. The method for preparing the water/oxygen barrier polymer-based composite film according to claim 7, is characterized in that it comprises the following steps: S1. Prepare the organic polymer solution required for the polymer surface layer and apply or melt process to form a film, and obtain the lower surface layer of the polymer after solidification; S2. First prepare the water/oxygen barrier polymer-based composite material sol according to the following steps: (1) Stir the inorganic layered filler with water to make a suspension, and after standing, take the upper layer of the suspension and centrifuge to obtain the small particle size inorganic layered filler; (2) Intercalation treatment: disperse the small particle size inorganic layered filler into the intercalation agent, take the reaction precipitate after fully reacting, wash and dry at 100°C for 24 hours to obtain the intercalated inorganic layered filler; (3) adding the intercalated inorganic layered filler into the organic modifier, fully stirring, filtering to take the precipitate, drying and grinding to obtain the organically modified intercalated inorganic layered filler; (4) Preparation of the prepolymer of the polymer matrix material: take the prepolymer monomer of the polymer matrix material, fully mix to form a sol; (5) Add the organically modified intercalated inorganic layered filler obtained in step (3) to the sol in step (4), and stir it mechanically for 5 hours to obtain a water/oxygen barrier polymer-based composite material sol; Then apply the water/oxygen barrier polymer-based composite material sol on the surface of the polymer lower surface layer prepared in S1, and form a water/oxygen barrier layer on the surface of the lower polymer surface layer after curing; S3. Prepare a polymer surface layer solution and apply it on the surface of the water/oxygen barrier layer prepared in S2, and form a polymer upper surface layer on the surface of the water/oxygen barrier layer after curing; S4. Heat-treating the composite film obtained in S3 to obtain a water/oxygen barrier polymer-based composite film. 9. An application of the water/oxygen barrier polymer-based composite material according to any one of claims 1 to 5 in a multi-layer packaging structure. 10. An application of the water/oxygen barrier polymer-based composite film material according to claim 7 in flexible electronics or flexible display devices, said flexible electronics or flexible display devices are preferably electronic paper, flexible TFT devices, flexible OLED devices, sensors or printed electronics.