CN115926712A - Bi-component silane modified polyether conductive sealant and preparation method thereof - Google Patents

Abstract

The invention relates to a two-component silane-modified polyether conductive sealant and a preparation method thereof. The invention uses silane-modified polyether as a prepolymer to develop a two-component conductive silane-modified polyether glue , after mixing components A and B, the inner and outer layers of the glue are cured at the same time, and it can be completely cured in about 2 days. Compared with the one-component formula, its storage period and service life are improved; at the same time, the invention endows the silane-modified polyether adhesive with good electrical conductivity by adding modified carbon nanotubes.

Description

A two-component silane-modified polyether conductive sealant and preparation method thereof

Technical Field

The invention belongs to the technical field of sealants, and particularly relates to a two-component silane-modified polyether conductive sealant and a preparation method thereof.

Background Art

Conductive adhesive is an adhesive that has certain conductive properties after curing or drying. It usually has a matrix resin and conductive fillers, i.e. conductive particles, as the main components. The conductive particles are combined together through the bonding effect of the matrix resin to form a conductive path and realize the conductive connection of the bonded materials. At present, most of the conductive adhesives used in the market are filler-type, mainly epoxy, polyurethane, and acrylic resin. Among them, epoxy has high bonding strength, a wide bonding range, and high hardness, but due to the high cross-linking density of epoxy adhesive polymers, its elasticity is relatively poor, and it is brittle after curing, and its use is limited in places with certain displacement capacity; polyurethane has relatively large bonding strength, but its disadvantage is that the preparation of the resin is not environmentally friendly, the alkali resistance is relatively poor, and _CO2 is released during the cross-linking reaction, which may cause certain corrosion during application; acrylic resin has good optical properties, water-resistant, oil-resistant, and alkali-resistant, but the disadvantage is that the heat resistance is poor, and it is easy to crack when the ambient temperature changes rapidly.

Silane-modified polyether has the characteristics of a main chain of polyether and a silane-terminated end group, so it has the advantages of both silicone glue and polyurethane glue. It has a wide bonding range, high bonding strength, good elasticity and impact resistance, and releases few small molecules during curing, and it will hardly cause corrosion to the substrate and the environment during application. At present, there are relatively few studies on conductive polyether glue. Chinese patent CN110527474A invented a one-component conductive silane-modified polyether glue, but due to its single-component characteristic curing speed of basically 3-6mm/24h, it cannot quickly achieve deep curing in application scenarios that require deep and rapid curing, resulting in failure. Therefore, it is necessary to provide a silane-modified polyether conductive sealant that can quickly achieve deep curing.

Summary of the invention

The purpose of the present invention is to develop a two-component silane-modified polyether conductive sealant, wherein after the two components are mixed, the sealant is cured from the inside to the outside at the same time, thereby achieving the purpose of rapid curing.

Another object of the present invention is to provide a method for preparing the above two-component silane-modified polyether conductive sealant.

The technical solution adopted to achieve the above-mentioned invention object is:

A two-component silane-modified polyether conductive sealant, characterized in that it comprises a component A and a component B, wherein the component A comprises raw materials in the following weight ratio:

The B component includes the following raw materials in weight ratio:

The modified carbon nanotubes are obtained by: 1) heating a chemical vapor deposition device to 700-900° C., first introducing a mixed gas of hydrogen and nitrogen, and then introducing ethylene gas, on a gold-plated silicon wafer substrate, and obtaining carbon nanotubes after 5-10 minutes; 2) adding carbon nanotubes and a coupling agent in a mass ratio of 1.1:1 to 10 parts of a toluene solvent, fully mixing and reacting for 10-15 minutes, and then filtering to obtain the modified carbon nanotubes.

The silane-modified polyether is one or a mixture of dimethoxysilyl-terminated polyether, diethoxysilyl-terminated polyether, trimethoxysilyl-terminated polyether and triethoxysilyl-terminated polyether.

The coupling agent is selected from one or a mixture of γ-aminopropyltriethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

The reinforcing filler is one or a mixture of nano calcium carbonate, heavy calcium carbonate, silicon micropowder, talcum powder and kaolin.

The thixotropic agent is one or a mixture of polyamide wax, fumed silica, nano-diatomaceous earth, and hydrogenated castor oil; the light stabilizer is one or a mixture of BASF ultraviolet absorbers Tinuvin UV-P, Tinuvin UV-9, Tinuvin 326, Tinuvin, Tinuvin 540, and Tinuvin 770; the heat stabilizer is one or a mixture of BASF antioxidants Irganox 245, Irganox 1010, and Irganox 1035.

The plasticizer is a polyether polyol plasticizer or a phthalate plasticizer, or a mixture of more than one of them; the catalyst is one or more of dibutyltin dilaurate (DBTDL), dioctyltin diacetate, chelated tin, stannous octoate or diorganotin bis(β-diketone ester).

The preparation method of the above-mentioned two-component silane-modified polyether conductive sealant is characterized in that it comprises the following steps:

1) adding silane-modified polyether, modified carbon nanotubes, reinforcing filler, thixotropic agent, light stabilizer, heat stabilizer and plasticizer into a kneader for vacuum high-speed kneading, with a material temperature of 60 to 120° C., a vacuum degree of -0.06 to -0.099 MPa, a mixing time of 60 to 180 min, and cooling to room temperature to obtain component A;

2) Add the formula amount of reinforcing filler, plasticizer, coupling agent and catalyst into a high-speed disperser, stir at high speed under vacuum for 30 to 60 minutes, the vacuum degree is -0.06 to -0.099 MPa, and obtain component B after cooling to room temperature.

The present invention uses silane-modified polyether as a basic prepolymer to develop a two-component conductive silane-modified polyether adhesive. After components A and B are mixed, the adhesive is cured from the inside out at the same time, and can be completely cured in about 2 days. The deep curing speed is fast, and it has excellent advantages in applications such as repairing and filling seams of some deep conductive modules. Compared with a single-component formula, its storage life and application period are improved. At the same time, the present invention gives the silane-modified polyether adhesive good conductive properties by adding modified carbon nanotubes.

DETAILED DESCRIPTION

The technical scheme of the present invention is described in detail below through specific embodiments, and the description is only for the convenience of those skilled in the art to understand and apply the present application. It is obvious that those familiar with the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without having to pay creative labor. Therefore, the present application is not limited to the embodiments here, and improvements and modifications made by those skilled in the art based on the contents disclosed in the present application without departing from the scope and spirit of the present application are within the scope of the present application.

The modified carbon nanotubes in the following embodiments are obtained as follows:

1) The chemical vapor deposition equipment is heated to 800° C. A mixed gas of hydrogen and nitrogen is first introduced on a gold-plated silicon wafer substrate, and then ethylene gas is introduced to obtain carbon nanotubes after 10 minutes; 2) The carbon nanotubes and the coupling agent are added to 10 parts of toluene solvent in a mass ratio of 1.1:1, and the mixture is fully mixed and reacted for 12 minutes. After filtration, the modified carbon nanotubes can be obtained.

Example 1

The two-component silane-modified polyether conductive sealant of this embodiment is prepared by the following method, based on parts by weight:

1) Preparation of component A:

100 parts of trimethoxysilyl-terminated polyether, 40 parts of modified carbon nanotubes, 70 parts of nano-calcium carbonate, 5 parts of polyamide wax, 6 parts of Tinuvin 326, 6 parts of Irganox 1010, and 10 parts of polyoxypropylene triol PPG3000 were added to a kneader, mixed at a temperature of 90° C. and a vacuum degree of -0.09 MPa for 120 minutes, and cooled to room temperature to obtain component A.

2) Preparation of component B:

Take 50 parts of heavy calcium carbonate, 40 parts of DIDP (diisodecyl phthalate), 8 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane, and 0.5 parts of DBTDL and add them into a reaction kettle. Stir at a high speed in vacuum with a vacuum degree of -0.09 MPa, blend for 40 minutes, and cool to room temperature to obtain component B.

When in use, the above-mentioned component A and component B are mixed evenly in a volume ratio of 1:1 to prepare a two-component silane-modified polyether conductive sealant. The performance indicators are shown in Table 1.

Example 2

The two-component silane-modified polyether conductive sealant of this embodiment is prepared by the following method, based on parts by weight:

1) Preparation of component A:

100 parts of trimethoxysilyl-terminated polyether, 70 parts of modified carbon nanotubes, 70 parts of nano-calcium carbonate, 3 parts of polyamide wax, 6 parts of Tinuvin 326, 6 parts of Irganox 1010, and 30 parts of polyoxypropylene triol PPG3000 were added to a kneader, mixed at a temperature of 90° C. and a vacuum degree of -0.09 MPa for 150 minutes, and cooled to room temperature to obtain component A.

2) Preparation of component B:

60 parts of heavy calcium carbonate, 50 parts of DIDP, 10 parts of γ-aminopropyltriethoxysilane and 0.8 parts of DBTDL were added into a reaction kettle, stirred at high speed in vacuum with a vacuum degree of -0.09 MPa, blended for 40 minutes, and cooled to room temperature to obtain component B.

When in use, the above-mentioned component A and component B are mixed evenly in a volume ratio of 1:1 to prepare a two-component silane-modified polyether conductive sealant. The performance indicators are shown in Table 1.

Example 3

The two-component silane-modified polyether conductive sealant of this embodiment is prepared by the following method, based on parts by weight:

1) Preparation of component A:

100 parts of trimethoxysilyl-terminated polyether, 100 parts of modified carbon nanotubes, 70 parts of heavy calcium carbonate, 6 parts of hydrogenated castor oil, 6 parts of Tinuvin 326, 6 parts of Irganox 1010, and 20 parts of polyoxypropylene triol PPG3000 were added to a kneader, mixed at a temperature of 90° C. and a vacuum degree of -0.09 MPa for 150 minutes, and cooled to room temperature to obtain component A.

2) Preparation of component B:

Take 50 parts of kaolin, 50 parts of DIDP, 5 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane and 0.8 parts of DBTDL and add them into a reaction kettle. Stir at a high speed in vacuum with a vacuum degree of -0.09 MPa, blend for 40 minutes, and cool to room temperature to obtain component B.

When in use, the above-mentioned component A and component B are mixed evenly in a volume ratio of 1:1 to prepare a two-component silane-modified polyether conductive sealant. The performance indicators are shown in Table 1.

Example 4

The two-component silane-modified polyether conductive sealant of this embodiment is prepared by the following method, based on parts by weight:

1) Preparation of component A:

100 parts of dimethoxysilyl-terminated polyether, 40 parts of modified carbon nanotubes, 70 parts of nano-calcium carbonate, 5 parts of fumed silica, 6 parts of Tinuvin 326, 6 parts of Irganox 1010, and 10 parts of polyoxypropylene glycol PPG2000 were added to a kneader, mixed at a temperature of 90° C. and a vacuum degree of -0.09 MPa for 120 minutes, and cooled to room temperature to obtain component A.

2) Preparation of component B:

Take 50 parts of kaolin, 40 parts of DIDP, 8 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane, and 1.2 parts of chelated tin and add them into a reaction kettle, stir at a high speed in vacuum with a vacuum degree of -0.09 MPa, blend for 40 minutes, and cool to room temperature to obtain component B.

When in use, the above-mentioned component A and component B are mixed evenly in a volume ratio of 1:1 to prepare a two-component silane-modified polyether conductive sealant. The performance indicators are shown in Table 1.

Example 5

The two-component silane-modified polyether conductive sealant of this embodiment is prepared by the following method, based on parts by weight:

1) Preparation of component A:

100 parts of dimethoxysilyl-terminated polyether, 70 parts of modified carbon nanotubes, 70 parts of nano-calcium carbonate, 4 parts of polyamide wax, 6 parts of Tinuvin 326, 6 parts of Irganox 1010, and 10 parts of polyoxypropylene glycol PPG2000 were added to a kneader, mixed at a temperature of 90° C. and a vacuum degree of -0.09 MPa for 120 minutes, and cooled to room temperature to obtain component A.

2) Preparation of component B:

60 parts of heavy calcium carbonate, 50 parts of DIDP, 5 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane and 1.8 parts of chelated tin were added to a reaction kettle, stirred at high speed in vacuum with a vacuum degree of -0.09 MPa, blended for 40 minutes, and cooled to room temperature to obtain component B.

When in use, the above-mentioned component A and component B are mixed evenly in a volume ratio of 1:1 to prepare a two-component silane-modified polyether conductive sealant. The performance indicators are shown in Table 1.

Comparative Example 1

The silane-modified polyether adhesive of this comparative example is prepared by the following method, calculated by weight:

1) Preparation of component A:

100 parts of trimethoxysilyl-terminated polyether, 110 parts of nano-calcium carbonate, 5 parts of polyamide wax, 6 parts of Tinuvin 326, 6 parts of Irganox 1010, and 10 parts of polyoxypropylene triol PPG3000 were added to a kneader, mixed at a high speed for 120 minutes at a temperature of 90° C. and a vacuum degree of -0.09 MPa, and cooled to room temperature to obtain component A.

3) Preparation of component B:

Take 50 parts of heavy calcium carbonate, 40 parts of DIDP, 8 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane, and 0.5 parts of DBTDL and add them into a reaction kettle. Stir at a high speed in vacuum with a vacuum degree of -0.09 MPa, blend for 40 minutes, and cool to room temperature to obtain component B.

When in use, the above-mentioned component A and component B are mixed evenly in a volume ratio of 1:1 to prepare a two-component silane-modified polyether adhesive. The performance indicators are shown in Table 1.

Comparative Example 2

The silane-modified polyether adhesive of this embodiment is prepared by the following method, based on parts by weight:

1) Preparation of component A:

100 parts of trimethoxysilyl-terminated polyether, 40 parts of silver powder, 70 parts of nano-calcium carbonate, 5 parts of polyamide wax, 6 parts of Tinuvin 326, 6 parts of Irganox 1010, and 10 parts of PPG3000 were added to a kneader, mixed at a high speed for 120 minutes at a temperature of 90°C and a vacuum degree of -0.09 MPa, and cooled to room temperature to obtain component A.

3) Preparation of component B:

Take 50 parts of heavy calcium carbonate, 40 parts of DIDP, 8 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane, and 0.5 parts of DBTDL and add them into a reaction kettle. Stir at a high speed in vacuum with a vacuum degree of -0.09 MPa, blend for 40 minutes, and cool to room temperature to obtain component B.

When in use, the above-mentioned component A and component B are mixed evenly in a volume ratio of 1:1 to prepare a two-component silane-modified conductive polyether adhesive. The performance indicators are shown in Table 1.

Table 1 Product performance indicators

It can be seen from Table 1 that the conductive effect of the two-component silane-modified polyether conductive sealant prepared by adding modified carbon nanotubes is better than that of the two-component silane-modified conductive polyether sealant prepared by using traditional conductive materials.

Claims (7)

1. A two-component silane-modified polyether conductive sealant, characterized in that it comprises component A and component B, wherein component A comprises raw materials in the following weight ratio:

The B component includes the following raw materials in weight ratio:

The modified carbon nanotubes are obtained by: 1) heating a chemical vapor deposition device to 700-900° C., first introducing a mixed gas of hydrogen and nitrogen, and then introducing ethylene gas, on a gold-plated silicon wafer substrate, and obtaining carbon nanotubes after 5-10 minutes; 2) adding carbon nanotubes and a coupling agent in a mass ratio of 1.1:1 to 10 parts of a toluene solvent, fully mixing and reacting for 10-15 minutes, and then filtering to obtain the modified carbon nanotubes. 2. The two-component silane-modified polyether conductive sealant as described in claim 1, characterized in that the silane-modified polyether is one or a mixture of more than one of a dimethoxysilyl-terminated polyether, a diethoxysilyl-terminated polyether, a trimethoxysilyl-terminated polyether and a triethoxysilyl-terminated polyether. 3. The two-component silane-modified polyether conductive sealant as described in claim 1, characterized in that the coupling agent is selected from one or a mixture of more than one of γ-aminopropyltriethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane. 4. The two-component silane-modified polyether conductive sealant according to claim 1, characterized in that the reinforcing filler is one or a mixture of more than one of nano calcium carbonate, heavy calcium carbonate, silicon micropowder, talc, and kaolin. 5. The two-component silane-modified polyether conductive sealant according to claim 1, characterized in that the thixotropic agent is one or a mixture of polyamide wax, fumed silica, nano-diatomaceous earth, and hydrogenated castor oil; the light stabilizer is one or a mixture of BASF ultraviolet absorbers Tinuvin UV-P, Tinuvin UV-9, Tinuvin 326, Tinuvin, Tinuvin540, and Tinuvin 770; the heat stabilizer is one or a mixture of BASF antioxidants Irganox245, Irganox 1010, and Irganox 1035. 6. The two-component silane-modified polyether conductive sealant as described in claim 1, characterized in that the plasticizer is a polyether polyol plasticizer, a phthalate plasticizer, or a mixture of more than one; and the catalyst is one or more of dibutyltin dilaurate, dioctyltin diacetate, chelated tin, stannous octoate or diorganotin bis(β-diketone ester). 7. A method for preparing the two-component silane-modified polyether conductive sealant according to claims 1 to 6, characterized in that it comprises the following steps: 1) adding silane-modified polyether, modified carbon nanotubes, reinforcing filler, thixotropic agent, light stabilizer, heat stabilizer and plasticizer into a kneader for vacuum high-speed kneading, with a material temperature of 60 to 120° C., a vacuum degree of -0.06 to -0.099 MPa, a mixing time of 60 to 180 min, and cooling to room temperature to obtain component A; 2) Add the formula amount of reinforcing filler, plasticizer, coupling agent and catalyst into a high-speed disperser, stir at high speed under vacuum for 30 to 60 minutes, the vacuum degree is -0.06 to -0.099 MPa, and obtain component B after cooling to room temperature.