CN108192561A - Ketoxime removing type silicone sealant and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of ketoxime removing type silicone sealants and preparation method thereof.The ketoxime removing type silicone sealant, in parts by weight, including the following raw material component：100 parts of polysiloxanediol, 40~80 parts of dimethicone, composition A0.5~2 part, composition B0.5~2 part, 15~25 parts of filler, 5~12 parts of crosslinking agent, 0.5~3 part of silane coupling agent, 0.05~0.5 part of catalyst；Wherein, the composition A includes the nano silver being carried on carrier；The composition B includes thiazole compound.It is good that the ketoxime removing type silicone sealant is not easy xanthochromia, anti-mold effect, and surface drying, hardening time are short, facilitate construction.

Description

Deketoxime type silicone sealant and preparation method thereof

technical field

The invention relates to a silicone sealant, in particular to a deketoxime type silicone sealant and a preparation method thereof.

Background technique

In recent years, more and more attention has been paid to the anti-mildew effect of silicone sealants for home decoration, especially for the kitchen and bathroom decoration of high-end hotels and villas. These application sites have been in a warm and humid environment for a long time, and the sealant is not cleaned properly before use or the stains adhered after use provide nutrients for mold, resulting in mildew of the sealant, which seriously affects the appearance, pollutes the environment, and even causes the sealant to fail. .

Transparent silicone sealant is widely used in the fields of glass lighting roof seam sealing, plexiglass and other light shed seam sealing, coated glass and mirror glass sealing and other fields because of its transparent characteristics. With the expansion of the interior decoration market, transparent silicone sealants are gradually used in kitchen and bathroom waterproof sealing, so there are certain requirements for the mildew resistance of transparent silicone sealants. Therefore, anti-mildew transparent silicone sealant products have great market potential and development space.

Adding antifungal agents is the most direct and effective way to prepare antifungal sealants, but some antifungal agents are easy to cause yellowing of the colloid, which seriously affects the transparency and aesthetics of the sealant. Some methods use organic arsenic compounds with polyether polyols as carriers as antifungal agents to prepare one-component antifungal transparent dealcoholized silicone sealants, but their long-term antifungal properties remain to be investigated. Another method uses thiazole compounds as antifungal agents to prepare one-component room temperature vulcanization transparent dealcoholized antifungal silicone sealant, but the colloid of this type of sealant is prone to yellowing.

Contents of the invention

Based on this, it is necessary to provide a deketoxime type silicone sealant. The deketoxime type silicone sealant is not easy to yellow, has good anti-mildew effect, is dry on the surface, has a short curing time, and is convenient for construction.

A deketoxime type silicone sealant, in parts by weight, comprising the following raw material components:

Wherein, the composition A includes nano-silver loaded on a carrier;

The composition B includes thiazole compounds.

In one of the embodiments, the deketoxime type silicone sealant includes the following raw material components in parts by weight:

In one embodiment, the carrier includes at least one of apatite, calcium phosphate, and zirconium phosphate.

The nano-silver can be loaded on the carrier by conventional methods. In one embodiment of the present invention, the carrier can be used to support silver ions through ion exchange or adsorption.

In one embodiment, the composition B includes 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4- At least one of isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one.

In one of the embodiments, the structural formula of the dihydroxy polysiloxane is The viscosity is 8~200Pa.s (25°C).

In one embodiment, the viscosity of the simethicone oil is 0.1-50 Pa.s (25° C.).

In one embodiment, the crosslinking agent is a silane containing ketoxime group.

In one of the embodiments, the crosslinking agent is methyl tributylketoxime silane, vinyl tributylketoxime silane, propyl tributylketoxime silane, phenyl tributylketoxime silane, tetra Butylketoximosilane, Methyltris(methylisobutylketoxime)silane, Vinyltris(methylisobutylketoxime)silane, Tetrakis(methylisobutylketoxime)silane, Methyltriacetone At least one of oximinosilane and vinyltriacetone oximinosilane. It is preferably at least two of the above types of crosslinking agents.

In one of the embodiments, the crosslinking agent is methyl tributylketoxime silane and vinyl tributylketoxime silane, preferably the weight ratio of the two is 5-9:2-3; or, methyl Three (methyl isobutyl ketoxime base) silane and vinyl three (methyl isobutyl ketoxime base) silane, preferably the weight ratio of the two is 5～7:1～3; Or, tetrabutyl ketoxime base silane and For methyl tributylketoxime silane, the weight ratio of the two is preferably 3-5:5-7.

In one of the embodiments, the silane coupling agent is chloropropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-βaminoethyl At least one of γ-aminopropyltrimethoxysilane, N-βaminoethyl γ-aminopropyltriethoxysilane, glycidyltriethoxysilane, and mercaptopropyltrimethoxysilane.

In one of the embodiments, the silane coupling agent is γ-aminopropyltriethoxysilane, N-βaminoethylγ-aminopropyltrimethoxysilane or N-βaminoethylγ-ammonia Propyltriethoxysilane.

In one of the embodiments, the catalyst is dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dibutyltin di(dodecylsulfide), stannous octoate, tin dibutyl acetylacetonate at least one.

In one embodiment, the filler is an inorganic filler. Fumed silica (silica) is preferred.

The present invention also provides a preparation method of the deketoxime type silicone sealant, comprising the following steps:

Mix and stir the dihydroxy polysiloxane, dimethyl silicone oil, composition A, composition B, filler, crosslinking agent, silane coupling agent, and catalyst, control the vacuum degree to 0.09-0.10MPa, and the rotation speed to 10-800rpm, Stir for 30 to 180 minutes.

Compared with the prior art, the present invention has the following beneficial effects:

The deketoxime type silicone sealant of the present invention is based on the organosilicon system composed of dihydroxy polysiloxane and dimethyl silicone oil, combined with nano silver and thiazole compounds loaded on the carrier to prepare the deketoxime type silicone sealant Ketone sealant, the combination of various raw materials shows a good synergistic effect, so that the deketoxime type silicone sealant has excellent anti-mold effect and long-term effect under the premise of maintaining transparency, and is suitable for applications with higher requirements for anti-mold. High interior decoration, while avoiding the yellowing of the colloid during storage, the surface is dry and the curing time is shorter, and it has good adhesion to most substrates. It can be widely used for waterproof sealing of interior decoration, and the construction operation is convenient. High construction efficiency.

Detailed ways

The deketoxime type silicone sealant of the present invention and its preparation method will be further described in detail below in conjunction with specific examples.

The dihydroxy polysiloxane structural formula adopted in the embodiment of the present invention is Viscosity of 8 ~ 200Pa.s (25 ℃), purchased from Dow Corning;

The viscosity of simethicone oil is 0.1～50Pa.s (25℃), purchased from Dow Corning;

Nanosilver loaded on a carrier is purchased from Lonza, and the carrier is apatite, calcium phosphate or zirconium phosphate.

Example 1:

In this embodiment, a deketoxime type silicone sealant is composed of the following raw materials in parts by weight:

100 parts of dihydroxy polysiloxane, 60 parts of dimethyl silicone oil, 20 parts of fumed silica, 1 part of nano silver loaded on apatite, 1 part of 1,2-benzisothiazolin-3-one , 6 parts of methyl tributylketoxime silane, 2 parts of vinyl tributylketoxime silane, 1.5 parts of γ-aminopropyl triethoxysilane, 0.25 part of dibutyltin diacetate.

The preparation method of the above-mentioned deketoxime type silicone sealant comprises the following steps:

The above-mentioned raw material composition was added to the double planetary equipment, and the chemical reaction was carried out at a vacuum degree of 0.09MPa and a rotation speed of 300rpm for 90min. The product performance indicators are shown in Table 1.

Example 2:

In this embodiment, a deketoxime type silicone sealant is composed of the following raw materials in parts by weight:

100 parts of dihydroxypolysiloxane, 80 parts of dimethyl silicone oil, 25 parts of fumed silica, 2 parts of nano silver loaded on apatite, 2 parts of 1,2-benzisothiazolin-3-one , 9 parts of methyl tributylketoxime silane, 3 parts of vinyl tributylketoxime silane, 3 parts of γ-aminopropyl triethoxysilane, 0.5 part of dibutyltin diacetate.

The preparation method of the above-mentioned deketoxime type silicone sealant comprises the following steps:

Add the above raw materials into the double planetary equipment, and carry out the chemical reaction for 90 minutes at a vacuum degree of 0.09MPa and a rotation speed of 300rpm. The product performance indicators are shown in Table 1.

Example 3:

In this embodiment, a deketoxime type silicone sealant is composed of the following raw materials in parts by weight:

100 parts of dihydroxy polysiloxane, 40 parts of simethicone, 15 parts of fumed silica, 0.5 parts of nano silver loaded on calcium phosphate, 0.5 parts of 2-methyl-4-isothiazolin-3-one , 5 parts of methyl tributylketoxime silane, 2 parts of vinyl tributylketoxime silane, 0.5 part of γ-aminopropyl triethoxysilane, 0.05 part of dibutyltin diacetate.

The preparation method of the above-mentioned deketoxime type silicone sealant comprises the following steps:

Add the above raw materials into the double planetary equipment, and carry out the chemical reaction for 90 minutes at a vacuum degree of 0.09MPa and a rotation speed of 300rpm. The product performance indicators are shown in Table 1.

Example 4:

In this embodiment, a deketoxime type silicone sealant is composed of the following raw materials in parts by weight:

100 parts of dihydroxy polysiloxane, 60 parts of dimethyl silicone oil, 20 parts of fumed silica, 0.5 parts of nano silver loaded on zirconium phosphate, 2-n-octyl-4-isothiazolin-3-one 2 parts, 4 parts of tetrabutylketoxime silane, 6 parts of methyl tributylketoxime silane, 1.5 parts of N-β aminoethyl γ-aminopropyl trimethoxysilane, 0.25 part of dibutyltin diacetate.

The preparation method of the above-mentioned deketoxime type silicone sealant comprises the following steps:

Add the above raw materials into the double planetary equipment, and carry out the chemical reaction for 90 minutes at a vacuum degree of 0.09MPa and a rotation speed of 300rpm. The product performance indicators are shown in Table 1.

Example 5:

In this embodiment, a deketoxime type silicone sealant is composed of the following raw materials in parts by weight:

100 parts of dihydroxy polysiloxane, 60 parts of dimethyl silicone oil, 20 parts of fumed silica, 2 parts of nano silver loaded on zirconium phosphate, 5-chloro-2-methyl-4-isothiazoline-3 - 0.5 parts of ketone, 6 parts of methyl tris (methyl isobutyl ketoxime) silane, 2 parts of vinyl tris (methyl isobutyl ketoxime) silane, N-β aminoethyl γ-aminopropyl triethyl 1.5 parts of oxysilane, 0.5 parts of dibutyltin dilaurate.

The preparation method of the above-mentioned deketoxime type silicone sealant comprises the following steps:

The above-mentioned raw materials were added to the double planetary equipment, and the chemical reaction was carried out for 90 minutes at a vacuum degree of 0.0 MPa and a rotation speed of 300 rpm. The product performance indicators are shown in Table 1.

Comparative example 1:

In this comparative example, a deketoxime type silicone sealant is composed of the following raw materials in parts by weight:

100 parts of dihydroxy polysiloxane, 60 parts of dimethyl silicone oil, 20 parts of fumed silica, 1 part of nano silver loaded on apatite, 6 parts of methyl tributyl ketoxime silane, vinyl tributyl 2 parts of ketoximosilane, 1.5 parts of γ-aminopropyltriethoxysilane, and 0.25 parts of dibutyltin diacetate.

The preparation method of the above-mentioned deketoxime type silicone sealant comprises the following steps:

Add the above raw materials into the double planetary equipment, and carry out the chemical reaction for 90 minutes at a vacuum degree of 0.09MPa and a rotation speed of 300rpm. The product performance indicators are shown in Table 1.

Comparative example 2:

In this comparative example, a deketoxime type silicone sealant is composed of the following raw materials in parts by weight:

100 parts of dihydroxy polysiloxane, 60 parts of dimethyl silicone oil, 20 parts of fumed silica, 1 part of 1,2-benzisothiazolin-3-one, 6 parts of methyl tributylketoxime silane, 2 parts of vinyl tributylketoxime silane, 1.5 parts of γ-aminopropyl triethoxysilane, 0.25 parts of dibutyltin diacetate.

The preparation method of the above-mentioned deketoxime type silicone sealant comprises the following steps:

Add the above raw materials into the double planetary equipment, and carry out the chemical reaction for 90 minutes at a vacuum degree of 0.09MPa and a rotation speed of 300rpm. The product performance indicators are shown in Table 1.

Carry out performance test to the deketoxime type silicone sealant of embodiment 1-5 and comparative example 1-2:

The test method is as follows:

1. Surface drying time: test according to the method specified in GB 13477.5-2002;

2. Shore hardness: make and maintain test samples according to the method specified in GB 16776-2005, and use Shore A hardness tester for testing according to GB/T531-2008;

3. Curing degree: test according to the method specified in GB/T 32369 Appendix A-2015;

4. Aging and yellowing: Visually inspect the deketoxime silicone sealants just prepared in Examples 1-5 and Comparative Examples 1-2 are all transparent, and then place the deketoxime silicone sealants at 70°C 7d, observe the yellowing of the rubber sample after aging, and judge visually;

5. Displacement capacity: According to JC/T 885-2016, the test shall be carried out according to the provisions of JC/T 885-2016 on mildew-proof sealant grade 25;

6. Anti-mildew performance: according to the method stipulated in GB/T 1741-2007, the anti-mildew grade test is carried out;

7. Long-term anti-mildew performance: According to the test period of GB/T 1741-2007, the anti-mildew level test is carried out twice.

The performance contrast of each embodiment of table 1 and comparative example

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (10)

1. A deketoxime type silicone sealant, characterized in that, in parts by weight, comprising the following raw material components: Wherein, the composition A includes nano-silver loaded on a carrier; The composition B includes thiazole compounds. 2. The deketoxime type silicone sealant according to claim 1, characterized in that, in parts by weight, comprising the following raw material components: 3. The deketoxime type silicone sealant according to claim 1 or 2, characterized in that the carrier comprises at least one of apatite, calcium phosphate, and zirconium phosphate. 4. The deketoxime type silicone sealant according to claim 1 or 2, wherein the composition B comprises 1,2-benzisothiazolin-3-one, 2-n-octyl- At least one of 4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one. 5. The deketoxime type silicone sealant according to claim 1 or 2, wherein the structural formula of the dihydroxy polysiloxane is The viscosity is 8～200Pa.s. 6. The deketoxime type silicone sealant according to claim 1 or 2, characterized in that the viscosity of the simethicone oil is 0.1-50 Pa.s. 7. The deketoxime type silicone sealant according to claim 1 or 2, wherein the crosslinking agent is methyl tributylketoxime silane, vinyl tributylketoxime silane, propyl Tributanoximinosilane, Phenyltributanoximinosilane, Tetrabutanoximinosilane, Methyltris(methylisobutylketoxime)silane, Vinyltris(methylisobutylketoxime)silane , At least one of tetrakis(methyl isobutyl ketoxime) silane, methyl triacetone oximino silane, vinyl triacetone oximino silane. 8. The deketoxime type silicone sealant according to claim 1 or 2, wherein the silane coupling agent is chloropropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-Aminopropyltriethoxysilane, N-βAminoethylγ-Aminopropyltrimethoxysilane, N-βAminoethylγ-Aminopropyltriethoxysilane, Glycidyltriethyl At least one of oxysilane and mercaptopropyltrimethoxysilane. 9. The deketoxime type silicone sealant according to claim 1 or 2, wherein the catalyst is dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, didodecane At least one of dibutyltin, stannous octoate, and dibutyltin acetylacetonate. 10. The preparation method of the deketoxime type silicone sealant described in any one of claims 1-9, is characterized in that, comprises the steps: The dihydroxypolysiloxane, dimethyl silicone oil, composition A, composition B, filler, crosslinking agent, silane coupling agent, and catalyst are mixed and stirred, and the vacuum degree is controlled to be 0.09-0.1MPa, and the rotation speed is 10-800rpm. Stir for 30 to 180 minutes.