CN110791101A

CN110791101A - Organic silicon waterproof anti-aging material and preparation method thereof

Info

Publication number: CN110791101A
Application number: CN201911134306.5A
Authority: CN
Inventors: 刘正辉; 王长杰; 杨丽芳
Original assignee: Guangzhou Xinyue New Material Technology Co Ltd
Current assignee: Guangzhou Xinyue New Material Technology Co Ltd
Priority date: 2019-11-19
Filing date: 2019-11-19
Publication date: 2020-02-14
Anticipated expiration: 2039-11-19
Also published as: CN110791101B

Abstract

The invention belongs to the field of organic silicon, and discloses an organic silicon waterproof anti-aging material which comprises the following components in percentage by weight: 20-40% of hydroxy silicone oil; 2-5% of hydrogen terminated silicone oil; 2-4% of dimethyl silicone oil; 1-5% of nano calcium carbonate; 5-15% of flame retardant powder; 0-1.5% of titanium dioxide; 4-8% of hydrophobic white carbon black; 0.1 to 0.5 percent of coupling agent; 1-5% of a cross-linking agent; 0.01 to 0.05 percent of catalyst; the solvent was added to 100%. The material has excellent waterproof and aging-resistant performances, and the surface drying performance is 5 min; the aging resistance time is 24 months without crystallization.

Description

Organic silicon waterproof anti-aging material and preparation method thereof

Technical Field

The invention relates to the field of organic silicon modification, in particular to an organic silicon waterproof anti-aging material and a preparation method thereof.

Background

Modification of silicone rubber using ketoximosilanes as crosslinkers has been a common practice in the art. The following comparison documents can be seen in detail.

An invention patent application CN201810175826.X is proposed by the applicant Dongguan megashu organosilicon science and technology company, and discloses a preparation method of an organosilicon polymer, which comprises the following steps of (1) hydrolyzing raw material butanone oxime silane, removing butanone oxime generated by hydrolysis, adding higher alcohol into the butanone oxime silane for condensation reaction, and removing residual micromolecules by vacuum treatment to obtain a condensation product; (2) adding dialkyl cyclosiloxane and a catalyst into the condensation product obtained in the step (1), maintaining the vacuum degree unchanged, stirring at constant temperature for chain extension reaction to obtain a chain extension product with the viscosity of 500-50000 mPa & s; (3) adding a chain terminator into the chain extension product obtained in the step (2) to carry out chain termination reaction, stirring at constant temperature to carry out catalyst breaking treatment, and then carrying out vacuum treatment to obtain the organic silicon polymer. The butanone oxime silane is any one or a mixture of at least two of methyl tributyrinoxime silane, tetrabutanone oxime silane and vinyl tributyrinoxime silane.

The applicant proposed an invention patent application CN201710987364.7 in 2017, which uses dimethyl dibutyloximosilane and methyl triacetoneximosilane as ketoximosilane to improve the elasticity of silicone rubber.

The applicant proposed an invention patent application CN201710986129.8 in 2017, which uses dimethyldibutyloximino silane to improve the toughness of silicone rubber.

The applicant, new materials ltd, blue star (chengdu), filed an invention patent application CN201510568542.3 in 2015, which uses dimethyldibutylketoximosilane and methyltributylketoximosilane for improving the flexibility of silicone rubber.

The applicant developed an invention patent application CN201110440529.1 in 2011 by developping chemical industry limited company, which adopts methyl tributyl ketoxime silane and vinyl tributyrinoxime silane to improve the properties of fast curing, high strength and high toughness.

The applicant of zeiper proposes an invention patent application CN2004100139487 in 2004, and discloses a preparation method of vinyl tris (methyl isobutyl ketoximyl) silane, which is mainly used for solving the problems of poor corrosion, poor stability, poor transparency, easy cracking and the like of the traditional silicon rubber crosslinking agent.

Therefore, in summary, the following conclusions can be drawn:

1. ketoximosilanes have been widely used as silicone rubber crosslinkers;

2. ketoximosilanes are built into many silicone rubber formulations to improve one or more properties.

The technical problem that this application will solve is: how to improve the aging resistance and the waterproof performance of the silicon rubber.

Disclosure of Invention

The invention aims to provide an organosilicon waterproof anti-aging material which has excellent waterproof and anti-aging performances, and the surface drying performance of the organosilicon waterproof anti-aging material is 5 min; the aging resistance time is 24 months without crystallization.

Unless otherwise specified, the% and parts in the present invention are weight percentages and parts by weight.

In order to achieve the purpose, the invention provides the following technical scheme:

an organosilicon waterproof aging-resistant material comprises the following components in percentage by weight:

20-40% of hydroxyl silicone oil;

2 to 5 percent of hydrogen end silicone oil

2-4% of dimethyl silicone oil;

1-5% of nano calcium carbonate;

5-15% of flame retardant powder;

0-1.5% of titanium dioxide;

4-8% of hydrophobic white carbon black;

0.1 to 0.5 percent of coupling agent;

1-5% of a cross-linking agent;

0.01 to 0.05 percent of catalyst;

solvent addition to 100%;

the cross-linking agent consists of the following components in percentage by weight:

80% of methyl tributyrinoxime silane;

20% of tetrabutylketoxime silane;

the coupling agent is chloro (dimethyl) vinylsilane.

For the purpose of avoiding misunderstandings, the hydroxyl silicone oil of the present application means a linear polydimethylsiloxane having a hydroxyl group at the end of the polymer; the hydrogen terminated silicone oil refers to linear polydimethylsiloxane with H as a polymer end; dimethicone refers to a linear polydimethylsiloxane in which all substituents are methyl groups.

In the organic silicon waterproof and ageing-resistant material, the viscosity of the hydroxyl silicone oil is 20000 cp; the viscosity of the simethicone is 350 cp; the molecular weight of the hydrogen-terminated silicone oil is 500-600 and the viscosity is 2-3 cp.

In this application, viscosity refers to viscosity at 25 ℃.

In the above organosilicon waterproof aging-resistant material, the flame-retardant powder is aluminum hydroxide, magnesium hydroxide or zinc oxide.

In the organic silicon waterproof anti-aging material, the catalyst is a mixture of a platinum catalyst and an organic tin catalyst, and the ratio of the platinum catalyst to the organic tin catalyst is 1: 1.

The organic tin catalyst is dibutyltin dilaurate or dibutyltin diacetate;

in the organic silicon waterproof anti-aging material, the solvent is a composite solvent, and the composite solvent is a combination of at least two of No. 120, No. 150 and No. 200 solvent oils.

Meanwhile, the invention also discloses a preparation method of the organic silicon waterproof anti-aging material, which comprises the following steps:

step 1: dehydrating the raw materials to a water content of less than 0.3 wt%;

step 2: hydroxyl silicone oil, hydrogen-terminated silicone oil, dimethyl silicone oil, nano calcium carbonate, flame retardant powder, titanium dioxide, hydrophobic white carbon black, a coupling agent, a catalyst and a solvent are added into a planetary barrel, and the mixture is stirred and dispersed uniformly;

and step 3: adding a cross-linking agent, vacuumizing, and heating to 50-60 ℃; stirring is continued for 1-2h to complete the reaction.

Compared with the prior art, the invention has the beneficial effects that:

compared with the traditional silicon rubber, the surface drying time of the invention is shortened to 5min from 20-30 min; the invention can realize 24-month surface crystallization prevention. The surface crystallization phenomenon generally occurs in no more than 24 months in the traditional formula adopting the tetrabutoxime silane as the cross-linking agent.

The following conclusions are obtained in the process of adjusting the formula:

1. the consumption of the tetrabutyralkoxysilane is reduced, and the introduction of the methyltribuutyralkoxysilane can avoid the crystallization phenomenon in a long period of time and shorten the surface drying time to 5 min.

2. The introduction of the organosilicon terminated by chlorine can effectively prolong the time of crystallization; in the application, the catalyst not only catalyzes the substitution reaction between hydroxyl and ketoxime groups, but also catalyzes the addition reaction between chlorine (dimethyl) vinyl silane and end hydrogen silicone oil at normal temperature, the end hydrogen silicone oil can be added to form small molecule silicone oil with end sealed chlorine atoms, the end sealed chlorine atoms are slowly hydrolyzed in the using process of a product to form end hydroxyl groups, the end hydroxyl groups can be combined with free radicals on side methyl groups generated by aging of the hydroxyl silicone oil under the action of the environment, and the conditions of crystallization and brittle cracking caused by crosslinking between the hydroxyl silicone oil are avoided.

3. Chlorine atoms can be converted into hydrogen chloride under the hydrolysis condition, the hydrogen chloride can be absorbed by the flame retardant powder, and compared with the traditional silane coupling agent with neutral hydrolysis functional groups, the silane coupling agent does not have excessive free hydrolysis functional groups in polymers, so that the condition that the free hydrolysis functional groups are accelerated to age is avoided.

4. In a high-temperature humid environment, if free oxygen in the air reacts with water vapor to produce hydrogen peroxide, the hydrogen peroxide can be decomposed into 2 active hydroxyl groups, and the micromolecule silicone oil with the chlorine atom at the end can preferentially perform hydrolysis reaction with the active hydroxyl groups, so that the influence of the active hydroxyl groups on the hydroxyl silicone oil is avoided, the premature free radical reaction of side methyl groups of the hydroxyl silicone oil is avoided, and the premature oxidation of the hydroxyl silicone oil is avoided.

5. A small amount of dimethyl silicone oil is added to play a role in assisting in shortening the surface drying time.

Detailed Description

Specific embodiments of the present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

20% of hydroxyl silicone oil (20000 cp);

hydrogen-terminated silicone oil (2-3cp) 2%

3% of dimethyl silicone oil (350 cp);

2 percent of nano calcium carbonate;

8% of aluminum hydroxide;

1% of titanium dioxide;

5% of hydrophobic white carbon black;

chloro (dimethyl) vinylsilane 0.1%;

1.6 percent of methyl tributyrinoxime silane;

0.4 percent of tetrabutoxime silane;

0.01 percent of platinum catalyst;

0.01 percent of dibutyltin dilaurate;

solvent addition to 100%;

the preparation process comprises the following steps:

step 1: dehydrating the raw materials to a water content of less than 0.3 wt%;

step 2: adding hydroxyl silicone oil, hydrogen-terminated silicone oil, dimethyl silicone oil, nano calcium carbonate, flame retardant powder, titanium dioxide, hydrophobic white carbon black, a coupling agent, a catalyst and a solvent into a planetary barrel, heating to 80-100 ℃, stirring for 1h, and uniformly dispersing;

and step 3: adding a cross-linking agent, vacuumizing, and heating to 50-60 ℃; stirring was continued for 1h to complete the reaction.

Example 2

The preparation method is the same as that of example 1, and the specific formula comprises the following components in percentage by weight:

30% of hydroxyl silicone oil (20000 cp);

hydrogen-terminated silicone oil (2-3cp) 4%

2% of dimethyl silicone oil (350 cp);

4 percent of nano calcium carbonate;

15% of magnesium hydroxide;

7% of hydrophobic white carbon black;

chloro (dimethyl) vinylsilane 0.2%;

2.4 percent of methyl tributyrinoxime silane;

0.6 percent of tetrabutoxime silane;

0.015% of platinum catalyst;

0.015% of dibutyltin diacetate;

the solvent was added to 100%.

Example 3

40% of hydroxyl silicone oil (20000 cp);

hydrogen-terminated silicone oil (2-3cp) 5%

4% of dimethyl silicone oil (350 cp);

2 percent of nano calcium carbonate;

10% of aluminum hydroxide;

1 percent of titanium dioxide

4% of hydrophobic white carbon black;

chloro (dimethyl) vinylsilane 0.4%;

4% of methyl tributyrinoxime silane;

1% of tetrabutylketoxime silane;

0.02% of platinum catalyst;

0.02 percent of dibutyltin diacetate;

the solvent was added to 100%.

Example 4

25% of hydroxyl silicone oil (20000 cp);

hydrogen-terminated silicone oil (2-3cp) 5%

2% of dimethyl silicone oil (350 cp);

4 percent of nano calcium carbonate;

5% of aluminum hydroxide;

0.5 percent of titanium dioxide

8% of hydrophobic white carbon black;

chloro (dimethyl) vinylsilane 0.5%;

2.4 percent of methyl tributyrinoxime silane;

0.6 percent of tetrabutoxime silane;

0.01 percent of platinum catalyst;

0.005% of dibutyltin dilaurate;

the solvent was added to 100%.

Example 5

35% of hydroxyl silicone oil (20000 cp);

hydrogen-terminated silicone oil (2-3cp) 3%

3% of dimethyl silicone oil (350 cp);

3 percent of nano calcium carbonate;

10% of zinc oxide;

1 percent of titanium dioxide

5% of hydrophobic white carbon black;

chloro (dimethyl) vinylsilane 0.3%;

3.2 percent of methyl tributyrinoxime silane;

0.8 percent of tetrabutoxime silane;

0.015% of platinum catalyst;

0.02% of dibutyltin dilaurate;

the solvent was added to 100%.

Comparative example 1

The process steps are the same as example 2, except that the formula is as follows:

30% of hydroxyl silicone oil (20000 cp);

hydrogen-terminated silicone oil (2-3cp) 4%

2% of dimethyl silicone oil (350 cp);

4 percent of nano calcium carbonate;

15% of magnesium hydroxide;

7% of hydrophobic white carbon black;

0.2 percent of dimethylvinylmethoxysilane;

2.4 percent of methyl tributyrinoxime silane;

0.6 percent of tetrabutoxime silane;

0.015% of platinum catalyst;

0.015% of dibutyltin diacetate;

the solvent was added to 100%.

Comparative example 2

The process steps are the same as example 2, except that the formula is as follows: 32% of hydroxyl silicone oil (20000 cp);

4% of dimethyl silicone oil (350 cp);

4 percent of nano calcium carbonate;

15% of magnesium hydroxide;

7% of hydrophobic white carbon black;

2.4 percent of methyl tributyrinoxime silane;

0.6 percent of tetrabutoxime silane;

0.015% of platinum catalyst;

0.015% of dibutyltin diacetate;

adding the solvent to 100 percent

Comparative example 3

36% of hydroxyl silicone oil (20000 cp);

4 percent of nano calcium carbonate;

15% of magnesium hydroxide;

7% of hydrophobic white carbon black;

3% of tetrabutylketoxime silane;

0.015% of platinum catalyst;

0.015% of dibutyltin diacetate;

the solvent was added to 100%.

Performance testing

The test results are shown in Table 1 below

Table 1: test results of example 2 and comparative examples 1 to 3

The following conclusions can be drawn from the tests of the above examples and comparative examples:

The application range of the product is as follows:

1. water-proof and moisture-proof facilities such as building outer walls, roofs, garages, toilets, balconies and the like.

2. The outdoor used live equipment, the waterproof, antifouling and insulating of the facility housing.

3. The exterior of various chemical pipelines and storage tanks is waterproof, antifouling, anticorrosive, and light-weighted.

4. The wall, ground, working platform and equipment shell of the detection room of various research institutions, and the like are antifouling, anticorrosion, antistatic and insulating.

And 5, the bridge inhaul cable, the guardrail, the electrified railway, the high-speed rail and the subway are waterproof, moistureproof, antifouling, anticorrosive and insulating for the shells of various electrified equipment facilities.

Claims

1. The organic silicon waterproof anti-aging material is characterized by comprising the following components in percentage by weight:

20-40% of hydroxyl silicone oil;

2 to 5 percent of hydrogen end silicone oil

2-4% of dimethyl silicone oil;

1-5% of nano calcium carbonate;

5-15% of flame retardant powder;

0-1.5% of titanium dioxide;

4-8% of hydrophobic white carbon black;

0.1 to 0.5 percent of coupling agent;

1-5% of a cross-linking agent;

0.01 to 0.05 percent of catalyst;

solvent addition to 100%;

80% of methyl tributyrinoxime silane;

20% of tetrabutylketoxime silane;

the coupling agent is chloro (dimethyl) vinylsilane.

2. The silicone waterproof aging-resistant material according to claim 1, wherein the hydroxyl silicone oil has a viscosity of 20000 cp; the viscosity of the simethicone is 350 cp; the molecular weight of the hydrogen-terminated silicone oil is 500-600 and the viscosity is 2-3cp at 25 ℃.

3. The silicone waterproof and anti-aging material according to claim 1, wherein the flame retardant powder is aluminum hydroxide, magnesium hydroxide or zinc oxide.

4. The silicone waterproof aging-resistant material according to claim 1, wherein the catalyst is a mixture of a platinum catalyst and an organotin catalyst, and the ratio of the platinum catalyst to the organotin catalyst is 1: 1.

5. The silicone waterproof and anti-aging material according to claim 1, wherein the solvent is a composite solvent, and the composite solvent is a combination of at least two of No. 120, No. 150 and No. 200 solvent oils.

6. A method for preparing the organosilicon waterproof aging-resistant material as claimed in any of claims 1 to 5, which comprises the following steps:

step 1: dehydrating the raw materials to a water content of less than 0.3 wt%;