CN106366916A - Normal temperature curable epoxy modified organic silicone resin, preparation method thereof and application - Google Patents

Abstract

The invention belongs to the technical field of coatings, and discloses a normal-temperature curing epoxy-modified silicone resin, a preparation method and application thereof. The preparation method is as follows: in parts by weight, sequentially add 10-20 parts of organosilicon intermediate, 1-2 parts of silane coupling agent, and 11-27 parts of solvent into the reactor, stir evenly, and heat up to 50-90°C , then add 0.01 to 0.1 parts of catalyst, react for 2 to 5 hours to obtain a silicone polymer; then add 5 to 30 parts of epoxy resin and 5 to 30 parts of solvent to the obtained silicone polymer, stir evenly, and heat up to 60 React at ~90°C for 3-6 hours to obtain the room temperature curing epoxy-modified silicone resin. The epoxy-modified silicone resin obtained in the present invention has high silicon content (up to 75%) and good storage stability. It can be applied to metal high-temperature resistant anti-corrosion coatings, and has the characteristics of high temperature resistance, corrosion resistance, good adhesion and high hardness.

Description

A kind of normal temperature curing epoxy modified silicone resin and its preparation method and application

technical field

The invention belongs to the technical field of coatings, and in particular relates to a normal-temperature curing epoxy-modified silicone resin and a preparation method and application thereof.

Background technique

With the continuous development of my country's modern industry, especially the development of metallurgy, petrochemical, aerospace and military industries, the application of high-temperature equipment and supporting facilities is increasing. Oxidation reaction or reaction with organic solvents, acids, and alkalis will cause corrosion, which will gradually lose strength of metal materials and lead to structural loss, becoming a hidden danger of various accidents. Therefore, the surface of high-temperature equipment generally needs to be protected by coating with high-temperature resistant anti-corrosion coatings to prevent oxidation and corrosion of metal materials and prolong the service life of high-temperature equipment.

Silicone resin is a polymer with -Si-O-Si- as the main molecular chain, in which the bond energy of Si-O is 460kJ/mol, which is much higher than that of C-C, which makes silicone resin have excellent heat resistance , At the same time, silicone resin also has good weather resistance, UV aging resistance, moisture resistance and water repellency. However, silicone resins also have significant disadvantages, such as high temperature (150-200°C) curing and long curing time, poor resistance to organic solvents, poor adhesion to substrates, and insufficient mechanical strength. This largely limits its wide-ranging application. Epoxy resin has good solvent resistance, remarkable adhesion, and excellent mechanical properties. Using epoxy resin to modify silicone resin can significantly improve its adhesion and solvent resistance.

At present, there are many reports on epoxy-modified organic resins at home and abroad, but the reported epoxy-modified silicone resins have low silicon content and require high temperature curing. Z.Ahmad etc. utilize the epoxy-modified silicone resin prepared by γ-glycidyl ether oxypropyltrimethoxysilane, aminophenyltrimethoxysilane, tetraethoxysilane, its silicon content is only 25%, and It needs to be cured at a high temperature of 130°C. Chinese patent CN102031061A utilizes bisphenol A type epoxy resin, amino-containing silane coupling agent, methyl or phenylalkoxysilane to prepare epoxy-modified silicone resin, which requires high temperature curing and has poor adhesion . The preparation process of patents CN102559048A and CN102206322 is complicated, and both need to be reacted under high temperature conditions. The phenolic epoxy modified silicone resin prepared by patent CN103059304A has a very low silicon content, the highest being only 33%.

Contents of the invention

In order to solve the above shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a method for preparing a room temperature curing epoxy-modified silicone resin.

Another object of the present invention is to provide a room temperature curing epoxy-modified silicone resin prepared by the above method.

Another object of the present invention is to provide the application of the above room temperature curing epoxy-modified silicone resin in metal high temperature resistant anticorrosion coatings.

The object of the invention is achieved through the following technical solutions:

A preparation method of normal temperature curing epoxy modified silicone resin, comprising the following preparation steps:

In parts by weight, sequentially add 10-20 parts of organosilicon intermediate, 1-2 parts of silane coupling agent, 11-27 parts of solvent into the reactor, stir evenly, heat up to 50-90°C, and then add 0.01-0.1 Parts of catalyst, react for 2-5 hours to obtain organosilicon polymer; then add 5-30 parts of epoxy resin and 5-30 parts of solvent into the obtained organosilicon polymer, stir evenly, heat up to 60-90°C and react for 3- 6h, to obtain the normal temperature curing epoxy-modified silicone resin.

The organosilicon intermediate is selected from compounds of the following structural formulas:

Wherein X and Y are the same or different, and are selected from C ₁ -C ₆ linear or branched alkyl or phenyl.

Preferably, the silicone intermediate is at least one of Dow Corning RSN-6018, Dow Corning LX-0301, Dow Corning PMX-0156, Dow Corning PMX-0930, and Wacker SY-300.

Described silane coupling agent refers to aminosilane coupling agent, preferably aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminophenyltriethoxysilane, anilinomethyltrimethoxysilane , at least one of aminoethylaminopropyltrimethoxysilane.

The solvent is preferably at least one of toluene, xylene, butanone, cyclohexanone, ethyl acetate, butyl acetate, n-butanol, and tetrahydrofuran.

The catalyst is preferably at least one of dibutyltin dilaurate, zinc naphthenate, hydrochloric acid, nitric acid, salicylic acid, and tetramethylammonium hydroxide.

The epoxy resin is preferably at least one of bisphenol A epoxy resins E20, E21, E42, E44, and E51.

A room temperature curing epoxy-modified silicone resin is prepared by the above method.

The application of the above room temperature curing epoxy-modified silicone resin in metal high temperature resistant anti-corrosion coatings, the specific application steps are as follows:

Mix the epoxy-modified silicone resin cured at room temperature with an amine curing agent, stir evenly, and then brush it on the metal substrate, place it at room temperature for 5-9 days, and obtain an epoxy-modified silicone resin coating film after it is completely cured .

The amine curing agent is preferably at least one of ethylenediamine, diethylenetriamine, phenylenediamine, polyamide curing agents such as polyamide 650 and polyamide 651, and phenalkamine curing agents such as T31.

The reaction schematic diagram of the room temperature curing epoxy-modified silicone resin of the present invention is shown in Figure 1, wherein R' is a group such as CH ₃ , CH ₂ CH ₃ , and R" is H, CH ₃ , CH ₂ CH ₃ atoms or groups.

The preparation method of the present invention and the resulting product have the following advantages and beneficial effects:

(1) The preparation method of the present invention adopts step-by-step preparation. The epoxy-modified silicone resin is prepared by reacting an amino-containing silicone polymer with an epoxy resin. The overall reaction is fast and efficient, the process is simple, and the conditions are easy to control. The process is stable and the consistency is good.

(2) The epoxy-modified silicone resin prepared by the present invention solves the problem of poor compatibility between epoxy resin and silicone resin through the action of a silane coupling agent, so that the resin can be stored stably for a long time. At the same time, due to the effect of silane coupling agent and epoxy resin, the coating film has good adhesion to the metal surface. In addition, it also has high hardness. The hardness of the cured coating film is as high as 6H, so that the coated metal is not easy to scratch , has multiple protective effects.

(3) The epoxy-modified silicone resin prepared by the present invention has a wide range of applications because the resin can be cured at room temperature. At the same time, due to the high silicon content (up to 75%), the cured coating film can be used for a long time at a high temperature of 400 ° C, so it can be widely used in various industrial equipment.

Description of drawings

Fig. 1 is a schematic diagram of the reaction of the room temperature curing epoxy-modified silicone resin of the present invention.

detailed description

The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

Example 1

(1) Add 10g of silicone intermediate LX-0301, 1g of silane coupling agent aminopropyltrimethoxysilane, and 11g of solvent cyclohexanone into a 250ml three-necked flask in sequence, stir evenly, heat up to 50°C, and then Add 0.01g of catalyst dibutyltin dilaurate and react for 2h to obtain organosilicon polymer.

(2) Add 5 g of epoxy resin E20 and 5 g of solvent cyclohexanone into the above-mentioned three-necked flask in sequence, stir evenly, heat up to 60° C. and continue to react for 3 h to obtain epoxy-modified silicone resin.

(3) Take 10g of the above-mentioned epoxy-modified silicone resin, mix it with 1g of polyamide curing agent, mix it evenly, brush it on the Q235 steel plate, and leave it at room temperature for 5 days to obtain an epoxy-modified silicone resin coating film. Its performance test results are shown in Table 1.

Example 2

(1) Add 10g of silicone intermediate LX-0301, 1.5g of silane coupling agent aminopropyltriethoxysilane, and 11.5g of solvent xylene into a 250ml three-necked flask, stir well, and heat up to 60°C , Then add 0.03g catalyst dibutyltin dilaurate, react for 3h, and obtain organosilicon polymer.

(2) Add 10 g of epoxy resin E44 and 10 g of solvent xylene into the above-mentioned three-necked flask in sequence, stir evenly, heat up to 70° C. and continue to react for 4 hours to obtain epoxy-modified silicone resin.

(3) Take 10g of the above-mentioned epoxy-modified silicone resin, mix it with 1.5g of polyamide curing agent, brush it on the Q235 steel plate after stirring evenly, and place it at room temperature for 6 days to obtain an epoxy-modified silicone resin coating film . Its performance test results are shown in Table 1.

Example 3

(1) Add 15g of silicone intermediate RSN-6018, 2g of silane coupling agent aminophenyltriethoxysilane, and 17g of solvent butyl acetate into a 250ml three-necked flask in sequence, stir evenly, and heat up to 70°C. Then, 0.05 g of catalyst zinc naphthenate was added and reacted for 4 hours to obtain an organosilicon polymer.

(2) Add 20 g of epoxy resin E44 and 20 g of solvent butyl acetate into the above-mentioned three-necked flask in sequence, stir evenly, heat up to 80° C. and continue to react for 5 h to obtain epoxy-modified silicone resin.

(3) Take 10g of the above-mentioned epoxy-modified silicone resin, mix it with 2g of polyamide curing agent, brush it on the Q235 steel plate after stirring evenly, and leave it at room temperature for 7 days to obtain an epoxy-modified silicone resin coating film. Its performance test results are shown in Table 1.

Example 4

(1) Add 20g of silicone intermediate RSN-6018, 1g of silane coupling agent anilinomethyltrimethoxysilane, and 21g of solvent cyclohexanone into a 250ml three-necked flask in sequence, stir evenly, and heat up to 80°C. Then add 0.1 g of catalyst zinc naphthenate and react for 5 hours to obtain organosilicon polymer.

(2) Add 25g of epoxy resin E51 and 25g of solvent cyclohexanone into the above-mentioned three-necked flask in sequence, stir evenly, heat up to 90°C and continue to react for 6h to obtain epoxy-modified silicone resin.

(3) Take 10g of the above-mentioned epoxy-modified silicone resin, mix it with 2g of curing agent diethylenetriamine, brush it on the Q235 steel plate after stirring evenly, and place it at room temperature for 8 days to obtain the epoxy-modified silicone resin coating. membrane. Its performance test results are shown in Table 1.

Example 5

(1) Add 25g of organic silicon intermediate SY-300, 2g of silane coupling agent aminoethylaminopropyltrimethoxysilane, 27g of mixed solvent of xylene and cyclohexanone into a 250ml three-necked flask, and stir evenly , heated to 90°C, then added 0.1g catalyst salicylic acid, and reacted for 3h to obtain organosilicon polymer.

(2) Add 15g of epoxy resin E20, 15g of mixed solvent of xylene and cyclohexanone into the above-mentioned three-necked flask in sequence, stir evenly, heat up to 60°C and continue to react for 6h to obtain epoxy-modified silicone resin.

(3) Take 10g of the above-mentioned epoxy-modified silicone resin, mix it with 1.5g of polyamide curing agent, brush it on the Q235 steel plate after stirring evenly, and place it at room temperature for 9 days to obtain an epoxy-modified silicone resin coating film . Its performance test results are shown in Table 1.

Example 6

(1) Add 15g of organic silicon intermediate SY-300, 2g of silane coupling agent aminopropyltrimethoxysilane, 17g of mixed solvent of butyl acetate and xylene into a 250ml three-necked flask, stir evenly, and heat up to 70° C., then add 0.04 g of salicylic acid as a catalyst, and react for 4 hours to obtain an organosilicon polymer.

(2) Add 30g of epoxy resin E42, 30g of mixed solvent of butyl acetate and xylene into the above-mentioned three-necked flask in sequence, stir evenly, heat up to 70°C and continue to react for 4h to obtain epoxy-modified silicone resin.

(3) Take 10 g of the above-mentioned epoxy-modified silicone resin, mix it with 2 g of curing agent T31, mix it evenly, brush it on the Q235 steel plate, and leave it at room temperature for 7 days to obtain an epoxy-modified silicone resin coating film. Its performance test results are shown in Table 1.

Table I

The above test results refer to the following test standards:

Method for determination of solvent wiping resistance of coatings, GB/T 23989-2009;

Determination of adhesion by cross-hatch test of paint and varnish film, GB/T 9286-1998;

Paint and varnish pencil method for determination of paint film hardness, GB/T 6739-2006.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of normal-temperature curing epoxy modified organic silicone resin is it is characterised in that include following preparation process:

By weight, sequentially add in reactor 10～20 parts of silicone intermediates, 1～2 part of silane coupler, 11～27 Part solvent, stirs, is warming up to 50～90 DEG C, is subsequently adding 0.01～0.1 part of catalyst, reacts 2～5h, obtains organosilicon Polymer；Then 5～30 parts of epoxy resin, 5～30 parts of solvents are added in gained organosilicon polymer, stir, rise Temperature, to 60～90 DEG C of reaction 3～6h, obtains described normal-temperature curing epoxy modified organic silicone resin.

2. a kind of normal-temperature curing epoxy modified organic silicone resin according to claim 1 preparation method it is characterised in that: Described silicone intermediate is selected from following structure general formula:

Wherein x and y is identical or different, selected from c₁～c₆Straight or branched alkyl or phenyl.

3. a kind of normal-temperature curing epoxy modified organic silicone resin according to claim 2 preparation method it is characterised in that: Described silicone intermediate includes DOW CORNING rsn-6018, DOW CORNING lx-0301, DOW CORNING pmx-0156, DOW CORNING pmx- 0930th, at least one in watt gram sy-300.

4. a kind of normal-temperature curing epoxy modified organic silicone resin according to claim 1 preparation method it is characterised in that: Described silane coupler include aminopropyl trimethoxysilane, aminopropyl triethoxysilane, aminophenyl triethoxysilane, At least one in phenylaminomethyl trimethoxy silane, aminoethylaminopropyl trimethoxy silane.

5. a kind of normal-temperature curing epoxy modified organic silicone resin according to claim 1 preparation method it is characterised in that: Described solvent include toluene, dimethylbenzene, butanone, Ketohexamethylene, ethyl acetate, butyl acetate, n-butyl alcohol, in oxolane extremely Few one kind.

6. a kind of normal-temperature curing epoxy modified organic silicone resin according to claim 1 preparation method it is characterised in that: Described catalyst include dibutyl tin laurate, zinc naphthenate, hydrochloric acid, nitric acid, salicylic acid, in Tetramethylammonium hydroxide At least one.

7. a kind of normal-temperature curing epoxy modified organic silicone resin according to claim 1 preparation method it is characterised in that: Described epoxy resin includes at least one in Bisphenol-a Epoxy Resin e20, e21, e42, e44, e51.

8. a kind of normal-temperature curing epoxy modified organic silicone resin it is characterised in that: by described in any one of claim 1～7 Method prepares.

9. application in metal fire-resistant anticorrosion paint for the normal-temperature curing epoxy modified organic silicone resin described in claim 8, It is characterized in that concrete application step is as follows:

Normal-temperature curing epoxy modified organic silicone resin is mixed with amine curing agent, is brushed in metal base after stirring On, place 5～9 days under room temperature, after being fully cured, obtain epoxy modified silicone resin film.

10. normal-temperature curing epoxy modified organic silicone resin according to claim 9 is in metal fire-resistant anticorrosion paint Application it is characterised in that: described amine curing agent includes ethylenediamine, diethylenetriamine, phenylenediamine, polyamide curing agent, phenol At least one in aldehyde amine hardener.