CN112029383B

CN112029383B - Expanded graphene fire-resistant, antistatic and anticorrosive coating

Info

Publication number: CN112029383B
Application number: CN202010767813.9A
Authority: CN
Inventors: 慕雷
Original assignee: BEIJING MUCHEN FIREPROOF HEAT INSULATION SPECIAL MATERIALS CO LTD
Current assignee: BEIJING MUCHEN FIREPROOF HEAT INSULATION SPECIAL MATERIALS CO LTD
Priority date: 2020-08-03
Filing date: 2020-08-03
Publication date: 2022-06-14
Anticipated expiration: 2040-08-03
Also published as: CN112029383A; WO2022027923A1

Abstract

The expanded graphene fire-resistant, antistatic and anticorrosive coating is characterized by comprising the following components in parts by weight: A. 20-30 parts of phenolic epoxy base material, 15-25 parts of an expansion flame-retardant system, 3-7 parts of graphene functional filler, 20-30 parts of carbon accelerator, 3-7 parts of auxiliary agent and 15-25 parts of active diluent; 5-10 parts of reinforcing fiber; B. a curing agent; the component A comprises: the component B comprises: 1.8-2.2: 1; wherein the intumescent flame retardant system is an aryl phosphate ester system; the graphene functional filler is formed by mixing graphene and Fe3O4 powder; the char promoter comprises a char promoter and a post-char enhancer; the curing agent is a polyfunctional amine compound, and the auxiliary agent comprises a wetting agent, a defoaming agent and a dispersing agent. The coating is mainly hydrocarbon fire resistant coating, can resist hydrocarbon fire for 90mins, has excellent anti-corrosion and antistatic functions of graphene, simplifies product construction and operation, eliminates interface damage among multiple components, and has economic benefit.

Description

Expanded graphene fire-resistant, antistatic and anticorrosive coating

Technical Field

The invention relates to a coating, in particular to a novel coating integrating three functions of an expansion system and graphene.

Background

Heavy-duty anticorrosive coatings, fire-resistant coatings and antistatic coatings are protection measures which must be applied to steel structures and are extremely important in building structures. For special environment (high-rise), difficult environment (construction) and extreme environment (climate), the construction and maintenance of the coating face great examination.

Although the coating for hydrocarbon fire resistance in China has been studied intensively, most laboratory test conditions are not tested in a furnace according to temperature rise due to the limitation of test conditions, physical and chemical indexes are also measured separately, and the result is greatly changed.

For steel structure parts which must perform three kinds of function protection, the international requirements are usually adopted for separate bidding, and products of different companies form interface layering, so that the quality weakness exists.

At present, although the multifunctional coating is available in the market, the multifunctional coating has the defects of insolubility and difficult dispersion caused by a plurality of functional components, and the main functions are influenced to cause damage.

The expansion system consists of an acid source, a carbon source and a gas source. The existing expansion flame-retardant system mostly uses APP ammonium polyphosphate as an acid source, APP is easy to absorb water, and the APP is easy to migrate out from the surface after being used for a period of time, so that the fire-resistant condition of the coating is influenced, and the safety is influenced greatly when a fire comes. In addition, at present, pentaerythritol is mostly used as a carbon source and melamine is used as a gas source in the expansion system. The lack of thermal stability and poor water absorption characteristics also affect the durability requirements of the overall intumescent system.

Disclosure of Invention

In order to solve the problems, the invention provides an intumescent three-function-in-one solvent-free fire-resistant coating.

The technical scheme of the invention is as follows:

the expanded graphene fire-resistant, antistatic and anticorrosive coating is characterized by comprising the following components in parts by weight:

A. 20-30 parts of phenolic epoxy base material,

15-25 parts of an expansion flame-retardant system,

3-7 parts of graphene functional filler,

B. curing agent

The component A comprises: the component B comprises: 1.8-2.2: 1;

wherein the intumescent flame retardant system is an aryl phosphate ester system;

the graphene functional filler is graphene and Fe₃O₄Mixing the powders;

the carbon promoter comprises a carbon forming promoter and a carbon forming reinforcing agent, the carbon forming promoter mainly comprises metal oxides and/or metal compounds, and the carbon forming reinforcing agent mainly comprises organosilicon compounds;

the curing agent is a polyfunctional amine compound,

the auxiliary agent comprises a wetting agent, a defoaming agent and a dispersing agent.

Preferred said novolac epoxy binders are NP400, NP600 and/or NP 900.

A further preferred said novolac epoxy binder is NP 900.

Preferably, the aryl phosphate ester system is a mass ratio of 3:2, RDP is resorcinol-bis (diphenyl phosphate), DMP is dimethyl phthalate, and TPP is triphenyl phosphate.

The further preferable aryl phosphate ester system is RDP-DMP composite, and the mass ratio of the RDP to the DMP is 3: 2.

Preferably, the graphene functional material is prepared by mixing a graphene oxide material and a graphene oxide material in a mass ratio of 0.8-1.2: 1 graphite with Fe₃O₄Dry-milling nanometer iron powder in ball mill for 1-3hrs to make graphite layer be graphene and Fe₃O₄And compounding to form magnetized graphene, and controlling the direction in a magnetic field to form magnetic guiding arrangement.

Further preferably, the number of layers of the graphene is less than 10, the C/O ratio is less than 5%, and the electric conductivity is more than 10000S/cm²And the purity is more than 99.5 percent.

Preferably, the metal oxide is ZnO and/or MnO, and the metal compound is ZnSO₄·7H₂O，Zn₃B₄O₉·5H₂O，MnAc·4H₂O，MnSO₄·H₂O，ZnAc·2H₂And one or more of O.

Preferably, the organosilicon is one or more of a borosilicate ceramic BSi precursor, an organo-boron siloxane OBS, a vinyltriethoxysilane VTS and a borosilicate surfactant.

Preferably, the polyfunctional amine is one or more of ethylenediamine, diethylenediamine and diethylaminopropylamine.

Preferably the reactive diluent is 1,6 hexanediol diacrylate glycidyl ether and/or alkyd glycidyl ether.

Preferably, the reinforcing fibers are carbon fibers, high silica alumina fibers, glass fibers and/or magnesia whiskers.

The invention has the following technical effects:

the Novolac epoxy binder in the coating of the present invention may consist of NP400, 600, 900, preferably NP900(NP450, NP600, NP900 represent the relative molecular masses of Novolac Novolac epoxy resins, respectively). In addition to being a coating base material, is also a component of a char source which reacts with the aryl phosphate ester (i.e., acid source) of the flame retardant to form char.

The novel expansion flame-retardant system consists of aryl phosphate esters such as RDP, DMP, TPP and the like, the mass ratio of RDP-DMP is preferably 3:2, and the composite system is a flame-retardant and acid source system. In addition, both react thermally at elevated temperatures to produce H₂O is the gas source of the gas source, and finally the carbon foam layer is formed.

Graphene is a two-dimensional nano sheet, and besides excellent material properties such as mechanics, electronics, thermal, electrochemistry and the like, the appearance of the nano sheet is microscopic shielding and blocking properties, and is also the warping of related materials, and particularly has excellent blocking and blocking effects after magnetic guiding to form a labyrinth effect (Zig-Zag). The fire-resistant material can prevent the invasion of bad factors into the base material at ordinary times, and can prevent combustible gas when a fire is burnt. The flake graphene sheets are all paramagnetic and horizontal through magnetization, and the shielding and blocking conditions are greatly improved. The graphene has high conductivity, antistatic capability and excellent shielding and blocking properties, not only plays an electrochemical anticorrosion role in a paint film, but also blocks environmental factors (including acid rain, moisture, microorganisms and the like), and greatly contributes to anticorrosion. The graphene has an ultraviolet-resistant function, can shield ultraviolet rays from irradiating, damaging and aging a paint film, and prolongs the service life. The graphene is a nano material, and can reach the expected target without adding a large amount of graphene, so that the influence on the solid content of a paint film system is greatly reduced, and the original strength is maintained. In combination with the advantages and characteristics, the coating composition simultaneously provides antistatic and anticorrosion functions.

The char forming accelerant catalyzes and promotes the char formation in the process of acidification to form char, and after the char formation forms a foam layer, the reinforcing agent after the char formation can be matched with the foam layer to further enhance the fire erosion resistance of the foam layer.

The coating is mainly hydrocarbon fire resistant coating, the basic components formed by the formula of the coating are matched with each other stably, the thickness of the coating is 6-7mm, the coating can resist hydrocarbon fire for 90mins, and the coating has excellent anti-corrosion and anti-static functions of graphene, so that the product construction and operation are simplified, the interface damage among various components is eliminated, and the coating has economic benefits.

Drawings

FIG. 1 is a flow chart of the preparation of component A of example 1.

FIG. 2 is a flow chart of the preparation of component B of example 1.

Detailed Description

In order that the invention may be better understood, the invention will now be further explained with reference to specific examples.

Example 1

The formulation of the coating of this example is as follows:

a component (mass fraction)

Component B

Diethylenetriamine

A:B＝2:1

The preparation process of the magnetized graphene functional material comprises the following steps: crystalline flake graphite with mass ratio of 1:1 and particle size of 2000 meshes and commercially available Fe₃O₄Grinding in planetary ball mill (zirconia balls 2:1) for 1hr, mechanically stripping to obtain graphene, and mixing with Fe₃O₄Forming the coated composite magnetic material. The composite material forms controllable guiding arrangement in the magnetic field control direction of 1TB, the magnetic guiding work is made by adding a permanent magnet ring on the paint spray gun head, and the magnetic guiding is formed in the spraying process of the magnetic field.

The preparation process of the coating comprises the following steps:

the component A comprises:

as shown in figure 1, the novolac epoxy, the reactive diluent and the auxiliary agent are added with DMP-RDP to be ground and dispersed at high speed in a basket type high-speed dispersion grinder together, then the reinforcing fiber and zinc oxide/zinc borate are added to be dispersed at high speed, and the obtained product is packaged.

The component B comprises:

as shown in fig. 2, for the convenience of processing and storage, the magnetized graphene (i.e. the magnetized graphene functional material) in the component a is added and mixed with the curing agent in the component B, and then the mixture is ground and dispersed at high speed and then packaged.

Example 2

The formulation of the coating of this example is as follows:

component A

Component B

Diethylaminopropylamine A: B ═ 2:1

The procedure was as in example 1.

The product prepared by the embodiment is extremely stable in special environment (high-rise), difficult environment (construction) and extreme environment (climate) and is not layered for a long time.

And performing a combustion test, wherein the expansion system adopts a P-N-C (phosphorus, nitrogen and carbon) ternary system. On combustion, the first two stages lose about 15% of mass, and the chemical reaction of the thermal decomposition process takes place in the two stages, namely condensation of hydroxyl groups of PEDP (pentaerythritol diphosphate), dehydration, with the major volatile product released being water. Meanwhile, ester bond breakage and single bond transfer of the ester condensation product are completed through a carbonium ion mechanism under the catalysis of acid, and a series of chemical reactions of phosphate ester containing olefin and phosphoric acid are released. The olefin-containing phosphate ester is further subjected to a D-A reaction (Diels-Alder reaction) to produce an aromatic structure product. By repeating the D-A reaction, a foamy carbonaceous char having an aromatic structure can be further produced. The addition and orientation of the magnetic graphene can promote the reaction and greatly improve the strength and oxidation resistance of the carbon foam.

The carbon foam layer of the above example has a thickness of about 6CM and a strength of about 18N/CM²It can resist hydrocarbon fire for over 90 mins.

Claims

1. The expanded graphene fire-resistant, antistatic and anticorrosive coating is characterized by comprising the following components in parts by weight:

A. 20-30 parts of phenolic epoxy base material,

15-25 parts of an intumescent flame-retardant system,

3-7 parts of graphene functional filler,

20-30 parts of a carbon promoter, namely,

3-7 parts of an auxiliary agent,

15-25 parts of a reactive diluent, namely,

5-10 parts of reinforcing fiber,

B. curing agent

The component A comprises: the component B comprises: 1.8-2.2: 1;

wherein the intumescent flame retardant system is an aryl phosphate ester system; the aryl phosphate ester system is a RDP-DMP composite, and the mass ratio of the RDP to the DMP is 3: 2;

the phenolic epoxy base stock is NP400, NP600 and/or NP900,

the carbon promoter comprises a carbon formation promoter and a carbon formation rear reinforcing agent, the carbon formation promoter mainly comprises metal oxide and/or metal compound, the metal oxide is ZnO and/or MnO, and the metal compound is ZnSO₄·7H₂O，Zn₃B₄O₉·5H₂O， MnSO₄·H₂One or more of O, wherein the reinforcing agent after char formation mainly comprises organic silicon compounds, and the organic silicon compounds are boron siloxane ceramic BSi precursor and/or vinyl triethoxysilane;

the curing agent is polyfunctional amine compound, the polyfunctional amine is one or more of ethylenediamine, diethylenediamine and diethylaminopropylamine,

the auxiliary agent comprises a wetting agent, a defoaming agent and a dispersing agent,

the graphene functional material is prepared by mixing a graphene functional material and a graphene oxide, wherein the mass ratio of the graphene functional material to the graphene functional material is 0.8-1.2: 1 graphite with Fe₃O₄Dry-milling nanometer iron powder in ball mill for 1-3hrs to make graphite layer be graphene and Fe₃O₄Compounding to form magnetized graphene;

the number of layers of the selected graphene is less than 10, the C/O ratio is less than 5%, and the electric conductivity is more than 10000S/cm²And the purity is more than 99.5 percent.

2. The coating of claim 1, wherein the novolac epoxy binder is NP 900.

3. The coating according to claim 1, characterized in that the reactive diluent is 1, 6-hexanediol diglycidyl ether diacrylate and/or alkyd glycidyl ether.

4. The coating according to claim 1, characterized in that the reinforcing fibers are carbon fibers, glass fibers and/or magnesium oxide whiskers.