CN108546493B - Epoxy resin coating and application thereof - Google Patents
Epoxy resin coating and application thereof Download PDFInfo
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- CN108546493B CN108546493B CN201810383739.3A CN201810383739A CN108546493B CN 108546493 B CN108546493 B CN 108546493B CN 201810383739 A CN201810383739 A CN 201810383739A CN 108546493 B CN108546493 B CN 108546493B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an epoxy resin coating which can be used in the manufacturing process of a flame-retardant door and has excellent heat-resistant effect and continuous flame-retardant effect. The specific technical scheme is as follows: the coating consists of A, B two components, wherein the mass ratio of the component A to the component B is 1-3: 1; the component A comprises the following components: 100 parts of epoxy resin, 20-40 parts of organic silicon resin, 50-200 parts of flame-retardant filler, 2-5 parts of antioxidant, 1-8 parts of toughening agent and 30-200 parts of diluent; the component B comprises the following components: 10-20 parts of 2- (6-oxa-6H-diphenyl-l, 2-oxyphos-6-alkyl) phenol formaldehyde linear phenolic resin and 12-18 parts of flame retardant. The phosphorus-containing epoxy resin, the organic silicon resin, the flame-retardant filler, the toughening agent and the curing agent are matched with each other, so that the requirements are met, and an excellent technical effect is achieved.
Description
The application is a divisional application of a patent with the application number of 2016106119367 and the application date of 2016, 07 and 31, and the invention creates a name of 'a flame-retardant two-component epoxy resin coating for a flame-retardant door and application thereof'.
Technical Field
The invention relates to a two-component epoxy resin coating, in particular to a flame-retardant two-component epoxy resin coating for a flame-retardant door.
Background
The epoxy resin has excellent performance, excellent mechanical performance, insulating performance, chemical resistance and bonding performance, and can be widely applied to coatings, casting materials, adhesives and laminated materials. However, the common epoxy resin has the problem of low oxygen index, and the application of the epoxy resin is limited due to flammability and nature of the epoxy resin, so that the epoxy resin is difficult to meet the application in the fields of high temperature and flame retardance.
In order to overcome the problems, in the prior art, the epoxy resin is modified in various ways, most commonly, a flame retardant is used, and the flame retardant mainly relates to an additive type and a reactive type, so that the flame retardant property is greatly improved; modification of the epoxy resin structure is also a common technical means in the prior art. However, the performance of the epoxy resin for continuous flame retardance in use still needs to be improved. The flame-retardant door is an important structure in the existing building, and the surface coating of the flame-retardant door plays an important role in initial flame retardance, so that the flame-retardant coating with excellent heat-resistant and continuous flame-retardant effects is urgently needed in the prior art.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems in the prior art, the invention provides a two-component epoxy resin coating with excellent heat-resistant effect and continuous flame-retardant effect, which can be used in the manufacturing process of a flame-retardant door, and particularly meets the requirements through the mutual matching of phosphorus-containing epoxy resin, organic silicon resin, flame-retardant filler, toughening agent and curing agent, thereby achieving excellent technical effect.
The technical scheme for solving the technical problems is as follows:
the flame-retardant two-component epoxy resin coating for the flame-retardant door consists of A, B two components, wherein the mass ratio of the component A to the component B is 1-3: 1;
the component A comprises the following components: 100 parts of epoxy resin, 20-40 parts of organic silicon resin, 50-200 parts of flame-retardant filler, 2-5 parts of antioxidant, 1-8 parts of toughening agent and 30-200 parts of diluent;
the component B comprises the following components: 10-20 parts of 2- (6-oxa-6H-diphenyl-l, 2-oxyphos-6-alkyl) phenol formaldehyde linear phenolic resin and 12-18 parts of flame retardant.
The organic silicon resin containing epoxy groups is cured together with the epoxy resin through the epoxy groups, so that the dispersibility is good, and the hardness of a final cured product is higher.
The epoxy resin adopts phosphorus-containing epoxy resin, the flame-retardant component phosphorus is introduced into the epoxy resin, the phosphorus-containing epoxy resin is preferably obtained by reacting DOPO HQ and ERL4221, the phosphorus content is further preferably controlled to be more than 2% of the epoxy resin, the oxygen index reaches 28%, the vertical combustion reaches v-0, and the flame-retardant effect is very excellent.
As the additive type flame-retardant filler, two flame-retardant fillers are preferably compounded, and unexpected effects are generated by utilizing different properties and sizes of the flame-retardant fillers. The flame-retardant filler uses aluminum hydroxide and montmorillonite, the aluminum hydroxide belongs to a decomposition type flame retardant, the aluminum hydroxide decomposes and absorbs heat in the processes of heating and decomposition, the montmorillonite belongs to a barrier flame retardant, and the aluminum hydroxide and the montmorillonite are flame-retardant through different mechanisms.
As a preferred technical scheme, the flame-retardant filler aluminum hydroxide and the montmorillonite are composed in a weight ratio of 3-6:2, the particle size of the aluminum hydroxide is 80-120 mu m, and the particle size of the montmorillonite is 10-200 nm. The aluminum hydroxide forms more stable aluminum oxide after decomposition, the montmorillonite has smaller particle size, larger specific surface area is matched by the montmorillonite and the aluminum hydroxide in a specific ratio, and the respective particle sizes are combined and mutually crossed and filled, so that the flame retardant property is improved. If the particle diameter and the amount are outside the above ranges, the flame retardancy is deteriorated and the surface of the coating layer is easily damaged in a fire.
The antioxidant is antioxidant 1010, antioxidant 1076 or antioxidant 168.
The toughening agent is large graphene oxide, the preferred particle size is larger than 20 micrometers, the graphene oxide has excellent mechanical property and can bear large stress, and the toughening agent is added in the invention to overcome the stress generated by volume change of a large amount of fillers in combustion and avoid the phenomenon that the surface of a coating is damaged too fast to influence the flame retardant effect. Meanwhile, the graphene oxide is prepared by adopting a classical modified Hummers method, a large pi bond structure of part of benzene rings is reserved, the graphene oxide has high temperature resistance, and even if decomposition occurs, the product is more stable graphene, so that the flame retardance and the heat resistance can be further improved.
The flame retardant is a pre-crosslinked product of amino-cyclotriphosphazene and hexa (2-aminoethoxy) cyclotriphosphazene. The flame retardant is a cross-linked product of amino cyclotriphosphazene which is hexa (2-aminoethoxy) cyclotriphosphazene after polycondensation for 3 hours under an acidic condition. The amino-containing cyclotriphosphazene is a pre-crosslinked product of hexa (2-aminoethoxy) cyclotriphosphazene, has larger molecular weight, and a small amount of peripheral amino groups can also be used as a curing agent to be crosslinked with epoxy resin and epoxy organic silicon resin in preparation, and the epoxy cyclotriphosphazene is matched with polyamide to realize better crosslinking effect.
Meanwhile, the amino-containing cyclotriphosphazene is a pre-crosslinked product of hexa (2-aminoethoxy) cyclotriphosphazene, the self-movement is increased at high temperature, and the amino wrapped inside can partially leak out to be used as a curing agent to be further cured with epoxy resin, so that the crosslinking degree of the epoxy resin is improved, and the flame retardance and the high temperature resistance are improved.
The flame-retardant two-component epoxy resin coating for the flame-retardant door can be applied to the inner side, the outer side and each layer of a laminated board, or used as a primer and a surface treatment agent (non-outermost layer). After the flame-retardant door is coated with the coating and cured, the flame-retardant door has excellent flame-retardant effect, and each index is superior to relevant regulations.
Has the advantages that:
the invention integrates a plurality of flame-retardant modes, and the various modes are mutually promoted and matched, thereby obtaining beneficial technical effects. The method specifically comprises the following steps: the high-phosphorus-content epoxy resin and the epoxy organic silicon resin are matched to serve as matrix resin, so that the heat resistance and the flame retardance are improved, the aluminum hydroxide and the montmorillonite are matched in a specific proportion and particle size, effective obstruction of heat is achieved through decomposition and mutual matching, and the flame retardance is greatly improved; by utilizing the excellent mechanical property of the graphene oxide, the large-scale graphene oxide sheet is adopted in the invention, the stress dispersed in the combustion process is dispersed, and the surface of the scale coating is stable and does not crack. The flame retardant is used for being matched with polyamide to obtain good initial crosslinking, and secondary crosslinking in the combustion process is realized. The combined action of the various means ensures that the coating has excellent flame retardant effect after being cured, and each index is superior to relevant regulations and exceeds the effect of the existing flame retardant coating.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
The flame-retardant two-component epoxy resin coating for the flame-retardant door consists of A, B two components, wherein the mass ratio of the component A to the component B is 1: 1; the component A comprises the following components: 100 parts of epoxy resin with the phosphorus content of more than 2 percent, 20 parts of organic silicon resin containing epoxy groups, 30 parts of 100 mu m aluminum hydroxide, 20 parts of 100nm montmorillonite, 2 parts of antioxidant, 4 parts of graphene oxide with the particle size of 20 mu m and 50 parts of diluent; the component B comprises the following components: 10 parts by weight of 2- (6-oxa-6H-diphenyl-l, 2-oxyphosphorus-6-alkyl) phenol formaldehyde novolac resin (hereinafter referred to as curing agent) and 12 parts by weight of amino cyclotriphosphazene which is a pre-crosslinked hexa (2-aminoethoxy) cyclotriphosphazene (hereinafter referred to as flame retardant).
Example 2
The flame-retardant two-component epoxy resin coating for the flame-retardant door consists of A, B two components, wherein the mass ratio of the component A to the component B is 3: 1; the component A comprises the following components: 100 parts of epoxy resin with the phosphorus content of more than 2 percent, 40 parts of organic silicon resin containing epoxy groups, 120 parts of 100 mu m aluminum hydroxide, 40 parts of 100nm montmorillonite, 5 parts of antioxidant, 8 parts of graphene oxide with the particle size of 20 mu m and 150 parts of diluent; the component B comprises the following components: 20 parts by weight of 2- (6-oxa-6H-diphenyl-l, 2-oxyphosphorus-6-alkyl) phenol formaldehyde novolac resin (hereinafter referred to as curing agent) and 18 parts by weight of amino cyclotriphosphazene which is a pre-crosslinked product of hexa (2-aminoethoxy) cyclotriphosphazene (hereinafter referred to as flame retardant).
Comparative examples 1-8 had A, B components in a ratio of 1:1, and the specific compositions and ratios are shown in the following table.
*: the smearing condition is divided into four grades according to whether cracks and breakage exist or not: and (3) excellent: no crack, good: minor cracking, medium: moderate amount of cracking, poor: a large number of breakages;
Claims (6)
1. an epoxy resin coating is characterized in that: the epoxy resin coating comprises A, B two components, wherein the mass ratio of the component A to the component B is 1-3: 1;
the component A comprises the following components: 100 parts of epoxy resin, 20-40 parts of organic silicon resin, 50-200 parts of flame-retardant filler, 2-5 parts of antioxidant, 1-8 parts of toughening agent and 30-200 parts of diluent;
the component B comprises the following components: 10-20 parts of 2- (6-oxa-6H-diphenyl-l, 2-oxyphosphorus-6-alkyl) -phenol formaldehyde linear phenolic resin and 12-18 parts of flame retardant;
the epoxy resin is phosphorus-containing epoxy resin, and the phosphorus content accounts for more than 2% of the mass of the epoxy resin;
the organic silicon is organic silicon resin containing epoxy groups;
the toughening agent is large graphene oxide, and the particle size of the toughening agent is larger than 20 microns.
2. The epoxy resin coating according to claim 1, wherein: the flame-retardant filler is composed of aluminum hydroxide and montmorillonite in a weight ratio of 3-6:2, the particle size of the aluminum hydroxide is 80-120 mu m, and the particle size of the montmorillonite is 10-200 nm.
3. The epoxy resin coating according to claim 1, wherein: the antioxidant is antioxidant 1010, antioxidant 1076 or antioxidant 168.
4. The epoxy resin coating according to claim 1, wherein: the flame retardant is a hexa (2-aminoethoxy) cyclotriphosphazene pre-crosslinking substance.
5. The epoxy resin coating according to claim 4, wherein: the flame retardant is a product of condensation polymerization of hexa (2-aminoethoxy) cyclotriphosphazene for 3 hours under an acidic condition.
6. Use of an epoxy resin coating according to any one of claims 1 to 5 in the preparation of a flame retardant door.
Priority Applications (1)
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CN201810383739.3A CN108546493B (en) | 2016-07-31 | 2016-07-31 | Epoxy resin coating and application thereof |
Applications Claiming Priority (2)
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CN201810383739.3A CN108546493B (en) | 2016-07-31 | 2016-07-31 | Epoxy resin coating and application thereof |
CN201610611936.7A CN106243916B (en) | 2016-07-31 | 2016-07-31 | A kind of Flame-proof door fire-retardant bicomponent epoxy resin coating and its application |
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CN201610611936.7A Division CN106243916B (en) | 2016-07-31 | 2016-07-31 | A kind of Flame-proof door fire-retardant bicomponent epoxy resin coating and its application |
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CN108546493B true CN108546493B (en) | 2020-09-18 |
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CN201810383739.3A Active CN108546493B (en) | 2016-07-31 | 2016-07-31 | Epoxy resin coating and application thereof |
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Families Citing this family (6)
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CN109306040A (en) * | 2017-07-26 | 2019-02-05 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it |
CN109306039A (en) * | 2017-07-26 | 2019-02-05 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it |
CN109306044A (en) * | 2017-07-26 | 2019-02-05 | 郑州大学 | A kind of intrinsic flame-retarded resin of low polarity and its preparation method and application |
CN108912336B (en) * | 2018-08-01 | 2021-03-12 | 河北大学 | Active amino cross-linked phosphazene derivative, preparation method and application thereof, and flame-retardant epoxy resin |
CN114106672A (en) * | 2021-11-09 | 2022-03-01 | 广西南宁都宁通风防护设备有限公司 | Modification and toughening method for high-molecular composite explosion-proof door panel and coating raw material liquid used by same |
CN114213915A (en) * | 2021-12-17 | 2022-03-22 | 东莞市春蕾涂料有限公司 | Natural nontoxic water-based paint and preparation method thereof |
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CN104736589A (en) * | 2012-10-19 | 2015-06-24 | 三菱瓦斯化学株式会社 | Resin composition, pre-preg, laminate, metal foil-clad laminate, and printed wiring board |
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CN103031041A (en) * | 2013-01-16 | 2013-04-10 | 中昊北方涂料工业研究设计院有限公司 | High-solid epoxy expansion type fireproof and heat insulation coating and preparation method thereof |
CN103468097A (en) * | 2013-09-22 | 2013-12-25 | 苏州市湘园特种精细化工有限公司 | Expansive type fireproof and heat insulating coating |
CN104479499A (en) * | 2014-12-18 | 2015-04-01 | 江苏柏鹤涂料有限公司 | Reactive halogen-free flame retardant epoxy coating |
CN104927353B (en) * | 2015-06-12 | 2017-07-11 | 四川东材科技集团股份有限公司 | Fire-retardant non-halogen non-phosphate resin combination and application thereof and for prepreg, laminate, copper-clad plate preparation method |
CN105238263A (en) * | 2015-11-02 | 2016-01-13 | 华北理工大学 | Flame-retardant coating |
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CN104736589A (en) * | 2012-10-19 | 2015-06-24 | 三菱瓦斯化学株式会社 | Resin composition, pre-preg, laminate, metal foil-clad laminate, and printed wiring board |
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CN108546493A (en) | 2018-09-18 |
CN106243916B (en) | 2018-05-15 |
CN106243916A (en) | 2016-12-21 |
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