CN113372747B - Intrinsic flame-retardant transparent organic silicon fireproof coating and preparation method thereof - Google Patents

Intrinsic flame-retardant transparent organic silicon fireproof coating and preparation method thereof Download PDF

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CN113372747B
CN113372747B CN202110650020.3A CN202110650020A CN113372747B CN 113372747 B CN113372747 B CN 113372747B CN 202110650020 A CN202110650020 A CN 202110650020A CN 113372747 B CN113372747 B CN 113372747B
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polysiloxane
phosphate
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CN113372747A (en
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史翎
周伯龙
刘永壮
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Beijing University of Chemical Technology
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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
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates
    • 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
    • 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
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Abstract

The invention discloses an intrinsic flame-retardant transparent organic silicon fireproof coating and a preparation method thereof. The intrinsic flame-retardant transparent organic silicon fireproof coating is prepared from raw materials comprising polysiloxane, phosphate or phosphonate, amino resin and a curing catalyst; based on 100 parts by weight of polysiloxane: 100 parts by weight of polysiloxane; 1-100 parts by weight of phosphate or phosphonate; 50-500 parts by weight of amino resin; 0.01-5 parts by weight of a curing catalyst. According to the invention, polysiloxane, a nitrogen-containing compound, a phosphorus-containing compound and other additives are co-cured under the action of a catalyst to prepare the transparent fireproof coating with good fireproof performance and high transparency, and the transparent fireproof coating has the advantages of no halogen, environmental protection, high efficiency and the like, and has wide application prospects in the fields of ancient building fire prevention and the like.

Description

Intrinsic flame-retardant transparent organic silicon fireproof coating and preparation method thereof
Technical Field
The invention relates to the field of fireproof materials, in particular to an intrinsic flame-retardant transparent organic silicon fireproof coating and a preparation method thereof.
Background
The ancient architecture has extremely high cultural value and mental significance. However, because the wood-based fire retardant building is mostly of a wood structure, the fire retardant property is poor, in recent years, fire related to ancient buildings frequently occurs, and once the fire occurs, the ancient buildings do not exist. Therefore, there is a need for better fire protection of historic buildings. The coating of the transparent fireproof coating on the surface of the historic building is an effective fireproof means which is commonly used at present and is characterized in that: on the premise of not damaging the building and not affecting the ornamental value, the fireproof coating can play a role in fire prevention and flame retardance, namely, the fireproof coating needs to have transparency and cannot cover the surface of the ancient building, and meanwhile, the fireproof coating needs to have a good fireproof and flame retardant effect.
The transparent fireproof coating is a great research hotspot at present, and a great deal of research is carried out by a plurality of scientific research institutions and personnel at home and abroad. The research on transparent fireproof coatings in foreign countries is earlier, but the development of flame retardant systems is more favored, and the attention on the transparency is less. The research on the transparent fireproof coating in China is relatively late, and in recent years, the research is focused on a flame retardant system integrating fireproof performance and transparency. The fire-proof performance of the common wood material is mainly considered, and in order to ensure the fire-proof effect, a large amount of expansion flame-retardant systems are often adopted, so that the transparency is poor. In order to obtain a good transparency effect, a water-based intumescent flame retardant system needs to be coated, but the coating is easy to absorb moisture, the coating can fall off or crack for a long time, and the fireproof performance, the water resistance and the like are poor. At present, most researches cannot simultaneously ensure good transparency and flame retardance or obtain good flame retardance effect, but the transparency is poor, a coating is easy to crack, or the flame retardance is poor.
Patent CN103275604A discloses a phosphorus-containing alkyd resin transparent fire-retardant coating, which is prepared by dispersing and grinding 62-80% of phosphorus-containing alkyd resin, 2-3% of drier and 18-35% of solvent. The preparation of the phosphorus-containing alkyd resin is complicated, and the use of the organic solvent is not in accordance with the development trend of ecological environment protection. Patent CN104046201A discloses a flexible intumescent transparent fire-retardant coating, which is prepared by mixing polyphosphate ester with amino resin, and a large amount of organic solvent is still introduced into the prepared transparent fire-retardant coating.
After the polysiloxane is decomposed, no harmful substances are generated, and silicon is easy to migrate to the surface to form a good protective layer. Polysiloxane can be introduced into a transparent fireproof coating system, on one hand, the polysiloxane has good heat resistance because the main chain of the polysiloxane is a siloxane bond and the bond energy is high, and on the other hand, the side group of the polysiloxane has diversity and can increase the compatibility with other resins.
Therefore, polysiloxane can be introduced into an expansion flame-retardant system to prepare the transparent historic building fireproof coating containing Si, P, N and C, but in the prior art, the transparent fireproof coating containing polysiloxane is mostly a water-based coating, the compatibility among all components is poor, the reaction activity of polysiloxane is not fully utilized, when the expansion flame-retardant system is formed together with other raw materials, a homogeneous system is formed through the cross-linking reaction between the polysiloxane and other components, and the compatibility of the system is improved while the transparency of the system is realized.
Therefore, a solvent-free transparent fireproof coating taking polysiloxane with reactivity as a main matrix needs to be prepared, the compatibility among the components is good, the film forming strength is high, the transparency after curing is good, the process is simple, the coated material is not damaged, and the transparent fireproof coating with high transparency and good fireproof performance is obtained by improving and optimizing the formula, so that the fireproof protection of ancient buildings can be enhanced.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides an intrinsic flame-retardant transparent organic silicon fireproof coating and a preparation method thereof.
The polysiloxane with reactivity, the nitrogen-containing compound, the phosphorus-containing compound and other additives form an expansion flame-retardant system together, and the expansion flame-retardant system is co-cured under the action of the catalyst to prepare the transparent fireproof coating with good fireproof performance and high transparency. The main factor for controlling the transparency of the composite material is that each component in the matrix is transparent, cross-linking reaction occurs among the components to form a large cross-linked network, so that an integral structure is formed, the components mutually permeate without phase separation, and the product is a homogeneous system without phase interfaces, so that the transparency is realized. The solvent-free transparent fireproof coating has the advantages of good compatibility among the components, high film forming strength, good transparency after curing, simple process and no damage to the coated material.
One of the purposes of the invention is to provide an intrinsic flame-retardant transparent organic silicon fireproof coating.
The intrinsic flame-retardant transparent organic silicon fireproof coating is prepared from raw materials comprising polysiloxane, phosphate or phosphonate, amino resin, a curing catalyst, an antioxidant, a neutralizer and other auxiliaries;
based on 100 parts by weight of polysiloxane:
Figure BDA0003110760940000031
the polysiloxane is preferably linear polysiloxane, and the linear polysiloxane has high reactivity, adjustable viscosity, good leveling property, high film forming strength and good flame retardance;
the antioxidant is a conventional antioxidant, preferably triphenyl phosphite, and can enhance the aging resistance of the coating;
the neutralizer is a conventional neutralizer, preferably acetic acid or aminoacetic acid, and can be added to make the system neutral, improve the stability and reduce the damage to the coated material;
the other auxiliary agents are conventional auxiliary agents, such as organic bentonite, o-phenylphenol and the like; the viscosity of the system can be adjusted, and the construction is facilitated.
In a preferred embodiment of the present invention,
the polysiloxane is polysiloxane A1, or a mixture of polysiloxane A1 and polysiloxane A2.
The polysiloxane A1 has the structural formula:
Figure BDA0003110760940000041
R1is one of hydrogen, chlorine, hydroxyl, alkoxy, epoxy group, alkenyl, ketoxime group, carboxyl and amino; wherein, the hydroxyl group preferably has 0 to 8 carbon atoms, the alkoxy group, the ketoxime group, the carboxyl group and the amino group preferably have 1 to 8 carbon atoms, and the epoxy group and the alkenyl group preferably have 2 to 8 carbon atoms; more preferably one of vinyl, methoxy, ethoxy, butoxy, hydroxyl, hydroxyethyl, epoxypropyl, epoxymethyl, aminopropyl, carboxypropyl, and carboxymethyl; repeated R1The same or different;
R2～R8each independently selected from phenyl or alkyl with 1-8 carbon atoms; preferably one of methyl, ethyl, isopropyl, butyl and octyl; repeated R4The same or different; repeated R5The same or different; repeated R6The same or different;
X1、X2each independently is one selected from hydrogen, chlorine, hydroxyl, amino, epoxy, alkoxy, alkenyl, ketoxime group, carboxyl, sulfydryl, alkyl and phenyl; wherein, the hydroxyl group preferably has 0 to 8 carbon atoms, the alkoxy group, the ketoxime group, the carboxyl group and the amino group preferably have 1 to 8 carbon atoms, and the epoxy group and the alkenyl group preferably have 2 to 8 carbon atoms; more preferably one of methyl, ethyl, phenyl, methoxy, ethoxy, vinyl, carboxypropyl, epoxypropyl and aminopropyl;
m is 0. ltoreq. m.ltoreq.6000, preferably 0. ltoreq. m.ltoreq.1000, X when m is 01、X2Neither is alkyl nor phenyl;
n is 0. ltoreq. n.ltoreq.7000, preferably 0. ltoreq. n.ltoreq.800.
The polysiloxane A2 has the structural formula:
Figure BDA0003110760940000042
M1、M2、M3each independently selected from alkyl or alkoxy with 1-8 carbon atoms, preferably one of methoxyl, ethoxyl, methyl and ethyl, wherein M1、M2、M3At least 1 of them is selected from methoxy or ethoxy;
y is one of phenyl, aminopropyl, aminoethyl, anilinomethyl, methyl, ethyl, propyl, butyl, dodecyl, hydroxypropyl, hydroxybutyl, glycidoxypropyl, vinyl, epoxy, methacryloxy, mercapto and ureido.
In a preferred embodiment of the present invention,
the mass ratio of the polysiloxane A1 to the polysiloxane A2 is 1: 0.05-0.8, and preferably 1: 0.1-0.4.
The polysiloxane A1 is side active polysiloxane, can provide higher silicon content, has adjustable active group content and variety, and can participate in the curing reaction of the coating to enhance the flame retardance; polysiloxane A2 can improve system compatibility, has groups capable of reacting with A1 and amino resin, can adjust system crosslinking density, improves flexibility, and if A2 is too much, can increase system crosslinking degree, and increases brittleness of the cured coating, so that a proper proportion needs to be set.
In a preferred embodiment of the present invention,
the structural formula of the phosphate or phosphonate is:
Figure BDA0003110760940000051
wherein Y is1、Y2、Y3Each independently is one selected from hydrogen, chlorine, hydroxyl, alkyl, amino, imino and alkoxy; wherein, the number of carbon atoms of chlorine, hydroxyl and amino is preferably 0 to 10, and the number of carbon atoms of alkyl, imino and alkoxy is preferably 1 to 10;
wherein Y is1、Y2、Y3At least one of them is hydrogen, chlorine, hydroxyl or amino; the hydroxyl-terminated group or amino-terminated group having 0 to 10 carbon atoms is preferred.
In a preferred embodiment of the present invention,
the structure of the phosphate or phosphonate contains at least one hydroxyl, amino or chlorine; and/or the presence of a gas in the gas,
the amino resin is at least one of melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, melamine urea copolycondensation resin and melamine benzoguanamine copolycondensation resin; and/or the presence of a gas in the gas,
the curing catalyst is at least one of organic tin, amine, acid anhydride, titanate, organic acid and platinum-containing complex.
In a preferred embodiment of the present invention,
the phosphate or phosphonate is at least one of hydroxyethyl phosphate dimethyl ester, hydroxyethyl phosphate diethyl ester, hydroxyethyl phosphate dipropyl ester, hydroxyethyl phosphate dibutyl ester, hydroxyethyl phosphate diphenyl ester, dihydroxyethyl phosphate butyl ester, hydroxyethyl phosphate diphenyl ester, phenyl dichlorophosphate, aminopropyl phosphate dimethyl ester, aminopropyl phosphate diethyl ester, n-butyl bis (3-hydroxypropyl) phosphine oxide and tris (3-hydroxypropyl) phosphine oxide; and/or the presence of a gas in the gas,
the amino resin is melamine-formaldehyde resin etherified with methanol, the molar ratio of melamine to formaldehyde to methanol is 1:4.5: 3-1: 4.5:6, the etherification degree is 1: 3-1: 6, and the amino resin is in a liquid state; and/or the presence of a gas in the gas,
the curing catalyst is at least one of stannous octoate, dibutyltin dilaurate, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, p-toluenesulfonic acid, ethylenediamine, triethanolamine, triethylamine, n-butylamine, butyl titanate, chloroplatinic acid and Karstedt catalyst.
The invention also provides a preparation method of the intrinsic flame-retardant transparent organic silicon fireproof coating, which comprises the following steps:
and mixing and curing the components according to the using amount to obtain the intrinsic flame-retardant transparent organic silicon fireproof coating.
The invention can adopt the following technical scheme:
fully mixing the polysiloxane A, the reactive phosphate or phosphonate component B, the amino resin component C, the curing catalyst and other auxiliary agents according to the using amount of each component; preferably, the polysiloxane component A and a curing catalyst are mixed, then amino resin, reactive phosphate or phosphonate and other auxiliary agents are sequentially added, the transparent fireproof coating is obtained after full mixing, and the fireproof transparent coating can be obtained after curing for a certain time at a certain temperature.
Figure BDA0003110760940000061
Compared with the prior art, the invention has the following beneficial effects:
(1) the polysiloxane used in the invention is prepared by a solvent-free system, is safer and more environment-friendly, has a linear structure and is liquid at normal temperature;
(2) the linear polysiloxane used in the invention can be cured in the air at normal temperature and normal pressure, only the humidity needs to be adjusted, no complex process and equipment are needed, and the curing process is simple;
(3) the invention selects reactive polysiloxane, amino resin, phosphate or phosphonate ester to carry out co-curing reaction to obtain uniform-phase solvent-free coating without phase interface, thus having good transparency; the polysiloxane, the amino resin, the phosphate ester or the phosphonate ester have the flame retardant function, so that the flame retardant function of multiple systems and multiple effects is formed; therefore, the intrinsic flame-retardant transparent organic silicon fireproof coating has good transparency and flame retardant property, and the visible light transmittance can be higher than 90%. The UL-94 flame retardant rating reaches a V-0 rating, and the limiting oxygen index can be more than 32;
(4) the transparent historic building fireproof coating has the advantages of no halogen, environmental protection, high efficiency and the like, and has wide application prospect in the fields of historic building fire prevention and the like.
Drawings
FIG. 1 is a photograph of the coating formulation of example 1 after curing;
the coating is prepared according to a formula, the coating is taken out after being completely cured in a cup to obtain a cured coating, the thickness of the coating is 3mm, the following characters can be clearly seen through the coating, and the transparency is excellent.
Detailed Description
While the present invention will be described in detail and with reference to the specific drawings and examples, it is to be understood that the following examples are included merely for purposes of illustration and are not intended to limit the scope of the invention, as other insubstantial modifications and adaptations of the invention may occur to those skilled in the art in light of the present disclosure.
The raw materials used in the examples are all conventional commercially available raw materials;
test methods and related standards in the examples:
limiting oxygen index standard: GB/T2406.2-2009;
vertical burning standard: GB/T2408-2008;
and (3) a thermogravimetric testing step: taking a 5-10mg sample and an alumina crucible, and heating to 600 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere to obtain a thermal weight loss curve;
and (3) transparency test: the maximum transmittance of a 1mm thick coating in the wavelength range of 400nm to 700nm was measured.
The parts in the examples are parts by weight.
TABLE 1 specifications for polysiloxane A1 in examples 1-6
Polysiloxane A1 Number plate Company(s)
Amino silicone oil DY－N322D2 SHANDONG DAYI CHEMICAL Co.,Ltd.
Amino silicone oil DY-N323 SHANDONG DAYI CHEMICAL Co.,Ltd.
Methyl hydrogen-containing silicone oil DY-H212 SHANDONG DAYI CHEMICAL Co.,Ltd.
Methyl phenyl hydrogen-containing silicone oil PH212 SHANDONG DAYI CHEMICAL Co.,Ltd.
Methyl phenyl vinyl silicone oil IOTA252 Anhui Aiyota Silicone oil Co Ltd
Hydroxyl-terminated methyl vinyl silicone oil IOTA 1203V Anhui Aiyota Silicone oil Co Ltd
Example 1
The amino silicone oil is DY-N322D 2 of Shandong Dayichan chemical industry Co., Ltd, and has the following structural formula:
Figure BDA0003110760940000081
m is about 20 and n is about 50.
Preparing a transparent fireproof coating:
the raw materials and the dosage are as follows: 83 parts of amino silicone oil, 17 parts of gamma-aminopropyltriethoxysilane, 150 parts of methyl alcohol etherified melamine formaldehyde resin with the etherification degree of 1:5, 15 parts of dibutyl hydroxyethyl phosphate and 0.01 part of stannous octoate catalyst.
The transparent fireproof coating comprises the following steps:
(1) weighing amino silicone oil and stannous octoate catalyst according to the proportion, and uniformly stirring;
(2) weighing melamine formaldehyde resin, gamma-aminopropyltriethoxysilane and dibutyl hydroxyethyl phosphate according to a proportion, slowly adding into a beaker, stirring while adding, uniformly mixing, standing in air for 3h, and carrying out pre-curing reaction;
(3) and (3) placing the mixture into a blast drying oven, curing for 3 hours at 90 ℃ to obtain a transparent coating, namely the transparent fireproof coating, and testing the fireproof performance and the transparent performance of the transparent fireproof coating.
Through UL-94 vertical burning test and limit oxygen index test, the flame retardant grade reaches V-0 standard, and the limit oxygen index is more than 32; the thermal weight loss test is carried out under the nitrogen atmosphere, the residual weight is 39% at 600 ℃, the transparency test is carried out by using an ultraviolet visible spectrum, and the visible light transmittance is more than 90%.
Example 2
The amino silicone oil is DY-N323 of Shandong Dayihua chemical Co., Ltd, and has the following structural formula:
Figure BDA0003110760940000091
m is about 180 and n is about 320.
Preparing a transparent fireproof coating:
the raw materials and the dosage are as follows: 83 parts of amino silicone oil, 17 parts of gamma-glycidyl ether oxypropyltrimethoxysilane, 100 parts of methyl alcohol etherified melamine formaldehyde resin with the etherification degree of 1:5, 40 parts of n-butyl bis (3-hydroxypropyl) phosphine oxide and 2 parts of stannous octoate catalyst.
The transparent fireproof coating comprises the following steps:
(1) weighing amino silicone oil and stannous octoate catalyst according to the proportion, and uniformly stirring;
(2) weighing melamine formaldehyde resin, gamma-glycidoxypropyltrimethoxysilane and n-butyl bis (3-hydroxypropyl) phosphine oxide according to a certain proportion, slowly adding the materials into a beaker, stirring while adding, uniformly mixing, standing for 4 hours at normal temperature, and carrying out pre-curing reaction;
(3) and (3) placing the mixture into a blast drying oven, curing for 3 hours at 90 ℃ to obtain a transparent coating, namely the transparent fireproof coating, and testing the fireproof performance and the transparent performance of the transparent fireproof coating.
Through UL-94 vertical burning test and limit oxygen index test, the flame retardant grade reaches V-0 standard, and the limit oxygen index is more than 29; the thermal weight loss test is carried out under the nitrogen atmosphere, the residual weight is 28% at 600 ℃, the transparency test is carried out by using an ultraviolet visible spectrum, and the visible light transmittance is more than 90%.
Example 3
The methyl hydrogen-containing silicone oil is DY-H212 of Shandong Dayihua chemical industry Co., Ltd, and has the following structural formula:
Figure BDA0003110760940000101
m is about 22 and n is about 280.
Preparing a transparent fireproof coating:
the raw materials and the dosage are as follows: 100 parts of methyl hydrogen-containing silicone oil, 300 parts of benzoguanamine formaldehyde resin, 2 parts of hydroxypropyl dibutyl phosphate and 1 part of stannous octoate catalyst.
The transparent fireproof coating comprises the following steps:
(1) weighing methyl hydrogen-containing silicone oil and a stannous octoate catalyst in a beaker according to the proportion, and uniformly stirring;
(2) weighing the benzoguanamine formaldehyde resin and the hydroxypropyl dibutyl phosphate according to the proportion, slowly adding the benzoguanamine formaldehyde resin and the hydroxypropyl dibutyl phosphate into a beaker, stirring the benzoguanamine formaldehyde resin and the hydroxypropyl dibutyl phosphate while adding the benzoguanamine formaldehyde resin and the hydroxypropyl dibutyl phosphate, uniformly mixing the benzoguanamine formaldehyde resin and the hydroxypropyl dibutyl phosphate, and standing the mixture in air for 6 hours to perform pre-curing reaction;
(3) and (3) placing the mixture into a blast drying oven, curing for 3 hours at 90 ℃ to obtain a transparent coating, namely the transparent fireproof coating, and testing the fireproof performance and the transparent performance of the transparent fireproof coating.
Through UL-94 vertical burning test and limit oxygen index test, the flame retardant grade reaches V-0 standard, and the limit oxygen index is more than 33; the thermal weight loss test is carried out under the nitrogen atmosphere, the residual weight is 21% at 600 ℃, the transparency test is carried out by using an ultraviolet visible spectrum, and the visible light transmittance is more than 76%.
Example 4
The methyl phenyl hydrogen-containing silicone oil is PH212 of Shandong Dayichang chemical Co., Ltd, and has the following structural formula:
Figure BDA0003110760940000102
m is about 25 and n is about 175.
Preparing a transparent fireproof coating:
the raw materials and the dosage are as follows: 75 parts of methyl phenyl hydrogen-containing silicone oil, 25 parts of hydroxypropyl triethoxysilane, 100 parts of benzoguanamine formaldehyde resin, 30 parts of diphenyl hydroxyethyl phosphate and 3 parts of stannous octoate catalyst.
The transparent fireproof coating comprises the following steps:
(1) weighing methyl phenyl hydrogen-containing silicone oil and a stannous octoate catalyst according to the proportion, and uniformly stirring;
(2) weighing the benzoguanamine formaldehyde resin, the hydroxypropyl triethoxysilane and the hydroxyethyl diphenyl phosphate according to the proportion, slowly adding into a beaker, stirring while adding, uniformly mixing, standing in the air for 4 hours, and carrying out pre-curing reaction;
(3) and (3) placing the mixture into a blast drying oven, curing for 3 hours at 90 ℃ to obtain a transparent coating, namely the transparent fireproof coating, and testing the fireproof performance and the transparent performance of the transparent fireproof coating.
Through UL-94 vertical burning test and limit oxygen index test, the flame retardant grade reaches V-0 standard, and the limit oxygen index is more than 27; the thermal weight loss test is carried out under the nitrogen atmosphere, the residual weight is 24% at 600 ℃, the transparency test is carried out by using an ultraviolet visible spectrum, and the visible light transmittance is more than 90%.
Example 5
The methyl phenyl vinyl silicone oil is IOTA252 of Anhui Eyota silicone oil Co., Ltd, and the structural formula is as follows:
Figure BDA0003110760940000111
m is 0 and n is about 800.
Preparing a transparent fireproof coating:
the raw materials and the dosage are as follows: 90 parts of methyl phenyl vinyl silicone oil, 10 parts of gamma-aminopropyltriethoxysilane, 1 part of etherification degree: 100 parts by weight of a methanol-etherified melamine formaldehyde resin of 5, 20 parts by weight of tris (3-hydroxypropyl) phosphine oxide, and 0.5 part by weight of a dibutyltin dilaurate catalyst.
The transparent fireproof coating comprises the following steps:
(1) weighing lateral methyl phenyl vinyl silicone oil and dibutyltin dilaurate catalyst in a beaker according to the proportion, and uniformly stirring;
(2) weighing melamine formaldehyde resin, gamma-aminopropyltriethoxysilane and tris (3-hydroxypropyl) phosphine oxide according to a proportion, slowly adding into a beaker, stirring while adding, uniformly mixing, standing for 4h at normal temperature, and carrying out pre-curing reaction;
(3) and (3) placing the mixture into a forced air drying oven, curing for 3 hours at 100 ℃ to obtain a transparent coating, namely the transparent fireproof coating, and testing the fireproof performance and the transparent performance of the transparent fireproof coating.
Through UL-94 vertical burning test and limit oxygen index test, the flame retardant grade reaches V-0 standard, and the limit oxygen index is more than 33; the thermal weight loss test is carried out under the nitrogen atmosphere, the residual weight is 37% at 600 ℃, the transparency test is carried out by using an ultraviolet visible spectrum, and the visible light transmittance is more than 90%.
Example 6
The hydroxyl-terminated methyl vinyl silicone oil is IOTA 1203V of Anhui Eyota silicone oil Co., Ltd, and the structural formula is as follows:
Figure BDA0003110760940000121
m is about 100 and n is about 800.
Preparing a transparent fireproof coating:
the raw materials and the dosage are as follows: 90 parts of hydroxyl-terminated methyl vinyl silicone oil, 10 parts of hydroxybutyl triethoxysilane, 100 parts of urea-formaldehyde resin, 5 parts of aminopropyl diethyl phosphate and 4 parts of dibutyltin dilaurate catalyst.
The transparent fireproof coating comprises the following steps:
(1) weighing hydroxyl-terminated methyl vinyl silicone oil and dibutyltin dilaurate catalyst in a beaker according to the proportion, and uniformly stirring;
(2) weighing urea-formaldehyde resin, hydroxybutyl triethoxysilane and aminopropyl diethyl phosphate according to a proportion, slowly adding into a beaker, stirring while adding, uniformly mixing, standing for 4h at normal temperature, and carrying out pre-curing reaction;
(3) and (3) placing the mixture into a forced air drying oven, curing for 3 hours at 100 ℃ to obtain a transparent coating, namely the transparent fireproof coating, and testing the fireproof performance and the transparent performance of the transparent fireproof coating.
Through UL-94 vertical burning test and limit oxygen index test, the flame retardant grade reaches V-0 standard, and the limit oxygen index is more than 30; the thermal weight loss test is carried out under the nitrogen atmosphere, the residual weight is 32% at 600 ℃, the transparency test is carried out by using an ultraviolet visible spectrum, and the visible light transmittance is more than 90%.
The test results of the examples 1 to 6 show that the UL-94 flame retardant rating reaches a V-0 rating, the limiting oxygen index is greater than 27, the visible light transmittances of the intrinsic flame-retardant transparent organosilicon fireproof coatings prepared in the examples except the example 3 are greater than 90%, and the limiting oxygen indexes of the examples 1, 3 and 5 are greater than 32.

Claims (11)

1. An intrinsic flame-retardant transparent organic silicon fireproof coating is characterized in that:
the intrinsic flame-retardant transparent organic silicon fireproof coating is prepared from raw materials consisting of polysiloxane, phosphate or phosphonate, amino resin and a curing catalyst;
based on 100 parts by weight of polysiloxane:
100 parts by weight of polysiloxane;
1-100 parts by weight of phosphate or phosphonate;
50-500 parts by weight of amino resin;
0.01-5 parts by weight of a curing catalyst;
the phosphate or phosphonate is at least one of hydroxyethyl dimethyl phosphate, hydroxyethyl diethyl phosphate, hydroxyethyl dipropyl phosphate, hydroxyethyl dibutyl phosphate, hydroxyethyl diphenyl phosphate, dihydroxyethyl butyl phosphate, phenyl dichlorophosphate, aminopropyl dimethyl phosphate, aminopropyl diethyl phosphate, n-butyl bis (3-hydroxypropyl) phosphine oxide and tris (3-hydroxypropyl) phosphine oxide;
the polysiloxane is polysiloxane A1 or a mixture of polysiloxane A1 and polysiloxane A2;
the polysiloxane A1 has the structural formula:
Figure 746502DEST_PATH_IMAGE001
R1is one of hydrogen, chlorine, hydroxyl, alkoxy, epoxy group, alkenyl, ketoxime group, carboxyl and amino; repeated R1The same or different;
R2~R8each independently selected from phenyl or alkyl with 1-8 carbon atoms; repeated R4The same or different; repeated R5The same or different; repeated R6The same or different;
X1、X2each independently is one selected from hydrogen, chlorine, hydroxyl, amino, epoxy, alkoxy, alkenyl, ketoxime group, carboxyl, sulfydryl, alkyl and phenyl;
m is more than or equal to 0 and less than or equal to 6000, and X is greater than or equal to m =01、X2Neither is alkyl nor phenyl;
0≤n≤7000；
the polysiloxane A2 has the structural formula:
Figure 194801DEST_PATH_IMAGE003
M1、M2、M3each independently selected from alkyl or alkoxy with 1-8 carbon atoms;
y is one of phenyl, aminopropyl, aminoethyl, anilinomethyl, methyl, ethyl, propyl, butyl, dodecyl, hydroxypropyl, hydroxybutyl, glycidoxypropyl, vinyl, epoxy, methacryloxy, mercapto and ureido.
2. The intrinsic flame retardant transparent silicone fire retardant coating of claim 1, characterized in that:
based on 100 parts by weight of polysiloxane:
100 parts by weight of polysiloxane;
5-40 parts by weight of phosphate or phosphonate;
100-300 parts by weight of amino resin;
0.01-4 parts by weight of a curing catalyst.
3. The intrinsic flame retardant transparent silicone fire retardant coating of claim 1, characterized in that:
R1a hydroxyl group having 0 to 8 carbon atoms, or an alkoxy group, a ketoxime group, a carboxyl group or an amino group having 1 to 8 carbon atoms, or an epoxy group or an alkenyl group having 2 to 8 carbon atoms;
R2~R8each is independently selected from one of methyl, ethyl, isopropyl, butyl and octyl;
X1、X2independently selected from hydroxyl with 0-8 carbon atoms, alkoxy with 1-8 carbon atoms, ketoxime group, carboxyl or amino, epoxy or alkenyl with 2-8 carbon atoms;
0≤m≤1000；
0≤n≤800；
M1、M2、M3each independently selected from one of methoxyl, ethoxyl, methyl and ethyl, wherein M is1、M2、M3At least 1 of them is selected from methoxy or ethoxy.
4. The intrinsic flame retardant transparent silicone fire retardant coating of claim 3, characterized in that:
R1is one of vinyl, methoxy, ethoxy, butoxy, hydroxyl, hydroxyethyl, epoxypropyl, epoxymethyl, aminopropyl, carboxypropyl and carboxymethyl;
X1、X2each independently selected from one of methyl, ethyl, phenyl, methoxy, ethoxy, vinyl, carboxypropyl, epoxypropyl and aminopropyl.
5. The intrinsic flame retardant transparent silicone fire retardant coating of claim 1, characterized in that:
the mass ratio of the polysiloxane A1 to the polysiloxane A2 is 1: 0.05-0.8.
6. The intrinsically flame retardant transparent silicone fire retardant coating of claim 5, wherein:
the mass ratio of the polysiloxane A1 to the polysiloxane A2 is 1: 0.1-0.4.
7. The intrinsic flame retardant transparent silicone fire retardant coating of claim 1, characterized in that:
the structural formula of the phosphate or phosphonate is:
Figure DEST_PATH_IMAGE005
wherein Y is1、Y2、Y3Each independently is one selected from hydrogen, chlorine, hydroxyl, alkyl, amino, imino and alkoxy;
wherein Y is1、Y2、Y3At least one of them is hydrogen, chlorine, hydroxyl or amino.
8. The intrinsically flame retardant transparent silicone fire retardant coating of claim 7, wherein:
Y1、Y2、Y3each independently selected from chlorine, hydroxyl or amino with 0-10 carbon atoms, or alkyl, imino or alkoxy with 1-10 carbon atoms;
wherein Y is1、Y2、Y3At least one of the hydroxyl groups or amino groups is a terminal hydroxyl group or amino group having 0 to 10 carbon atoms.
9. The intrinsic flame retardant transparent silicone fire retardant coating of claim 1, characterized in that:
the amino resin is at least one of melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, melamine urea copolycondensation resin and melamine benzoguanamine copolycondensation resin; and/or the presence of a gas in the gas,
the curing catalyst is at least one of organic tin, amine, acid anhydride, titanate, organic acid and platinum-containing complex.
10. The intrinsic flame retardant transparent silicone fire retardant coating of claim 9, characterized in that:
the amino resin is melamine formaldehyde resin etherified with methanol; and/or the presence of a gas in the gas,
the curing catalyst is at least one of stannous octoate, dibutyltin dilaurate, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, p-toluenesulfonic acid, ethylenediamine, triethanolamine, triethylamine, n-butylamine, butyl titanate, chloroplatinic acid and Karstedt catalyst.
11. A method for preparing an intrinsic flame retardant transparent silicone fire retardant coating according to any one of claims 1 to 10, characterized in that the method comprises:
and mixing and curing the components according to the using amount to obtain the intrinsic flame-retardant transparent organic silicon fireproof coating.
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