CN114644880A - Two-component polyurethane fireproof coating and preparation method and application thereof - Google Patents
Two-component polyurethane fireproof coating and preparation method and application thereof Download PDFInfo
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- CN114644880A CN114644880A CN202210482815.2A CN202210482815A CN114644880A CN 114644880 A CN114644880 A CN 114644880A CN 202210482815 A CN202210482815 A CN 202210482815A CN 114644880 A CN114644880 A CN 114644880A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a two-component polyurethane fireproof coating, and a preparation method and application thereof, and belongs to the field of fireproof coatings. According to the invention, the non-linear micromolecular chain extender is added into the polyether component, so that a large number of hard segments can be generated, and a very high G modulus and a very wide G modulus range can be obtained; the addition of ingredients with primary amino groups such as polyoxypropylene diamine or polyoxypropylene triamine greatly improves the anti-sagging property of the product; the mechanical strength such as G modulus, tearing strength and tensile strength are improved, and meanwhile, the elongation is not reduced or even improved.
Description
Technical Field
The invention relates to the technical field of fireproof coatings, in particular to a two-component polyurethane fireproof coating and a preparation method and application thereof.
Background
The fireproof paint in the current market mainly comprises a single-component water-based acrylic acid system, a two-component polyurethane system and a two-component epoxy system. The sag resistance after construction is an important property for a two-component polyurethane fireproof coating. The fire-retardant coating needs to exhibit non-sagging properties, i.e., the fire-retardant coating needs to be maintained in a fixed position and shape after application to a substrate, and a primary amino group-containing component such as polyoxypropylene diamine or polyoxypropylene triamine is added to exhibit good sag resistance when mixed with a polyisocyanate component; open time and cure speed are also critical properties for two-component polyurethane fire-retardant coatings. Longer open times and rapid curing are most desirable, the combination of catalysts also plays an important role, with catalysts that delay the reaction being more suitable; the stiffness of the adhesive is described by G-modulus/E-modulus, and in elastomeric polyurethane fire-blocking coatings the stiffness can be increased by adding hard segments, which can be achieved by increasing the proportion of chain extender and isocyanate.
China CN107353803A discloses a high-efficiency fire-retardant polyurethane coating material, which mainly uses polyether polyol and small-molecule chain extender to compound, and adds different kinds of fire retardants to form a polyol component, on the basis of the traditional fire-retardant coating, polyurethane is fused as a film-forming substance of a new material, so that the mechanical properties and fire-retardant properties of the product are greatly improved, but the addition of the chain extender can cause the reduction of elongation, the poor mixing property of the polyether component and the occurrence of phase separation while improving the mechanical strength, and the linear chain extender cannot be added into the isocyanate component, because the reaction product of the isocyanate and the linear chain extender can be crystallized, the viscosity of the polymer is too high and even becomes solid.
Disclosure of Invention
In view of the above, the present invention aims to provide a two-component polyurethane fireproof coating, a preparation method thereof and an application thereof. The invention provides a two-component polyurethane fireproof coating which has high strength, high toughness and high elongation.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a two-component polyurethane fireproof coating which is prepared from a polyol component and an isocyanate component, wherein the volume ratio of the polyol component to the isocyanate component is 20: 1-2: 1;
the polyol component comprises the following components in percentage by mass:
30-50% of polyether polyol, 2-10% of a non-linear small-molecular chain extender, 0.5-2% of polyetheramine, 10-20% of expanded graphite, 5-15% of ammonium polyphosphate, 5-15% of melamine, 10-25% of aluminum hydroxide, 0.2-2% of a water absorbent, 0.2-2% of a silane coupling agent and 0.01-1% of a catalyst.
Preferably, the volume ratio of the polyol component to the isocyanate component is 10:1 to 4: 1.
Preferably, the isocyanate component comprises a polyisocyanate.
Preferably, the polyether polyol is polyether triol and/or polyether diol.
Preferably, the polyether triol has an average molecular weight of 3000-6000 and a hydroxyl value of 28-56 mgKOH/g.
Preferably, the polyether glycol has an average molecular weight of 1000-4000 and a hydroxyl value of 28-112 mgKOH/g.
Preferably, the non-linear small molecule chain extender is diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 2-methyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol or 2-ethyl-1, 3-hexanediol.
Preferably, the polyether amine has an average molecular weight of 200-4000.
The invention also provides a preparation method of the two-component polyurethane fireproof coating, which comprises the following steps:
mixing polyether polyol, a nonlinear micromolecule chain extender, polyether amine, expanded graphite, ammonium polyphosphate, melamine, aluminum hydroxide, a water absorbent, a silane coupling agent and a catalyst to obtain a polyol component;
and mixing the polyol component and the isocyanate component for reaction to obtain the two-component polyurethane fireproof coating.
The invention also provides the application of the two-component polyurethane fireproof coating in the technical scheme or the two-component polyurethane fireproof coating prepared by the preparation method in the technical scheme in the fields of new energy power batteries, rail transit vehicles and high-rise buildings.
According to the invention, the non-linear micromolecular chain extender is added into the polyether component, so that a large number of hard segments can be generated, and a very high G modulus and a very wide G modulus range can be obtained; the addition of the components of primary amino groups in the polyether amine, such as polyoxypropylene diamine or polyoxypropylene triamine, greatly improves the anti-sagging property of the product; the mechanical strength such as G modulus, tearing strength and tensile strength are improved, and the elongation is not reduced or even improved.
Detailed Description
The invention provides a two-component polyurethane fireproof coating which is prepared from a polyol component and an isocyanate component, wherein the volume ratio of the polyol component to the isocyanate component is 20: 1-2: 1;
the polyol component comprises the following components in percentage by mass:
30-50% of polyether polyol, 2-10% of a non-linear small-molecular chain extender, 0.5-2% of polyetheramine, 10-20% of expanded graphite, 5-15% of ammonium polyphosphate, 5-15% of melamine, 10-25% of aluminum hydroxide, 0.2-2% of a water absorbent, 0.2-2% of a silane coupling agent and 0.01-1% of a catalyst.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
In the present invention, the volume ratio of the polyol component to the isocyanate component is preferably 10:1 to 4: 1.
In the present invention, the isocyanate component preferably includes a polyisocyanate, and the mass percentage of the polyisocyanate in the isocyanate component is preferably 100%.
In the invention, the content of the polyether polyol in the polyol component is preferably 35-40 wt%.
In the present invention, the polyether polyol is preferably a polyether triol and/or a polyether diol.
In the invention, the average molecular weight of the polyether triol is preferably 3000-6000, more preferably 4500-5000, and the hydroxyl value is preferably 28-56 mgKOH/g, more preferably 33.6-37.3 mgKOH/g.
In the present invention, the polyether glycol preferably has an average molecular weight of 1000 to 4000, more preferably 2000 to 3000, and most preferably 2000, and a hydroxyl value of 28 to 112mgKOH/g, more preferably 37.3 to 56mgKOH/g, and most preferably 56 mgKOH/g.
In a particular embodiment of the present invention, the polyether polyol is preferably a Wanhua F3135 polyether polyol.
In the invention, the content of the non-linear small molecule chain extender in the polyol component is preferably 4 to 8 wt%, and most preferably 6 wt%.
In the present invention, the non-linear small molecule chain extender is preferably diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 2-methyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, or 2-ethyl-1, 3-hexanediol.
In the invention, the content of the polyether amine in the polyol component is preferably 1-1.5 wt%.
In the invention, the average molecular weight of the polyether amine is preferably 200-4000, more preferably 200-400, and the polyether amine is preferably polyoxypropylene diamine or polyoxypropylene triamine, specifically Jeffamine 230, Jeffamine D-400 and Jeffamine T-403.
In the present invention, the swelling ratio of the expanded graphite in the polyol component is preferably 100 to 500 times, and more preferably 200 to 300 times.
In the invention, the content of the expanded graphite in the polyol component is preferably 13-14 wt%.
In the invention, the content of ammonium polyphosphate in the polyol component is preferably 9-10 wt%.
In the invention, the content of melamine in the polyol component is preferably 9-10 wt%.
In the present invention, the content of aluminum hydroxide in the polyol component is preferably 20% by weight.
In the present invention, the content of the water absorbing agent in the polyol component is preferably 0.2 wt%.
In the present invention, the water absorbing agent is preferably calcium oxide, alkyl sulfonic acid isocyanate or molecular sieve.
In the present invention, the content of the silane coupling agent in the polyol component is preferably 0.5 wt%.
In the present invention, the silane coupling agent is preferably an aminosilane, a mercaptosilane, an epoxysilane, or an allylsilane.
In the present invention, the content of the catalyst in the polyol component is preferably 0.2 wt%.
In the present invention, the catalyst is preferably a combination of an organotin-based catalyst, which is preferably one of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide, or octyltin oxide, and an amine-based catalyst; the amine catalyst is preferably one of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, bis-morpholine diethyl ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine or N, N-dimethylbenzylamine.
In the invention, the mass ratio of the organic tin catalyst to the amine catalyst is preferably 1: 20-1: 2, and more preferably 1: 10-1: 5.
In the present invention, the polyisocyanate is preferably polymeric MDI, TDI biuret, MDI biuret, IPDI biuret, HDI biuret, XDI biuret, H12MDI biuret, TDI trimer, MDI trimer, IPDI trimer, HDI trimer, XDI trimer, H12MDI trimer, TDI trimer or HDI trimer, more preferably TDI trimer or HDI trimer.
The invention also provides a preparation method of the two-component polyurethane fireproof coating, which comprises the following steps:
mixing polyether polyol, a nonlinear micromolecule chain extender, polyether amine, expanded graphite, ammonium polyphosphate, melamine, aluminum hydroxide, a water absorbent, a silane coupling agent and a catalyst to obtain a polyol component;
and mixing the polyol component and the isocyanate component for reaction to obtain the two-component polyurethane fireproof coating.
The preparation method preferably comprises the steps of heating polyether polyol, a nonlinear micromolecule chain extender, polyether amine, expanded graphite, ammonium polyphosphate, melamine and aluminum hydroxide to 110-130 ℃ under stirring, vacuumizing and dehydrating for 2 hours, then cooling to 50 ℃, adding a water absorbent, stirring for 0.5 hour, then adding a silane coupling agent and a catalyst, vacuumizing and stirring for 0.5 hour to obtain the polyol component.
The invention also provides the application of the two-component polyurethane fireproof coating in the technical scheme or the two-component polyurethane fireproof coating prepared by the preparation method in the technical scheme in the fields of new energy power batteries, rail transit vehicles and high-rise buildings.
In the present invention, the two-component polyurethane fire-retardant coating is preferably ready-to-use formulated, and the polyol component and the isocyanate component are reacted.
In order to further illustrate the present invention, the following two-component polyurethane fire-retardant coating provided by the present invention, its preparation method and application are described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Tensile strength, elongation at break, tensile shear strength, G modulus were performed with reference to the criteria in HJ/T4363-;
the anti-sagging performance is carried out according to the standard GB/T9264-2012;
thermal conductivity was performed according to the standard in ASTM C201-1998.
Examples
The raw materials of the components of the examples and the comparative examples are in mass percentage, and are shown in Table 1.
Table 1 examples and comparative examples each component raw material amount is mass percentage content
The preparation method of the two-component polyurethane fireproof coating of the embodiments 1 to 5 and the comparative example is as follows:
the preparation method of the two-component polyurethane fireproof coating preferably comprises the following steps:
(1) heating polyether polyol, a non-linear small-molecule chain extender, polyether amine, expanded graphite, ammonium polyphosphate, melamine and aluminum hydroxide to 110 ℃ under stirring, vacuumizing and dehydrating for 2 hours, then cooling to 50 ℃, adding a water absorbent, stirring for 0.5 hour, then adding a silane coupling agent and a catalyst, vacuumizing and stirring for 0.5 hour to obtain the double-component polyurethane fireproof coating polyol component.
(2) And mixing the polyol component and the isocyanate component according to a certain proportion to obtain the two-component polyurethane fireproof coating.
Table 2 shows the results of the physical property tests of the two-component polyurethane fire-retardant coatings obtained in the examples and the comparative examples, and it can be seen from table 2 that the two-component polyurethane fire-retardant coating provided by the present invention has high strength, high toughness and high elongation.
Table 2 results of physical property test of two-component polyurethane fire-retardant coating materials of examples and comparative examples
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The two-component polyurethane fireproof coating is characterized by comprising a polyol component and an isocyanate component, wherein the volume ratio of the polyol component to the isocyanate component is 20: 1-2: 1;
the polyol component comprises the following components in percentage by mass:
30-50% of polyether polyol, 2-10% of a non-linear small-molecular chain extender, 0.5-2% of polyetheramine, 10-20% of expanded graphite, 5-15% of ammonium polyphosphate, 5-15% of melamine, 10-25% of aluminum hydroxide, 0.2-2% of a water absorbent, 0.2-2% of a silane coupling agent and 0.01-1% of a catalyst.
2. The two-component polyurethane fireproof coating according to claim 1, wherein the volume ratio of the polyol component to the isocyanate component is 10:1 to 4: 1.
3. The two-component polyurethane fire-retardant coating according to claim 1 or 2, characterized in that the isocyanate component comprises a polyisocyanate.
4. The two-component polyurethane fire retardant coating according to claim 1, characterized in that the polyether polyol is polyether triol and/or polyether diol.
5. The two-component polyurethane fireproof coating according to claim 4, wherein the polyether triol has an average molecular weight of 3000 to 6000 and a hydroxyl value of 28 to 56 mgKOH/g.
6. The two-component polyurethane fireproof coating of claim 4, wherein the polyether glycol has an average molecular weight of 1000 to 4000 and a hydroxyl value of 28 to 112 mgKOH/g.
7. The two-component polyurethane fire retardant coating according to claim 1, wherein the non-linear small molecule chain extender is diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 2-methyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol or 2-ethyl-1, 3-hexanediol.
8. The two-component polyurethane fireproof paint according to claim 1, wherein the polyether amine has an average molecular weight of 200-4000.
9. The preparation method of the two-component polyurethane fireproof coating of any one of claims 1 to 8, which is characterized by comprising the following steps:
mixing polyether polyol, a nonlinear micromolecule chain extender, polyether amine, expanded graphite, ammonium polyphosphate, melamine, aluminum hydroxide, a water absorbent, a silane coupling agent and a catalyst to obtain a polyol component;
and mixing the polyol component and the isocyanate component for reaction to obtain the two-component polyurethane fireproof coating.
10. The two-component polyurethane fireproof coating of any one of claims 1 to 8 or the two-component polyurethane fireproof coating prepared by the preparation method of claim 9 is applied to the fields of new energy power batteries, rail transit vehicles and high-rise buildings.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115197391A (en) * | 2022-08-15 | 2022-10-18 | 河北邦泰氨纶科技有限公司 | Fiber-grade polyurethane slice and preparation method and application thereof |
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Cited By (2)
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| CN115197391B (en) * | 2022-08-15 | 2023-10-31 | 河北邦泰氨纶科技有限公司 | Fiber-grade polyurethane slice and preparation method and application thereof |
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Application publication date: 20220621 |