CN104762009B - Nano modified polyurethane flame-retardant waterproof coating and preparation method thereof - Google Patents
Nano modified polyurethane flame-retardant waterproof coating and preparation method thereof Download PDFInfo
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- CN104762009B CN104762009B CN201510162951.3A CN201510162951A CN104762009B CN 104762009 B CN104762009 B CN 104762009B CN 201510162951 A CN201510162951 A CN 201510162951A CN 104762009 B CN104762009 B CN 104762009B
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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
- 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
Abstract
The invention discloses a kind of nano modified polyurethane flame-retardant waterproof coating, by weight percentage, raw material consists of：The fire-retardant MDI of nano modification 15～30%；Polyether polyol 10～30%；Inserts 20～40%；Chain extender 20～40%；Silane coupler 0.5～5%；The preparation method of the fire-retardant MDI of described nano modification is：Soluble magnesium salt, aluminum soluble salt and water are mixed to get mixed solution, again mixed solution is added drop-wise in sodium dodecyl benzene sulfonate aqueous solution, and keep reaction system pH value be 8～13, after completion of dropping through ageing, be filtrated to get nano modification AI/Mg Composite Flame Retaradant；MDI and nano modification AI/Mg Composite Flame Retaradant blending and modifying are obtained the fire-retardant MDI of nano modification.The present invention provides a kind of storage time long, fire resistance, toughness and the excellent nano modified polyurethane flame-retardant waterproof coating of heat-proof combustion-resistant performance.
Description
Technical field
The present invention relates to the technical field of polyurethane flame-proof water-repellent paint, more particularly, to a kind of nano modified polyurethane is fire-retardant
Water-repellent paint and preparation method thereof.
Background technology
Polyurethane water-proof paint is the water-repellent paint with polyurethane as main film forming substance for the class, and it is good to have a mechanical property,
Wearability projects, and chemical resistance is good, many advantages, such as waterproof effect is excellent, is widely used in the basement of building construction,
Roofing, urban road bridges etc., closely bound up with industry and daily life.But not fire retardant treated polyurethane water-proof paint
Belong to combustible material, oxygen index (OI) is 17% about, during burning, flame is big, has dense smoke, can discharge the toxic gas such as HCN, CO, to people
Body and environment have very major injury, therefore, it is necessary to carry out flame-retardant modified to it.
The flame retardant epoxy moulding material patent of invention of announcement at present, adopts halogen containing flame-retardant mostly.As Publication No.
The Chinese patent literature of CN102863736A discloses a kind of fire-retardant MDI moulding material, comprises following components：MDI60～64 part；
MDI8～11 part；4.5～7.8 parts of firming agent；1.5～2.6 parts of metal-oxide；5～8 parts of fire retardant；3～5 parts of phosphate ester；Multiple
Close 1.4～2.3 parts of releasing agent；51～55 parts of inorganic filler；12～16 parts of carbon nano-fiber；28～32 parts of reinforcing fiber；Surface
0.7～1.1 part of reinforcing agent.The bending strength of fire-retardant MDI moulding material of preparation and heat distortion temperature are high, but what it was used
Fire retardant is TDE, is halogen containing flame-retardant, it adopts carbon nano-fiber as reinforcing material in addition, its production cost
Too high, practical application is caused to limit.
And for example the Chinese patent literature of Publication No. CN103635500A discloses a kind of sprayable type flame retardant polyurethane and applies
Feed composition.Its formula comprises A side and B side, and A side comprises isocyanate prepolymer and flame retardant compound, and B side comprises red phosphorus and exists
Dispersion in aromatic polyester polyols and other flame-retardant compounds.Flame retardant compound be selected from TCPP, 3,4,5,
The bromo- 1,2- benzene of 6- tetra--dicarboxylic acids or Firebrake ZB etc..This formula is more complicated, adopts multiple fire retardants simultaneously, relatively costly.More than
Fire-retardant using the TDE arriving and this kind of halogen-containing class of the bromo- 1,2- benzene-dicarboxylic acids of 3,4,5,6- tetra- in two patents
Agent, all can produce toxic and harmful in combustion, and its preparation, use and last handling process are for human health and environment
There is larger harm, therefore, exploitation halogen-free flame retardants is very necessary.The cost of coating in development, to be taken into account simultaneously, make
With performance, fire resistance and environmental-protecting performance etc..
The Chinese patent literature of Publication No. CN104109457A disclose fire-retardant with water proofing property aqueous polyurethane coating with
The preparation method of adhesive, selects modified fullerenes to make catalyst, will have Isosorbide-5-Nitrae-bis- (dimethyl hydroxyls of anti-flammability and water proofing property
Base silicon substrate) benzene and isophorone diisobutyrate reacted and as chain extender, is simultaneously introduced modified time strong phosphorus of smoke-suppressing
Sour manganese, to reduce the release amount of smoke of burning, to reach fire-retardant effect.Using fire retardant as chain extender and solvent in this invention
The fire resistance that polyurethane can be made is obviously improved, and the modified fullerenes for catalyst also have certain anti-flammability.But should
The technique of formula is complex, relatively costly, has certain restriction in actual applications.
Disclose a kind of epoxy plastics in United States Patent (USP) US 6838509B2, make the heat-resisting of material by adding organic clay
Property and mechanical strength get a promotion.But meanwhile due to there being the presence of clay larger for the loss of production equipment, add
Organic clay needs certain cost in itself, and such material price may be lacked competitiveness.Further, since organic clay plus
Enter, its injection performance can be affected.
United States Patent (USP) US 6664343B2 discloses a kind of preparation method of epoxy composite material, and its key component is greater than
70% epoxy plastics, along with a certain amount of silicone rubber component and firming agent, its curing rate is fast, and humidity resistance is good, but
Because raw material uses silicone rubber and MDI in a large number, its production cost is higher, and application is restricted.
Content of the invention
The invention provides a kind of storage time is long, insulating properties, toughness and the excellent nanometer of heat-proof combustion-resistant performance change
Property polyurethane flame-proof water-repellent paint.
A kind of nano modified polyurethane flame-retardant waterproof coating, by weight percentage, raw material consists of：
The preparation method of the fire-retardant MDI of described nano modification is as follows：
(1) soluble magnesium salt, aluminum soluble salt and water are mixed to get mixed solution, then mixed solution is added drop-wise to 12
In alkyl benzene sulphonate sodium water solution, and keep reaction system pH value be 8～13, after completion of dropping through ageing, be filtrated to get and receive
Modified magnesium-aluminum the composite flame-retardant agent of rice；
In described mixed solution, metal ion total concentration is 0.05～2mol/L, and magnalium mol ratio is 2:1；
(2) MDI (MDI) and described nano modification magnesium-aluminum composite flame-retardant agent blending are changed
Property be obtained the fire-retardant MDI of nano modification.
Preferably, described soluble magnesium salt be magnesium nitrate and/or magnesium chloride, aluminum soluble salt be aluminum nitrate and/or
Aluminum chloride.
Preferably, metal ion total concentration is 0.1～1mol/L in described mixed solution.Further preferably, described
In mixed solution, metal ion total concentration is 0.15～0.3mol/L.
Preferably, the concentration of described sodium dodecyl benzene sulfonate aqueous solution is 0.005～0.1mol/L, further preferably
For 0.05～0.1mol/L.
Preferably, described soluble magnesium salt is 0.1～10 with the mol ratio of dodecylbenzene sodium sulfonate:1, excellent further
Elect 0.2～0.4 as:1.
Preferably, passing through Deca sodium hydrate aqueous solution, the pH value keeping reaction system is 9～11.
Preferably, the temperature of described ageing is 60～80 DEG C, the time is 10～30h.
Preferably, the addition of described nano modification magnesium-aluminum composite flame-retardant agent is the 1～10% of MDI weight.
Preferably, the degree of polymerization of described polyether polyol is 2000～5000.
Preferably, described silane coupler is KH560 (γ-glycidoxypropyltrime,hoxysilane), KH570
(γ-methacryloxypropyl trimethoxy silane), KH580 (γ-mercaptopropyl trimethoxysilane), KBM303 (β-(3,
4- epoxycyclohexylethyl) trimethoxy silane), KBM803 (3-mercaptopropyi trimethoxy silane), KBM603 (N-2 ammonia second
Base -3- aminopropyl trimethoxysilane) at least one；
Described chain extender is amine chain extender；
Described inserts are Calcium Carbonate, silicon powder, Pulvis Talci, at least one in quartz sand.
Compared with prior art, beneficial effects of the present invention are embodied in：
(1) with soluble magnesium salt, aluminium salt as raw material, dodecylbenzene sodium sulfonate, as intercalator, forms lamella to the present invention
Spacing is the layer structure of Nano grade, is more beneficial for the raising of its dispersive property.This nano modification magnesium-aluminum composite flame-retardant agent is
Efficient halogen-free anti-inflaming agent, the less pollution that environment is caused, flame retardant effect projects.
(2) find through test, add the MDI viscosity of nano modification magnesium-aluminum composite flame-retardant agent low that good fluidity is made
Paint film weatherability and fire resistance are obviously improved than common MDI, the either anti-flammability of the paint film after solidification, toughness, also
It is that thermostability all has raising by a relatively large margin than conventional polyurethanes coating.
Brief description：
Fig. 1 is the X-ray diffractogram of the nano modification magnesium-aluminum composite flame-retardant agent of embodiment 1 preparation；
Fig. 2 is the structural representation of the nano modification magnesium-aluminum composite flame-retardant agent of embodiment 1 preparation.
Specific embodiment
Embodiment 1
At room temperature 0.2mol/L magnesium nitrate and 0.1mol/L aluminum nitrate mixed solution (100ml) are slowly added dropwise into concentration
In 500mL dodecylbenzene sodium sulfonate solution for 0.1mol/L, system pH is kept to be 9～11, at 60 DEG C after completion of dropping
Ageing 20 hours, filters and washs, and gained white powder is nano modification magnesium-aluminum composite flame-retardant agent.This reaction yield is
92%.
Fig. 1 is the X-ray diffractogram of nano modification magnesium-aluminum composite flame-retardant agent manufactured in the present embodiment, can from figure
Go out, first-order diffraction peak (003) occurs in 3.10 °, corresponding interlamellar spacing is 2.84nm, the strictly modifying agent of nanoscale.
Fig. 2 is the structural representation of nano modification magnesium-aluminum composite flame-retardant agent manufactured in the present embodiment, main between its lamella
It is dodecylbenzene sodium sulfonate intercalator, there is also a small amount of nitrate ion, interlamellar spacing is 2.84nm.
Will be enterprising in three-roller with 120 grams of MDI (BASF) for the nano modification magnesium-aluminum composite flame-retardant agent of 20 grams of this enforcement preparations
Row blending, is sufficiently mixed 30 minutes, that is, makes the fire-retardant MDI-A of nano modification.
Nano modified polyurethane flame-retardant waterproof coating has been obtained final product, by it after each component is mixed by the percetage by weight of table 1
Film-forming, obtains sample property indices and refers to table 4.
Table 1
Embodiment 2
At room temperature 0.1mol/L magnesium nitrate and 0.05mol/L aluminum nitrate mixed solution (50ml) are slowly added dropwise into concentration
In 500mL dodecylbenzene sodium sulfonate solution for 0.05mol/L, system pH is kept to be 9～11, at 80 DEG C after completion of dropping
Ageing 15 hours, filters and washs, and gained white powder is nano modification magnesium-aluminum composite flame-retardant agent.This reaction yield is
95%.
Will be enterprising in three-roller with 120 grams of MDI (BASF) for the nano modification magnesium-aluminum composite flame-retardant agent of 20 grams of this enforcement preparations
Row blending, is sufficiently mixed 30 minutes, that is, makes the fire-retardant MDI-B of nano modification.
Nano modified polyurethane flame-retardant waterproof coating has been obtained final product, by it after each component is mixed by the percetage by weight of table 2
Film-forming, obtains sample property indices and refers to table 4
Table 2
Comparative example
Nano modified polyurethane flame-retardant waterproof coating has been obtained final product, by it after each component is mixed by the percetage by weight of table 3
Film-forming, obtains sample property indices and refers to table 4
Table 3
Table 4
| Performance | Embodiment 1 | Embodiment 2 | Comparative example |
| Film outward appearance (resistance to water 48h) | Transparent | Transparent | Opaque |
| Elongation at break (%) | 154 | 149 | 126 |
| Oxygen index (OI) | 30 | 28 | 23 |
Performance according to embodiment and comparative example resulting materials understands, the introducing of nano modification magnesium-aluminum composite flame-retardant agent exists
While effectively improving polyurethane film resistance to water, fracture strength, its fire resistance is also improved significantly.
Performance characterization method：
1. limiting oxygen index determination is according to ISO4589-1984《Plastics-oxygen index method measures flammability oxygen index method and measures burning
Property》Test, batten size 130.0 × 6.5 × 3 (mm).
Above nano modified polyurethane flame-retardant waterproof coating preparation method provided by the present invention is described in detail.
Specific case used herein is set forth to the principle of the present invention and embodiment, and the explanation of above embodiment is
Help understands the inventive method and key point.This specification content should not be construed as limitation of the present invention.
Claims (7)
1. it is characterised in that by weight percentage, raw material consists of a kind of nano modified polyurethane flame-retardant waterproof coating：
The preparation method of the fire-retardant MDI of described nano modification is as follows：
(1) soluble magnesium salt, aluminum soluble salt and water are mixed to get mixed solution, then mixed solution is added drop-wise to dodecyl
In benzene sulfonate aqueous solution, and keep the pH value of reaction system to be 8～13, after completion of dropping through ageing, be filtrated to get nanometer and change
Property magnesium-aluminum composite flame-retardant agent；
In described mixed solution, metal ion total concentration is 0.15～0.3mol/L, and magnalium mol ratio is 2:1；
The concentration of described sodium dodecyl benzene sulfonate aqueous solution is 0.05～0.1mol/L, soluble magnesium salt and detergent alkylate sulphur
The mol ratio of sour sodium is 0.2～0.4:1；
(2) MDI and described nano modification magnesium-aluminum composite flame-retardant agent blending and modifying are obtained the fire-retardant MDI of nano modification.
2. nano modified polyurethane flame-retardant waterproof coating according to claim 1 is it is characterised in that described soluble magnesium
Salt is magnesium nitrate and/or magnesium chloride, and aluminum soluble salt is aluminum nitrate and/or aluminum chloride.
3. nano modified polyurethane flame-retardant waterproof coating according to claim 1 is it is characterised in that pass through Deca hydroxide
Sodium water solution, the pH value keeping reaction system is 9～11.
4. nano modified polyurethane flame-retardant waterproof coating according to claim 1 is it is characterised in that the temperature of described ageing
For 60～80 DEG C, the time is 10～30h.
5. nano modified polyurethane flame-retardant waterproof coating according to claim 1 is it is characterised in that described nano modification
The addition of magnesium-aluminum composite flame-retardant agent is the 1～10% of MDI weight.
6. nano modified polyurethane flame-retardant waterproof coating according to claim 1 is it is characterised in that described polyether polyol
The degree of polymerization be 2000～5000.
7. nano modified polyurethane flame-retardant waterproof coating according to claim 1 is it is characterised in that described is silane coupled
Agent is at least one in KH560, KH570, KH580, KBM303, KBM803, KBM603；
Described chain extender is amine chain extender；
Described inserts are Calcium Carbonate, silicon powder, Pulvis Talci, at least one in quartz sand.
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| CN105255153A (en) * | 2015-10-09 | 2016-01-20 | 滁州环球聚氨酯科技有限公司 | Anticorrosion fireproof polyurethane foam joint filling material |
| CN105238010A (en) * | 2015-10-09 | 2016-01-13 | 滁州环球聚氨酯科技有限公司 | Heat-resistant insect-proofing polyurethane foam gap filling material |
| CN106590689B (en) * | 2016-12-26 | 2018-06-19 | 荆门市格林美新材料有限公司 | The method that magnalium prepares composite flame-retardant agent is recycled from different sludge |
| CN116515374A (en) * | 2022-11-29 | 2023-08-01 | 海口正宇企业管理咨询服务有限公司 | Fireproof water-based polyurethane mortar floor coating and preparation method thereof |
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| KR20050117629A (en) * | 2004-02-28 | 2005-12-15 | 학교법인고려중앙학원 | Clay-polyurethane nano composite and method for preparing the same |
| JP4573116B2 (en) * | 2005-03-03 | 2010-11-04 | 東邦化学工業株式会社 | Rigid polyurethane foam |
| US20070149675A1 (en) * | 2005-12-26 | 2007-06-28 | Industrial Technology Research Institute | Organic polymer/inorganic particles composite materials |
| EP2274254B1 (en) * | 2008-05-06 | 2016-09-28 | Huntsman International LLC | Clay-isocyanate nanodispersions and polyurethane nanocomposite produced therewith |
| CN103788622B (en) * | 2012-10-27 | 2016-02-24 | 北京市建筑工程研究院有限责任公司 | A kind of nanoparticle fire retardant modified rigid polyurethane PIR foam materials and preparation method thereof |
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