CN108003774B - A kind of nano-material modified no-solvent polyurethane woodcare paint and preparation method thereof - Google Patents
A kind of nano-material modified no-solvent polyurethane woodcare paint and preparation method thereof Download PDFInfo
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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
- C09D175/06—Polyurethanes from polyesters
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2003/329—Phosphorus containing acids
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The present invention provides a kind of nano-material modified no-solvent polyurethane woodcare paint and preparation method thereof, the component of product, by weight, including MDI, polyether polyol, polyester polyol, prefabricated additive, wherein prefabricated additive includes phosphoric acid, silane coupling agent, neopentyl glycol, polybutene, Nano carbon white and nano-titanium dioxide, specifically the preparation method comprises the following steps: by after the reaction kettle checked heating, under nitrogen atmosphere, liquid MDI stirring is added, polyether polyol is added, continues to stir to get base polyurethane prepolymer for use as；Then the stirring of some polyesters polyalcohol is added, adds prefabricated additive, is evacuated to absolute pressure 20mbar, heating stirring is eventually adding remaining polyester polyol, under vacuum state, continues to stir, discharges, obtain nano-material modified no-solvent polyurethane woodcare paint.Nano material can integrate as polyurethane skeleton structure and crystalline structure and improve the ageing-resistant of woodcare paint, hydrolysis and wear-resisting property in polyurethane aqueous woodcare paint prepared by the present invention.
Description
Technical field
The invention belongs to polyurethane aqueous woodcare paint field of material technology, and in particular to a kind of nano-material modified without molten
Agent polyurethane carpentry paint and preparation method thereof.
Background technique
With the enhancing of people's environmental consciousness, especially various countries' environmental regulation is to volatile organic compounds in coating system
(VOC) strict control of content, woodwork coating industry are gradually friendly from high energy consumption, the traditional solvent type coating of high pollution to environment
Good, resource-conserving water paint transformation, promotes using water paint as the development of the low-contamination type coating of representative.Polyurethane
Coating has excellent wear-resisting, chemical-resistant and toughness, aqueous polyurethane have VOC content is low, pollution is small, at low cost, point
Minor structure Scalability, dilutable water, it is easy to clean the advantages that, paint film has high, wear-resistant and good toughness of intensity etc. special
Point gradually obtains extensive approval and application.But due to containing hydrophilic radical, and the crosslinking of paint film on aqueous polyurethane segment
Density is low, causes hardness of paint film low, and the performances such as poor, chemicals-resistant of richness are insufficient, and limit it makes as aqueous woodware paint
With needing to carry out it cross-linking modified, epoxy-modified, acrylic acid modified, composite modified and nano-material modified etc..
The special nature of nano material can allow aqueous polyurethane coating to possess the property such as radiation-screening, conduction, heat-insulated, wear-resisting
Can, prepare high performance aqueous polyurethane film, common nano-material modified dose have aluminium oxide, silica, titanium dioxide,
Zinc oxide, calcium carbonate, montmorillonite etc..A kind of nano antibacterial water woodenware paint disclosed in Chinese patent CN 100503753C and its
Preparation method, by aqueous polyurethane resin emulsion, aqueous acrylic modified ester-polyurethane resin emulsion and nanometer water acrylic acid tree
The mixture of fat liquor is main film forming substance, with loading nano silvery, nano zine oxide, nano aluminium oxide, nano-titanium dioxide
It is mixed with the nano composite inorganic antibacterial agent of the prefabricated colloidal sol preparation of organic expander soil of nano silica, and aided nano is anti-settling
Thickener, the agent of nanometer stain resistant, nanometer aging-resistant agent, nano double dredge agent, nano wearproof curing agent, wetting dispersing agent, defoaming agent
Slurry is mixed into levelling agent, and nano antibacterial water woodenware paint is prepared in ground filtering packing, and the aqueous woodware paint is by three
The mixing of kind of resin emulsion different proportion is used as film forming matter, not only reduces cost, and guarantee woodcare paint have low VOC value,
It is anti-be adhered, the feature that damage resistant, anti-pollution, color inhibition and closure are good, and a variety of inorganic nano ingredients contained assign aqueous
Woodcare paint broad-spectrum antiseptic and the lasting advantage of antibacterial, a variety of nano multifunctional assistants of selection are all Diamond Search and inorganic product,
Assigning, aqueous woodware paint is functional simultaneously, guarantees the environmentally protective performance of product, but product adds in preparation process needs
The solid content of solubilizer, product is low, and using effect is limited.One kind disclosed in Chinese patent CN 105482587B is environmentally friendly
Water nano structure woodcare paint and preparation method thereof, the woodcare paint include self-crosslinking acrylic nanoemulsions, aqueous polyurethane tree
Fat liquor, silver ion solution, nano titania slurry, coalescing agent, emulsifier, crosslinking agent, dispersing agent, defoaming agent, other
Auxiliary agent and deionized water, the film forming agent of the woodcare paint of this method preparation are acrylate/nano lotion and tung oil-modified polyurethane resin
Lotion, and nano-functional material nano titania slurry and silver ion solution are added, make the woodcare paint of preparation that there is stability
Well, hardness is big, stain resistant performance is good, nontoxic the advantages of having no irritating odor.By the above-mentioned prior art it is found that nano modification
Woodcare paint containing polyurethane can assign the multiple functions such as woodcare paint flame-proof antibiotic enhancing, but currently based on the nothing of nano modification
Research in terms of solvent borne polyurethane single-component woodenware paint is actually rare, and the prior art is mostly by nano materials such as silica
It being mixed with sold resin lotion simple physical to improve performance, nano material is difficult to infiltrate through in the resin macromolecule of molecular weight,
It is be easy to cause gathering for nano material, directly affects the performance and stability of product.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of nano-material modified no-solvent polyurethane woodcare paint and its
Prefabricated nanometer additive is added in the preparation process of polyurethane aqueous woodcare paint, has both improved nanometer and added by preparation method
Add dispersibility of the agent in polyurethane aqueous woodcare paint, and nanometer additive can be used as aggregate and crystalline structure, promotes poly- ammonia
Ester large molecule forms regular oriented structure around nanometer additive, is conducive to the film forming for improving polyurethane aqueous woodcare paint
And mechanical property, and assign ageing-resistant polyurethane aqueous woodcare paint uvioresistant, hydrolysis and wear-resisting property, excellent combination property.
In order to solve the above technical problems, the technical scheme is that
A kind of nano-material modified no-solvent polyurethane woodcare paint, which is characterized in that the nano-material modified nothing
The component of solvent polyurethane woodcare paint, by weight, including 35-40 parts of MDI, prefabricated polyether polyol 10-15 parts, polyester
45-50 parts of polyalcohol, additive 1-5 parts prefabricated, total amount is 100 parts, the component of the prefabricated additive, by weight percentage
Meter, including 0.001% phosphoric acid, 17% silane coupling agent, 5.6% polybutene, 0.4% Nano carbon white, 4% nano-silica
Change titanium, surplus is neopentyl glycol.
The present invention also provides a kind of preparation method of nano-material modified no-solvent polyurethane woodcare paint, feature exists
In: the following steps are included:
(1) reaction kettle air-tightness, agitating paddle and kettle wall cleanliness are checked, it is ensured that completely protect valve without steam and water droplet in kettle
Door is closed, and feeding port is opened, and filter installation is correct, for use；
(2) temperature for the reaction kettle that step (1) has checked is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40
DEG C liquid MDI, stir 10-15min at 60-100r/min, prefabricated polyether polyol be added, with the rate of 45-60r/min
Continue to stir 10-15min, obtains base polyurethane prepolymer for use as；
(3) by weight percentage, 0.001% phosphoric acid, 17% silane coupling agent, 5.6% polybutene, 0.4% are received
Off-white carbon black and 4% nano-titanium dioxide are added in neopentyl glycol, and total amount 100% is uniformly mixed, obtains prefabricated additive,
For use；
(4) some polyesters polyalcohol will first be added in the base polyurethane prepolymer for use as of step (2) preparation, with the speed of 45-60r/min
Rate continues to stir 10-15min, and the prefabricated additive of step (3) preparation is then added, is evacuated to absolute pressure 20mbar, heats up
To 80-85 DEG C, continues to stir 50-60min with the rate of 45-60r/min, be eventually adding remaining polyester polyol, vacuum state
Under, continue to stir 1-2h with the rate of 50-80r/min, discharging detects nco value to 5.5-6.5%, obtains nano-material modified
No-solvent polyurethane woodcare paint.
As a preferred embodiment of the above technical solution, in the step (2), 4,4 '-methyl diphenylene diisocyanate of MDI,
Or mixtures thereof one of 2,4 '-methyl diphenylene diisocyanates and 2,2 '-methyl diphenylene diisocyanates.
As a preferred embodiment of the above technical solution, in the step (2), MDI is modified MDI, HDI, XDI by TDI, IPDI,
PAPI is replaced.
As a preferred embodiment of the above technical solution, in the step (2), the molecular weight of prefabricated polyether polyol is 2600-
3000。
As a preferred embodiment of the above technical solution, in the step (3), phosphoric acid is that the analysis of 100-300PPM is pure.
As a preferred embodiment of the above technical solution, in the step (3), stand-by timeliness is lower than 20min.
As a preferred embodiment of the above technical solution, in the step (4), some polyesters polyalcohol and remaining polyester polyol
Mass ratio is 1:2.5-3.
As a preferred embodiment of the above technical solution, in the step (4), nano-material modified no-solvent polyurethane woodcare paint
Component, by weight, including 35-40 parts of MDI, prefabricated polyether polyol 10-15 parts, 45-50 parts of polyester polyol, pre-
Additive 1-5 parts processed, total amount is 100 parts, the prefabricated polyether polyol by adipic acid, terephthalic acid (TPA) and M-phthalic acid with
Diethylene glycol (DEG) and ethylene glycol hybrid reaction are made.
As a preferred embodiment of the above technical solution, in the step (4), nano-material modified no-solvent polyurethane woodcare paint
Component, by weight, including 39 parts of MDI, 10 parts of prefabricated polyether polyol, 48 parts of polyester polyol, prefabricated additive 3
Part, total amount is 100 parts.
Compared with prior art, the invention has the following advantages:
It (1) include MDI, prefabricated polyether polyols in nano-material modified no-solvent polyurethane woodcare paint prepared by the present invention
The pure and mild prefabricated additive of alcohol, polyester polyols, wherein prefabricated polyether polyol is by adipic acid, terephthalic acid (TPA) and M-phthalic acid
It is made with diethylene glycol (DEG) and ethylene glycol hybrid reaction, prefabricated polyether polyol is mixed into synthesis of polyurethane Waterborne wood with polyester polyol
Device paint assigns the excellent anti-hydrolytic performance of polyurethane aqueous woodcare paint, resistance to low temperature, oil resistance, good combination property.
It (2) include MDI, prefabricated polyether polyols in nano-material modified no-solvent polyurethane woodcare paint prepared by the present invention
The pure and mild prefabricated additive of alcohol, polyester polyols, wherein prefabricated additive include phosphoric acid, silane coupling agent, neopentyl glycol, polybutene,
Inhibition is played in Nano carbon white and nano-titanium dioxide, the polymerization that phosphoric acid can prevent MDI too fast, and silane coupling agent is same
When there is polarity and nonpolar moiety, by the polyurethane end of the chain-NCO group is converted into hydrolyzable alkoxy grp, therefore poly-
Urethane aqueous woodware paint micro-moisture in using air will not generate carbon dioxide, therefore as when crosslinking accelerator solidification
Not will cause lacquer painting has bubble, influences the mechanical performance and aesthetic appearance of coating, furthermore neopentyl glycol passes through as plasticizer
Nano-titanium dioxide is added and nano silica (Nano carbon white) is used as nano modifier, the activity of nano-titanium dioxide
Height is easy to reunite, nano silica is cooperateed with use with nano-titanium dioxide, nano silica can be deposited on nano-silica
The surface for changing titanium, reduces the activity of nano-titanium dioxide, and nano silica and nano-titanium dioxide are in silane coupling agent
Under effect, the compatibility performance with MDI and polyurethane is improved, promotes nano silica and nano-titanium dioxide surface more
Bonding action occurs for the group in hydroxyl and MDI and polyurethane, forms three-dimensional net structure in polyurethane aqueous woodcare paint, mentions
The compactness of polyurethane aqueous woodcare paint, thermal stability, ultraviolet light, ageing-resistant, hydrolysis and wear-resisting property after high solidification, and
Nano material is added in the preparation process of polyurethane, and compared with traditional be simply mixed, the present invention first promotes a small amount of poly- ammonia
A possibility that then Lipase absobed is added into nano material, reduce dispersion difficulty of the nano material in polyurethane and reunite, makes
Nano material dispersion is more uniform, and in the synthesis process of polyurethane later, promotes polyurethane as skeleton and crystalline structure
Molecule is aligned in nano-material surface, further increases the mechanical performance of polyurethane aqueous lacquer wood.
(3) solvent is not contained in nano-material modified no-solvent polyurethane woodcare paint prepared by the present invention, simplifies fortune
Defeated, sale, storage and use process, and there is no any solvent to volatilize in work progress, it is nontoxic to environment and construction personnel,
It is also very easy to make and use process, controllability is strong, and product is had excellent performance, and function is more, belongs to high-quality polyurethane water
Property woodcare paint, is suitable for large-scale industrial production, good in economic efficiency.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1:
(1) by 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl
Methane diisocyanate mixing, and it is preheated to 40 DEG C of liquid storages.
(2) by weight percentage, by 0.001% phosphoric acid, 17% silane coupling agent, 72.999% neopentyl glycol,
5.6% polybutene, 0.4% Nano carbon white (150) and 4% modified nano-titanium dioxide are uniformly mixed, and total amount 100% obtains
To prefabricated additive, for use, it is ensured that added in 20 minutes.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without aqueous vapor, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
10min is stirred under 60r/min, polyether polyol is added, and is continued to stir 10min with the rate of 45r/min, is obtained polyurethane prepolymer
Some polyesters polyalcohol PE1000 will be first added in body in base polyurethane prepolymer for use as, continue to stir 10min with the rate of 45r/min, so
The prefabricated additive being added afterwards, is evacuated to absolute pressure 20mbar, is warming up to 80 DEG C, continues to stir with the rate of 45r/min
50min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1h with the rate of 50r/min, discharging,
Nco value is detected to 5.5%, obtains nano-material modified no-solvent polyurethane woodcare paint.
Embodiment 2:
(1) by 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl
Methane diisocyanate mixing, and it is preheated to 40 DEG C of liquid storages.
(2) by weight percentage, by 0.001% phosphoric acid, 17% silane coupling agent, 72.999% neopentyl glycol,
5.6% polybutene, 0.4% Nano carbon white (150) and 4% modified nano-titanium dioxide are uniformly mixed, and total amount 100% obtains
To prefabricated additive, for use, it is ensured that added in 20 minutes.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
15min is stirred under 100r/min, polyether polyol is added, and continues to stir 15min with the rate of 60r/min, it is pre- to obtain polyurethane
Some polyesters polyalcohol PE1000 will be first added in aggressiveness in base polyurethane prepolymer for use as, continue to stir 15min with the rate of 60r/min,
Then the prefabricated additive being added, is evacuated to absolute pressure 20mbar, is warming up to 85 DEG C, continues to stir with the rate of 60r/min
60min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 2h with the rate of 80r/min, discharging,
Nco value is detected to 6.5%, obtains nano-material modified no-solvent polyurethane woodcare paint.
Embodiment 3:
(1) by 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl
Methane diisocyanate mixing, and it is preheated to 40 DEG C of liquid storages.
(2) by weight percentage, by 0.001% phosphoric acid, 17% silane coupling agent, 72.999% neopentyl glycol,
5.6% polybutene, 0.4% Nano carbon white (150) and 4% modified nano-titanium dioxide are uniformly mixed, and total amount 100% obtains
To prefabricated additive, for use, it is ensured that added in 20 minutes.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
13min is stirred under 80r/min, polyether polyol is added, and is continued to stir 13min with the rate of 50r/min, is obtained polyurethane prepolymer
Some polyesters polyalcohol PE1000 will be first added in body in base polyurethane prepolymer for use as, continue to stir 12min with the rate of 55r/min, so
The prefabricated additive being added afterwards, is evacuated to absolute pressure 20mbar, is warming up to 83 DEG C, continues to stir with the rate of 50r/min
55min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1.5h with the rate of 60r/min, out
Material detects nco value to 6%, obtains nano-material modified no-solvent polyurethane woodcare paint.
Embodiment 4:
(1) by 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl
Methane diisocyanate mixing, and it is preheated to 40 DEG C of liquid storages.
(2) Japan that nanometer titanium dioxide and molecular weight are 17,000 is spun 673 armorphous saturated polyester resin 1:1 and mediated and divided
Dissipate, gas-phase silica is then added it is common mediate 30 minutes, by mediate 0.001% phosphoric acid of material addition, 17% silane coupling agent,
The 45 DEG C of storages that cool down after 90 DEG C of high speed dispersions dissolution stirring 1h of heating in 72.999% neopentyl glycol, 5.6% polybutene obtain pre-
Additive processed, for use, it is ensured that added in 20min.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
13min is stirred under 70r/min, polyether polyol is added, and is continued to stir 13min with the rate of 50r/min, is obtained polyurethane prepolymer
Body will first be added some polyesters polyalcohol PE1000, continue to stir with the rate of 45-60r/min in base polyurethane prepolymer for use as
10min, the prefabricated additive being then added, is evacuated to absolute pressure 20mbar, is warming up to 80 DEG C, is continued with the rate of 60r/min
50min is stirred, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1h with the rate of 80r/min,
Discharging detects nco value to 5.9%, obtains nano-material modified no-solvent polyurethane woodcare paint.
Embodiment 5:
(1) by 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl
Methane diisocyanate mixing, and it is preheated to 40 DEG C of liquid storages.
(2) by nanometer titanium dioxide, fumed silica and polyether polyol (2600 molecular weight), silane coupling agent is jointly pre-
It is mixed, in the rate of 2500r/min and 45 DEG C of at a temperature of high speed dispersion, prefabricated additive is made, for use, it is ensured that throw in 20 minutes
Add.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
15min is stirred under 100r/min, polyether polyol is added, and continues to stir 15min with the rate of 60r/min, it is pre- to obtain polyurethane
Some polyesters polyalcohol PE1000 will be first added in aggressiveness in base polyurethane prepolymer for use as, continue to stir 10min with the rate of 45r/min,
Then the prefabricated additive being added, is evacuated to absolute pressure 20mbar, is warming up to 80 DEG C, continues to stir with the rate of 45r/min
50min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1h with the rate of 50r/min, discharging,
Nco value is detected to 5.5%, obtains nano-material modified no-solvent polyurethane woodcare paint.
Embodiment 6:
(1) MDI2460 (Bayer) is preheated to 40 DEG C of liquid storages.
(2) by nanometer titanium dioxide, fumed silica and polyether polyol (2600 molecular weight), silane coupling agent is jointly pre-
It is mixed, in the rate of 2500r/min and 45 DEG C of at a temperature of high speed dispersion, prefabricated additive is made, for use, it is ensured that throw in 20 minutes
Add.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
14min is stirred under 90r/min, polyether polyol is added, and is continued to stir 13min with the rate of 50r/min, is obtained polyurethane prepolymer
Some polyesters polyalcohol PE1000 will be first added in body in base polyurethane prepolymer for use as, continue to stir 10min with the rate of 50r/min, so
The prefabricated additive being added afterwards, is evacuated to absolute pressure 20mbar, is warming up to 85 DEG C, continues to stir with the rate of 45r/min
60min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 2h with the rate of 50r/min, discharging,
Nco value is detected to 5.5%, obtains nano-material modified no-solvent polyurethane woodcare paint.
Embodiment 7:
(1) by 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl
Methane diisocyanate mixing, and it is preheated to 40 DEG C of liquid storages.
(2) by nanometer titanium dioxide, fumed silica and polyester polyol (2600 molecular weight), silane coupling agent is jointly pre-
It is mixed, in the rate of 2500r/min and 45 DEG C of at a temperature of high speed dispersion, prefabricated additive is made, for use, it is ensured that throw in 20 minutes
Add.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
14min is stirred under 90r/min, polyether polyol is added, and is continued to stir 14min with the rate of 55r/min, is obtained polyurethane prepolymer
Some polyesters polyalcohol PE1000 will be first added in body in base polyurethane prepolymer for use as, continue to stir 15min with the rate of 45r/min, so
The prefabricated additive being added afterwards, is evacuated to absolute pressure 20mbar, is warming up to 80 DEG C, continues to stir with the rate of 60r/min
50min, is eventually adding remaining polyester polyol PE1000, under vacuum state, continues to stir 1h with the rate of 80r/min, discharging,
Nco value is detected to 6.5%, obtains nano-material modified no-solvent polyurethane woodcare paint.
Embodiment 8:
(1) by 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl
Methane diisocyanate mixing, and it is preheated to 40 DEG C of liquid storages.
(2) by nanometer titanium dioxide, fumed silica and polyester polyol (2600 molecular weight), silane coupling agent is jointly pre-
It is mixed, in the rate of 2500r/min and 45 DEG C of at a temperature of high speed dispersion, prefabricated additive is made, for use, it is ensured that throw in 20 minutes
Add.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without steam, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
13min is stirred under 90r/min, polyether polyol is added, and is continued to stir 14min with the rate of 50r/min, is obtained polyurethane prepolymer
Some polyesters polyalcohol PPG2000 will be first added in body in base polyurethane prepolymer for use as, continue to stir 15min with the rate of 60r/min,
Then the prefabricated additive being added, is evacuated to absolute pressure 20mbar, is warming up to 85 DEG C, continues to stir with the rate of 60r/min
50min, is eventually adding remaining polyester polyol PPG2000, under vacuum state, continues to stir 2h with the rate of 50r/min, out
Material detects nco value to 6.25%, obtains nano-material modified no-solvent polyurethane woodcare paint.
Comparative example 1:
(1) by 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl
Methane diisocyanate mixing, and it is preheated to 40 DEG C of liquid storages.
(2) by weight percentage, by 0.001% phosphoric acid, 17% silane coupling agent, 72.999% neopentyl glycol,
5.6% polybutene, 0.4% Nano carbon white (150) and 4% modified nano-titanium dioxide are uniformly mixed, and total amount 100% obtains
To prefabricated additive, for use, it is ensured that added in 20 minutes.
(3) reaction kettle air-tightness and agitating paddle, kettle wall cleanliness, it is ensured that completely without aqueous vapor, water droplet in kettle are checked.Ensure
Valve is closed, and feeding port is opened, and filter installation is correct.
(4) temperature of reaction kettle is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C of liquid MDI,
10min is stirred under 60r/min, polyether polyol is added, and is continued to stir 60min with the rate of 45r/min, is obtained polyurethane prepolymer
Polyester polyol PE1000 will be first added in body in base polyurethane prepolymer for use as, with the rate of 45r/min continue stir 10min, then plus
The prefabricated additive entered continues to stir 1h with the rate of 50r/min, and discharging detects nco value to 5.5%, obtains nano material and change
The no-solvent polyurethane woodcare paint of property.
Through detecting, the table of the nano-material modified no-solvent polyurethane woodcare paint of embodiment 1-6 and comparative example preparation
Face free energy, hardness, wearability, the result of adhesive force grade and stability are as follows:
As seen from the above table, nano-material modified no-solvent polyurethane woodcare paint prepared by the present invention is prepared than comparative example
The mechanical performance and stability of polyurethane aqueous woodcare paint significantly improve, and can also be obtained preferably by reducing other auxiliary agents
Effect.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (9)
1. a kind of nano-material modified no-solvent polyurethane woodcare paint, which is characterized in that described nano-material modified without molten
The component of agent polyurethane carpentry paint, by weight, including 35-40 parts of MDI, prefabricated polyether polyol 10-15 parts, polyester it is more
First alcohol 45-50 parts, it is additive 1-5 parts prefabricated, total amount be 100 parts, the component of the prefabricated additive, by weight percentage,
It is remaining including 0.001% phosphoric acid, 17% silane coupling agent, 5.6% polybutene, 0.4% Nano carbon white, 4% nano-titanium dioxide
Amount is neopentyl glycol；
The preparation method of the nano-material modified no-solvent polyurethane woodcare paint, comprising the following steps:
(1) reaction kettle air-tightness, agitating paddle and kettle wall cleanliness are checked, it is ensured that completely without steam and water droplet in kettle, it is ensured that valve
It closes, feeding port is opened, and filter installation is correct, for use；
(2) temperature for the reaction kettle that step (1) has checked is adjusted to 65 DEG C, under nitrogen atmosphere, addition is preheated to 40 DEG C
Liquid MDI stirs 10-15min at 60-100r/min, and prefabricated polyether polyol is added, and is continued with the rate of 45-60r/min
10-15min is stirred, base polyurethane prepolymer for use as is obtained；
(3) by weight percentage, by 0.001% phosphoric acid, 17% silane coupling agent, 5.6% polybutene, 0.4% Nano carbon white
It is added in neopentyl glycol with 4% nano-titanium dioxide, total amount 100%, is uniformly mixed, obtains prefabricated additive, for use；
(4) will step (2) preparation base polyurethane prepolymer for use as in some polyesters polyalcohol first be added, with the rate of 45-60r/min after
Continuous stirring 10-15min, is then added the prefabricated additive of step (3) preparation, is evacuated to absolute pressure 20mbar, is warming up to 80-85
DEG C, continue to stir 50-60min with the rate of 45-60r/min, be eventually adding remaining polyester polyol, under vacuum state, with 50-
The rate of 80r/min continues to stir 1-2h, and discharging obtains nano-material modified no-solvent polyurethane woodcare paint.
2. the nano-material modified no-solvent polyurethane woodcare paint of one kind according to claim 1, it is characterised in that: described
In step (2), 4,4 '-methyl diphenylene diisocyanate of MDI, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-hexichol
Or mixtures thereof one of dicyclohexylmethane diisocyanate.
3. the nano-material modified no-solvent polyurethane woodcare paint of one kind according to claim 1, it is characterised in that: described
In step (2), MDI is replaced by TDI, IPDI, modified MDI, HDI, XDI, PAPI.
4. the nano-material modified no-solvent polyurethane woodcare paint of one kind according to claim 1, it is characterised in that: described
In step (2), the molecular weight of prefabricated polyether polyol is 2600-3000.
5. the nano-material modified no-solvent polyurethane woodcare paint of one kind according to claim 1, it is characterised in that: described
In step (3), phosphoric acid is that the analysis of 100-300ppm is pure.
6. the nano-material modified no-solvent polyurethane woodcare paint of one kind according to claim 1, it is characterised in that: described
In step (3), stand-by timeliness is lower than 20min.
7. the nano-material modified no-solvent polyurethane woodcare paint of one kind according to claim 1, it is characterised in that: described
In step (4), the mass ratio of some polyesters polyalcohol and remaining polyester polyol is 1:2.5-3.
8. the nano-material modified no-solvent polyurethane woodcare paint of one kind according to claim 1, it is characterised in that: described
In step (4), the component of nano-material modified no-solvent polyurethane woodcare paint, by weight, including 35-40 parts of MDI,
Prefabricated polyether polyol 10-15 parts, it is 45-50 parts of polyester polyol, additive 1-5 parts prefabricated, total amount is 100 parts, described prefabricated
Polyether polyol is made by adipic acid, terephthalic acid (TPA) and M-phthalic acid and diethylene glycol (DEG) and ethylene glycol hybrid reaction.
9. the nano-material modified no-solvent polyurethane woodcare paint of one kind according to claim 8, it is characterised in that: described
In step (4), the component of nano-material modified no-solvent polyurethane woodcare paint, by weight, including 39 parts of MDI, it is prefabricated
10 parts of polyether polyol, 48 parts of polyester polyol, 3 parts of prefabricated additive, total amount are 100 parts.
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| US5508340A (en) * | 1993-03-10 | 1996-04-16 | R. E. Hart Labs, Inc. | Water-based, solvent-free or low voc, two-component polyurethane coatings |
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